CN101663415A - Fluorine-containing polymer thin film and method for producing the same - Google Patents
Fluorine-containing polymer thin film and method for producing the same Download PDFInfo
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- CN101663415A CN101663415A CN200880012513A CN200880012513A CN101663415A CN 101663415 A CN101663415 A CN 101663415A CN 200880012513 A CN200880012513 A CN 200880012513A CN 200880012513 A CN200880012513 A CN 200880012513A CN 101663415 A CN101663415 A CN 101663415A
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- fluoro
- fluoropolymer
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Abstract
To provide a method for producing a fluoropolymer excellent in adhesion to a substrate and film strength. A method for producing a fluoropolymer thin film, which comprises forming a fluoropolymer thinfilm on a substrate by a physical vapor deposition method using, as an evaporation source, a fluoropolymer having a fluorinated aliphatic ring structure in its main chain and having a weight averagemolecular weight of from 3,000 to 80,000.
Description
Technical field
The present invention relates to fluoro-containing copolymer film, particularly have the fluoro-containing copolymer film and the manufacture method thereof of fluorine-containing aliphatics ring structure.
Background technology
The thermotolerance, chemical-resistant, repellency, weathering resistance, electrical insulating property, optical characteristics, non-adhesive, low frictional properties, flame retardant resistance etc. that with polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyvinylidene difluoride (PVDF) (PVDF) etc. are the fluoropolymer of representative are good, based on this characteristic, be used to each field such as electric and electronic, semi-conductor, building, automobile.
In recent years, along with the development of Micrometer-Nanometer Processing Technologies such as the semiconductor fabrication in the manufacturing of semi-conductor or electronic material, MEMS Technology, nanometer embossing, require the technology that forms the fluoro-containing copolymer film of atresia and homogeneous on the substrate surface of microtexture and give chemical-resistant water-repellancy moisture resistance release property etc. having.
Formation method as fluoro-containing copolymer film, known have a such damp process of spin-coating method, casting or dip coating, but owing to contain the relation of viscosity of the liquid of this fluoropolymer, exist to be difficult to the problem that forms the fluoro-containing copolymer film of atresia and homogeneous on the substrate surface of microtexture having.
On the other hand, when generally forming film by drying process, owing to the mean free path of the gas molecule that becomes film formation raw material is long, therefore think that this gas molecule can arrive in the structure with microtexture equably, compare with damp process, expected and to have the film that forms atresia and homogeneous on the substrate surface of microtexture.
As the method that forms fluoro-containing copolymer film by drying process, disclosed utilize sputtering method form the method (with reference to non-patent literature 1 etc.) of polytetrafluoroethylene (PTFE) film at substrate surface.In addition, also has the method that forms fluoro-containing copolymer film by vacuum vapour deposition at substrate surface.Generally, when forming fluoro-containing copolymer film by vacuum vapour deposition, the fluoropolymer of giving as vapor deposition source with electron beam, ionic fluid, heat etc. that is situated between makes its gasification with high-energy.But, the high-octane fluorine atom that causes in the fluoropolymer that applies in this physical vapor deposition process breaks away from, fluorine content in the formed fluoro-containing copolymer film is compared with the fluorine content of vapor deposition source significantly and is reduced, consequently, degradation problem under the painted such characteristic that fluoro-containing copolymer film possessed of fluoro-containing copolymer film that occurs forming.In addition, the main chain of fluoropolymer is cut off, and molecular weight and molecular weight is like this with regard to the film toughness that causes formed fluoro-containing copolymer film and the problem that descends with the adaptation of base material.
In order to solve above problem, as the manufacture method of the fluoro-containing copolymer film that has used vacuum vapour deposition, what proposed following record comes film forming method or importing to be used to improve with the method for the 2nd composition of the adaptation of base material etc. as raw material the fluoropolymer vapor deposition source of easier gasification.
(1) manufacture method of fluorine family macromolecule film the method is characterized in that, is that the physical vapor deposition of vapor deposition source comes film forming (with reference to patent documentation 1) by the multipolymer with tetrafluoroethylene and at least a kind of comonomer.
(2) fluorine resin be the method is characterized in that by the formation method of overlay film, with the low-molecular-weight fluorine resin of molecular-weight average in 600～1500 scope as target, by vacuum-deposited coating this fluorine resin (with reference to patent documentation 2) that on matrix, is covered.
(3) have the manufacture method of the base material that contains fluorine film, the method is characterized in that, when substrate surface is piled up organic fluorocompound by vapour deposition method, pile up non-fluorine-containing material (with reference to patent documentation 3) by ion beam sputtering at this substrate surface.
The method of patent documentation 1 record is the method that makes the crystallinity of polymkeric substance descend and vapour pressure is improved as vapor deposition source by the multipolymer with tetrafluoroethylene and at least a kind of comonomer, among the embodiment, under 450～470 ℃ temperature, make teflon (Teflon, registered trademark) AF (E.I.Du Pont Company's system) evaporation.But, because teflon AF is in about 350 ℃ of beginning thermolysiss (with reference to non-patent literature 2), therefore, there are the molecular weight and molecular weight of the fluoropolymer in the fluoro-containing copolymer film that forms by the evaporation under surpassing the high temperature of heat decomposition temperature, the problem that film toughness descends.
The method of patent documentation 2 record is the method that as target the vapour pressure of fluoropolymer is increased the low-molecular-weight fluorine resin (fluoropolymer) of molecular-weight average in 600～1500 scope, can be under 250～300 ℃ lower temperature film forming.But because low as the molecular weight of the fluorine resin (fluoropolymer) of vapor deposition source, therefore the molecular weight of formed fluoro-containing copolymer film also descends the strength degradation of fluoro-containing copolymer film.In addition, owing to do not form chemical bond, therefore there is the problem of easily peeling off with the adaptation deterioration of base material with base material.
In the method for patent documentation 3 records, by vapour deposition method separately when substrate surface has formed the organic fluorocompound film, because film toughness is not enough, therefore with non-fluorine-containing material as the 2nd composition by ion beam sputtering film forming simultaneously, can make the film toughness raising by making formed compoundization of film.But, owing to imported SiO
2Grade in an imperial examination 2 compositions, the problem that the characteristic that therefore has fluoro-containing copolymer film and had descends.
Non-patent literature 1: solid film (Thin Solid Films), 15, p87 (1973)
Non-patent literature 2: modern fluorine type polymer (Modern Fluoropolymer), 22, p411 (1997)
Patent documentation 1: Japanese patent laid-open 04-006266 communique
Patent documentation 2: Japanese patent laid-open 01-304936 communique
Patent documentation 3: the Japanese Patent spy opens the 2006-001014 communique
The announcement of invention
The purpose of this invention is to provide the method that is used to solve above-mentioned prior art problems, this method is the manufacture method with the good fluoro-containing copolymer film of the adaptation of base material and film toughness.
