CN109675775A - The method of protective layer and the product of surface formation matcoveredn are formed in body surface - Google Patents
The method of protective layer and the product of surface formation matcoveredn are formed in body surface Download PDFInfo
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- CN109675775A CN109675775A CN201710971352.5A CN201710971352A CN109675775A CN 109675775 A CN109675775 A CN 109675775A CN 201710971352 A CN201710971352 A CN 201710971352A CN 109675775 A CN109675775 A CN 109675775A
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- protective layer
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- 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
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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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
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- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention provides a kind of method for forming protective layer in body surface, including at least part surface of object to be exposed in the first plasma, to form the first protective layer at least part surface of object；It is exposed in the second plasma with by least part surface for being formed with the object of the first protective layer, to form the second protective layer.The present invention also provides the product that a kind of surface forms matcoveredn, which includes the first protective layer and the second protective layer.First protective layer is formed at least part surface of the product by being exposed in the first plasma.At least part surface for the product for being formed with the first protective layer by being exposed to the outer surface for being formed in first protective layer in the second plasma by the second protective layer.
Description
Technical field
The present invention relates to a kind of products of method and surface formation matcoveredn that protective layer is formed in body surface.
Background technique
People production and daily life in, it is often necessary to its object used from by liquid (water, oil, aqueous solution or
Person other mixing liquids etc. for containing water, oil) its surface is contacted, cause object to be contaminated, soak, or because these liquid
It acts on and causes physical damage.Here, the object that people use is product.For example, product include electrical equipment, electronic equipment,
Filter membrane, wrist-watch and wearing product.
In the existing technology for preventing object from being contacted by liquid, disclose it is a kind of by using containing polymer it is equal from
Daughter forms protective polymers layer in body surface, exists for example, Chinese Patent Application No. CN200780002557 discloses one kind
Body surface forms protective polymers layer, to prevent object to be contaminated by the liquid or soak.In another example Chinese Patent Application No.
CN2013100842664 discloses a kind of electrical or electronic equipment or the surface of its component is formed with protective polymers layer
Product and a kind of method for forming protective polymers layer on the surface of electrical or electronic equipment or its component.In in another example
State number of patent application CN200880114449 discloses the filter membrane that a kind of surface is formed with polymeric layer.However, existing
By the way that using the plasma containing polymer, in the technology that body surface forms protective polymers layer, existing prevents object quilt
The problems such as ability of fluid contact surface is weak, and the binding force of protective polymers layer and body surface is poor.
Summary of the invention
To solve the above-mentioned problems, the present invention proposes a kind of method for forming protective layer in body surface, through the invention
The method for forming protective layer in body surface proposed, can be improved the ability for preventing object by fluid contact surface, meanwhile, energy
Enough improve the binding force of protective layer and body surface.The present invention also proposes that a kind of surface forms the product of matcoveredn, the product
Protective layer can be improved the ability for preventing product by fluid contact surface, and improve the binding force of protective layer and product surface.
According to an aspect of the present invention, the present invention provides a kind of method for forming protective layer in body surface, including will
At least part surface of object is exposed in the first plasma, to form the first protection at least part surface of object
Layer；It is exposed in the second plasma with by least part surface for being formed with the object of the first protective layer, to form second
Protective layer.
The method for forming protective layer in body surface according to an aspect of the present invention, can be improved prevents object by liquid
The ability of body contact surface, meanwhile, it is capable to the binding force of protective layer and body surface be improved, to improve the protection longevity of protective layer
Life.
The method for forming protective layer in body surface according to an aspect of the present invention, forms the of the second plasma
Two gases are different from forming the first gas of the first plasma.
The method for forming protective layer in body surface according to an aspect of the present invention, the first protective layer are closely knit protection
Layer；And second protective layer be lyophobicity protective layer.
The method for forming protective layer in body surface according to an aspect of the present invention, forms the of the first plasma
One gas includes the compound indicated by chemical formula (I),
Wherein, T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately generation
Table hydrogen, halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen.
The method for forming protective layer in body surface according to an aspect of the present invention, works as T1-T6In have and only there are two
When for methyl, preferably at least having one in the atom or substituent group of other non-methyl is not hydrogen.
The method for forming protective layer in body surface according to an aspect of the present invention, forms the of the second plasma
Two gases include the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated virtue
Base；X is the arbitrary integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n is equal to (2l+1-
m)。
The method for forming protective layer in body surface according to an aspect of the present invention, R1、R2、R3For hydrogen or methyl.
The method for forming protective layer in body surface according to an aspect of the present invention, R1、R2、R3For hydrogen.
The method for forming protective layer in body surface according to an aspect of the present invention is protected that will be formed with described first
Before at least part surface of the object of sheath is exposed in the second plasma, it will first be formed with first protection
At least part surface of the object of layer is exposed in the third plasma formed by the third gas comprising fluorohydrocarbon,
To form middle layer.
In this way, by between the first protective layer and the second protective layer be arranged middle layer can further increase protective layer with
The binding force of body surface, to improve the protection service life of protective layer, while raising prevents energy of the object by fluid contact surface
Power.
