CN1312870A - Surface coating - Google Patents

Surface coating Download PDF

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Publication number
CN1312870A
CN1312870A CN 99809477 CN99809477A CN1312870A CN 1312870 A CN1312870 A CN 1312870A CN 99809477 CN99809477 CN 99809477 CN 99809477 A CN99809477 A CN 99809477A CN 1312870 A CN1312870 A CN 1312870A
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Prior art keywords
compound
haloalkyl
alkyl
general formula
formula
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CN 99809477
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Chinese (zh)
Inventor
J·P·S·巴德亚尔
C·R·维利斯
S·A·布鲁尔
S·R·库尔森
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UK Secretary of State for Defence
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UK Secretary of State for Defence
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Publication of CN1312870A publication Critical patent/CN1312870A/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation

Abstract

A method of coating a surface with a polymer layer, which method comprises exposing said surface to a plasma comprising one or more organic monomeric compounds, at least one of which comprises two carbon-carbon double bonds, so as to form a layer of cross-linked polymer on said surface. Suitable organic compounds include compounds of formula(I)where R<1>, R<2>, R<3>, R<4>, R<5>, and R<6> are all independently selected from hydrogen, alkyl, haloalkyl or aryl optionally substituted by halo; and Z is a bridging group. The method is suitable for applying oil and/or water repellent coatings onto substrates such as fabrics.