To achieve these goals, the invention provides the manufacture method of fluoro-containing copolymer film, the method is characterized in that, by have fluorine-containing aliphatics ring structure, weight-average molecular weight with main chain is that 3000～80000 fluoropolymer is the physical vapor deposition of vapor deposition source, forms fluoro-containing copolymer film on base material.
In the manufacture method of fluoro-containing copolymer film of the present invention, being preferably the fluoropolymer that described main chain has fluorine-containing aliphatics ring structure is the fluoropolymer with the repeating unit that is selected from following general formula (1)～(5),
In general formula (1)～(5), h is 0～5 integer, and i is 0～4 integer, and j is 0 or 1, and h+i+j is 1～6, and s is 0～5 integer, and t is 0～4 integer, and u is 0 or 1, and s+t+u is 1～6, and p, q and r are respectively 0～5 integer independently, and p+q+r is 1～6, R
1, R
2, R
3, R
4, X
1And X
2Be H, D (deuterium), F, Cl, OCF independently respectively
3Or CF
3, R
5, R
6, R
7, R
8Be H, D (deuterium), F, Cl, C independently respectively
nF
2n+1, C
nF
2n+1-mCl
mO
kOr C
nF
2n+1-mH
mO
k, R
5, R
6, X
1And X
2In at least 1 n is 1～5 integer in order to contain the group of F, m is 0～5 integer, 2n+1-m 〉=0, k is 0～1 integer, R
7And R
8Can connect into ring.
In the manufacture method of fluoro-containing copolymer film of the present invention, being preferably the fluoropolymer that described main chain has fluorine-containing aliphatics ring structure is (per) fluoropolymer, and being more preferably this fluoropolymer is the perfluor homopolymer.
In the manufacture method of fluoro-containing copolymer film of the present invention, be preferably fluoropolymer that described main chain has fluorine-containing aliphatics ring structure and be in following (I)～(V) any:
(I) comprise by fluorochemical monomer (a) cyclopolymerization with the two keys of polymerizability more than 2 the fluoropolymer of repeating unit,
(II) comprise by (b) polymerization of the fluorochemical monomer with fluorine-containing ring structure the fluoropolymer of repeating unit,
(III) comprise by (a) cyclopolymerization of described fluorochemical monomer repeating unit and by (b) polymerization of described fluorochemical monomer the fluoropolymer of repeating unit,
(IV) comprise by (a) cyclopolymerization of described fluorochemical monomer repeating unit and by fluorochemical monomer (c) polymerization beyond the described fluorochemical monomer (a) and (b) the fluoropolymer of repeating unit,
(V) comprise by (b) polymerization of described fluorochemical monomer repeating unit and by fluorochemical monomer (c) polymerization beyond the described fluorochemical monomer (a) and (b) the fluoropolymer of repeating unit.
In the manufacture method of fluoro-containing copolymer film of the present invention, being preferably physical vapor deposition is vacuum vapour deposition.
The Heating temperature that is preferably the vapor deposition source in the vacuum vapour deposition is 100 ℃～400 ℃ a scope.
It is the fluoro-containing copolymer film of 10nm～100 μ m that the present invention also provides the thickness by the manufacture method acquisition of fluoro-containing copolymer film of the present invention.
Utilize the present invention can make adaptation and the good fluoro-containing copolymer film of film toughness with base material.The present invention is specially adapted to fluoro-containing copolymer film is set having on the substrate surface of microtexture.
The best mode that carries out an invention
Below, the present invention is described in detail.
The manufacture method of fluoro-containing copolymer film of the present invention is that 3000～80000 fluoropolymer is the physical vapor deposition of vapor deposition source by have fluorine-containing aliphatics ring structure, weight-average molecular weight with main chain, forms fluoro-containing copolymer film on base material.
[fluoropolymer vapor deposition source]
Consider that from the angle of film forming speed the vapor deposition source of fluoropolymer of the present invention must possess the required enough vapour pressures of practicability.Based on this viewpoint, adopt the low main chain of crystallinity to have the fluoropolymer of fluorine-containing aliphatics ring structure.Have the fluoropolymer of fluorine-containing aliphatics ring structure as main chain, but illustration has and is selected from following general formula (the 1)～main chain of (5) and has the fluoropolymer of the repeating unit of fluorine-containing aliphatics ring structure.
In general formula (1)～(5), h is 0～5 integer, and i is 0～4 integer, and j is 0 or 1, and h+i+j is 1～6, and s is 0～5 integer, and t is 0～4 integer, and u is 0 or 1, and s+t+u is 1～6, and p, q and r are respectively 0～5 integer independently, and p+q+r is 1～6, R
1, R
2, R
3, R
4, X
1And X
2Be H, D (deuterium), F, Cl, OCF independently respectively
3Or CF
3, R
5, R
6, R
7, R
8Be H, D (deuterium), F, Cl, C independently respectively
nF
2n+1, C
nF
2n+1-mCl
mO
kOr C
nF
2n+1-mH
mO
k, R
5, R
6, X
1And X
2In at least 1 n is 1～5 integer in order to contain the group of F, m is 0～5 integer, 2n+1-m 〉=0, k is 0～1 integer, R
7And R
8Can connect into ring.
The fluoropolymer that main chain has fluorine-containing aliphatics ring structure can be the polymkeric substance that only has the wantonly a kind of repeating unit in the repeating unit that is selected from described general formula (1)～(5), also can be the polymkeric substance with the repeating unit more than 2 kinds in the repeating unit that is selected from described general formula (1)～(5).In addition, the fluoropolymer that main chain has a fluorine-containing aliphatics ring structure can also be to have the repeating unit that is selected from described general formula (1)～(5) and the polymkeric substance of described general formula (1)～(5) repeating unit in addition, specifically, this general formula (1)～(5) repeating unit in addition is the repeating unit fluorine-containing repeating unit (hereinafter referred to as other fluorine-containing repeating unit) in addition that main chain has fluorine-containing aliphatics ring structure.
In addition, main chain has the little (per) fluoropolymer of intermolecular interaction of the fluoropolymer preferred polymers of fluorine-containing aliphatics ring structure.Therefore, the fluoropolymer with the repeating unit that is selected from described general formula (1)～(5) better is a (per) fluoropolymer.
Perfluor homopolymer particularly preferably in the (per) fluoropolymer.Therefore, the perfluor homopolymer particularly preferably of the fluoropolymer with the repeating unit that is selected from described general formula (1)～(5).
