CN109476785A - Fluoro-containing copolymer composition, fluorine resin coating, coated article - Google Patents
Fluoro-containing copolymer composition, fluorine resin coating, coated article Download PDFInfo
- Publication number
- CN109476785A CN109476785A CN201780043675.6A CN201780043675A CN109476785A CN 109476785 A CN109476785 A CN 109476785A CN 201780043675 A CN201780043675 A CN 201780043675A CN 109476785 A CN109476785 A CN 109476785A
- Authority
- CN
- China
- Prior art keywords
- fluoropolymer
- fluoro
- peak
- area
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The fluoro-containing copolymer composition of excellent storage stability is provided.A kind of fluoro-containing copolymer composition, containing fluoropolymer and solvent, the fluoropolymer includes fluoroolefins unit and cyclohexyl vinyl ether unit, and calculating the area ratio AR that method is found out by area ratio is 0.1~3%.
Description
Technical field
The present invention relates to fluoro-containing copolymer composition, fluorine resin coating and coated articles.
Background technique
Composition containing fluoropolymer and solvent is suitable as the raw material of fluorine resin coating.It is being contained in fluoropolymer
Fluoroolefins unit and the unit based on monomer in addition to this are generally comprised in fluoropolymer in compositions.
Disclose in patent document 1 containing the fluoropolymer comprising fluoroolefins unit and cyclohexyl vinyl ether unit and
The fluoro-containing copolymer composition of solvent.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 61-174210 bulletin
Summary of the invention
Problems to be solved by the invention
In recent years, according to the extension of the purposes of fluorine resin coating, it is desirable that the fluoropolymer combination used as its raw material
The further raising of the storage-stable of object.It should be noted that storage-stable refers under heating environment herein, it is fluorine-containing
Fluoropolymer-containing matter average molecular weight contained in polymer composition does not increase.
The method recorded in the present inventor's referenced patent document 1 has been manufactured containing comprising fluoroolefins unit and cyclohexyl. vinyl
The fluoropolymer of base ether unit and the fluoro-containing copolymer composition of solvent, and its storage-stable is studied, as a result
It was found that it is horizontal to be unsatisfactory for recent requirement sometimes.
The present invention has been made in view of the above problems, it is intended that providing the fluoropolymer of excellent storage stability
Compositions and fluoropolymer-containing manufacturing method.
In addition, the present invention also aims to provide fluorine resin coating and painting object containing fluoro-containing copolymer composition
Product.
The solution to the problem
The inventors of the present invention have made intensive studies to solve the above-mentioned problems, as a result, it has been found that, due to fluoropolymer group
The presence of the specific impurity component in object is closed, storage-stable is affected, and then finds, its amount is adjusted to defined model
When enclosing, desired effect can be obtained, so as to complete the present invention.
That is, the present invention is as follows.
[1] a kind of fluoro-containing copolymer composition, which is characterized in that containing fluoropolymer and solvent (wherein, do not include first
Benzene and acetone), the fluoropolymer includes fluoroolefins unit and cyclohexyl vinyl ether unit, passes through area ratio below
The area ratio AR that calculating method is found out is 0.1~3%.
Area ratio calculates method: 200 mass parts of acetone are added relative to 100 mass parts of aforementioned fluoropolymer composition,
Preparation is by dilute solution made of the dilution of aforementioned fluoropolymer composition, in turn, is added in aforementioned dilute solution relative to preceding
The toluene that dilute solution gross mass is 1 mass % is stated, sample solution is prepared, using obtained aforementioned sample solution, implements gas phase
Chromatographic determination, it is 0.5 times of peak below of the peak area at the peak from toluene that extracting, which has peak area, by the aforementioned peak of extraction
The summation of peak area is set as area A, will be originated from the time side appearance short in the retention time than cyclohexanol in the aforementioned peak of extraction
The summation of peak area at peak of ingredient be set as area B, will be by value that formula below (1) is found out as area ratio AR.
Formula (1): area ratio AR (%)=(area B/area A) × 100
[2] fluoro-containing copolymer composition according to [1], wherein the content of aforementioned fluoroolefins unit is relative to aforementioned
Whole units that fluoropolymer is included are 30~70 moles of %, and the content of aforementioned cyclohexyl vinyl ether unit is relative to preceding
Stating whole units that fluoropolymer is included is 10~50 moles of %.
[3] fluoro-containing copolymer composition according to [1] or [2], wherein foregoing area ratio AR be 0.1~
1.5%.
[4] fluoro-containing copolymer composition according to any one of [1]~[3], wherein aforementioned fluoroolefins unit is four
Vinyl fluoride unit or chlorotrifluoroethylene unit.
[5] fluoro-containing copolymer composition according to any one of [1]~[4], wherein fluoropolymer also includes tool
The unit of crosslinking property group.
[6] fluoro-containing copolymer composition according to [5], wherein the aforementioned unit with crosslinkable groups be with
The unit of hydroxyl.
[7] fluoro-containing copolymer composition according to any one of [1]~[6], wherein fluoropolymer also includes base
In except fluoroolefins, cyclohexyl vinyl ether and with the monomer of crosslinkable groups in addition to the 4th monomer unit.
[8] fluoro-containing copolymer composition according to [7], wherein the aforementioned unit based on the 4th monomer is based on not having
There is the unit of the monomer of fluorine atom.
[9] a kind of fluoropolymer-containing manufacturing method, which is characterized in that it makes comprising fluoroolefins and cyclohexyl vinyl ether
Monomer mixture polymerize to manufacture fluoropolymer, wherein cyclohexyl vinyl ether is purified, cyclohexyl. vinyl is made
Contain in base ether, boiling point is 0.15% cyclohexylvinyl below than following the area ratios of the compound of cyclohexanol low boiling point
The cyclohexyl vinyl ether after purification is used for aforementioned polymeric by ether.
The area ratio: in the measurement of the cyclohexyl vinyl ether based on gas-chromatography, being originated from obtained gas-chromatography
In peak face of the summation relative to whole peaks of the peak area at the peak for the ingredient that the short time side of the retention time than cyclohexanol occurs
The ratio of long-pending summation.
[10] the fluoropolymer-containing manufacturing method according to [9], wherein make in the presence of solvent or decentralized medium
The polymerization of aforementioned monomer mixture.