Description

Face coat
The present invention relates to face coat, the preparation of particularly grease proofing and water-proof surface also relates to the coated article that obtains thus.
Waterproof and anti-oil processing for various surfaces are extensive use of.For example, can require this performance is imparted on the surface of solids, as metal, glass, pottery, paper, polymer etc., purpose is to improve its antiseptic property, or stops or suppress and stain.
Needing the special matrix of this coating is fabric, especially for Application Areas, sportswear, Casual Wear and the Military Application field of outdoor clothes.Their processing requires in conjunction with fluoropolymer usually or more particularly, is anchored on the surface of apparel fabrics.Grease proofing and water resistance is the quantity of the function of fluorocarbon group quantity and the length material that maybe can be inserted into the effective clearance and the function of length.The concentration of this material is big more, and the repellency of arrangement is big more.
In addition, polymeric compounds must form the key of durability with matrix.Grease proofing and waterproof textile treatment is usually based on fluoropolymer, and this fluoropolymer is applied on the fabric with the form of aqueous emulsion.Because handle just simple with very thin, liquid repellent film coated fibre, so fabric keeps the gas permeability and the permeability of air.In order to make these arrangements keep durability, they carry out common application processing with bonding fluorine polymer with crosslinked resin sometimes to fabric.And can obtain for washing and dry-cleaning, all to have good durability in this way, crosslinked resin can seriously destroy cellulose fibre and reduce the mechanical strength of material. and be used to prepare the grease proofing and chemical method waterproof textiles and for example be disclosed in WO97/13024 and " fibre science and technical manual " (Marcel and Dekker companies such as BP No1102903 or M.Lewin, New York, 1984, the 2nd volume, the 2nd chapter B part).
Plasma-deposited method is widely used in polyradical is coated with and is deposited on the kinds of surface, this method be considered to a kind of cleaning, the dry state method, compare the generation less waste with traditional hygrometric state chemical method.Make in this way, plasma generation is from the organic molecule of small-molecular weight, this organic molecule is in the ionized electric field under the low pressure condition, when finishing plasma in the presence of matrix when, poly-being incorporated on the matrix in gas phase of the active molecule in the ion in the plasma, free radical and the compound reacts with the thin polymer film that is increasing.Traditional polymer synthetic method is tended to generate and is contained the structure that has extremely similar constitutional repeating unit to monomeric substance, and the polymer network of use plasma generation may be quite complicated.
The plasma polymerization success or not is relevant with several factors, and the characteristic that includes organic compounds is interior.The compound such as the maleic anhydride that contain reactive oxygen were used for plasma polymerization process (" chemical material " 1996 the 8th the 1st phases of volume) in the past always.
U.S. Patent No. 5328576 has been described the processing of fabric or paper surface, gives the liquid repellent performance by with oxygen plasma preliminary treatment being carried out on the surface, carries out the plasma polymerization of methane then.
But wish to obtain grease proofing and verified difficult realization of fluorocarbons waterproof by plasma polymerization.Once reported the ring-type fluorocarbons through plasma polymerization than acyclic homologue easier (" polymer chemistry " part of H.Yasuda etc. " polymer science magazine ", 1977 15 volume 2411 pages).The plasma polymerization of the perfluor cyclohexane monomer that trifluoromethyl replaces once had report (A.M.Hynes etc., " big molecule ", 1996 the 29th volumes, the 18th～21 page).
Described a kind of method among the SU-1158-634: fabric is handled with plasma discharge in the presence of inert gas, is exposed in the fluoro-acrylate monomer then.A kind of fluoro-alkyl acrylate resist agent is deposited on the similar approach on the solid matrix, sees to be set forth in european patent application No.0049884.
Describe and applied for that the preparation surface has the improving one's methods of polymer coating of grease proofing and/or waterproof based on the co-pending patent application of UK Patent Application Nos.9712338.4 and 9720078.6.A kind of method with the polymeric layer coating surface has been described in this patent application, this method comprises described surface is exposed in the plasma, the unsaturated organic compound that comprises some monomer in this plasma, this compound comprises the alkyl of optional replacement, wherein optional substituting group is a halogen, and purpose is to form grease proofing or waterproof coating on described matrix.
