U.S. patent application number 15/830872 was filed with the patent office on 2018-03-29 for amorphous fluorine-containing resin composition and a manufacturing method of thin films.
The applicant listed for this patent is Dupont-Mitsui Fluorochemicals Co., Ltd.. Invention is credited to Jeong Chang Lee, Yuji Mochizuki, Masaki Mugisawa.
Application Number | 20180086934 15/830872 |
Document ID | / |
Family ID | 50023799 |
Filed Date | 2018-03-29 |
United States Patent
Application |
20180086934 |
Kind Code |
A1 |
Mugisawa; Masaki ; et
al. |
March 29, 2018 |
AMORPHOUS FLUORINE-CONTAINING RESIN COMPOSITION AND A MANUFACTURING
METHOD OF THIN FILMS
Abstract
[Object of this Invention] To provide the amorphous
fluorine-containing resin composition that has superior
film-forming ability, and has a small impact on the global
environment due to its very small global warming potential, and can
fully satisfy the requirement from the perspective of the
environmental protection of the earth; and to provide the article
that contains the coating that is formed from the thin films that
are made from this amorphous fluorine-containing resin.
composition.
Inventors: |
Mugisawa; Masaki; (Shizuoka,
JP) ; Mochizuki; Yuji; (Shizuoka, JP) ; Lee;
Jeong Chang; (Shizuoka-Shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dupont-Mitsui Fluorochemicals Co., Ltd. |
Tokyo |
|
JP |
|
|
Family ID: |
50023799 |
Appl. No.: |
15/830872 |
Filed: |
December 4, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14430622 |
Mar 24, 2015 |
9862852 |
|
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PCT/IB2013/002818 |
Dec 20, 2013 |
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15830872 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
Y10T 428/31544 20150401;
C09D 127/18 20130101; C09D 127/12 20130101; C08J 3/093 20130101;
C08J 2327/12 20130101; C08F 214/262 20130101; C08J 3/11 20130101;
C08J 2327/18 20130101 |
International
Class: |
C09D 127/18 20060101
C09D127/18; C09D 127/12 20060101 C09D127/12; C08F 214/26 20060101
C08F214/26; C08J 3/09 20060101 C08J003/09 |
Claims
1. An amorphous fluorine-containing resin composition comprising
amorphous fluorine-containing resin dissolved in alkoxy
perfluoroalkene, wherein the number of carbon atoms in the
perfluoroalkene group of said alkoxy perfluoroalkene is from 5-8,
and wherein said amorphous fluorine-containing resin is at least
one resin selected from the group consisting of copolymer of
tetrafluoroethylene and perfluoro(dimethyl dioxole), and copolymer
of tetrafluoroethylene and perfluoro(butenyl vinyl ether).
2. (canceled)
3. (canceled)
4. The amorphous fluorine-containing resin composition as described
in claim 1, wherein said alkoxy perfluoroalkene is methoxy
perfluoroalkene.
5. The amorphous fluorine-containing resin composition as described
in claim 4, wherein methoxy perfluoroalkene is methoxy
perfluoroheptene.
6. The amorphous fluorine resin composition as described in claim
1, wherein the heat of fusion of the amorphous fluorine-containing
resin is less than 3 J/g when measured at a heating rate of
10.degree. C./min by a differential scanning calorimetry.
7. (canceled)
8. The amorphous fluorine-containing resin composition as described
in claim 1, wherein the amorphous fluorine-containing resin is
0.01-10 wt % of the composition.
9. A method of forming a thin films of amorphous
fluorine-containing resin on a base material, comprising applying
to said base material an amorphous fluorine-containing resin
composition of claim 1 and drying the coated based material,
thereby forming a thin film of said amorphous fluorine-containing
resin on said base material.
10. An article that contains a coating that is formed from the
composition as described in claim 1.
Description
TECHNICAL FIELD
[0001] This invention is related to an amorphous
fluorine-containing resin composition that dissolves the amorphous
fluorine-containing resin in a fluorinated solvent, and is related
to a manufacturing method of thin films.