[11] a kind of fluoropolymer-containing manufacturing method, which is characterized in that it makes comprising fluoroolefins and cyclohexylvinyl
The monomer mixture of ether polymerize fluorine-containing to manufacture in the presence of radical polymerization initiator, alkali carbonate and polymer solvent
Polymer, wherein polymer solvent be carbon number 1~6 alcohol and 20 DEG C higher than the boiling point of the alcohol of boiling point or more of organic solvent it is mixed
Bonding solvent, from vacuum distillation is removed aforementioned alcohol and the aforementioned alkali-metal carbonate removal that is precipitated in reaction mixture after polymerization,
And the usually used temperature and degree of decompression and aforementioned organic solvents are not depressurized steaming in the vacuum distillation removal for being more than the alcohol
The vacuum distillation removal for carrying out aforementioned alcohol under conditions of removing is evaporated, the fluoropolymer for being dissolved in aforementioned organic solvents is obtained.
[12] the fluoropolymer-containing manufacturing method according to [11], wherein aforementioned organic solvents be with 110 DEG C with
On boiling point organic solvent, aforementioned alcohol be ethyl alcohol, carry out ethyl alcohol under 65 DEG C or more of temperature, 45Torr degree of decompression below
Vacuum distillation removal.
[13] according to the fluoropolymer-containing manufacturing method of [11] or [12], wherein aforementioned cyclohexyl vinyl ether contains
Boiling point than cyclohexanol low boiling point compound, and following the area ratios of the compound be 0.15% or less.
The area ratio: in the measurement of the cyclohexyl vinyl ether based on gas-chromatography, being originated from obtained gas-chromatography
In peak face of the summation relative to whole peaks of the peak area at the peak for the ingredient that the short time side of the retention time than cyclohexanol occurs
The ratio of long-pending summation.
[14] a kind of fluorine resin coating, it includes the fluoro-containing copolymer compositions described in any one of aforementioned [1]~[8].
[15] a kind of coated article is formed in items with article and the fluorine resin coating as described in [14]
Film.
The effect of invention
In accordance with the invention it is possible to provide the fluoro-containing copolymer composition of excellent storage stability.
In addition, in accordance with the present invention it is further possible to provide fluorine resin coating and coated article containing fluoro-containing copolymer composition.
Specific embodiment
The meaning of term in the present invention is as follows.
" unit " refers to atomic group directly formed by the polymerization of monomer, from 1 molecule of monomer and by the atom
A part of group carries out the general name of atomic group obtained from chemical conversion.All lists that each unit is included relative to polymer
The content (mole %) of member is analyze finding out to polymer by nuclear magnetic resonance method.It should be noted that will be based on
The unit of specific monomer adds " unit " nominally in monomer to indicate.
" number-average molecular weight " and " matter average molecular weight " is to be surveyed using polystyrene as standard substance by gel permeation chromatography
Fixed value." number-average molecular weight " is also referred to as " Mn ", and " matter average molecular weight " is also referred to as " Mw ".
" median particle size " refers to the partial size for quality % being accumulated and being become from the small side of partial size 50 mass %.
As fluoro-containing copolymer composition of the invention (hereinafter also referred to as " this composition ".) characteristic point, can enumerate
It is this point of defined range by the range that the area ratio described in detail in back segment calculates the area ratio AR that method obtains.
The inventors of the present invention study the prior art, as a result, it has been found that, in this composition it is micro containing it is specific at
Divide (impurity component) adverse effect can be brought to the storage-stable of composition.Specifically, firstly, in this original composition just
Inevitably containing the impurity component for being originated from the monomer used to manufacture fluoropolymer.As foregoing impurities ingredient,
The pair generated when the residue of used cyclohexanol, synthesizing cyclohexyl vinyl ethers when can enumerate synthesizing cyclohexyl vinyl ethers
Product residue etc..Wherein, the inventors of the present invention have found, in gas Chromatographic Determination (hereinafter also referred to as " GC measurement ".) in, mainly exist
The ingredient that the time side shorter than the retention time of cyclohexanol occurs (wherein, as described later, does not include acetone, toluene etc..) right
The storage-stable of this composition affects.
Therefore, the inventors of the present invention have found that when controlling the content of aforesaid ingredients for below specified amount, storage-stable can be mentioned
It is high.It should be noted that aforesaid ingredients it is associated with storage-stable it is detailed the reason is not yet clear, but be speculated as, it is aforementioned
Promote the mutual crosslinking of the fluoropolymer in this composition at branch, therefore storage-stable deteriorates.
Hereinafter, firstly, to the calculation method of area ratio AR (hereinafter also referred to as " area ratio calculating method ".) carry out in detail
Thin narration.
In the area ratio calculating method, it is measured using GC.The preparation method of sample solution for GC measurement is as follows.
Firstly, preparing fluoro-containing copolymer composition, acetone 200 is added relative to 100 mass parts of fluoro-containing copolymer composition
Mass parts, dilute solution made of preparation dilutes fluoro-containing copolymer composition.
Then, the toluene for being 1 mass % relative to aforementioned dilute solution gross mass, preparation are added in aforementioned dilute solution
Sample solution.As described later, in GC measurement, in order to as the peak for extracting micro constitutent contained in fluoro-containing copolymer composition
Benchmark and add toluene.
Then, using obtained sample solution, implement GC measurement.
GC is measured, using the gas-chromatography (detector: FID) of Agilent Technologies corporation, with
It is carried out under conditions of lower.
(sample injection rate) 1.0 μ L, (injection way) shunting, (carrier gas) He, 240 DEG C of (inlet temperature), (pressure)
199.9kPa, (total flow) 179mL/min, (split ratio) 100:1, (bypass flow) 174mL/min, (column) capillary column,
DB1301 (1.00 μm of length 60m × internal diameter 0.25mm, film thickness), it (column pressure) 199.9kPa, (column flow) 1.7mL/min, (puts down
Equal linear velocity) 29.0cm/sec, (column program oven temperature) keep after ten minutes, heating up with 10 DEG C/min at 40 DEG C,
25 minutes, (detector) hydrogen flameionization detection method (FID), 250 DEG C of (detector temperature) are kept at 250 DEG C.