The method for forming protective layer in body surface according to an aspect of the present invention, forms the of the first plasma
One gas further includes the first carrier gas.First carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.Also, it is formed
The second gas of second plasma further includes the second carrier gas.Second carrier gas is selected from inert gas, CF4、C3F8、N2、H2In extremely
Few one kind.
The method for forming protective layer in body surface according to an aspect of the present invention, forms the of third plasma
Three gases further include third carrier gas, and third carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.
According to a further aspect of the invention, the present invention provides a kind of product of surface formation matcoveredn, the protective layer
Including the first protective layer and the second protective layer.First protective layer is formed in the product by being exposed in the first plasma
At least part surface.Second protective layer, which passes through, is exposed at least part surface for the product for being formed with the first protective layer
The outer surface of first protective layer is formed in two plasmas.
Surface according to an aspect of the present invention forms the product of matcoveredn, and can be improved prevents product from being connect by liquid
It touches surface and then invades the ability in product, meanwhile, it is capable to the binding force of protective layer and product surface be improved, to improve protection
The protection service life of layer.
Surface according to a further aspect of the invention forms the product of matcoveredn, forms the second of the second plasma
Gas is different from forming the first gas of the first plasma.
Surface according to a further aspect of the invention forms the product of matcoveredn, and the first protective layer is closely knit protection
Layer；And second protective layer be lyophobicity protective layer.
Surface according to a further aspect of the invention forms the product of matcoveredn, forms first plasma
First gas includes the compound indicated by chemical formula (I),
Wherein,
T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately represent hydrogen,
Halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen.
Surface according to a further aspect of the invention forms the product of matcoveredn, works as T1-T6In have and only there are two being
When methyl, preferably at least having one in the atom or substituent group of other non-methyl is not hydrogen.
Surface according to a further aspect of the invention forms the product of matcoveredn, forms second plasma
Second gas includes the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated virtue
Base；X is the arbitrary integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n is equal to (2l+
1-m)。
Surface according to a further aspect of the invention forms the product of matcoveredn, R1、R2、R3For hydrogen or methyl.
Surface according to a further aspect of the invention forms the product of matcoveredn, R1、R2、R3For hydrogen.
Surface according to a further aspect of the invention forms the product of matcoveredn, will be formed with the first protective layer
Before at least part surface of product is exposed in the second plasma, it will first be formed with the product of first protective layer
At least part surface is exposed in the third plasma formed by the third gas comprising fluorohydrocarbon, forms middle layer.
In this way, by between the first protective layer and the second protective layer be arranged middle layer can further increase protective layer with
The binding force of product surface, to improve the protection service life of protective layer, while raising prevents energy of the product by fluid contact surface
Power.
Surface according to a further aspect of the invention forms the product of matcoveredn, forms the first of the first plasma
Gas further includes the first carrier gas, and the first carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.And form described the
The second gas of two plasmas further includes the second carrier gas, and the second carrier gas is selected from inert gas, CF4、C3F8、N2、H2In at least
It is a kind of.
Surface according to a further aspect of the invention forms the product of matcoveredn, forms the third of third plasma
Gas further includes third carrier gas, and third carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.
Surface according to a further aspect of the invention forms the product of matcoveredn, and product includes electrical equipment, electronics
At least one of equipment, wrist-watch, cloth, permeable membrane and wearing product.
Surface according to a further aspect of the invention forms the product of matcoveredn, and the electrical equipment includes: communication
Any one of base station, transformer equipment, data switching equipment, the vehicles, outdoor lightings and/or communication base station, change
Any component of any one of electric equipment, data switching equipment, the vehicles, outdoor lightings.
Surface according to a further aspect of the invention forms the product of matcoveredn, and the electronic equipment includes: hand-held
Any one of communication equipment, electronic game station, wearable electronic and/or handheld communication devices, electronic game are set
Any component of any one of standby, wearable electronic.
Surface according to a further aspect of the invention forms the product of matcoveredn, the wearing product include clothes,
Shoes and hats and/or ornaments.
Surface according to an aspect of the present invention forms the product of matcoveredn, and can be improved prevents product from being connect by liquid
It touches surface and then invades the ability in product, meanwhile, it is capable to the binding force of protective layer and product surface be improved, to improve protection
The protection service life of layer.
Specific embodiment
The technical solution of more than one embodiment of the invention is described below.Obviously, reality as described herein
It applies example to be only a part of the embodiment of the present invention, instead of all the embodiments.It should be noted that based on these in the present invention
Embodiment, those of ordinary skill in the art's every other embodiment obtained, shall fall within the protection scope of the present invention.
It should be noted that in the present invention, the statement of " gas " refer to individually or the gas of form of mixtures or
Steam and aerosol.
" closely knit protective layer " refers to that the protective layer can either prevent liquid by that can prevent gas from passing through again.
" lyophobicity protective layer " refers to that the protective layer can prevent liquid from passing through, and allows gas to pass through under normal circumstances.
" liquid " refers to liquid, including water, oil, aqueous solution or other contain at least one of water or mixing liquid etc. of oil.
In one embodiment of the invention, a kind of method for forming protective layer in body surface is provided, including by object
At least part surface be exposed in the first plasma, at least part surface of object formed the first protective layer.
At least part surface for being formed with the object of the first protective layer is exposed in the second plasma, to form the second protection
Layer.