Example with fluoropolymer of the repeating unit that is selected from described general formula (1)～(5) is the fluoropolymer that comprises the repeating unit that is got by fluorochemical monomer (a) cyclopolymerization with the two keys of polymerizability more than 2.Here, the concrete example as the fluorochemical monomer (a) with the two keys of polymerizability more than 2 can exemplify perfluor (butenyl vinyl ether) (CF
2=CFOCF
2CF
2CF=CF
2), perfluor (allyl vinyl ether) (CF
2=CFOCF
2CF=CF
2), perfluor (1-methyl-3-butenyl vinyl ether) (CF
2=CFCF
2CF (CF
3) OCF=CF
2) and the non-conjugated diene represented of following formula etc.
CFX
3＝CX
4OCX
5X
6OCX
4＝CX
3F
(in the formula, X
3And X
4Be F, Cl or H, X
5And X
6Be F or CF
3)
Another example with fluoropolymer of the repeating unit that is selected from described general formula (1)～(5) is the fluoropolymer that comprises the repeating unit that is got by (b) polymerization of the fluorochemical monomer with fluorine-containing ring structure.Here, as the concrete example of the fluorochemical monomer with fluorine-containing ring structure (b), can exemplify the fluoro dioxole of following general formula (6) expression etc.
In the described general formula (6), R '
FBe F, R
FOr OR
FHere, R
FBe the perfluoroalkyl with 1～5 carbon atom of straight chain shape or branch-like, X
7And X
8Be F or CF independently respectively
3
In the described general formula (6), be preferably R '
FBe OCF
3, X
7And X
8Be F.In addition, be preferably R '
FBe F, X
7And X
8Be CF
3
Another example with fluoropolymer of the repeating unit that is selected from described general formula (1)～(5) is the fluoropolymer that comprises repeating unit that is got by fluorochemical monomer (a) cyclopolymerization with the two keys of polymerizability more than 2 and the repeating unit that is got by (b) polymerization of the fluorochemical monomer with fluorine-containing ring structure.
As mentioned above, to have the fluoropolymer of fluorine-containing aliphatics ring structure can be to have to be selected from described general formula (the 1)～repeating unit of (5) and the polymkeric substance of other fluorine-containing repeating unit to main chain.Here, as the concrete example of other fluorine-containing repeating unit, can exemplify C such as tetrafluoroethylene, R 1216
2～C
8Perfluoroolefine, C such as trifluorochloroethylene
2～C
8The chlorine fluoroolefin, the polymerizations such as (alkoxyalkyl vinyl ether) of perfluor (alkyl vinyl ether) or perfluor and repeating unit.
The fluoropolymer that main chain has a fluorine-containing aliphatics ring structure be more preferably fully by fluorochemical monomer (a) cyclopolymerization with the two keys of polymerizability more than 2 the perfluor homopolymer that forms of repeating unit, the spy be well fully by perfluor (butenyl vinyl ether) cyclopolymerization must the perfluor homopolymer that forms of repeating unit.As the perfluor homopolymer that the repeating unit that is got by perfluor (butenyl vinyl ether) cyclopolymerization fully forms, can exemplify the CYTOP (registered trademark) of Asahi Glass Co., Ltd's system.
Fully by perfluor (butenyl vinyl ether) cyclopolymerization the preferred reason of the perfluor homopolymer that forms of repeating unit be: even under the situation of having used the polymkeric substance that the end of the initiator that do not possess functional group etc. has been carried out complete fluoridation, enough film toughnesss reach and the fluoro-containing copolymer film of the adaptation of base material in the time of also can obtaining to have actual use.Though it is also indeterminate for this reason, may be based on following consideration: even different with used fluoropolymer raw material in the manufacture method of existing fluoro-containing copolymer film, (for example have larger molecular weight, weight-average molecular weight is about 3000～80000) time, also can under the low temperature (specifically 100～400 ℃) of the indehiscent degree of main chain, carry out evaporation, can form structure with vapor deposition source identical contain fluorine film.
Enough film toughnesss reached and the adaptation of base material when the fluoro-containing copolymer film that the present invention forms had actual uses, but for the adaptation of further raising with base material, have the fluoropolymer of fluorine-containing aliphatics ring structure as main chain, preferred adopt possess can with base material form chemical bond functional group and/or can be at the polymkeric substance of the functional group of the intermolecular formation chemical bond of fluoropolymer.Functional group as forming chemical bond with base material, better be-the COF base ,-the COOH base ,-NH
2Base ,-COOR base (R represents alkyl), SiR
3-x(OR)
xBase (R represents alkyl, and X represents 1～3 integer) ,-SiCl
3Base ,-N=C=O base or-the OH base.Described-COOR base or SiR
3-x(OR)
xThe carbon number of the alkyl in the base is preferably 1～4.Functional group as forming chemical bond with base material, be more preferably-the COOH base ,-NH
2The base or-the COOR base.As can except above functional group, exemplifying two keys of carbon atom-carbon atom, the triple bond of carbon atom-carbon atom etc. in the functional group of the intermolecular formation chemical bond of fluoropolymer.
The fluoropolymer that main chain has a fluorine-containing aliphatics ring structure possess described can with base material form chemical bond functional group and/or can be when the functional group of the intermolecular formation chemical bond of fluoropolymer, functional group densities is different because of the kind of the kind of fluoropolymer and functional group.For example, fully by perfluor (butenyl vinyl ether) cyclopolymerization the perfluor homopolymer of the weight-average molecular weight 20000 that forms of repeating unit have as can with base material form chemical bond functional group-when COOH was basic, functional group densities was preferably 2.5 * 10
-6～1 * 10
-2Mol/g.Functional group densities less than 2.5 * 10
-6During mol/g, lack the effect of the adaptation of raising and base material.On the other hand, if functional group densities surpasses 1 * 10
-2Mol/g then because be unfavorable for photoabsorption occurring with the relation of the functional group of the adaptation of base material, diminishes the transparency of film.
The weight-average molecular weight that the main chain that uses as vapor deposition source has the (per) fluoropolymer of fluorine-containing aliphatics ring structure is 3000～80000, is preferably 10000～80000, more preferably 10000～40000.During weight-average molecular weight less than 3000, formed fluoro-containing copolymer film can't obtain enough film toughnesss.On the other hand, if weight-average molecular weight surpasses 80000, then do not possess and give the practical required vapour pressure of film forming speed, therefore vapor deposition source must be heated to high temperature, specifically be to surpass 400 ℃ temperature, the main chain of fluoropolymer cracking in evaporate process, the fluoropolymer lower molecular weightization, the film toughness of formed fluoro-containing copolymer film is not enough.About this point, put down in writing following situation in the comparative example 1 of patent documentation 3: use the system CYTOP (registered trademark) of Asahi Glass Co., Ltd as the organic fluorocompound target that is used for vapour deposition method, in the poor durability that is warming up to the film that makes its accumulation in 250～700 ℃ and get.Patent documentation 3 does not disclose the weight-average molecular weight of the CYTOP that uses in the comparative example 1, but (model: the weight-average molecular weight CTL-A type) is 150000 to the CYTOP of molecular weight minimum in the commercially available product, so think that the weight-average molecular weight of the CYTOP that uses in the comparative example 1 is more than 150000.The fluoropolymer raw material that uses in the manufacture method of CYTOP and existing fluoro-containing copolymer film is compared, evaporation at low temperatures, but when the polymkeric substance that this weight-average molecular weight is bigger uses as vapor deposition source, vapor deposition source must be heated to 700 ℃ of high like this temperature, the main chain of fluoropolymer cracking in evaporate process, the fluoropolymer lower molecular weightization, consequently, the film toughness of fluoro-containing copolymer film is not enough.