Firstly, extracting the peak area that there is peak area for the peak from toluene from the gas-chromatography measured by GC
0.5 times of peak below.Herein, the peak area at the peak for the toluene being added using specified amount into this composition will be originated from as benchmark,
Extract peak associated with micro constitutent contained in this composition.The amount for the acetone being added in aforementioned sample solution compares toluene
It is more, therefore the peak of acetone is revealed as the peak bigger than the peak of toluene, is excluded at the extraction.In addition, for molten in this composition
Agent, its usual content is more than toluene, therefore at the extraction, peak corresponding with solvent is excluded.That is, by extracting, Neng Gouti
Take peak associated with micro constitutent contained in this composition (predominantly impurity component).
Then, the summation of the peak area at the peak of extraction is set as area A.
In addition, by the peak at the peak for being originated from the ingredient occurred in the short time side of the retention time than cyclohexanol in the peak of extraction
The summation of area is set as area B.It should be noted that not including the peak for being originated from solvent in the peak extracted due to script, being originated from third
The peak of ketone and peak from toluene, therefore when calculating area B, it does not include the peak area at the peak from solvent, from acetone
The peak area of the peak area at peak and the peak from toluene.
It should be noted that, in order to calculate the retention time of cyclohexanol, using hexamethylene alcohol monomer when calculating foregoing area B
GC measurement is carried out, the retention time of cyclohexanol can be obtained in advance.
Using obtained area A and area B, area ratio AR is found out by formula below (1).
Formula (1): area ratio AR (%)=(area B/area A) × 100
From the range of the area ratio AR in the storage-stable aspect of this composition, this composition be 0.1~
3%, preferably 0.1~3.0%, more preferable 0.1~1.5%, particularly preferred 0.1~1.0%.
In the case that area ratio AR is more than 3%, the storage-stable of this composition is poor.In addition, as this can be removed
The technical limit of micro constitutent in composition, there are the lower limit value of foregoing area ratio AR (0.1%).In order to make area
Ratio AR is less than 0.1%, it is necessary to cyclohexyl vinyl ether very high using purity, expensive, therefore it is unfavorable in industrial aspect.
This composition contains fluoropolymer and solvent comprising defined unit.
Fluoropolymer includes fluoroolefins unit and cyclohexyl vinyl ether unit.It should be noted that hereinafter, by hexamethylene
Base vinyl ethers is also referred to as " CHVE ".
Fluoroolefins is alkene made of 1 or more hydrogen atom is replaced by fluorine atoms.In fluoroolefins, it is not replaced by fluorine atoms
1 or more of hydrogen atom can also be substituted by a chlorine atom both.
As fluoroolefins, preferably CF2=CF2、CF2=CFCl, CF2=CFCF3And CF2=CH2, more preferable CF2=CF2(four
Vinyl fluoride) and CF2=CFCl (chlorotrifluoroethylene).
Fluoroolefins can be used singly or in combination of two or more.
It is whole units preferably 30~70 moles of % that the content of fluoroolefins unit is included relative to fluoropolymer, more excellent
Select 40~60 moles of %, particularly preferred 45~55 moles of %.When the content of fluoroolefins unit is 30 moles of % or more, by the present invention
Fluorine resin coating formed film (hereinafter also referred to as " this film ".) weatherability it is more excellent.The content of fluoroolefins unit is
When 70 moles of % or less, dissolubility, the dispersibility of fluoropolymer in a solvent are more excellent.
Whole units preferably 10~50 moles of % that the content of CHVE unit is included relative to fluoropolymer, more preferably
10~45 moles of %, particularly preferred 15~40 moles of %.When the content of CHVE unit is 10 moles of % or more, fluoropolymer exists
Dissolubility, dispersibility in solvent is more excellent.When the content of CHVE unit is 50 moles of % or less, the excellent weather resistance and hard of this film
It is different.
It may include the unit other than fluorine removal olefin unit and CHVE unit in fluoropolymer.Hereinafter, fluoroolefins will be removed
And the monomer other than CHVE is known as " other monomers ", and the unit based on the other monomers is known as " other units ".
Other units contained in fluoropolymer can be two or more.In addition, other units can be for fluorine atom
Unit, or the unit without fluorine atom.In addition, other units may be aftermentioned with crosslinkable groups
Unit.Unit in other units other than the unit with crosslinkable groups is Unit the 4th.Fluoropolymer preferably comprises
Other at least one kind of units.
As other units, preferably do not have the unit of fluorine atom.In addition, not having as contained in fluoropolymer
The unit of fluorine atom, more preferably comprising having the unit of crosslinkable groups and Unit the 4th (that is, not having the list of crosslinkable groups
Member) other at least two kinds of units.
As the other monomers for not having fluorine atom, as long as without fluorine atom and with the chemical combination of polymerizable group
Object can enumerate the vinyl ethers without fluorine atom, the allyl ether without fluorine atom, not have as concrete example
Have the vinyl esters of fluorine atom, the allyl ester without fluorine atom, the alpha-olefin without fluorine atom, without fluorine atom
Acrylate, the methacrylate without fluorine atom.
It should be noted that as the monomer for not having fluorine atom, from the reactive aspect with fluoroolefins, preferably
Vinyl monomer without fluorine atom does not have vinyl ethers, the vinyl without fluorine atom of fluorine atom more preferably
Ester.
One of mode appropriate as the aforementioned other monomers without fluorine atom, can enumerate with crosslinkable groups
Monomer (hereinafter also referred to as " monomer I ".).As narration in detail in back segment, there are crosslinkable groups in fluoropolymer
In the case of, contain curing agent in fluorine resin coating by making, so as to further increase the weatherability of this film, water resistance,
Chemical resistance, heat resistance etc..
As crosslinkable groups, functional group's (hydroxyl, carboxyl, amino etc.) of preferably active hydrogen, water-disintegrable monosilane
Base (alkoxysilyl etc.) etc., particularly preferred hydroxyl.
As monomer I, can enumerate hydroxyalkyl vinyl ether, hydroxyalkyl vinyl base ester, hydroxy alkyl allyl ether,
Hydroxy alkyl allyl ester, hydroxy alkyl acrylate, hydroxy alkyl methacrylate etc., from fluoroolefins copolymerizable and
It sets out in terms of the weatherability of this film, preferably hydroxyalkyl vinyl ether.