Here, object includes being not limited to any one of present invention product.It further says, the second protective layer and
One protective layer is at least partly laminated on the surface of object.
The method according to an embodiment of the invention for forming protective layer in body surface, can be improved prevents object quilt
The ability of fluid contact surface, meanwhile, it is capable to the binding force of protective layer and body surface be improved, to improve the protection of protective layer
Service life.
It further says, the second gas for forming the second plasma is different from forming the first gas of the first plasma
Body.
The method according to an embodiment of the invention for forming protective layer in body surface, the first protective layer are closely knit guarantor
Sheath.Second protective layer is lyophobicity protective layer.
The method according to an embodiment of the invention for forming protective layer in body surface, forms the first plasma
First gas includes the compound indicated by chemical formula (I),
Wherein, T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately generation
Table hydrogen, halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen.
The compound that above-mentioned formula (I) indicates be, for example, o-methyl styrene, 1,4- divinylbenzene, 1,2,4- trimethylbenzene,
Mesitylene, durol, to two benzotrifluorides etc..
The method according to an embodiment of the invention for forming protective layer in body surface, in chemical formula (I), works as T1-T6
In have and only there are two for methyl when, preferably at least having one in the atom or substituent group of other non-methyl is not hydrogen.
Above-mentioned preferred compound is, for example, 2- chloro-p-xylene, tetrafluoro paraxylene etc..
It is recognised that at least part surface of object be exposed to by include compound that chemical formula (I) indicates the
In the first plasma that one gas is formed after the scheduled time, it is deposited at least part surface of the object based on chemistry
The first polymer layer for the compound that formula (I) indicates.
The method according to an embodiment of the invention for forming protective layer in body surface, forms the second plasma
Second gas includes the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated virtue
Base.X is the arbitrary integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n is equal to (2l+
1-m)。
It is recognised that being exposed at least part surface for being formed with the object of the first protective layer by including chemical formula
(II) in the second plasma that the second gas of the compound indicated is formed after the scheduled time, at least part of the object
The second polymer layer of the compound indicated based on chemical formula (II) is deposited on surface.
One example of the method according to an embodiment of the invention that protective layer is formed in body surface, R1、R2、R3
For hydrogen, methyl or halogen.
Specifically, as alkyl, it can be C1-C3Alkyl can enumerate methyl, ethyl, n-propyl and isopropyl.
The halogen is fluorine, chlorine, bromine, iodine.
As the halogen atom in halogenated alkyl, fluorine, chlorine, bromine, iodine can be enumerated.
As the alkyl in halogenated alkyl, with the example of abovementioned alkyl.
One example of the method according to an embodiment of the invention that protective layer is formed in body surface, R1、R2、R3
For hydrogen.
One example of the method according to an embodiment of the invention that protective layer is formed in body surface, will form
Before thering is at least part surface of the object of first protective layer to be exposed in the second plasma, will first it be formed with
At least part surface of the object of first protective layer is exposed to formed by the third gas comprising fluorohydrocarbon
In three plasma body, to form middle layer.
The fluorohydrocarbon can enumerate CF4、C2F4、C2F6、C3F6、C3F8、C4F8。
In this way, by between the first protective layer and the second protective layer be arranged middle layer can further increase protective layer with
The binding force of body surface, to improve the protection service life of protective layer, while raising prevents energy of the object by fluid contact surface
Power.
One example of the method according to an embodiment of the invention that protective layer is formed in body surface, forms first
The first gas of plasma further includes the first carrier gas.First carrier gas is selected from inert gas, CF4、C3F8、N2、H2In at least one
Kind.Also, the second gas for forming the second plasma further includes the second carrier gas.Second carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of.
One example of the method according to an embodiment of the invention that protective layer is formed in body surface, forms third
The third gas of plasma further includes third carrier gas.Third carrier gas is selected from inert gas, CF4、C3F8、N2、H2In at least one
Kind.
According to one embodiment of present invention, including the first plasma of formation of the compound indicated by chemical formula (I)
First gas the first plasma is formed in the plasma chamber of plasma apparatus.Plasma apparatus includes pairs of
The electrode of setting, the electrode being arranged in pairs are contained in plasma chamber.
According to one embodiment of present invention, including the second plasma of formation of the compound indicated by chemical formula (II)
Second gas the second plasma is formed in the plasma chamber of plasma apparatus.Plasma apparatus includes pairs of
The electrode of setting, the electrode being arranged in pairs are contained in plasma chamber.
According to one embodiment of present invention, it is being waited including the third gas by forming third plasma comprising fluorohydrocarbon
Third plasma is formed in the plasma chamber of gas ions equipment.Plasma apparatus includes the electrode being arranged in pairs, at
The electrode of setting is contained in plasma chamber.
According to still another embodiment of the invention, the present invention provides a kind of product of surface formation matcoveredn, the protection
Layer includes the first protective layer and the second protective layer.First protective layer is formed in the product by being exposed in the first plasma
At least part surface.Second protective layer is by the way that at least part surface for the product for being formed with the first protective layer to be exposed to
The outer surface of first protective layer is formed in second plasma.