During perfluor homopolymer that the (per) fluoropolymer that the main chain that uses as vapor deposition source has a fluorine-containing aliphatics ring structure forms for the repeating unit that is got by perfluor (butenyl vinyl ether) cyclopolymerization fully, intrinsic viscosity [η] during its in perfluor (2-butyl tetrahydrofuran) 30 ℃ is preferably 0.01～0.14dl/g, more preferably 0.02～0.1dl/g, particularly preferably 0.02～0.08dl/g.During [η] is not enough 0.01dl/g, relatively the molecular weight of fluoropolymer diminishes, and the fluoro-containing copolymer film after the formation can't obtain enough film toughnesss.On the other hand, when [η] surpassed 0.2dl/g, the molecule quantitative change of fluoropolymer relatively was big, did not possess to give the practical required vapour pressure of film forming speed.
[base material]
Among the present invention,, can exemplify base materials such as metal, glass, pottery, organic polymer as the base material that is used to form the fluoro containing polymers film.The base material of shapes such as that these base materials can adopt is tabular, cylindric, spherical, bar-shaped, block, tabular, cylindric, lens-shaped, concavees lens shape also can adopt the surface to have the base material of nano level to the broad shapes such as base material of micron-sized microtexture.Preferred especially the use at substrate surface formed the base material of the fine pattern of stipulating or the rectangle base material that substrate surface has three-dimensional structure.
Shaping and working method as base material are not particularly limited, and can adopt known method.In addition, for example distribution made of copper or nesa coating etc. can be set on the surface of these base materials.
Among the present invention,, also can before forming fluoro-containing copolymer film, implement surface treatment to substrate surface in advance in order to improve the adaptation of itself and fluoro-containing copolymer film.As surface treatment, can adopt the surface treatment that utilizes silane coupling agent or primary coat treatment agent, utilize acid or the oxide treatment of ozone, the surface treatment that utilizes plasma body, the light carrying out washing treatment of utilizing UV light, the grinding that utilizes abrasive or known methods such as physics carrying out washing treatment such as polishing or wet blast(ing) such as sulfuric acid or hydrofluoric acid.Described surface treatment can use a kind also can be used in combination more than 2 kinds or 2 kinds separately.
With the adaptation that improves itself and fluoropolymer is purpose when implementing surface treatment, preferably forms chemical bond by surface treatment between substrate surface and the fluoro-containing copolymer film.Based on this viewpoint, described base material preferable alloy, glass or pottery, and be surface-treated base material through silane coupling agent.When base material is organic polymer, preferably utilize the surface treatment of primary coat treatment agent.
As silane coupling agent, better be the glycidyl silicane such as 3-glycidoxypropyltrime,hoxysilane, glycidoxy propyl group methyl dimethoxysilane that have aminosilane class such as amino 3-aminopropyltriethoxywerene werene, aminopropyl methyldiethoxysilane or have glycidyl, wherein be more preferably the aminosilane class.In addition, as the primary coat treatment agent, but illustration FS-10 (trade(brand)name: Shin-Etsu Chemial Co., Ltd's system) etc.
Silane coupling agent and primary coat treatment agent be fit to adopt drying processes such as damp process such as spin-coating method, casting or dip coating and vacuum vapour deposition.
In the damp process, use after silane coupling agent and primary coat treatment agent be adjusted to 0.001～20 quality % with soluble solvent with its concentration.Treatment process can consider that the shape of thickness, the homogeneity of silane coupled layer and undercoat, applied thing waits suitably and select, and is coated with method, curtain coating method, spraying method etc. but illustration spin-coating method, dip coating, casting, rolling method, rod are coated with method, print process, mould.
In the drying process, can directly use silane coupling agent and primary coat treatment agent, also available soluble solvent re-uses after its concentration is adjusted to 0.001～20 quality %.Treatment process can consider that the shape of thickness, the homogeneity of silane coupled layer and undercoat, applied thing waits suitably and select, preferably physical vapor deposition.
[physical vapor deposition]
Physical vapor deposition as the manufacture method that is applicable to fluoro-containing copolymer film of the present invention, can exemplify vacuum vapour deposition, sputtering method, but consider from suppressing fluorine atom breaks away from, suppresses the easy of the cracking of main chain of fluoropolymer and device from fluoropolymer angle, be fit to adopt vacuum vapour deposition.
Vacuum vapour deposition can be subdivided into electrical resistance heating, electron beam heating, high-frequency induction heating method, reactive evaporation, molecular ray epitaxial method, hot wall vapour deposition method, ion plating method, ionic fluid method etc., can adopt wantonly a kind of method.Consider from suppressing fluorine atom breaks away from, suppresses the easy of the cracking of main chain of fluoropolymer and device from fluoropolymer angle, be fit to adopt electrical resistance heating.The against vacuum evaporation coating device is not particularly limited, and can adopt well known device.
Filming condition is different because of the kind of used vacuum vapour deposition, and when adopting electrical resistance heating, evaporation initial vacuum degree is preferably 1 * 10
-3Below the Pa, more preferably 1 * 10
-4Below the Pa.
The Heating temperature of vapor deposition source is not particularly limited so long as the disengaging of fluorine atom can not occur or the cracking of fluoropolymer main chain, the temperature that this fluoropolymer vapor deposition source has enough vapour pressures get final product.
Specifically, be preferably 100 ℃～400 ℃, more preferably 150 ℃～400 ℃, particularly preferably 200 ℃～400 ℃.During 100 ℃ of Heating temperature less thaies, the required enough vapour pressures of film forming speed that sometimes can't accomplished practicality.On the other hand,, then occur the cracking of the main chain of the disengaging of fluorine atom or fluoropolymer sometimes, cause the degradation of fluoro-containing copolymer film if Heating temperature surpasses 400 ℃.
During vacuum evaporation, base material temperature better is the scope of normal temperature to 200 ℃.If base material temperature surpasses 200 ℃, the material that base material then can occur can be used as is limited, film forming speed descends, problems such as defective such as formation fold on the fluoro-containing copolymer film when making cooling because of the thermal expansion of base material.Base material temperature is preferably below 150 ℃, more preferably below 100 ℃.