As the concrete example of monomer I, 2- hydroxyethyl vinyl ether, 4- hydroxybutyl vinyl ether, hexamethylene can be enumerated
Alkane dimethanol monovinyl ether, 2- hydroxyethyl allyl ether, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxyl second
Ester.
Monomer I can be used singly or in combination of two or more.
As the mode appropriate of monomer I, monomer shown in following formula (2) can be enumerated.
Formula (2) CH2=CX1(CH2)n1-Q1-R1-Y
In formula, X1For hydrogen atom or methyl.
N1 is 0 or 1.
Q1For oxygen atom ,-C (O) O- or-O (O) C-, preferably oxygen atom.
R1For the alkylidene of the carbon number 2~20 optionally with branched structure or ring structure, preferably-two methylene of hexamethylene-Isosorbide-5-Nitrae
Base or positive nonylene.
Y is crosslinkable groups, preferably hydroxyl, carboxyl or amino, more preferable hydroxyl.
From the storage-stable aspect of this composition, the content of the unit based on monomer I is relative to fluoropolymer
Whole units that object is included preferably 0~20 mole of %, more preferable 0~18 mole of %, particularly preferred 0~15 mole of %.
As the mode appropriate for the monomer for forming Unit the 4th, can enumerate without fluorine atom, cyclic hydrocarbon group and crosslinking
The monomer of property group is (hereinafter also referred to as " monomer II ".).
As monomer II, the vinyl ethers without fluorine atom, cyclic hydrocarbon group and crosslinkable groups can be enumerated, do not had
Fluorine atom, the allyl ether of cyclic hydrocarbon group and crosslinkable groups, the ethylene without fluorine atom, cyclic hydrocarbon group and crosslinkable groups
Base ester, does not have fluorine atom, cyclic hydrocarbon group and crosslinking at the allyl ester without fluorine atom, cyclic hydrocarbon group and crosslinkable groups
Property the alkene of group, the acrylate without fluorine atom, cyclic hydrocarbon group and crosslinkable groups, do not have fluorine atom, cyclic hydrocarbon
Base and the methacrylate of crosslinkable groups etc..
As the concrete example of monomer II, nonyl vinyl ethers, 2- ethylhexyl vinyl ether, hexyl vinyl can be enumerated
Ether, ethyl vinyl ether, n-butyl vinyl ether, tert-Butyl vinyl ether, ethyl allyl ether, hexyl allyl ether, carboxylic acid
Vinyl esters, carboxylic acid (acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid of (acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid etc.)
Deng) allyl ester, ethylene, propylene, isobutene.
Monomer II can be used singly or in combination of two or more.
As the mode appropriate of monomer II, monomer shown in following formula (3) can be enumerated.
Formula (3) CH2=CX2(CH2)n2-Q2-R2
In formula, X2For hydrogen atom or methyl.
N2 is 0 or 1.
Q2For oxygen atom ,-C (O) O- or-O (O) C-.
R2For the alkyl of the carbon number 2~20 optionally with branched structure.
From the storage-stable aspect of this composition, the content of the unit based on monomer II is relative to fluoropolymer
Whole units that object is included preferably 0~50 mole of %, more preferable 5~45 moles of %, particularly preferred 15~40 moles of %.
Relative to whole units that fluoropolymer is included, fluoroolefins unit, CHVE unit, the unit based on monomer I,
And the content of the unit based on monomer II distinguishes successively preferably 30~70 moles of %, 10~50 moles of %, 0~20 mole of %, 0
~50 moles of %.
Fluoropolymer-containing Mn preferably 3000~40000.
Fluoropolymer-containing Mw preferably 5000~100000, more preferable 5000~80000.
Fluoropolymer-containing Mw change rate when for heating 2 weeks fluoropolymer at 70 DEG C, before and after heating
((Mw after heating)/(Mw before heating)), from fluoropolymer-containing storage-stable aspect, preferably 1.50 or less,
More preferable 1.40 or less, particularly preferred 1.30 or less.The lower limit of Mw change rate is usually 1.0.
When Mw change rate is 1.50 or less, the viscosity of fluoro-containing copolymer composition and fluorine system coating can be suitably maintained,
Operability when forming film by fluorine system coating is excellent.
This composition contains aforementioned fluoropolymer and solvent.Solvent contained in this composition is except based on area ratio
Solvent other than solvent used in the measurement of the area ratio AR of calculating method (toluene and acetone).It is molten contained in this composition
At least part of agent is preferred to the solvent for being manufactured aforementioned fluoropolymer by monomer mixture and being used.It, can as solvent
Enumerate water outlet, organic solvent.
As described later, in fluoropolymer-containing manufacturing method, for monomer mixture polymerization when used solvent
(hereinafter also referred to as " solvent for polymerization ".), usually using the pure and mild organic solvent in addition to alcohol.Solvent in this composition is excellent
It is elected to be the organic solvent in addition to alcohol used for the solvent for polymerization.In addition, the preferred boiling point ratio of the organic solvent is as polymerization
The high organic solvent of the boiling point of the alcohol used with solvent.
Organic solvent in this composition is preferably comprised selected from molten by aromatic hydrocarbon solvents, ketone solvent, ether-ether solvent, ester
At least one kind of organic solvent in the group of agent and Weak solvent composition.As organic solvent, fluoropolymer can preferably be dissolved
Organic solvent, this composition are preferably the solution containing fluoropolymer and the organic solvent dissolved.
It should be noted that ether-ether is the compound that intramolecular has both ehter bond and ester bond.In addition, Weak solvent refers to
It is classified as the solvent of the third organic solvent in Japan's law of labour safety and health.
The preferred dimethylbenzene of aromatic hydrocarbon solvents, ethylbenzene, aromatic naphthas, tetrahydronaphthalene, Solvesso#100 (Exxon
Chemical company's registered trademark), Solvesso#150 (Exxon chemical company registered trademark) etc., more preferable dimethylbenzene, ethylbenzene.
The preferred acetone of ketone solvent, methyl ethyl ketone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), ethyl isobutylo ketone, diisobutyl
Ketone, cyclohexanone etc..
The preferred 3- ethoxyl ethyl propionate of ether-ether solvent, propylene glycol methyl ether acetate, methoxy butyl acetate etc..