TECHNOLOGY BACKGROUND OF THE INVENTION
[0002] Among other fluorine resins, because the perfluoro polymer
that is particularly represented by the copolymer (PFA) of
tetrafluoroethylene (TFE) and perfluoro (alkyl vinyl ether) and
(PAVE) has the characteristics of superior heat resistance,
chemical resistance, purity, dielectric constant and so on, this
polymer is used for melt-molding of piping for transporting various
chemicals, joints of piping, transportation containers, storage
containers, pumps and filter housings, and so on in chemical plants
and semiconductors or the manufacturing process of the liquid
products; and is used for lining electronic boards, steel pipes,
pulps, fittings and so on.
[0003] However, because generally these perfluoro polymers are
insoluble, these polymers are being used in various applications in
the method of so-called hot melt molding.
[0004] In order to give the characteristics of this fluorine resin
to various base materials, attempts were made to dissolve the
amorphous fluorine resin in a solvent. For example, it has been
proposed that the amorphous tetrafluoroethylene copolymer is
dissolved and dispersed in the monoalkoxy-substituted solvent of
the perfluoroalkane and so on, to be the composition of the
coatings. Moreover, it has been proposed that the amorphous
fluorine-containing resin that has the fluorine-containing
aliphatic cyclic structure in the main chain is dissolved in a
specific perfluoro solvent, for example, perfluoro (2-butyl
tetrahydrofuran); and then the thin films of the
fluorine-containing polymer free from pinholes can be formed from
the perfluoro solvent solution of this fluorine-containing polymer.
(Patent document 1, Patent document 2, and Patent document 3).
[0005] However, the fluorine-containing solvents of
perfluoroalkane, hydrofluorocarbon, hydrofluoroether, and so on
that are used in the prior art have high global warming potential,
and cannot satisfy the requirements from the perspective of the
efforts to protect the global environment (refer to Table 1
mentioned below).
DOCUMENTS OF PRIOR ART
[Patent Document]
[0006] [Patent document 1] Patent Application Publication No.
2000-355677
[0007] [Patent document 2] Published Examined Patent Application
No. 8-22929
[0008] [Patent document 3] Patent Publication No. 3,968,899
[0009] [Patent document 4] U.S. Patent Publication No.
2011/0282104
SUMMARY OF THE INVENTION
[0010] [The Problems to be Solved by this Invention]
[0011] Therefore, in order to solve the above mentioned problems,
as a result of the extensive studies, the inventors of this
invention had found out the amorphous fluorine-containing resin
composition that has superior film-forming ability, and has a small
impact on the global environment because it has very small global
warming potential, and can fully satisfy the requirement from the
perspective of the environmental protection of the earth; and thus
this invention was achieved.
[0012] That is to say, this invention provides an amorphous
fluorine-containing resin composition that has superior
film-forming ability, and has a small impact on the global
environment.
[Means to Solve the Problems]
[0013] The inventors of this invention had found out that by using
alkoxy fluoroalkene as the solvent, the amorphous
fluorine-containing resin composition that has improved
film-forming ability, and has a small impact on the global
environment owing to its very small global warming potential, and
can fully satisfy the requirement from the perspective of the
environmental protection of the earth could be obtained; and thus
this invention was achieved.
[0014] That is to say, this invention provides an amorphous
fluorine-containing resin composition that dissolves the amorphous
fluorine-containing resin in alkoxy fluoroalkene.
[0015] The preferable embodiment of this invention is the above
mentioned amorphous fluorine resin composition having the heat of
fusion of the above mentioned amorphous fluorine-containing resin
of less than 3 J/g when measured at a heating rate of 10.degree.
C./min by a differential scanning calorimetry (DSC).
[0016] This invention further provides the method to form the thin
films of the amorphous fluorine-containing resin on the base
materials by applying the above mentioned amorphous fluorine resin
composition on the base materials, followed by drying.
[0017] Moreover, this invention provides an article that contains a
coating that is formed from the thin films that are made from the
above mentioned amorphous fluorine resin composition.