Yet the applicant finds that the durability of this coating can be improved.
According to the present invention, a kind of method with the polymeric layer coating surface is provided, this method comprises described surface is exposed in the plasma, this plasma comprises one or more organic monomer compounds, at least a organic monomer compound contains two two keys, and purpose is to form crosslinked polymer layer on described surface.
Comprise nonequilibrium plasma those with in the methods of the invention suitable plasma as producing by radio frequency (Rf), microwave or direct current (DC).They can or be lower than under the normal pressure at normal pressure operates, and this is well known in the art.
Contain the suitable combination thing of an above carbon-to-carbon double bond, or be used in this compound in the plasma and the mixture of other monomer organic compounds is suitable, they can obtain having the cross-linked polymer of grease proofing or water resistance.For water proofing property, wish to exist long-chain hydrocarbon chain, for example alkyl chain.For grease proofing or waterproof grease proofness again, preferably there is the haloalkyl chain, particularly in compound, there is the whole haloalkyl side chain.The cross-linked polymer base coating that obtains thus has excellent durability.For example, when being used for matrix such as fabric, grease proofing and/or waterproof coating can have better washing resistance.
The suitable compound that contains two keys more than comprises the compound of general formula (I): R wherein 1, R 2, R 3, R 4, R 5And R 6Whole aryl that are selected from hydrogen, halogen, alkyl, haloalkyl independently of each other or randomly replaced by halogen; And Z is an abutment.
The present invention uses term " halogeno-group " or " halogen " to refer to fluorine, chlorine, bromine and iodine.Particularly preferred halogeno-group is the fluoro base.Term " aryl " refers to aromatic group such as phenyl or naphthyl, particularly phenyl.Term " alkyl " refers to the straight or branched of carbon atom, and suitable chain length is to reach 20 carbon atoms.Term " alkenyl " refers to the suitable undersaturated straight or branched that contains 2～20 carbon atoms." haloalkyl " refers to alkyl chain as defined above, comprises at least one halo substituting group.
The example that is used for the suitable abutment Z of general formula (I) compound is known those in polymer arts, and they comprise the alkyl between the oxygen atom of can placing that randomly replaces especially.The optional substituting group suitable for abutment Z comprises whole haloalkyl, particularly perfluoroalkyl.
In particularly preferred embodiments, abutment Z comprises one or more acyloxy or ester group.Especially, the abutment of general formula Z is the group of sub-general formula (II) expression: Wherein n is 1～10 integer, suitable is 1～3 integer, each R 7, R 8Be irrespectively to be selected from hydrogen, alkyl or haloalkyl each other.
Suitable R 1, R 2, R 3, R 4, R 5And R 6Be haloalkyl such as fluoro-alkyl or hydrogen, particular case is that they are hydrogen entirely.
The compound of general formula (I) contains at least one haloalkyl suitably, preferred whole haloalkyl, and this can form the coating of grease proofing while waterproof.The position that this group is suitable is as the radicals R in the abutment Z 7Or R 8
Therefore the specific example of general formula (I) compound comprises following formula A and B:
Figure A9980947700081
Figure A9980947700082
The compound of general formula (I) is fit to mix with another monomeric compound that also can haloalkyl containing.This situation also can contain the middle compound of whole haloalkyl part, particularly general formula (I) and not comprise a such group.
The compound of general formula (I) mixes with additional compounds, and these also can comprise unsaturated organic compound, and this compound contains at least one two key, and this pair bond energy enough reacts the formation polymer compound.
No matter the perhalogeno compound is saturated or undersaturated, also can form grease proofing and/or water-proof surface, if particularly they comprise long-chain or ring, and they can form other components of plasma mixture.These compounds will comprise whole haloalkyl or the perhalogeno alkenyl that contains 3～20 carbon atoms, preferred 8～12 carbon atoms suitably.
Specially suitable other organic compounds are that general formula is those compounds of (III):
Figure A9980947700091
R wherein 9, R 10And R 11The aryl that is independently from each other hydrogen, alkyl, haloalkyl or randomly replaces by halogen; With
R 13Be radicals X-R 13, R wherein 13Be that alkyl or haloalkyl and X are keys; General formula-C (O) O (CH 2) mM is 1～10 integer in the group of Y-, and Y is a key or sulfoamido; Or the pR of group-(O) 14(O) q (CH 2) t-, wherein R 14Be the aryl that is randomly replaced by halogen, p is 0 or 1, q be 0 or 1 and t be an integer of 0 or 1～10, condition is that q is 1 o'clock, t is not 0.