The preferred methyl acetate of ester solvent, ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate etc..
Weak solvent be selected from by gasoline, coal tar naphtha (include solvent naphtha.), petroleum ether, naphtha, purification it is light
Matter industrial naptha (petroleum benzine), turpentine oil, Mineral spirits (comprising mineral thinner (mineral thinner),
Benzin (petroleum spirit), white spirit (white spirit), mineral turpentine.) etc. in the group of compositions
It is at least one kind of, from the aspect that flash-point is room temperature or more, preferably Mineral spirits.
Solvent can be only a kind of solvent, or mixed solvent of more than two kinds.
Gross mass preferably 30~70 mass %s, more preferable 45 of the content of solvent in this composition relative to this composition
~70 mass %.
In addition, in this composition, the system of the residue of the monomer used sometimes with fluoropolymer in order to obtain, monomer
The ingredient of raw material used in making, these ingredients are equivalent to above-mentioned micro constitutent (impurity component) sometimes.
It should be noted that the concrete example of the residue of the monomer used as fluoropolymer in order to obtain, can enumerate
The residue of the residue of cyclohexyl vinyl ether, above-mentioned monomer I (4- hydroxyvinyl ether etc.) out.
In addition, the concrete example as the raw material used to manufacture monomer, can enumerate to manufacture cyclohexyl. vinyl
Base ether and the cyclohexanol used.
In addition, the present invention is to manufacture fluoropolymer-containing 2 kinds of manufacturing methods of excellent storage stability.Manufacture of the invention
The 1st manufacturing method in method is to purify before polymerization to CHVE, manufactures fluoropolymer using purified CHVE
Method.The 2nd manufacturing method in the manufacturing method of the present invention is following method: making monomer polymerization and generates fluoropolymer
Afterwards, commonly required in the removal than alcohol when the alcohol as a part of polymer solvent being distilled removal from reaction mixture
Condition it is more harsh under conditions of carry out distillation removal, to also be removed to impurity component simultaneously, manufacture fluoropolymer.
For the fluoropolymer that method obtains either in manufacturing method through the invention, from the miscellaneous of monomer etc.
The content of matter ingredient is few, therefore the viscosity change in storage-stable height, its solvent solution etc. is also few.In turn, by real simultaneously
2 kinds of manufacturing methods are applied, compared with the case where implementing single manufacturing method, the content of impurity component can be further reduced.
Any one of the manufacturing method of the present invention is the manufacture suitable for aforementioned fluoro-containing copolymer composition of the invention
Method.But the manufacturing method of the present invention is not limited to the manufacture of this composition, what manufacturing method through the invention obtained
Fluoropolymer can be used for the manufacture of fluoropolymer solutions, dispersion liquid in addition to this composition.
Hereinafter, being illustrated by taking the manufacture of this composition as an example to the manufacturing method of the present invention.
1st manufacturing method of the invention is characterized in that, polymerize the monomer mixture comprising fluoroolefins and CHVE to make
Make fluoropolymer, wherein purify to CHVE, the chemical combination of the cyclohexanol low boiling point contained simultaneously in boiling point ratio CHVE is made
Following the area ratios of object are 0.15% CHVE below, which is used for aforementioned polymeric.
The area ratio: in the measurement of the CHVE based on gas-chromatography, being originated from than cyclohexanol in obtained gas-chromatography
Peak area of the summation of the peak area at the peak of ingredient that occurs of the short time side of retention time relative to whole peaks summation
Ratio.
The inventors of the present invention recognize, the ingredient for being fixed at the time side appearance shorter than the retention time of cyclohexanol is surveyed in GC
It is most of for low-boiling compound contained in the CHVE that is used as raw material.Furthermore it is possible to think that the low-boiling compound is
At least part for the impurity component for reducing the storage-stable of fluoropolymer solutions.Therefore, it is dropped by the distillation of CHVE
When the amount of the low-boiling compound contained simultaneously in low CHVE, the fluoropolymer of excellent storage stability can be manufactured.In addition,
It can reduce the area ratio AR in aforementioned fluoro-containing copolymer composition of the invention.It, can be with that is, by the 1st manufacturing method
Manufacture aforementioned fluoro-containing copolymer composition of the invention.
Foregoing area ratio preferably 0.1% or less, more preferable 0.05% or less, particularly preferred 0.01% or less.Lower limit does not have
There is special limitation, is 0%.
Fluoropolymer-containing method is manufactured for making the monomer mixture polymerization comprising fluoroolefins and CHVE, in addition to using
Other than this point of purified CHVE, well known method can be used.As polymerisation medium, solvent, decentralized medium can be used, it is excellent
Choosing uses the fluoropolymer-containing organic solvent that can dissolve generation.In turn, preferably in addition to alcohol vacuum distillation removal condition with
Manufacturing method same as aftermentioned 2nd manufacturing method outside, and then more preferably using including the vacuum distillation removal condition of alcohol
Aftermentioned 2nd manufacturing method.
2nd manufacturing method of the invention is characterized in that, makes the monomer mixture comprising fluoroolefins and CHVE in free radical
Polymerization is in the presence of polymerization initiator, alkali carbonate and polymer solvent to manufacture fluoropolymer, wherein polymer solvent is
20 DEG C higher than the boiling point of the alcohol of the alcohol and boiling point of carbon number 1~6 or more of organic solvent is (hereinafter also referred to as " higher boiling is organic molten
Agent ".) mixed solvent, from vacuum distillation is removed aforementioned alcohol and the aforementioned alkali-metal carbon that is precipitated in reaction mixture after polymerization
Hydrochlorate removal, and temperature and degree of decompression usually used in removal and aforementioned organic solvents are being evaporated under reduced pressure not more than the alcohol
It is depressurized the vacuum distillation removal for carrying out aforementioned alcohol under conditions of distillation removes, obtains being dissolved in the fluorine-containing poly- of aforementioned organic solvents
Close object.
In 2nd manufacturing method, when removing the alcohol of carbon number 1~6, in order to remove aforementioned low-boiling compound simultaneously, set
The removal condition more harsh than common alcohol removal condition.For example, in the vacuum distillation removal of alcohol, under the conditions of at low pressure,
Vacuum distillation removal is carried out under the conditions of at higher temperature, thus removes low-boiling compound simultaneously.On the other hand, in order to when alcohol removes
High boiling organic solvent be unlikely to be removed, it is preferable to use alcohol and high boiling organic solvent boiling-point difference it is larger, higher boiling has
High 30 DEG C of boiling point or more, more preferably high 50 DEG C or more of alcohol of the boiling point of solvent preferably than being applied in combination.