The product that surface according to still another embodiment of the invention forms matcoveredn, which can be improved, prevents product by liquid
Ability in body contact surface and then intrusion product, meanwhile, it is capable to the binding force of protective layer and product surface be improved, to improve
The protection service life of protective layer.
It further says, the second protective layer and the first protective layer are at least partly laminated on the surface of object.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, forms second etc.
The second gas of gas ions is different from forming the first gas of the first plasma.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, the first protective layer
For closely knit protective layer.Second protective layer is lyophobicity protective layer.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, forms described the
The first gas of one plasma includes the compound indicated by chemical formula (I),
Wherein,
T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately represent hydrogen,
Halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, chemical formula (I)
In, work as T1-T6In have and only there are two for methyl when, preferably at least having one in the atom or substituent group of other non-methyl is not
Hydrogen.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, forms second etc.
The second gas of gas ions includes the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated virtue
Base；X is any one integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n is equal to
(2l+1-m)。
Surface as another embodiment of the invention forms an example of the product of matcoveredn, R1、R2、R3For
Hydrogen or methyl.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, R1、R2、R3For
Hydrogen.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, will be formed with
Before at least part surface of the product of first protective layer is exposed in the second plasma, it will first be formed with described first and protect
At least part surface of the product of sheath is exposed in the third plasma formed by the third gas comprising fluorohydrocarbon, shape
At middle layer.That is, being additionally provided with middle layer between the first protective layer and the second protective layer.
In this way, by between the first protective layer and the second protective layer be arranged middle layer can further increase protective layer with
The binding force of product surface, to improve the protection service life of protective layer, while raising prevents energy of the product by fluid contact surface
Power.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, forms first etc.
The first gas of gas ions further includes the first carrier gas, and the first carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.
And the second gas for forming second plasma further includes the second carrier gas, the second carrier gas is selected from inert gas, CF4、C3F8、
N2、H2At least one of.
Surface as another embodiment of the invention forms an example of the product of matcoveredn, forms third etc.
The third gas of gas ions further includes third carrier gas, and third carrier gas is selected from inert gas, CF4、C3F8、N2、H2At least one of.
It is of the invention in the method that body surface forms protective layer, plasma polymerization occurs accurate in an efficient way
Condition can change according to the factor such as the property of polymer, processed product, and it is normal that these conditions are able to use this field
Method and/or technology are advised to determine.
Suitable plasma for methods described herein includes nonequilibrium plasma, for example, by radio frequency (Rf),
Microwave or direct current (DC) generate, and are preferably generated by radio frequency (Rf).They can be in atmospheric pressure as known in the art or low
In an atmosphere pressing operation.
Various forms of plasma apparatus can be used to generate gaseous plasma.In general, these devices include holding
Device, the plasma chamber that can produce plasma and the electrode being arranged in pairs, the electrode being arranged in pairs are contained in plasma
In body room.The specific example of such device is on the books in such as WO2005/089961 and WO02/28548, in addition to this, perhaps
Mostly other commercially available plasma generating devices, such as 160 integral type plasma handling system of Triton, Verus ICP etc. from
Daughter system (millet is manufactured with Science and Technology Ltd.) is also to be applicable in.
In general, product to be processed is placed in plasma chamber together with the gaseous polymer precursor to be deposited,
Glow discharge is lighted in the chamber and applies suitable voltage, can be pulse voltage or continuous voltage, preferably pulse electricity
Pressure.
The gas used in plasma may include the steam of individual monomeric compound, but it can be with carrier gas
Body especially inert gas (such as helium or argon gas), CF4、C3F8、N2、H2At least one of mixing.Particularly, due to can be with
The fragmentation of monomer is minimized, preferred carrier gas is helium.
In all cases it is possible to glow discharge is suitably ignited by applying high frequency voltage such as 13.56MHz, it can
To be applied by the electrode of plasma chamber interior.
It can be with the rate of the range of at least 1 sccm (sccm) and preferably 1-100sccm suitably
Gas, steam or admixture of gas are provided.
In the case of the monomer vapour, according to the property of monomer its with the 80-300mg/min for example, about speed of 120mg/min
Rate suitably provides, while applying pulse voltage.
Gas or steam can be inhaled into or be pumped into heating region.Particularly, when using plasma chamber, due to
Lead to the reduction of room pressure using aspiration pump, gas or steam can be inhaled into interior.
It is polymerize using steam of the invention, can be kept under the pressure of 0.0001-1000 millitorr, preferably about
It keeps under the pressure of 0.1-500 millitorr, is more preferably kept under the pressure of 0.1-200 millitorr.
Apply as impulse electric field, applied field has the peak power of 10-5000W, the preferably peak work of 30-1000W
Rate, the peak power of more preferable 50-500W.Pulse is applied with the sequence of fixed frequency, frequency 1-500Hz, preferably 10-
200Hz, more preferable 50-150Hz.Each sequence, which is divided into, opens and closes two parts, wherein service time account for sequence always continue when
Between ratio be known as duty ratio, duty cycle range can be 1%-95%, preferably 1%-50%, more preferable 5%-30%.With this
The Typical average powers that method obtains are 20W.