After forming, fluoro-containing copolymer film can heat-treat as required.Can make by thermal treatment describedly can to form the functional group of chemical bond with base material and/or can fully react, make the film toughness of fluoro-containing copolymer film and improve with the adaptation of base material in the functional group of the intermolecular formation chemical bond of fluoropolymer.In addition, make through between the surface-treated substrate surface of silane coupling agent or silane coupling agent and fluoro-containing copolymer film and carry out chemical reaction, can make the film toughness of fluoro-containing copolymer film sometimes and improve with the adaptation of base material.
Heat-treat condition is different because of the kind of the kind of the kind of base material, fluoropolymer and functional group, but preferably under rare gas element or air atmosphere in 50～200 ℃ of enforcements.If 50 ℃ of thermal treatment temp less thaies then can't obtain thermal effectiveness.On the other hand, if thermal treatment temp surpasses 200 ℃, polymer melt or softening then diminishes the flatness of film.
[fluoro-containing copolymer film]
The fluoro-containing copolymer film of the present invention that obtains according to above step is by having the film that the fluoropolymer of same structure forms with fluoropolymer as vapor deposition source in essence, and weight-average molecular weight is 3000～80000.When employing has the vapor deposition source of molecular weight distribution, may form the fluoro-containing copolymer film of weight-average molecular weight less than the fluoropolymer vapor deposition source, but it is, then good with the adaptation and the film toughness of base material as long as the weight-average molecular weight of the fluoro-containing copolymer film that forms is 3000～80000.
The thickness of fluoro-containing copolymer film of the present invention is preferably below the 100 μ m.More preferably below the 10 μ m.If thickness surpasses 100 μ m, then the film forming spended time is impracticable, and is low with the adaptation of base material.Be not particularly limited for lower limit, if can not consider the generation possibility of membrane portions (hole), then preferred 10nm.The thickness of fluoro-containing copolymer film of the present invention is 20nm～10 μ m more preferably, further 20nm～2 μ m more preferably.
Embodiment
The present invention will be described in more detail below to adopt embodiment, but the present invention is not limited thereto.Synthesis example 1～synthesis example 8, example 1～3, example 6～8, example 10～15 are embodiment, and example 4, example 5 and example 9 are comparative example.
(assessment item, evaluation method)
＜contact angle (CA) 〉
Adopt contact angle determination device (consonance interfacial chemistry Co., Ltd. system, ProductName: the CA-X150) contact angle of mensuration fluoro-containing copolymer film.Must measure contact angle with the clarifying state in determined surface.Make its method that is in clear state as the determined surface of washing, can in the scope of failure surface not, adopt known washing methods.For example can exemplify and carry out solvent wash, carry out light washing etc. by the UV lamp with organic solvents such as acetone or alcohol.Adopted the acetone solvent washing in the example 1～10.
＜weight-average molecular weight 〉
Measure the weight-average molecular weight of fluoropolymer vapor deposition source with gel permeation chromatography (GPC).At first, adopt the known fluoropolymer standard test specimen of GPC determining molecular weight, make working curve by the elution time and the molecular weight of summit (peaktop).Then, measure the fluoropolymer vapor deposition source, obtain molecular weight, try to achieve weight-average molecular weight by working curve.Mobile phase solvent adopts perfluor (2-butyl tetrahydrofuran).
＜functional group densities 〉
With
1H-NMR has measured the functional group densities of fluoropolymer vapor deposition source.
＜abrasion test 〉
(well unit makes Co., Ltd. of institute system with the wearing and tearing tester, trade(brand)name: wearing and tearing tester A 1566), (carat come (Network ラ レ) corporate system, model: VS-30C) behind the reciprocating friction 5 times, measure the contact angle of fray with 500g load with Network ラ Off レ ッ Network ス non-dust cloth.
(modulation of fluoropolymer vapor deposition source)
[synthesis example 1]
Perfluor (butenyl vinyl ether) 30g, 1,1,1,2,2,3,3,4,4,5,5,6 that in the glass reactor of internal volume 50ml, packs into, 6-ten trifluoro hexane 30g, methyl alcohol 0.5g and as the ((CH of initiator
3)
2-CH-OCOO)
20.44g.Carry out 24 hour polymerization to replacing the back in the system in 40 ℃ with highly purified nitrogen.With 666Pa (absolute pressure), 50 ℃ condition gained solution is carried out desolventizing and handle, obtain the 28g polymer A.Polymer A intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.04dl/g.
[synthesis example 2]
According to the method for Japanese patent laid-open 11-152310 record, utilize F
2Gas is substituted by the unstable end group of polymer A-CF
3Base obtains polymer B.Polymer B intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.04dl/g.
The weight-average molecular weight that records polymer B by described method is 20000.In addition, measure functional group densities, consequently, can utilize by described method
1The functional group densities that H-NMR records is detecting lower value (1 * 10
-6) below.
[synthesis example 3]
According to the method for Japanese patent laid-open 04-189880 record, in air, polymer A carried out be impregnated in the water after 8 hours the thermal treatment in 250 ℃, obtain to have-the polymkeric substance C of COOH base.Polymkeric substance C intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.04dl/g.
In addition, measure functional group densities by described method, consequently ,-COOH functional group densities is 2 * 10
-4Mol/g.
[synthesis example 4]
According to the method for Japanese patent laid-open 04-226177 record, with the 3-aminopropyltriethoxywerene werene polymkeric substance C is handled, obtain to have-Si (OC
2H
5)
3The polymkeric substance D of base.Polymkeric substance D intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.04dl/g.
In addition, measure functional group densities by described method, consequently ,-Si (OC
2H
5)
3Functional group densities is 2 * 10
-4Mol/g.
[synthesis example 5]
In air, polymer A carried out be impregnated in the methyl alcohol after 8 hours the thermal treatment, obtain to have-COOCH in 250 ℃
3The polymkeric substance E of base.Polymkeric substance E intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.04dl/g.
The weight-average molecular weight that records polymkeric substance E by described method is 30000.
In addition, measure functional group densities by described method, consequently ,-COOCH
3Functional group densities is 1 * 10
-4Mol/g.
[synthesis example 6]
Except methanol usage changes 0.03g into, as the ((CH of initiator
3)
2-CH-OCOO)
2Change into beyond the 0.44g, operate equally, obtain 14g polymkeric substance F with synthesis example 1.In air, polymkeric substance F carried out be impregnated in the methyl alcohol after 8 hours the thermal treatment, obtain to have-COOCH in 250 ℃
3The polymkeric substance G of base.Polymkeric substance G intrinsic viscosity [η] 30 ℃ time the in perfluor (2-butyl tetrahydrofuran) is 0.14dl/g.