As the alcohol of carbon number 1~6, preferred alcohol, in the case where using ethyl alcohol, more specifically, preferably at 65 DEG C or more
(preferably 85 DEG C of the upper limit of temperature.) under, be decompressed to 45Torr or less (preferably 30Torr or less.The preferred 5Torr of lower limit.), it carries out
Vacuum distillation.
In addition, can reduce the area ratio in aforementioned polymer composition of the invention by the 2nd manufacturing method
AR.That is, aforementioned fluoro-containing copolymer composition of the invention can be manufactured by the 2nd manufacturing method.
From productivity aspect, the 2nd manufacturing method of the invention preferably has 1~process of process 3 below.
Process 1 (polymerization process): radical polymerization initiator, alkali carbonate and carbon number 1~6 alcohol with it is high boiling
In the presence of the polymer solvent of the mixed solvent of point organic solvent, alkali carbonate at least part be dissolved in it is aforementioned poly-
Make the monomer mixture copolymerization comprising fluoroolefins and CHVE, the process for obtaining fluoropolymer-containing solution in the state of bonding solvent.
(process is precipitated) in process 2: removing aforementioned alcohol from fluoropolymer-containing solution, reduces the content of aforementioned alcohol, make
The process that alkali carbonate is precipitated.
Process 3 (removing step): being filtered fluoropolymer-containing solution obtained in foregoing sequence 2, by precipitation
Alkali carbonate removal, obtains the fluoropolymer-containing process for being dissolved in high boiling organic solvent.
In monomer mixture in process 1 other than containing fluoroolefins and CHVE, also it may include except it as needed
Other than monomer (monomer I, monomer II etc.).
As the concrete example of alkali carbonate used in process 1, potassium carbonate can be enumerated.
Quality ratio (the alkali metal carbonic acid of whole monomers in process 1, alkali carbonate and monomer mixture
Whole monomers in salt/monomer mixture) preferably 0.005/1~0.013/1, more preferable 0.008/1~0.012/1.By carbonic acid
When the quality ratio of whole monomers in potassium and monomer mixture is set as 0.005/1 or more, copolyreaction is successfully carried out, by carbon
When the quality ratio of whole monomers in sour potassium and monomer mixture is set as 0.013/1 or less, it can be ensured that polymerization stability, simultaneously
And inhibit the coloring of obtained fluoropolymer solutions.
It should be noted that the polymer solvent in process 1 includes the pure and mild high boiling organic solvent of carbon number 1~6, remove
Other than these solvents, solvent used in known polymerization can be used.
In the case where manufacturing this composition, the special processing such as solvent displacement is not needed, therefore preferably will be in this composition
Contained solvent is set as solvent identical with the high boiling organic solvent in polymer solvent, by fluoropolymer obtained in process 3
Object solution is directly as this composition.
The concrete example of alcohol as carbon number 1~6, can enumerate methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, amylalcohol,
Hexanol, from the deliquescent aspect of potassium carbonate, preferred alcohol.
As the high boiling organic solvent in polymer solvent, can enumerate as aromatic hydrocarbon solvents, except carbon number 1~6
Alcoholic solvent, ketone solvent, ether-ether solvent, ester solvent, Weak solvent other than alcohol etc., boiling point it is higher than the boiling point of the alcohol in polymerisation medium
20 DEG C or more of organic solvent.Aromatic hydrocarbon solvents, ketone solvent, ether-ether solvent, ester solvent and Weak solvent concrete example be this group
Close the organic solvent for meeting high boiling condition in the solvent preferably comprised in object.
As the concrete example of the alcoholic solvent in addition to the alcohol of carbon number 1~6, octanol, dodecanol can be enumerated.
The more preferable aromatic hydrocarbon solvents of high boiling organic solvent, ether-ether solvent or alcohol in addition to the alcohol of carbon number 1~6 are molten
Agent, particularly preferred aromatic hydrocarbon solvents.
In the case that the alcohol of carbon number 1~6 is ethyl alcohol (bp:78 DEG C), as high boiling organic solvent, preferably there are 110 DEG C
The organic solvent of above boiling point, can specifically enumerate toluene (bp:110 DEG C), ethylbenzene (bp:136 DEG C), dimethylbenzene (bp:
138~144 DEG C) etc. aromatic hydrocarbon solvents.
Relative to the gross mass of polymer solvent, the content of the alcohol of carbon number 1~6 preferably 10~95 mass %, more preferable 20~
90 mass %.
It is preferred that in the presence of radical polymerization initiator, alkali carbonate and aforementioned polymeric solvent, potassium carbonate extremely
Aforementioned monomer mixture combined polymerization is made by polymerisation in solution in the state of few a part dissolution.
It should be noted that " state of at least part dissolution of alkali carbonate " refers to alkali metal carbonic acid in solvent
A part of salt dissolves but can also be in the undissolved situation of at least part in the shape of dispersion (comprising swimming or precipitating)
State.
As the concrete example of radical polymerization initiator, can enumerate azo initiators (2,2 '-azobis isobutyronitriles,
2,2 '-azo bis cyclohexane formonitrile HCNs, 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methylbutyronitriles) etc.),
Ketone peroxide (cyclohexanone peroxide etc.), hydrogen peroxide (tert-butyl hydroperoxide etc.), diacyl peroxide (benzoyl peroxide
Formyl etc.), dialkyl peroxide (di-tert-butyl peroxide etc.), ketal peroxide (2,2- bis- (tert-butyl peroxide) fourth
Alkane etc.), alkyl super-acid ester (peroxidating pivalic acid tert-butyl ester (PBPV) etc.), percarbonic acid esters peroxide series initiators (mistake
Aoxidize two diisopropyl carbonates etc.).
In addition, known chain is added as needed and turns in the case where needing to adjust fluoropolymer-containing Mn and Mw
Move agent.