[Effect of the Invention]
[0018] Through the amorphous fluorine-containing resin composition
and the manufacturing method of that thin film, it is possible to
obtain the article that is coated by the amorphous
fluorine-containing resin wherein the thin films of the amorphous
fluorine-containing resin is formed on the surface of the article
without giving any adverse impact to the global warming, the used
solvent is removed immediately from the surface of the thin films,
causing no damage to the surface of the covered article by hot air,
and so on.
[0019] Through this invention, the amorphous fluorine-containing
resin composition that dissolves the amorphous fluorine-containing
resin in alkoxy fluoroalkene is provided.
[Embodiments to Execute this Invention]
[0020] In accordance with this invention, the amorphous
fluorine-containing resin composition that dissolves the amorphous
fluorine-containing resin in alkoxy fluoro alkene and the
manufacturing method of that thin film are provided.
[Solvent of this Invention]
[0021] In the amorphous fluorine-containing resin composition of
this invention, alkoxy fluoroalkene is fluoroolefin that has an
alkoxy group and a double bond.
[0022] The alkoxyl group is preferably the alkoxyl group with 1-5
carbon atoms, and is more preferably the methoxy group or the
ethoxy group with 1 or 2 carbon atoms.
[0023] It is desirable for the carbon number of fluoroalkene to be
2-10, with 5-8 being more preferable.
[0024] The preferable embodiment of this invention is the amorphous
fluorine-containing resin composition wherein ethoxy fluoroalkene
or methoxy fluoroalkene having the carbon number of the
fluoroalkene of 2-10, preferably 5-8 is used as the solvent.
[0025] For the preferable example of alkoxy fluoroalkene, alkoxy
perfluoroalkene can be mentioned. The perfluorinated alkene refers
to the compound wherein hydrocarbon that has 1 double bond, all the
hydrogen atoms are substituted by fluorine.
[0026] For the alkoxy perfluoroalkene of this invention, the carbon
number of perfluoroalkene is preferably 2-10, and the carbon number
is more preferably 5-8.
[0027] For the preferable examples of alkoxy perfluoroalkene,
methoxy perfluoroalkene of methoxy perfluoropentene, methoxy
perfluorohexane, methoxy perfluoroheptene, methoxy perfluorooctene,
and so on; and ethoxy perfluoroalkene of ethoxy perfluoropentene,
ethoxy perfluorohexane, ethoxy perfluoroheptene, ethoxy
perfluorooctene, and so on may be mentioned as the examples.
[0028] Although there are multiple structural isomers in the alkoxy
perfluoroalkene, there are no particular limitation on the
structure, the mixture of those isomers can also be accepted, and
it is possible to appropriately select the structure that is
suitable for the purposes of this invention. For example, for the
structure of methoxy perfluoroheptene, although the following
examples are mentioned, any structure can be accepted, and the
mixture of these isomers can also be accepted. In the case when
selecting from the structural isomers of alkoxy perfluoroalkene, it
is desirable to select the material that is more nonflammable.
[0029] (1) CF.sub.3(CF.sub.2).sub.2CF.dbd.CFCF(OCH.sub.3)CF.sub.3
[0030] (2)
CF.sub.3CF.sub.2CF.dbd.CF(CF.sub.3).sub.3(OCH.sub.2)CF.sub.3 [0031]
(3) CF.sub.3CF.sub.2CF.dbd.CFCF(OCH.sub.3)CF.sub.2CF.sub.3 [0032]
(4) CF.sub.3CF.dbd.CFCF(OCH.sub.3)(CF.sub.2).sub.2CF.sub.3 [0033]
(5) CF.sub.3CF.dbd.CFCF.sub.2CF(OCH.sub.3)CF.sub.2CF.sub.3 [0034]
(6) CF.sub.3CF.sub.2CF.dbd.C(OCH.sub.3)(CF.sub.2).sub.2CF.sub.3
[0035] (7)
CF.sub.3CF.sub.2C(OCH.sub.3).dbd.CFCF.sub.2CF.sub.2CF.sub.3
[0036] The preferable embodiment of this invention is the amorphous
fluorine-containing resin composition wherein alkoxy
perfluoroalkene or methoxy perfluoroalkene of which the carbon
number of the perfluoroalkene is 2-10, preferably 5-8 is used as
the solvent. In these compositions, the amorphous
fluorine-containing resin composition wherein the methoxy
perfluoroheptene is used as the solvent is more preferable.