Preferred R at least 9, R 10Or R 11In one of be hydrogen.
As R 9, R 10, R 11And R 13Suitable haloalkyl be fluoro-alkyl, alkyl chain can be a straight or branched, and also can comprise annulus.
For R 13, alkyl chain comprises 2 or 2 above carbon atoms, 2～20 carbon atoms and 6～12 carbon atoms preferably suitably suitably.
For R 9, R 10And R 11, alkyl chain preferably contains 1～6 carbon atom usually.
Preferred R 13Be haloalkyl, and more preferably whole haloalkyl, particularly general formula C sF 2s+1Perfluoroalkyl, wherein s is 1 or greater than 1 integer, scope is 1～20 suitably, and preferred 6～12 as 8 or 10.
As R 9, R 10And R 11Suitable alkyl contain 1～6 carbon atom.
But preferred R 9, R 10And R 11In at least one is hydrogen and preferred R 9, R 10And R 11Be hydrogen entirely.
Wherein X is group-C (O) O (CH 2) mY-, m is an integer, it provides suitable interval base, particularly m is 1～5, preferably is about 2.
Suitable sulfonamide (sulphonamide) group as Y comprises general formula-N (R 14) SO 2 3-those, R wherein 14Be hydrogen or alkyl such as C 1-4Alkyl, particularly methyl or ethyl.
In preferred embodiments, the compound of general formula (III) is the compound of general formula (IV):
CH 2=CH-R 13(IV) be R wherein 13Be that the same definition relevant with general formula (III) is identical.
In the compound of general formula (II), the X in the general formula (III) is a key.
In the embodiment preferred that substitutes, the compound of general formula (III) is the acrylate of general formula (V).
CH 2=CR 15C (O) O (CH 2) nR 13(V) be m and R wherein 13The definition relevant with general formula (III) is identical, R 15Be hydrogen or C 1-6Alkyl is as methyl.
Use these compounds, can prepare coating with hydrophobic value and oleophobicity values.
Other compounds of general formula (III) are styrene derivatives, and this is well-known in polymer arts.
All compounds or the compound known of general formula (I) and general formula (III) perhaps can prepare from compound known with conventional method.
The surface of coating can be any solid matrix according to the present invention, as fabric, metal, glass, pottery, paper or polymer.Especially, the surface comprises fabric substrate such as cellulosic fabric, can be used as grease proofing and/or waterproof.Alternatively, fabric can be synthetic textiles such as acrylic compounds/nylon fabrics.
Fabric can be without handling or can passing through preliminary treatment.For example, can strengthen water proofing property and make fabric have good oil resistant finish performance according to the processing of inventing, wherein fabric has had the only silicone arrangement of waterproof.
The accurate condition of the plasma polymerization that takes place with effective means will change along with the variation of multiple factor, as polymer property, matrix etc., and will with conventional method and/or below enumerate method and determine.Yet usually, to use the steam of plasma compound or pressure be 0.01～10mbar, suitably during the compound of about 0.2mbar, and polymerisation is suitable effective.
Light glow discharge by high frequency voltage such as 13.56MHz then.
The suitable mean power of the electric field that is adopted is up to 50 watts, and appropriate condition comprises pulse or electric field continuously, but preferably adopts impulse electric field.Follow procedure produces pulse, wherein produces very low average power, as the follow procedure 20 μ s that switch on, the 10000 μ s that cut off the power supply～20000 μ s.
The suitable time of using electric field is 30 seconds～20 minutes, preferred 2～15 minutes, depends on employed compound characteristic and matrix etc. in the plasma container.
According to the plasma polymerization of The compounds of this invention, particularly than causing under the low average power that height fluoridizes the deposition with super-hydrophobic coating.In addition, compound has the attach structure persistence in coating layer, and this can be owing to the direct polymerization of specific olefinic monomer, as extremely sensitive pair of key in the fluoroolefin monomer.
Suitably, adopting low powder pulsed plasma polymerization purpose is the coating that preparation has the good adhesive property of good waterproof and grease proofness.This method causes structure persistence largely, can and almost not have cataclasis in the load time owing to the radical polymerization that takes place at the discharge time of intermittent load.
When the plasma compound comprised perfluoroalkyl end group or part, method of the present invention can have oleophobic and hydrophobic surface property.
Therefore the present invention also provides hydrophobic or the oleophobic matrix, and this matrix comprises the matrix of haloalkyl containing polymer coating, and this haloalkyl polymer coating adopts said method to use.Especially, except matrix can be solid material such as biological medicine with the equipment, this matrix is a fabric.
Traditional plasma deposition apparatus as known in the art can use in application process of the present invention.