The weight-average molecular weight that records polymkeric substance G by described method is 80000.
[synthesis example 7]
Perfluor (the 4-methyl butene base vinyl ether) 5g, 1,1,1,2,2,3,3,4,4,5,5,6 that in the glass reactor of internal volume 100ml, packs into, 6-ten trifluoro hexane 5g, methyl alcohol 0.05g and as the ((CH of initiator
3)
2-CH-OCOO)
20.06g.Carry out 48 hour polymerization to replacing the back in the system in 40 ℃ with highly purified nitrogen.With 666Pa (absolute pressure), 90 ℃ condition gained solution is carried out desolventizing and handle, obtain 4g polymkeric substance H.Polymkeric substance H is 1,1,1,2,2,3,3,4,4,5,5,6, and the intrinsic viscosity [η] in the 6-ten trifluoro hexanes 30 ℃ the time is 0.06dl/g.
[synthesis example 8]
Make pack in the autoclave perfluor (butenyl vinyl ether) 23g, perfluor-2,2-dimethyl-1,3-dioxole 5g, 1,1,1 at the SUS of internal volume 200ml, 2,2,3,3,4,4,5,5,6,6-ten trifluoro hexane 30g, methyl alcohol 0.35g and as the ((CH of initiator
3)
2-CH-OCOO)
20.44g.Carry out 48 hour polymerization to replacing the back in the system in 40 ℃ with highly purified nitrogen.With 666Pa (absolute pressure), 90 ℃ condition gained solution is carried out desolventizing and handle, obtain 20g polymkeric substance I.Polymkeric substance I is 1,1,1,2,2,3,3,4,4,5,5,6, and the intrinsic viscosity [η] in the 6-ten trifluoro hexanes 30 ℃ the time is 0.05dl/g.By
19The perfluor (butenyl vinyl ether) and the perfluor-2 that comprise in the polymkeric substance that F-NMR measures, 2-dimethyl-1, the ratio of 3-dioxole is 65: 35.
[example 1]
Adopt polymer B and as the precise form of base material with mould (SUS316 system), adopt vacuum deposition apparatus (Ai Fake (ULVAC) corporate system: VPC-410) on base material, form fluoro-containing copolymer film.Insert the 3.5g polymer B in the oxidation aluminum crucible in vacuum deposition apparatus, carry out exhaust and make the pressure in the vacuum deposition apparatus reach 1 * 10
-3Below the Pa.With the heat-up rate heater configuration below 10 ℃/minute the combustion chamber of the crucible of polymer B is arranged, when chamber temperature surpasses 250 ℃, open the sluices, the film forming of beginning on base material.Closed shutter finishes the film forming on base material when chamber temperature surpasses 400 ℃.The temperature of the vapor deposition source when film forming finishes is 350 ℃.
The contact angle that records fluoro-containing copolymer film and water according to described method is 103 °, confirms to have formed fluoro-containing copolymer film on this base material.
The water contact angle that forms the preceding die surface of fluoro-containing copolymer film is 28 °.Measure the adaptation of film with enclosing the checker belt stripping test, the result shows the firm adaptation of this fluoro-containing copolymer film and base material.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.
[example 2]
Except with the polymkeric substance C replace polymeric B, similarly carry out vacuum evaporation with example 1.The contact angle that records substrate surface and water according to described method is 105 °, confirms to have formed on base material fluoro-containing copolymer film.Measure the adaptation of film with enclosing the checker belt stripping test, the result shows the firm adaptation of this fluoro-containing copolymer film and base material.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.
[example 3]
Except with the polymkeric substance D replace polymeric B, similarly carry out vacuum evaporation with example 1.The contact angle that records substrate surface and water according to described method is 105 °, confirms to have formed on base material fluoro-containing copolymer film.Measure the adaptation of film with enclosing the checker belt stripping test, the result shows the firm adaptation of this fluoro-containing copolymer film and base material.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.
[example 4]
Except with beyond CYTOP (registered trademark) (Asahi Glass Co., Ltd's system, model: CTL-A type, weight-average molecular weight are 150000) the replace polymeric B, similarly carry out vacuum evaporation with example 1.The contact angle that records substrate surface and water according to described method is 28 °, confirms not form fluoro-containing copolymer film on this base material.
[example 5]
Except usefulness CYTOP (registered trademark) (Asahi Glass Co., Ltd's system, model: CTL-A type, weight-average molecular weight are 150000) replace polymeric B, and closed shutter finishes similarly to carry out vacuum evaporation with example 1 beyond the film forming when chamber temperature surpasses 700 ℃.The contact angle that records substrate surface and water according to described method is 81 °, confirms to have formed on base material fluoro-containing copolymer film.But the result who carries out sensory evaluation by visual transparency to film is that this film is the painted film of brown.In addition, measure the adaptation of film with enclosing the checker belt stripping test, the result easily peels off, and does not obtain good adaptation.
[example 6]
By being spin-coated on precise form is dissolved in the solvent of ethanol/purified water=95/5 (weight ratio) with 0.05wt% with the surface coated of mould (SUS316 system) base material 3-aminopropyltriethoxywerene werene.Then, the surface treatment of silane coupling agent is implemented in seasoning to substrate surface.
Implemented the surface-treated base material and, similarly carried out vacuum evaporation according to above step except using, under air atmosphere, carried out heat treated again at 180 ℃ with example 1 with the polymkeric substance C replace polymeric B.
The contact angle that records substrate surface and water according to described method is 109 °, confirms to have formed on base material fluoro-containing copolymer film.Measure the adaptation of film with enclosing the checker belt stripping test, the result shows, the very firm adaptation of this fluoro-containing copolymer film and base material.In addition, the result who carries out sensory evaluation by visual transparency to film is that this film is water white film.
[example 7]
Use synthetic quartz glass (trade(brand)name: AQQ Asahi Glass Co., Ltd system), on base material, formed fluoro-containing copolymer film as base material with vacuum deposition apparatus.Molybdenum ware in vacuum deposition apparatus (Gu Nei KCC system trade(brand)name: insert the 1.2g polymer B VACOM Mo ware BP-21-0.3t), carry out exhaust and make the pressure in the vacuum deposition apparatus reach 1 * 10
-3Below the Pa.Electric current is flow through be filled with the molybdenum ware of polymer B, heating to make to insert polymer B fusion in the ware with the magnitude of current of 60A.Then, adjust the magnitude of current, utilize the quartz crystal film thickness gauge that film forming speed is adjusted into 0.3nm/ after second, open the sluices, come film forming with the film forming speed of 0.3nm/ second.Closed shutter when the thickness that utilizes the quartz crystal film thickness gauge to record reaches 1.2 μ m stops the heating to ware, finishes film forming.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 114 °, confirm to have formed fluoro-containing copolymer film on this base material.