According to embodiment of the present invention, when needed, the container for filling the compound of the present invention can be heated
To predetermined temperature, in the plasma chamber for guaranteeing to be transported to plasma apparatus in the form of gas by compound.Into one
Step ground says that when needed, the channel for the plasma chamber that plasma apparatus can be transported to compound is heated, and
Holding is heated to predetermined temperature.
According to embodiment of the present invention, the electrode being arranged in pairs first is connected with continuous radio-frequency power supply, and even
Continuous radio-frequency power supply applies above-mentioned continuous radio frequency power to the electrode being arranged in pairs and continues at the first time, then, to be arranged in pairs
Electrode is connected with pulse radiation frequency power supply, and pulse radiation frequency power supply applies above-mentioned pulse radiation frequency electric power to the electrode being arranged in pairs
And continued for the second time.
Embodiment
Experiment equipment: (160 integral type plasma handling system of Triton, Shanghai millet have plasma handling system with science and technology
The manufacture of limit company), every technical parameter please refers to product manual.
Embodiment 1
100 transistors are placed in plasma chamber body, cavity is emptied to the base pressure of 3-10 millitorr, then makes helium
Gas is passed through in cavity with 20sccm until pressure reaches 80 millitorrs.Then cause continuous function at 13.56MHz, 300W using RF
Rate plasma 5 minutes.
Then, two benzotrifluoride steam will be introduced into cavity with 120 mg minutes rates, and by the plasma
Body switches to following pulsed plasma: peak power 100W, frequency 50Hz, duty ratio 5%.To two benzotrifluorides
Ionize and formed with autoreactivity on the surface of transistor the first protective layer of continuous uniform.After continuing 15 minutes, close
Plasma electrical source simultaneously stops for coping with two benzotrifluoride steam.
The intracorporal vacuum of chamber is maintained, with 120 mg minutes rates by 1H, 1H, 2H, 2H- perfluoro decyl acrylate steams
Vapour is introduced into cavity, and the plasma is switched to following pulsed plasmas: peak power 150W, frequency are
50Hz, duty ratio 5%.1H, 1H, 2H, 2H- perfluoro decyl acrylate ionize and with autoreactivity in the table of transistor
Second protective layer of face formation continuous uniform.Continue after twenty minutes, to close plasma electrical source and stop supplying 1H, 1H, 2H,
2H- perfluoro decyl acrylate steam.
The cavity is emptied into base pressure, then ventilate again to atmospheric pressure and takes out sample, obtains that there is two layers of protective layer
Sample 1.
Embodiment 2
100 transistors are placed in plasma chamber body, cavity is emptied to the base pressure of 3-10 millitorr, then makes helium
Gas is passed through in cavity with 20sccm until pressure reaches 80 millitorrs.Then cause continuous function at 13.56MHz, 300W using RF
Rate plasma 5 minutes.
Then, two benzotrifluoride steam will be introduced into cavity with 120 mg minutes rates, and by the plasma
Body switches to following pulsed plasma: peak power 100W, frequency 100Hz, duty ratio 5%.To two fluoroforms
Benzene ionization and the first protective layer for forming continuous uniform on the surface of transistor with autoreactivity.After continuing 15 minutes, close
It closes plasma electrical source and stops for coping with two benzotrifluoride steam.
The intracorporal vacuum of chamber is maintained, hexafluoropropene steam is introduced into cavity with 120 mg minutes rates, and by institute
It states plasma and switches to following pulsed plasma: peak power 100W, frequency 100Hz, duty ratio 5%.Six
Fluoropropene ionization and the middle layer for forming continuous uniform on the surface of transistor with autoreactivity.Continue after ten minutes, to close
It closes plasma electrical source and stops supplying hexafluoropropene steam.
The intracorporal vacuum of chamber is maintained, with 120 mg minutes rates by 1H, 1H, 2H, 2H- perfluoro decyl acrylate steams
Vapour is introduced into cavity, and the plasma is switched to following pulsed plasmas: peak power 150W, frequency are
100Hz, duty ratio 5%.1H, 1H, 2H, 2H- perfluoro decyl acrylate ionize and with autoreactivity in transistor
Second protective layer of surface formation continuous uniform.Continue after twenty minutes, to close plasma electrical source and stop supplying 1H, 1H, 2H,
2H- perfluoro decyl acrylate steam.
The cavity is emptied into base pressure, then ventilate again to atmospheric pressure and takes out sample, is obtained with three-layer protection layer
Sample 2.
Embodiment 3
100 knitted gloves are placed in plasma chamber body, cavity is emptied to the base pressure of 3-10 millitorr, is then made
Nitrogen is passed through in cavity with 20sccm until pressure reaches 80 millitorrs.Then caused at 13.56MHz, 300W continuously using RF
Power plasma 5 minutes.
Then, 1,2,4- front three benzene vapour is introduced into cavity with 120 mg minutes rates, and by the plasma
Body switches to following pulsed plasma: peak power 100W, frequency 50Hz, duty ratio 25%.1,2,4- front three
Benzene ionization and the first protective layer for forming continuous uniform on the surface of transistor with autoreactivity.After continuing 15 minutes, close
It closes plasma electrical source and stops supplying 1,2,4- front three benzene vapour.