Polymerization reaction preferably under conditions of polymerization temperature is 65 DEG C ± 10 DEG C, polymerization time is 6 hours~36 hours into
Row.Polymerization temperature is suitable for setting according to the temperature of initial decomposition of the initiator used, half-life period.After the cooling period using pair
The polymerization inhibitors such as benzenediol monomethyl ether stop polymerization reaction.
Process 2 is to remove the alcoholic solvent of carbon number 1~6 from fluoropolymer-containing solution obtained in process 1, is preferably dropped
Down to relative to polymer solvent be 0~0.03 mass %, the process that alkali carbonate is precipitated in the solution.
It should be noted that can enumerate and be existed by vacuum distillation apparatus as by the method for the alcohol removal of carbon number 1~6
The method etc. being concentrated under heating under reduced pressure.
It is preferred that carrying out pre-filtering before the alcohol of removal carbon number 1~6.Pre-filtering is for will be in aforementioned fluoropolymer
The purpose that alkali carbonate or its modifier etc. for dispersing (comprising swimming or precipitating) in solution in solid form substantially filter out
And carry out.It should be noted that they are removed in following removing steps without in pre-filtered situation.
Process 3 be to obtained in aforementioned precipitation process, eliminate it is fluoropolymer-containing after the alcoholic solvent of carbon number 1~6
Solution is filtered, and the alkali carbonate of precipitation is removed, the fluoropolymer-containing process for being dissolved in organic solvent is obtained.
As the method for filtering, the filtering for having used diatomite can be enumerated.As diatomite, median particle size can be enumerated
25~40 μm of diatomite, dosage are 0.05~0.10g/cm preferably with respect to filter area2。
Filtering is specifically preferably as follows: aforementioned diatomite is used, to the pressurization for being equipped with viscous fluid filter paper No.63
Filter carries out liquid relief, is filtered under the pressurized conditions of 0.01~0.5MPa of pressure, carries out circulating filtration until visually lower filter
Until the appearance of liquid becomes without muddiness.
This composition can be suitable for fluorine resin coating (clear dope etc.).
For fluorine resin coating of the invention, can in the present compositions so that be added curing agent, except fluoropolymer with
It is prepared by the coating such as outer resin compounding ingredients.
Fluorine resin coating can be the coating of one-pack type, or the coating of two-component-type.The case where two-component-type
Under, curing agent preferably mixes immediately before use.
Can preferably have with monomer I for curing agent in the case where fluoropolymer includes the unit based on monomer I
Crosslinkable groups crosslinking curing agent.
In the case that the crosslinkable groups that monomer I has are hydroxyl, as curing agent, preferably normal temperature cured type isocyanates
Curing agent, thermohardening type blocked isocyanate curing agent, the coating curing agent such as melamine cured dose.
The content of curing agent in fluorine resin coating relative to 100 mass parts of fluoropolymer preferably 1~100 mass parts,
More preferable 1~50 mass parts.
Resin in addition to fluoropolymer can be suitable for using the well known resin being compounded in fluorine resin coating.
In order to improve the drying property of film, CAB (cellulose acetate-butyrate), NC (NC Nitroncellulose) etc. can be compounded.Separately
Outside, in order to improve this film gloss, hardness, coating application, can be compounded the polymer formed by acrylic acid or its ester,
The coating resins such as polyester.
In addition it is also possible to as needed be compounded silane coupling agent, ultraviolet absorbing agent, curing accelerator, light stabilizer,
The well known ingredient that toner, delustering agent etc. are compounded in coating is as additive.
Coated article of the invention is made of forming film on the surface of article as fluorine resin coating of the invention.
The concrete example of article as coating can enumerate transport equipment (automobile, electric car, aircraft etc.), building structure
Part (bridge member, steel tower etc.), industrial equipment (waterproof material piece, slot (tank), pipeline etc.), building element (building exterior,
Door, window component, memorial building object, bar etc.), road component (center isolation with, the guardrail, sound-proof wall etc. of road), communicator
Material, electrical and electronic component, the surface patch of solar cell module, backboard.
It is preferably 10~200 μm of the film thickness of film, 10~100 μm more preferable.
Fluorine resin coating can be directly coated at the surface of article, can also implement well known table on the surface to article
It is coated after surface treatment (base treatment etc.).
The concrete example of coating method as fluorine resin coating, can enumerate atomized spray painting, air-atomizing coating, brushing,
Infusion process, the method for having used roll coater, flow coater.
Preferably 15 DEG C~300 DEG C or so of drying temperature after coating.
Embodiment
Hereinafter, enumerating embodiment, the present invention will be described in detail.But the present invention is not limited to these embodiments.
Evaluation method and material used in each example described below.
<calculating of area ratio AR>
Method is calculated according to above-mentioned area ratio to calculate.
Prepare the fluoro-containing copolymer composition manufactured in aftermentioned Examples and Comparative Examples, relative to fluoropolymer group
It closes 100 mass parts of object and acetone (Wako Pure Chemical Industries, Ltd.'s system, special grade chemical) 200 mass parts is added, preparation will be fluorine-containing poly-
Dilute solution made of polymer composition dilution.
Then, toluene (the He Guangchun medicine work for being 1 mass % relative to the dilute solution gross mass is added in dilute solution
Industry Co. Ltd. system, special grade chemical), prepare sample solution.Using obtained sample solution, Agilent is utilized
Technologies corporation 6850SeriesII (detector: FID) carries out GC measurement under the conditions described above.According to obtaining
Chromatogram, area ratio AR is found out by above-mentioned method.It should be noted that the retention time of cyclohexanol is measurement hexamethylene
Alcohol (Wako Pure Chemical Industries, Ltd.'s system, special grade chemical) and confirm.
<storage-stable evaluation>
The fluoro-containing copolymer composition manufactured in the Examples and Comparative Examples that will be described below is put into sealing container, is being set
To be heated 2 weeks in 70 DEG C of baking ovens.The change rate of the fluoropolymer-containing Mw of heating front and back is evaluated.
Mw change rate=(Mw after heating)/(Mw before heating)
It should be noted that the measurement for Mw, use device: TOSOH Co., Ltd EcoSEC HLC-8320GPC,
As the sample solution for evaluating Mw, fluoro-containing copolymer composition is diluted with tetrahydrofuran and will be fluoropolymer-containing by use
Concentration is adjusted to sample solution made of 1 mass %.