[0037] Moreover, the amorphous fluorine-containing resin
composition may be used alone, and may also be used as a mixture.
In addition, because when manufacturing the thin films for the
surface of the article, the workability is improved by performing
the work at a high temperature within the range that does not
damage the surface of the covered article, it is preferable to
select alkene with higher boiling point from alkoxy fluoroalkenes
of this invention.
[Manufacturing Method of Alkoxy Perfluoroalkene]
[0038] In this invention, for the manufacturing method of the
alkoxy fluoroalkene that is used as the solvent for the amorphous
fluorine-containing resin composition, the alkoxy perfluoroalkene
that is the preferred example is introduced below as a
representative example. The manufacturing method is not limited to
these examples.
[0039] The alkoxy perfluoroalkene can be obtained by distilling the
product that is generated from the reaction for about 2 hours,
wherein in the perfluoroalkene that can be manufactured by the
following method, in the presence of the strong base such as KOH
and so on, alcohol and a small amount of water is added to conduct
an exothermal reaction. To be more specific, through the method
that was described in Patent Document 4, by selecting
perfluoroalkene as the appropriate reactant and alcohol to conduct
the reaction, various types of alkoxy perfluoroalkenes, that is to
say, methoxy perfluoropentene, methoxy perfluorohexane, methoxy
perfluoroheptene, or methoxy perfluorooctene, and ethoxy
perfluoropentene, ethoxy perfluorohexane, ethoxy perfluoroheptene
or ethoxy perfluorooctene and so on can be manufactured.
[Optional Components]
[0040] In the amorphous fluorine-containing resin composition of
this invention, corresponding to the necessity within the range of
not impairing the purpose of this invention, the following
components in addition to alkoxy fluoroalkene such as the solvents,
the stabilizers, and so on can be added.
[0041] As the solvent in addition to alkoxy fluoroalkene, at least
more than one type of solvent selected from, for example,
hydrocarbons, alcohols, ketones, ethers, esters, and so on can be
used alone or in combination. If these mixtures form an azeotropic
composition, because the mixture can be removed together with the
solvent of this invention, it is more preferable.
[0042] In the case when the solvent in addition to alkoxy
fluoroalkene is flammable, because when mixing a large amount of
the solvents, the whole composition will become flammable, it is
preferable to use within the range that considered the
flammability.
[0043] For the stabilizer, at least one type selected from
nitroalkanes, such as nitromethane, etc., epoxides such as
propylene oxide, etc., furans, benzotriazoles, phenols, amines, and
so on can be mentioned as examples.
[The Amorphous Fluorine-Containing Resin]
[0044] The amorphous fluorine-containing resin in this invention is
the resin wherein any heat of fusion of the resin that is detected
out by a differential scanning calorimetry (DSC) is less than 3
J/g; only weak heat-absorption is detected even during the heating
at the beginning, but no heat-absorption can be observed during the
second time of DSC heating.
[0045] In the amorphous fluorine-containing resin composition of
this invention, for the amorphous fluorine-containing resin, the
copolymer that at least contains tetrafluoroethylene (TFE) and is
composed of other comonomers that contains fluorine is preferable.
In that copolymer, the amount of other fluorine-containing
comonomers that are contained is the amount that gives the
amorphous nature to the fluorine-containing resin.
[0046] In addition, it is also possible to select from what is
known as the amorphous fluorine-containing resins or the perfluoro
elastomers that are available on the market for use.
[0047] For the examples of the amorphous fluorine-containing resin
of this invention, the copolymer of 1-70 wt % tetrafluoroethylene
and 99-30 wt % perfluoro (alkyl vinyl ether), the copolymer of
tetrafluoroethylene/perfluoro(butyl vinyl ether), the copolymer of
tetrafluoroethylene/perfluoro dimethyl dioxole, the copolymer of
tetrafluoroethylene/CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2-
SO.sub.2F, and so on may be mentioned as the examples. For the
preferable amorphous fluorine-containing resin of these resins, the
copolymer of 1-70 wt % tetrafluoroethylene and 99-30 wt % perfluoro
(alkyl vinyl ether) may be mentioned as the example.