The intracorporal vacuum of chamber is maintained, with 120 mg minutes rates by 1H, 1H, 2H, 2H- perfluoro decyl acrylate steams
Vapour is introduced into cavity, and the plasma is switched to following pulsed plasmas: peak power 150W, frequency are
50Hz, duty ratio 25%.1H, 1H, 2H, 2H- perfluoro decyl acrylate ionize and with autoreactivity in transistor
Second protective layer of surface formation continuous uniform.Continue after twenty minutes, to close plasma electrical source and stop supplying 1H, 1H, 2H,
2H- perfluoro decyl acrylate steam.
The cavity is emptied into base pressure, then ventilate again to atmospheric pressure and takes out sample, obtains that there is two layers of protective layer
Sample 3.
Embodiment 4
100 knitted gloves are placed in plasma chamber body, cavity is emptied to the base pressure of 3-10 millitorr, is then made
Nitrogen is passed through in cavity with 20sccm until pressure reaches 80 millitorrs.Then caused at 13.56MHz, 300W continuously using RF
Power plasma 5 minutes.
Then, durol steam is introduced into cavity with 120 mg minutes rates, and the plasma is cut
Shift to following pulsed plasma: peak power 100W, frequency 100Hz, duty ratio 3%.Durol ionizes simultaneously
The first protective layer of continuous uniform is formed on the surface of transistor with autoreactivity.After continuing 15 minutes, plasma is closed
Body power supply simultaneously stops supplying durol steam.
The intracorporal vacuum of chamber is maintained, hexafluoropropene steam is introduced into cavity with 120 mg minutes rates, and by institute
It states plasma and switches to following pulsed plasma: peak power 100W, frequency 100Hz, duty ratio 5%.Eight
The ionization of fluorine butylene and the middle layer for forming continuous uniform on the surface of transistor with autoreactivity.Continue after ten minutes, to close
It closes plasma electrical source and stops supplying octafluoro butylene steam.
The intracorporal vacuum of chamber is maintained, with 120 mg minutes rates by 1H, 1H, 2H, 2H- perfluoro capryl acrylate steams
Vapour is introduced into cavity, and the plasma is switched to following pulsed plasmas: peak power 150W, frequency are
100Hz, duty ratio 5%.1H, 1H, 2H, 2H- perfluoro capryl acrylate ionize and with autoreactivity in transistor
Second protective layer of surface formation continuous uniform.Continue after twenty minutes, to close plasma electrical source and stop supplying 1H, 1H, 2H,
2H- perfluoro capryl acrylate steam.
The cavity is emptied into base pressure, then ventilate again to atmospheric pressure and takes out sample, is obtained with three-layer protection layer
Sample 4.
Comparative example 1
Other than changing the gas for forming the second protective layer into hexafluoropropene, operates similarly with example 1, prepare ratio
Compared with example 1.
Comparative example 2
Other than changing the gas for forming the first protective layer into paraxylene, operates similarly with example 1, prepare ratio
Compared with example 2.
Comparative example 3
100 transistors are placed in plasma chamber body, cavity is emptied to the base pressure of 3-10 millitorr, then makes helium
Gas is passed through in cavity with 20sccm until pressure reaches 80 millitorrs.Then cause continuous function at 13.56MHz, 300W using RF
Rate plasma 5 minutes.
Then, with 120 mg minutes rates by 1H, 1H, 2H, 2H- perfluoro decyl acrylate steam introduces cavity
In, and the plasma is switched to following pulsed plasma: peak power 150W, frequency 50Hz, duty ratio
It is 10%.To 1H, 1H, 2H, the ionization of 2H- perfluoro decyl acrylate simultaneously connects with autoreactivity to be formed on the surface of transistor
Continue uniform protective layer.After continuing 15 minutes, closes plasma electrical source and stop supplying 1H, 1H, 2H, 2H- perfluoro decyl third
Olefin(e) acid ester steam, prepares the sample of comparative example 3.
Performance evaluation
1. hydrophobicity
1.1 test apparatus
Static Contact angle measuring instrument (manufacture of model Theta Lite:Biolin company)
1.2 test methods and result
Static Contact angle tester is mainly used for measuring the contact angle of liquid versus solid, the i.e. wellability of liquid versus solid,
Various liquid can be measured to the contact angle of a variety of materials.Static contact angle, which refers to, drips a drop in a solid level plane,
At solid-liquid-gas three-phase point of interface on the surface of solids, liquid phase is clipped in it by liquid-vapor interface and two tangent line of solid-liquid interface
Formed angle when middle.Contact angle is bigger, illustrates that this material is better to the repellency of test liquid, wellability is poorer.
The present invention adopts water as liquid, wellability of the test protective layer to water.Respectively from 100 samples of each embodiment
In randomly select 5, according to above-mentioned method, the protective layer of sample prepared by 1-4 of the embodiment of the present invention and comparative example into
Row contact angle test takes its average value as test result.
As a result as shown in table 1 below.
Table 1 (n=5)
2. water and salt fog permeability test
2.1 experimental method
Salt spray test (GB6458-86 standard, 48 hours, corrosion-free), this law are using salt spray tester by chlorination
The experimental liquid of sodium solution is sprayed on a kind of corrosion tests on protective layer with mist.This method is using 5% salt water at 35 DEG C
In the environment of with spraying form to sample carry out accelerated ageing corrosion experiment observe the embodiment of the present invention respectively after 48 hours
Whether the protective layer of the sample prepared in 1-4, comparative example is complete, that is, has corrosion-free.