The water contact angle that forms the preceding synthetic quartz glass surface of fluoro-containing copolymer film is 21 °.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 100 °, and this fluoro-containing copolymer film on the base material shows firm wearability.
By
19F-NMR measures the molecular structure of the fluoro-containing copolymer film of polymer B and gained, confirms that the molecular structure of polymer B and fluoro-containing copolymer film is identical.That is the cracking of the main chain of the disengaging of fluorine atom and fluoropolymer, does not take place in the film forming.
[example 8]
Except using 3mm float glass (Asahi Glass Co., Ltd's system) as base material, with polymkeric substance C replace polymeric B, film forming speed with the quartz crystal adjustment reaches 0.1nm/ second, when the thickness that records by the quartz crystal film thickness gauge reaches 500nm beyond the closed shutter, similarly implement vacuum evaporation with example 7, under air atmosphere, carry out heat treated again in 200 ℃.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 106 °, confirm to have formed fluoro-containing copolymer film on this base material.
The water contact angle that forms the preceding 3mm float glass surface of fluoro-containing copolymer film is 24 °.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 70 °, and this fluoro-containing copolymer film on the base material shows more firm wearability.
[example 9]
Except using 3mm float glass (Asahi Glass Co., Ltd's system) as base material, with CYTOP (registered trademark) (Asahi Glass Co., Ltd's system, model: CTL-S type, weight-average molecular weight 150000) replace polymeric B, film forming speed with the quartz crystal adjustment reaches 0.1nm/ second, when reaching 500nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 7.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 108 °, confirm to have formed fluoro-containing copolymer film on this base material.
Estimate by visual transparency, confirm that this film is the painted film of brown film.In addition, observe and be attached with small meal on the film, infer that the CYTOP as vapor deposition source decomposes in the film forming, this film be its resolvent again in conjunction with and the film that forms.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 45 °, and this fluoro-containing copolymer film on the base material is easily peeled off, and does not show wearability.
[example 10]
Be dissolved in the 3-aminopropyltriethoxywerene werene of the solvent of ethanol/purified water=95/5 (weight ratio) with 0.05wt% by the surface coated that is spin-coated on 3mm float glass base material.Then, the surface treatment of silane coupling agent is implemented in seasoning to substrate surface.
Implemented similarly to carry out vacuum evaporation with example 8 the surface-treated base material except using, under air atmosphere, carried out heat treated again in 200 ℃ according to above step.
The contact angle that records fluoro-containing copolymer film and water according to described method is 100 °.Affirmation has formed fluoro-containing copolymer film on this base material.In addition, by the visual result that the transparency of film is estimated be, this film is water white film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 106 °.Repeat described abrasion test once more, measure the contact angle that adds up to after 100 abrasion tests are implemented in circulation, the contact angle that 100 circulations are implemented after the abrasion test is 102 °, and this fluoro-containing copolymer film on the base material shows very firm wearability.
[example 11]
Molybdenum ware in vacuum deposition apparatus (Gu Nei KCC system trade(brand)name: after inserting the 3-aminopropyltriethoxywerene werene of 2ml VACOM Mo ware BP-21-0.3t), carrying out exhaust makes the pressure in the vacuum deposition apparatus reach below the 1Pa, 3-aminopropyltriethoxywerene werene steam is contacted with the surface of 3mm float glass base material, substrate surface is carried out surface treatment with silane coupling agent.
Implemented the surface-treated base material as base material except using according to above step, with polymkeric substance E replace polymeric B, film forming speed with the quartz crystal adjustment reaches 0.2nm/ second, when reaching 720nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 7.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 104 °.Affirmation has formed fluoro-containing copolymer film on this base material.In addition, estimate, confirm that this film is water white film by visual transparency to film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 103 °.Repeat described abrasion test once more, measure the contact angle that adds up to after 100 abrasion tests are implemented in circulation, the contact angle that 100 circulations are implemented after the abrasion test is 103 °, and this fluoro-containing copolymer film on the base material shows very firm wearability.
[example 12]
Except with polymkeric substance G replace polymeric B, reach 0.04nm/ second with the film forming speed of quartz crystal adjustment, when reaching 440nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 7.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 107 °, confirm to have formed fluoro-containing copolymer film on this base material.
In addition, estimate, confirm that this film is water white film by visual transparency to film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 93 °, and this fluoro-containing copolymer film on the base material shows firm wearability.
[example 13]
Except with polymkeric substance G replace polymeric E, reach 0.04nm/ second with the film forming speed of quartz crystal adjustment, when reaching 440nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 11.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 107 °.Affirmation has formed fluoro-containing copolymer film on this base material.In addition, estimate, confirm that this film is water white film by visual transparency to film.In addition, carry out the abrasion test of fluoro-containing copolymer film according to described method, the contact angle after the abrasion test is 109 °, and this fluoro-containing copolymer film on the base material shows firm wearability.
[example 14]
Except with polymkeric substance H replace polymeric B, reach 0.05nm/ second with the film forming speed of quartz crystal adjustment, when reaching 500nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 7.The substrate surface that records according to described method and the contact angle of water are 111 °, confirm to have formed fluoro-containing copolymer film on this base material.In addition, carry out sensory evaluation, confirm that this film is water white film by visual transparency to film.
[example 15]
Except with polymkeric substance I replace polymeric B, reach 0.05nm/ second with the film forming speed of quartz crystal adjustment, when reaching 500nm, the thickness that records by the quartz crystal film thickness gauge beyond the closed shutter, similarly implements vacuum evaporation with example 11.
The fluoro-containing copolymer film that records according to described method and the contact angle of water are 113 °.Affirmation has formed fluoro-containing copolymer film on this base material.In addition, estimate, confirm that this film is water white film by visual transparency to film.Repeat described method, measure the contact angle that adds up to after 100 abrasion tests are implemented in circulation, the contact angle that 100 circulations are implemented after the abrasion test is 110 °, and this fluoro-containing copolymer film on the base material shows very firm wearability.
The possibility of utilizing on the industry
The fluoro-containing copolymer film that is obtained by the present invention be applicable to scold water scold oil coating, low reflectance coating, Nonpolluting coating, non-adherent coating, waterproof dampproof coating, dielectric film, chemicals-resistant coating, etching Diaphragm, low refractive index film, scold the functional membrane of ink coating, vapour lock film, patterning etc.