[0048] For the resin that can be used as the amorphous
fluorine-containing resin of this invention, the following examples
described can be mentioned as concrete examples, but this invention
is not limited these examples. From these examples, one type or
more than two types that are suitable for the purpose of this
invention can be appropriately selected for use.
[0049] (a) The copolymer (the TFE/PEVE copolymer) of 1-70 wt %
tetrafluoroethylene and 99-30 wt % perfluoro (alkyl vinyl
ether)
[0050] (b) Teflon (registered trademark) AF 1600 [product name,
manufactured by DuPont Company, the copolymer of
tetrafluoroethylene/perfluoro dimethyl dioxole, Tg=160.degree.
C.]
[0051] (c) Teflon (registered trademark) AF 2400 [product name,
manufactured by DuPont Company, the copolymer of
tetrafluoroethylene/perfluoro dimethyl dioxole, Tg=240.degree.
C.]
[0052] (d) Teflon (registered trademark) SF-60 [product name,
manufactured by DuPont Company, the copolymer of
tetrafluoroethylene/perfluoro methyl vinyl ether/perfluoro ethyl
vinyl ether]
[0053] (e) Teflon (registered trademark) SF-50 [product name,
manufactured by DuPont Company, the copolymer of
tetrafluoroethylene/hexafluoropropylene]
[0054] (f) Cytop [product name, manufactured by Asahi Glass
Company, the copolymer of tetrafluoroethylene /perfluoro (butenyl
vinyl ether)]
[0055] (g) The sulfonyl fluorides of Nafion (registered trademark)
[manufactured by DuPont Company, the copolymer of
tetrafluoroethylene /CF.sub.2.dbd.CFO CF.sub.2 CF (CF.sub.3)
OCF.sub.2 CF.sub.2 SO.sub.2 F]
[0056] (h) Hyflon AD [product name, manufactured by Solvay Company,
the copolymer of tetrafluoroethylene /perfluoro dimethyl
dioxole]
[Preparation of the Amorphous Fluorine-Containing Resin
Composition]
[0057] In the amorphous fluorine-containing resin composition that
is obtained by dissolving the amorphous fluorine-containing resin
in alkoxy fluoroalkene, the concentration of the amorphous
fluorine-containing resin is preferably in the range of 0.01-10 wt
%, and more preferably 0.5-5 wt %.
[0058] For the method of dissolving the amorphous
fluorine-containing resin in alkoxy fluoroalkene, there is no
particular limitation, the conventionally known methods can be
adopted. At the time of dissolving the amorphous
fluorine-containing resin in alkoxy fluoroalkene, it is possible to
promote the dissolution if an ultrasonic treatment is
performed.
[0059] For the amorphous fluorine-containing resin composition of
this invention, it is also possible to mix and dissolve more than
two types of amorphous fluorine-containing resins in accordance
with the purpose of that use. The mixing ratio of the amorphous
fluorine polymer is in the range of 0.1-99.9% of the total weight
of the resin for one component, and 99.9-0.1% for the sum of other
components.
[Method to Form Thin Films that Used the Liquid Composition of the
Fluorine-Containing Polymer of this Invention]
[0060] Through drying after applying the amorphous
fluorine-containing resin composition of this invention on the base
materials, it is possible to form the thin films of the amorphous
fluorine-containing resin on the base materials.
[0061] For the method of applying the amorphous fluorine-containing
resin composition on the base materials, there is no particular
limitation, the conventionally known methods can be adopted. For
example, it is possible to use other dip methods, casting methods,
roll coating methods, spin coating methods and so on in addition to
the normal brushing and spraying methods. Through drying after
applying, it is possible to form the thin films of the amorphous
fluorine-containing resin on the base materials.