2.2 experimental result
Test result is as follows shown in table 2.
Table 2 (n=100)
3. adhesiveness
3.1 experimental method
Using pressure sensitive adhesive tape method test film to the adhesiveness of ground.
The experiment is used to evaluate the bond strength of protective layer and substrate, and this method uses the pressure sensitive adhesive tape of standard to test work
Tool, first with certain power by pressure surface adhesive tape pressure on the protection layer, then check protection layer is under a stable power traction
It is no to be removed from matrix surface.According to the method described above, the protective layer of the sample prepared by 1-4 of the embodiment of the present invention and comparative example
It is tested.
3.2 result
Test result shows that in 100 samples of each embodiment, 93% or more sample protective layer is not sent out with substrate
Raw peeling, and there is no removings for the sample protective layer and substrate that comparative example only has 80%.
Experimental result is listed in the table below shown in 3.
Table 3 (n=100)
As shown in Table 3, the binding force of the protective layer and ground that are formed by method of the invention is very secured.
4. high/low temperature experiment and high temperature and humidity experiment
This experiment is the environmental stability test in order to verify protective layer, and verifying protective layer is steady under various extreme conditions
Qualitative and reliability, it is real by carrying out accelerated ageing to sample in tropical deterioration equipment and high/low temperature aging equipment
It tests.
According to the test method of national standard GB/T2423.2, the protective layer sample of each sample of inventive embodiments preparation is carried out
48 hours senile experiments under the conditions of 48 hours senile experiments, and -40 DEG C under 85 DEG C/85% damp condition, test hair
In 100 samples of existing sample 1-4, its protective layer bubble-free/removing/layering/spot of 90% or more sample shows the present invention
The protective layer that is formed of method there is good environmental stability under the extreme conditions such as high temperature and humidity, low temperature, and compare
Only has 75% or so sample protective layer bubble-free/removing/layering/spot compared with example 1-3.
Although being not particularly illustrated above to the present invention, it will be understood to those skilled in the art that disclosed in the prior art
Content can be by connected applications into the present invention.For example, disclosed in Chinese Patent Application No. CN201380012311.3
The method and apparatus that the first gas of compound comprising being indicated by chemical formula (I) forms the first plasma is equally applicable to this
Invention corresponding method, and disclosed in it by the third gas comprising fluorohydrocarbon is formed third plasma method and
Equipment is equally applicable to corresponding method of the invention.In another example Chinese Patent Application No. CN200780002629,
Disclosed in CN200780048614, CN200980120491, CN200780002557 and CN200880114449 will comprising by
The method and apparatus that the second gas for the compound that chemical formula (II) indicates forms the second plasma is equally applicable to the present invention
Corresponding method.In another example equipment disclosed in the Chinese patent application that Chinese Patent Application No. is 201610815598.9, ginseng
Several and method, those skilled in the art may be incorporated into the present invention.Those skilled in the art is it is recognised that the present invention
In object and product and be not limited to defined by above description, can also include these patent disclosures all objects and
Product.For example, electronic equipment described in the invention further includes institute disclosed in Chinese Patent Application No. CN200780002557
There are electronic equipment and electrical equipment.In another example if the present invention does not illustrate, the ginseng of technique disclosed in these prior arts
Number, method, embodiment etc. can also be integrated in the present invention by way of replacement.
Above to it is provided by the present invention it is a kind of body surface formed protective layer method and surface be formed with protection
The product of layer is described in detail, and specific case used herein explains the principle of the present invention and embodiment
It states, method and inventive concept of the invention that the above embodiments are only used to help understand；Meanwhile for the one of this field
As technical staff, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, to sum up institute
It states, the contents of this specification are not to be construed as limiting the invention.
Claims (18)
1. a kind of method for forming protective layer in body surface characterized by comprising
At least part surface of the object is exposed in the first plasma, at least part table of the object
Face forms the first protective layer；With
At least part surface for being formed with the object of first protective layer is exposed in the second plasma, with shape
At the second protective layer；
The second gas for forming second plasma is different from forming the first gas of first plasma,
The second gas includes the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated aryl；x
For any one integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n=2l+1-
m。
2. the method according to claim 1 for forming protective layer in body surface, which is characterized in that the chemistry formula (II)
In, R1、R2、R3For hydrogen or methyl.
3. the method according to claim 1 for forming protective layer in body surface, which is characterized in that form described first etc.
The first gas of gas ions includes the compound indicated by chemical formula (I),
Wherein, T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately represent hydrogen,
Halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen.
4. the method according to claim 3 for forming protective layer in body surface, which is characterized in that the chemistry formula (I)
In, work as T1-T6In have and only there are two for methyl when, at least one in the atom or substituent group of other non-methyl is not hydrogen.
5. according to claim 1 to the method for forming protective layer in body surface described in 4, which is characterized in that will be formed with
Before at least part surface of the object of first protective layer is exposed in the second plasma, will first it be formed
At least part surface for stating the object of the first protective layer is exposed to the third formed by the third gas comprising fluorohydrocarbon
In plasma, to form middle layer.