More specifically, be applicable to surface protection film, the solar cell cover plate of optical filter for display Glass with the damp proof anti-reflection coating of antifouling antireflection film, hygroscopy crystallization or phosphoric acid class glass, The surface protection nonpolluting coating of phase shift mask, photomask, immersion lithography method with photoresist scold liquid The release coating of the release coating of coating, contact mask, nano impression mould, semiconductor devices or Vapour lock film, the liquid crystal of the silver electrode of the light-emitting components such as the passivating film of integrated circuit, circuit substrate or LED The liquid crystal orientation film of display element, the lubricant coating of magnetic recording media, gate insulating film, adopted electricity The coating of the chemicals-resistant of the equipment of wetting principle, foil electret, MEMS technology, medicine equipment antifouling Coating, utilized the antifouling anti-biology of chemicals-resistant of the equipment of micro jetting technology scold the liquid coating, The low refractive material of optical light filter multilayer coating, hydrophilic repellency material, pattern of scolding water patterns The optical element of changing etc.
Here quote of the announcement of the full content of Japanese patent application 2007-112141 number of filing an application on April 20th, 2007 and Japanese patent application 2007-241155 number specification sheets, claims and the summary of filing an application on September 18th, 2007 as specification sheets of the present invention.
Claims (11)
1. the manufacture method of fluoro-containing copolymer film is characterized in that, is that 3000～80000 fluoropolymer is the physical vapor deposition of vapor deposition source by have fluorine-containing aliphatics ring structure, weight-average molecular weight with main chain, forms fluoro-containing copolymer film on base material.
2. the manufacture method of fluoro-containing copolymer film as claimed in claim 1 is characterized in that, the fluoropolymer that described main chain has fluorine-containing aliphatics ring structure is the fluoropolymer with the repeating unit that is selected from following general formula (1)～(5),
In general formula (1)～(5), h is 0～5 integer, and i is 0～4 integer, and j is 0 or 1, and h+i+j is 1～6, and s is 0～5 integer, and t is 0～4 integer, and u is 0 or 1, and s+t+u is 1～6, and p, q and r are respectively 0～5 integer independently, and p+q+r is 1～6, R
1, R
2, R
3, R
4, X
1And X
2Be H, D (deuterium), F, Cl, OCF independently respectively
3Or CF
3, R
5, R
6, R
7, R
8Be H, D (deuterium), F, Cl, C independently respectively
nF
2n+1, C
nF
2n+1-mCl
mO
kOr C
nF
2n+1-mH
mO
k, R
5, R
6, X
1And X
2In at least 1 contain F, n is 1～5 integer, m is 0～5 integer, 2n+1-m 〉=0, k is 0～1 integer, R
7And R
8Can connect into ring.
3. the manufacture method of fluoro-containing copolymer film as claimed in claim 1 or 2 is characterized in that, the fluoropolymer that described main chain has fluorine-containing aliphatics ring structure is a (per) fluoropolymer.
4. as the manufacture method of each described fluoro-containing copolymer film in the claim 1～3, it is characterized in that, described main chain have in the fluoropolymer of fluorine-containing aliphatics ring structure as can comprise with the functional group that base material forms chemical bond-the COF base ,-the COOH base ,-NH
2Base ,-COOR base, SiR
3-x(OR)
xBase ,-SiCl
3Base ,-N=C=O base or-the OH base; Wherein, the R the in-COOR base represents alkyl, SiR
3-x(OR)
xR in the base represents alkyl, and X represents 1～3 integer.
5. the manufacture method of fluoro-containing copolymer film as claimed in claim 3 is characterized in that, described (per) fluoropolymer is the perfluor homopolymer.
6. as the manufacture method of each described fluoro-containing copolymer film in the claim 1～5, it is characterized in that described main chain has the perfluor homopolymer that the fluoropolymer of fluorine-containing aliphatics ring structure forms for the repeating unit that is got by perfluor (butenyl vinyl ether) cyclopolymerization fully.
7. as the manufacture method of each described fluoro-containing copolymer film in the claim 1～6, it is characterized in that the fluoropolymer that described main chain has a fluorine-containing aliphatics ring structure is any in following (I)～(V):
(I) comprise by fluorochemical monomer (a) cyclopolymerization with the two keys of polymerizability more than 2 the fluoropolymer of repeating unit,
(II) comprise by (b) polymerization of the fluorochemical monomer with fluorine-containing ring structure the fluoropolymer of repeating unit,
(III) comprise by (a) cyclopolymerization of described fluorochemical monomer repeating unit and by (b) polymerization of described fluorochemical monomer the fluoropolymer of repeating unit,
(IV) comprise by (a) cyclopolymerization of described fluorochemical monomer repeating unit and by fluorochemical monomer (c) polymerization beyond the described fluorochemical monomer (a) and (b) the fluoropolymer of repeating unit,
(V) comprise by (b) polymerization of described fluorochemical monomer repeating unit and by fluorochemical monomer (c) polymerization beyond the described fluorochemical monomer (a) and (b) the fluoropolymer of repeating unit.
8. as the manufacture method of each described fluoro-containing copolymer film in the claim 1～7, it is characterized in that described base material is metal, glass or pottery, and be to have implemented the surface-treated base material through silane coupling agent.
9. as the manufacture method of each described fluoro-containing copolymer film in the claim 1～8, it is characterized in that physical vapor deposition is a vacuum vapour deposition.
10. the manufacture method of fluoro-containing copolymer film as claimed in claim 9 is characterized in that, the Heating temperature of the vapor deposition source in the vacuum vapour deposition is 100 ℃～400 ℃ a scope.
11. fluoro-containing copolymer film is characterized in that, by the manufacture method acquisition of each described fluoro-containing copolymer film in the claim 1～10, its thickness is 10nm～100 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP112141/2007 | 2007-04-20 | ||
| JP2007112141 | 2007-04-20 | ||
| JP241155/2007 | 2007-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101663415A true CN101663415A (en) | 2010-03-03 |
Family
ID=41790632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880012513A Pending CN101663415A (en) | 2007-04-20 | 2008-04-14 | Fluorine-containing polymer thin film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101663415A (en) |
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| CN101879801A (en) * | 2010-06-21 | 2010-11-10 | 东莞劲胜精密组件股份有限公司 | Anti-fingerprint film and preparation method thereof |
| CN103764386A (en) * | 2011-08-24 | 2014-04-30 | 富士胶片株式会社 | Barrier laminate, and gas barrier film |
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| CN107531033A (en) * | 2015-04-27 | 2018-01-02 | 旭硝子株式会社 | Layered product and its manufacture method |
| CN108699394A (en) * | 2016-02-24 | 2018-10-23 | Ａｇｃ株式会社 | Coating fluid composition and used the coating fluid composition the article with film manufacturing method |
| CN108699394B (en) * | 2016-02-24 | 2020-07-31 | Ａｇｃ株式会社 | Coating liquid composition and method for producing article having film using same |
| CN114630875A (en) * | 2019-11-05 | 2022-06-14 | 大金工业株式会社 | Film and substrate coated with the same |
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Application publication date: 20100303 |