[0062] The obtained thin films can be used while the films are
closely adhered on the base materials or are peeled from the base
materials. The thickness of the thin films can be in the range of
1-30 .mu.m by adjusting the concentration and the like of the
dissolved amorphous fluorine-containing resin.
[0063] For the use of the obtained thin films, the pellicle films
and so on in the manufacturing process of semiconductors, the
protective films in electrical and electronic parts, optical parts,
precision machinery parts, automotive parts and so on can be
mentioned as the examples. For the base materials for the purpose
of obtaining the thin films through peeling from the base
materials, the flat plate-like shapes that are made from metals,
resins and so on are preferable, but this invention is not limited
those examples.
[0064] In the case when the thin films are used while the films are
closely adhered on the base materials, as the subject of the base
materials, wiring boards such as printed circuit boards, ceramic
wiring board, etc.; optical fibers, solar cells, touch panel, film
capacitors, liquid crystal, plasma display and other display
components can be mentioned as examples.
[0065] As optical components, lenses that are used in glasses,
cameras, and housings of the lenses can be mentioned as
examples.
EMBODIMENTS
[0066] In the following paragraphs, the embodiments are given to
further explain this invention in detail, but this invention is not
limited to these embodiments.
[0067] The test of the physical properties in this invention was
carried out by the following methods.
(1) Solubility
[0068] 19.8 g fluorine-containing solvent and 0.2 g
fluorine-containing resin were placed in the sample tube (50 mL),
by an ultrasonic treatment over a period of about 180 minutes at
50.degree. C., based on the combined weight of the resin and the
solvent, 1 wt % composition was created. After the treatment, the
composition was left standing for 10 minutes at 50.degree. C., and
then the state of the obtained composition was visually
observed.
[0069] The state in the sample tube after the ultrasonic treatment
was evaluated in accordance with the following criteria.
[0070] Soluble: cloudiness and precipitation cannot be observed
[0071] Insoluble: cloudiness and precipitation at the bottom can be
observed
(2) Film-Forming Ability
[0072] On one side of the glass plate in the size of 76 mm.times.26
mm, 2 mL solution of the fluorine-containing resin was applied,
after any excess solution was removed by tilting the glass plate at
90.degree., the plate was dried for 3 hours at 60.degree. C., and
then the state of the obtained coating film was visually
observed.
[0073] The state of the coating film after drying was evaluated in
accordance with the following criteria.
[0074] .smallcircle.: it was a good coating film
[0075] X: unevenness was observed
[0076] The Table 1 shows the global warming potential and the
boiling point of the fluorinated solvent that is conventionally
used and the amorphous fluorine-containing resin composition of
this invention. The value of the conventional fluorinated solvent
was transcribed from the report that was published, while the value
of the solvent of this invention was the value calculated by the
applicant for methoxy perfluoroheptane, which is described in the
following Embodiment 1. In addition, the (Global Warming Potential
GWP) is based on the carbon dioxide, and refers to a number that
indicates how much potential of global warming other greenhouse gas
has; and GWP is an estimated value of the ratio of the integrated
value (that is to say, the impact on global warming) of the
radiation energy that is applied to the earth in a given period of
time to O.sub.2 at the time when the greenhouse gas in the unit
mass is released into the atmosphere.
TABLE-US-00001 TABLE 1 Global Warming Potential Fluorine-containing
solvent Global Warming Potential Boiling point Methoxy
perfluoroheptene <10 (Note 2) 110.degree. C. 1,1,1,2,3,4,5,5,5-
1,640 (Note 1) 55.degree. C. decafluoropentane Methoxy
perfluorohexane 200 (Note 3) 98.degree. C.
F(CF.sub.2).sub.6OCH.sub.3 (Note 1) 2007 Fourth Assessment Report
from the Intergovernmental Panel on Climate Change (Abbreviated:
IPCC) (Note 2) Calculated by the applicant (Note 3) From Table 2 of
Patent Application Publication No. 2010-164043
Preparation Example 1
Preparation of the TFE/PEVE Copolymer (the Content of PEVE is 56 wt
%)
[0077] In a one gallon (3.8 L) reactor, 2400 mL deionized water,
the surfactant, and the polymerization initiator was used, 323 g
PEVE was supplied, by the reaction with TFE, the dispersion
solution of which the content of solid materials was 5 wt % was
obtained. The generated copolymer was washed clean using the
deionized water, and then dried for 1.5 hours at 150.degree. C. The
composition of the generated copolymer that was measured by 19
F-nuclear magnetic resonance (NMR) spectrum analysis was TFE/PEVE
=44/56 by weight. The melting point of this TFE/PEVE copolymer was
not detected by DSC, and the glass transition temperature was
20.degree. C.