6. the method as claimed in any of claims 1 to 4 for forming protective layer in body surface, which is characterized in that
The first gas for forming first plasma further includes the first carrier gas, and first carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of；And
The second gas for forming second plasma further includes the second carrier gas, and second carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of.
7. the method according to claim 5 for forming protective layer in body surface, which is characterized in that form described third etc.
The third gas of gas ions further includes third carrier gas, and the third carrier gas is selected from inert gas, CF4、C3F8、N2、H2In at least
It is a kind of.
8. the product that a kind of surface forms matcoveredn, which is characterized in that
The protective layer includes the first protective layer, first protective layer by be exposed in the first plasma be formed in it is described
At least part surface of product；With
Second protective layer, second protective layer pass through at least part that will be formed with the product of first protective layer
Surface is exposed to the outer surface that first protective layer is formed in the second plasma；
The second gas for forming second plasma is different from forming the first gas of first plasma；
The second gas includes the compound indicated by chemical formula (II),
Wherein, R1、R2、R3Separately it is selected from hydrogen, halogen, alkyl, aryl, halogenated alkyl, alkenyl halide or halogenated aryl；x
For any one integer in 0 to 3；L is the arbitrary integer in 2 to 14；M is the arbitrary integer in 0 to 3；And n=2l+1-
m。
9. the product that surface according to claim 8 forms matcoveredn, which is characterized in that R1、R2、R3For hydrogen or first
Base.
10. the product that surface according to claim 8 forms matcoveredn, which is characterized in that formed described first it is equal from
The first gas of daughter includes the compound indicated by chemical formula (I),
Wherein, T1Represent C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2、T3、T4、T5、T6Separately represent hydrogen,
Halogen, C1-C3Alkyl, C1-C3Halogenated alkyl or C2-C3Alkenyl；T2-T6In at least one be not hydrogen or halogen；And work as T1-T6
In have and only there are two for methyl when, at least one in the atom or substituent group of other non-methyl is not hydrogen.
11. the product that surface according to claim 10 forms matcoveredn, which is characterized in that in the chemistry formula (I),
Work as T1-T6In have and only there are two for methyl when, at least one in the atom or substituent group of other non-methyl is not hydrogen.
12. the product of the formation of the surface according to any one of claim 8 to 11 matcoveredn, which is characterized in that
At least part surface for being formed with the product of first protective layer is being exposed to it in the second plasma
Before, first at least part surface for being formed with the product of first protective layer is exposed to by the third comprising fluorohydrocarbon
In the third plasma that gas is formed, middle layer is formed.
13. the product that surface according to claim 12 forms matcoveredn, which is characterized in that
The third gas for forming the third plasma further includes third carrier gas, and the third carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of.
14. the product of the formation of the surface according to any one of claim 8 to 11 matcoveredn, which is characterized in that
The first gas for forming first plasma further includes the first carrier gas, and first carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of；And
The second gas for forming second plasma further includes the second carrier gas, and second carrier gas is selected from inert gas, CF4、
C3F8、N2、H2At least one of.
15. the product that surface according to claim 8 forms matcoveredn, which is characterized in that the product includes: electrical
At least one of equipment, electronic equipment, wrist-watch, cloth, permeable membrane and wearing product.
16. the product that surface according to claim 15 forms matcoveredn, which is characterized in that the electrical equipment packet
It includes: any one of communication base station, transformer equipment, data switching equipment, the vehicles, outdoor lightings and/or communication
Any component of any one of base station, transformer equipment, data switching equipment, the vehicles, outdoor lightings.
17. the product that surface according to claim 15 forms matcoveredn, which is characterized in that the electronic equipment packet
It includes: any one of handheld communication devices, electronic game station, wearable electronic and/or handheld communication devices, electronics
Any component of any one of game station, wearable electronic.
18. the product that surface according to claim 15 forms matcoveredn, which is characterized in that the wearing product includes
Clothes, shoes and hats and/or ornaments.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111321583A (en) * | 2020-02-18 | 2020-06-23 | 深圳奥拦科技有限责任公司 | Film coating method and coated part |
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|---|---|---|---|---|
| WO2014179283A2 (en) * | 2013-04-29 | 2014-11-06 | Gvd Corporation | Liquid-impregnated coatings and devices containing the same |
| CN104302412A (en) * | 2012-03-06 | 2015-01-21 | 赛姆布兰特有限公司 | Coated electrical assembly |
| WO2017051019A1 (en) * | 2015-09-24 | 2017-03-30 | Europlasma Nv | Polymer coatings and methods for depositing polymer coatings |
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2017
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|---|---|---|---|---|
| CN104302412A (en) * | 2012-03-06 | 2015-01-21 | 赛姆布兰特有限公司 | Coated electrical assembly |
| WO2014179283A2 (en) * | 2013-04-29 | 2014-11-06 | Gvd Corporation | Liquid-impregnated coatings and devices containing the same |
| WO2017051019A1 (en) * | 2015-09-24 | 2017-03-30 | Europlasma Nv | Polymer coatings and methods for depositing polymer coatings |
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| CN111321583A (en) * | 2020-02-18 | 2020-06-23 | 深圳奥拦科技有限责任公司 | Film coating method and coated part |
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