Claims (14)

1. use a kind of method of polymeric layer coating surface, this method comprises described surface is exposed in the plasma, this plasma comprises one or more organic monomer compounds, and one of them comprises two carbon-to-carbon double bonds at least, and purpose is to form crosslinked polymer layer on described surface.
2. according to the process of claim 1 wherein that the organic monomer compound comprises the compound of general formula (I):
Figure A9980947700021
R wherein 1, R 2, R 3, R 4, R 5And R 6Whole aryl that are selected from hydrogen, halogen, alkyl, haloalkyl independently of each other or randomly replaced by halogen; And Z is an abutment.
3. according to the method for right 2, wherein abutment Z comprises and can place alkyl between the oxygen atom, that randomly replace.
4. according to the method for claim 3, wherein abutment Z is the group of sub-general formula (II) expression: Wherein n is 1～10 integer, 1～3 integer suitably, each R 7, R 8Be irrespectively to be selected from hydrogen, alkyl or haloalkyl each other.
5. according to the method for arbitrary claim in the claim 2～4, the compound of its formula of (I) contains at least one haloalkyl.
6. according to the method for claim 5, wherein haloalkyl is a whole haloalkyl.
7. according to the method for arbitrary claim in the claim 2～6, the compound of its formula of (II) is
Figure A9980947700031
Figure A9980947700032
8. according to the method for arbitrary claim in the claim 2～7, the compound of its formula of (I) mixes with other monomeric compound.
9. method according to Claim 8, wherein said other monomeric compound comprises a kind of unsaturated organic compound or perhalogeno compound, and wherein this unsaturated organic compound contains at least one two key, and this pair bond energy enough reacts the formation polymer compound.
10. according to the method for claim 9, wherein said other organic compound is the compound of general formula (III):
Figure A9980947700033
R wherein 9, R 10And R 11The aryl that is independently from each other hydrogen, alkyl, haloalkyl or randomly replaces by halogen; With
R 12Be radicals X-R 13, R wherein 13Be that alkyl or haloalkyl and X are keys; General formula-C (O) O (CH 2) group of mY-, wherein, m is 1～10 integer, Y is a key or sulfoamido; Or the pR of group-(O) 14(O) q(CH 2) t-, wherein R 14Be the aryl that is randomly replaced by halogen, p is 0 or 1, q be 0 or 1 and t be 0 or 1～10 integer, condition is that q is 1 o'clock, t is not 0.
11. according to the method for claim 10, the compound of its formula of (III) is the compound of general formula (IV):
CH 2=CH-R 13(IV) be R wherein 13Identical with definition in the claim 10.
12. according to the method for claim 10, the compound of its formula of (III) is the acrylate of general formula (V):
CH 2=CR 15(O) O (CH 2) nR 13(V) be m and R wherein 13Identical with the definition in the claim 10, R 15Be hydrogen or C 1-6Alkyl is as methyl.
13. the matrix of the polymer coating that a method that contains in the arbitrary claim in good grounds front obtains.
14. according to a kind of matrix of claim 13, wherein this matrix is a fabric.
CN 99809477 1998-06-10 1999-06-03 Surface coating Pending CN1312870A (en)

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GBGB9812457.1A GB9812457D0 (en) 1998-06-10 1998-06-10 Surface coatings
GB9812457.1 1998-06-10

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AU (1) AU749176B2 (en)
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Cited By (3)

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CN1946488B (en) * 2004-03-18 2010-12-08 英国国防部 Coating of a polymer layer using low powder pulsed plasma in a plasma chamber of a large volume
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
CN109071966A (en) * 2015-06-09 2018-12-21 P2I有限公司 coating

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GB0713830D0 (en) * 2007-07-17 2007-08-29 P2I Ltd Novel products method
GB0810326D0 (en) * 2008-06-06 2008-07-09 P2I Ltd Filtration media
GB2475685A (en) 2009-11-25 2011-06-01 P2I Ltd Plasma polymerization for coating wool
GB201000538D0 (en) 2010-01-14 2010-03-03 P2I Ltd Liquid repellent surfaces
US11898248B2 (en) 2019-12-18 2024-02-13 Jiangsu Favored Nanotechnology Co., Ltd. Coating apparatus and coating method
CN113774363A (en) 2020-06-09 2021-12-10 江苏菲沃泰纳米科技股份有限公司 Film coating equipment and film coating method thereof

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Publication number Priority date Publication date Assignee Title
CN1946488B (en) * 2004-03-18 2010-12-08 英国国防部 Coating of a polymer layer using low powder pulsed plasma in a plasma chamber of a large volume
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
CN109071966A (en) * 2015-06-09 2018-12-21 P2I有限公司 coating
CN109071966B (en) * 2015-06-09 2022-07-22 P2I有限公司 Coating layer

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JP2003513108A (en) 2003-04-08
GB9812457D0 (en) 1998-08-05
AU4276399A (en) 1999-12-30
NZ508750A (en) 2002-11-26
GB2358635A (en) 2001-08-01
GB2358635B (en) 2002-10-02
EP1090178A1 (en) 2001-04-11
AU749176B2 (en) 2002-06-20
WO1999064662A1 (en) 1999-12-16
CA2334631A1 (en) 1999-12-16

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