Embodiment 1
[0078] 19.8 g methoxy perfluoroheptene, 0.2 g TFE/PEVE copolymer
(the content of PEVE was 56 wt %) as the fluorine-containing
polymer were placed in the sample tube (50 mL), by an ultrasonic
treatment over a period of about 180 minutes at 50.degree. C.,
based on the combined weight of the resin and the solvent, 1 wt %
composition was created. The film-manufacturing ability of the
obtained composition was tested. The results are shown in Table 2.
It is understood that the fluorine-containing polymer was dissolved
to form the solution.
[0079] The methoxy perfluoroheptene that was used was the mixture
of the isomers, the constitution of the mixture of the isomers
shown in paragraph [0016] was 49% isomer (3), 20% (4), 20% (7), 6%
(6), and the remaining percentage for other isomers.
Embodiment 2
[0080] Teflon (registered trademark) AF 1600 as the
fluorine-containing polymer was used, and the same procedures as
Embodiment 1 were conducted. The results are shown in Table 2.
Embodiment 3
[0081] Teflon (registered trademark) AF 2400 as the
fluorine-containing polymer was used, and the same procedures as in
Embodiment 1 were conducted. The results are shown in Table 2.
Embodiment 4
[0082] 19.8 g methoxy perfluoroheptene that was used in Embodiment
1, 0.1 g TFE/PEVE copolymer (the content of PEVE is 56 wt %) as the
fluorine-containing polymer, and 0.1 g Teflon (registered
trademark) AF 1600 were placed in the sample tube (50 mL), by the
ultrasonic treatment over a period of about 180 minutes at
50.degree. C., based on the combined weight of the resin and the
solvent, 1 wt % composition was created. The film-forming ability
of the obtained composition was tested. The results are shown in
Table 2. It is understood that the fluorine-containing polymer was
dissolved to form the solution.
Embodiment 5
[0083] The TFE/PEVE copolymer as fluorine-containing polymer (the
content of PEVE is 56 wt %) as the fluorine-containing polymer and
Teflon (registered trademark) AF 2400 were used, and the same
procedures as Embodiment 4 were conducted. The results are shown in
Table 2.
Comparative Example 1
[0084] 1,1,1,2,3,4,5,5,5-Decafluoropentane as the solvent
(manufactured by Dupont-Mitsui Fluorochemicals Co., Ltd., Vertrel
(registered trademark) XF) was used, and the same procedures as
Embodiment 1 were conducted. The results are shown in Table 2.
Comparative Example 2
[0085] 1,1,1,2,3,4,5,5,5-Decafluoropentane as the solvent
(manufactured by Dupont-Mitsui Fluorochemicals Co., Ltd., Vertrel
(registered trademark) XF) was used, and the same procedures as
Embodiment 2 were conducted. The results are shown in Table 2.
Comparative Example 3
[0086] Nonafluorobutyl methyl ether as the solvent (manufactured by
3M Company, Novec (registered trademark) HFE-7100) was used, and
the same procedures as Embodiment 2 were conducted. The results are
shown in Table 2.
TABLE-US-00002 TABLE 2 comparison of the solubility of the
amorphous fluorine-containing resin composition Solvent Polymer
Solubility Embodiment 1 Methoxy TFE/PEVE Soluble perfluoroheptene
Embodiment 2 Methoxy Teflon AF 1600 Soluble perfluoroheptene
Embodiment 3 Methoxy Teflon AF 2400 Soluble perfluoroheptene
Embodiment 4 Methoxy TFE/PEVE, and Soluble perfluoroheptene Teflon
AF 1600 Embodiment 5 Methoxy TFE/PEVE, and Soluble perfluoroheptene
Teflon AF 2400 Comparative 1,1,1,2,2,3,4,5,5,5- TFE/PEVE Insoluble
Example 1 decafluoropentane Comparative 1,1,1,2,2,3,4,5,5,5- Teflon
AF 1600 Insoluble Example 2 decafluoropentane Comparative
Nonafluorobutyl Teflon AF 1600 Insoluble Example 3 methyl ether
Embodiment 6-10
Test of the Film-Forming Ability
[0087] It is possible to form the uniform thin film without any
pinholes by the method wherein the composition that was obtained in
accordance with Embodiment 1-5 was applied on the glass plate, and
then dried for 3 hours at 60.degree. C. The state of the obtained
coating film was visually observed. The results are shown in Table
3.
[0088] The state of the coating film after drying was evaluated in
accordance with the following standard.
[0089] .smallcircle.: it was a good coating film
[0090] X: unevenness was observed
Embodiment 11
[0091] 19.0 g methoxy perfluoroheptene and 1.0 g Teflon (registered
trademark) AF 2400 as the fluorine-containing polymer were placed
in the sample tube (50 mL), by the ultrasonic treatment over a
period of about 180 minutes at 50.degree. C., based on the combined
weight of the resin and the solvent, 5 wt % solution was created.
This solution was applied on the glass plate, and then dried for 3
hours at 100.degree. C. The state of the obtained coating film was
visually observed. The results are shown in Table 3.
Comparative Example 6-8
[0092] The dispersion solution that was obtained in accordance with
Comparative Example 1-3 was applied on the glass plate, and then
dried for 3 hours at 60.degree. C. to form the thin films. The
pinholes were observed in the obtained coating film. The results
are shown in Table 3.
TABLE-US-00003 TABLE 3 comparison of the film-forming ability of
the amorphous fluorine-containing resin composition Film Film-
thick- forming ness Solvent Polymer ability (.mu.m) Embodiment 6
Methoxy TFE/PEVE .largecircle. 2.0 perfluoroheptene Embodiment 7
Methoxy Teflon .largecircle. 5.0 perfluoroheptene AF 1600
Embodiment 8 Methoxy Teflon .largecircle. 5.0 perfluoroheptene AF
2400 Embodiment 9 Methoxy TFE/PEVE, .largecircle. 3.5
perfluoroheptene Teflon AF 1600 Embodiment 10 Methoxy TFE/PEVE,
.largecircle. 3.0 perfluoroheptene Teflon AF 2400 Embodiment 11
Methoxy Teflon .largecircle. 30.0 perfluoroheptene AF 2400
Comparative 1,1,1,2,2,3,4,5,5,5- TFE/PEVE X -- Example 4
decafluoropentane Comparative 1,1,1,2,2,3,4,5,5,5- Teflon X --
Example 5 decafluoropentane AF 1600 Comparative Nonafluorobutyl
Teflon X -- Example 6 methyl ether AF 1600
[Applicability in the Industry]
[0093] In accordance with this invention, the amorphous
fluorine-containing resin composition that has superior
film-forming ability and has a small impact on the global
environment is provided.
[0094] In accordance with this invention, the amorphous
fluorine-containing resin composition and the manufacturing method
of that thin film are provided, wherein it is possible to form the
thin films of the amorphous fluorine-containing resin in a way that
the thin films of the amorphous fluorine-containing resin is formed
on the surface of the article without giving any adverse impact to
the global warming, the used solvent is removed immediately from
the surface of the thin films, and no damage is caused to the
surface of the covered article by the hot air, and so on.
[0095] By the method of using the amorphous fluorine-containing
resin composition of this invention to form the thin films, which
will have no adverse impact on the global warming, it is possible
to utilize various characteristics of the amorphous
fluorine-containing resin composition to form the thin films
quickly on the surface of the target article.
[0096] In accordance with this invention, the amorphous
fluorine-containing resin composition that dissolves the amorphous
fluorine-containing resin in alkoxy fluoroalkene is provided.
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