<CHVE>
In following Examples and Comparative Examples, CHVE1~3 of table 1 below record are used.It should be noted that in table 1
The column of " boiling point is than the area ratio (%) of the compound of cyclohexanol low boiling point " indicate: carry out above-mentioned GC using each CHVE and measure
To, the peak area at the peak for being originated from the ingredient occurred in the short time side of the retention time than cyclohexanol in gas-chromatography it is total
With the ratio (the area ratio) of the summation of the peak area relative to whole peaks.The area ratio is lower, it is meant that boiling point is boiled than cyclohexanol
The ratio of the low ingredient of point is fewer.
It should be noted that CHVE3 is market circulation product, CHVE1 is to carry out CHVE obtained from distillation processing to CHVE3
(distillation yield 70%), CHVE2 are to carry out CHVE obtained from distillation processing (distillation yield 90%) to CHVE3.
[table 1]
Table 1
(embodiment 1)
In the stainless steel pressure reactor (internal volume 2500mL) with blender, dimethylbenzene (587g), second are put into
Alcohol (168g), ethyl vinyl ether (EVE) (206g), 4- hydroxyvinyl ether (HBVE) (129g), cyclohexyl vinyl ether 1
(CHVE1) (208g), potassium carbonate (11g) and the peroxidating pivalic acid tert-butyl ester (PBPV) (3.5g) pass through adding based on nitrogen
Dissolved oxygen in pressure purging and degassing removal liquid.
Then, it imports chlorotrifluoroethylene (CTFE) (660g) slowly to heat up, continue when maintaining temperature to be 65 DEG C anti-
It answers.Carrying out water cooling to reactor after 12 hours stops reaction.After the reaction solution is cooled to room temperature, unreacted monomer is removed,
Open reactor.
By obtained reaction solution liquid relief to the pressure filter for being equipped with viscous fluid filter paper No.63, in pressure 0.05MPa
Under filter out potassium carbonate after, add hydroquinone monomethyl ether (HQMME) 0.1g.Then, by vacuum distillation apparatus, 65 DEG C,
It is removed under the heating under reduced pressure of 45Torr, by the ethanol distillation in reaction solution.Then, it adds in reaction solution relative to filter area
For 0.06g/cm2Diatomite (30.1 μm of median particle size), after mixing, liquid relief is to being equipped with viscous fluid filter paper No.63
Pressure filter, carried out at pressure 0.02MPa 2 times filtering, by filtered off through Celite, obtain fluoro-containing copolymer composition P1.
Thereafter, by the fluoropolymer-containing mass concentration in fluoro-containing copolymer composition P1 become 60 mass % in a manner of into
The adjustment of row concentration, obtains fluoro-containing copolymer composition 1.
Then, fluoro-containing copolymer composition 1 is analyzed by above-mentioned GC measurement, as a result confirms that area ratio AR is
0.8%.
(embodiment 2)
Using CHVE2 replace CHVE1, in addition to this, according to similarly to Example 1 the step of, obtain fluoropolymer group
Close object 2.
Then, fluoro-containing copolymer composition 2 is analyzed by above-mentioned GC measurement, as a result confirms that area ratio AR is
3.0%.
(embodiment 3)
In the stainless steel pressure reactor (internal volume 2500mL) with blender, dimethylbenzene (587g), second are put into
Alcohol (168g), EVE (206g), HBVE (129g), CHVE2 (208g), potassium carbonate (11g) and PBPV (3.5g), by being based on nitrogen
The pressure purge and degassing of gas remove the dissolved oxygen in liquid.
Then, it imports CTFE (660g) slowly to heat up, continues to react when maintaining temperature to be 65 DEG C.12 hours
Carrying out water cooling to reactor afterwards stops reaction.After the reaction solution is cooled to room temperature, unreacted monomer is removed, opens reaction
Device.
By obtained reaction solution liquid relief to the pressure filter for being equipped with viscous fluid filter paper No.63, in pressure 0.05MPa
Under filter out potassium carbonate after, add HQMME 0.1g.Then, by vacuum distillation apparatus, in 65 DEG C, the heating under reduced pressure of 15Torr
Under, by reaction solution ethanol distillation remove.Then, adding in reaction solution relative to filter area is 0.06g/cm2Silicon
Diatomaceous earth (30.1 μm of median particle size), after mixing, liquid relief to the pressure filter for being equipped with viscous fluid filter paper No.63,
2 filterings are carried out under pressure 0.02MPa, by filtered off through Celite, obtain fluoro-containing copolymer composition P3.
Thereafter, by the fluoropolymer-containing mass concentration in fluoro-containing copolymer composition P3 become 60 mass % in a manner of into
The adjustment of row concentration, obtains fluoro-containing copolymer composition 3.
Then, fluoro-containing copolymer composition 3 is analyzed by above-mentioned GC measurement, as a result confirms that area ratio AR is
1.3%.
(comparative example 1)
Using CHVE3 replace CHVE1, in addition to this, according to similarly to Example 1 the step of, obtain fluoropolymer group
Close object 4.
Then, fluoro-containing copolymer composition 4 is analyzed by above-mentioned gas Chromatographic Determination, as a result confirms area ratio
AR is 5.0%.
Using fluoro-containing copolymer composition obtained in foregoing embodiments and comparative example, implement above-mentioned storage-stable
Evaluation.Result is shown in table 2 below together.
[table 2]
Table 2
As shown in table 2, confirmation shows the excellent storage stability of this composition of defined area ratio AR.
It should be noted that by the specification of 07 month Japanese patent application filed in 14 days 2016-139553 in 2016,
The full content of claims and abstract be referenced to herein, as specification of the invention disclosure and be incorporated to.
Claims (15)
1. a kind of fluoro-containing copolymer composition, which is characterized in that contain fluoropolymer and solvent, wherein the solvent does not wrap
Toluene and acetone are included, the fluoropolymer includes fluoroolefins unit and cyclohexyl vinyl ether unit,
Calculating the area ratio AR that method is found out by area ratio below is 0.1~3%,
Area ratio calculates method: 200 mass parts of acetone, preparation is added relative to 100 mass parts of fluoro-containing copolymer composition
By dilute solution made of fluoro-containing copolymer composition dilution, in turn, it is added in the dilute solution relative to described
Dilute solution gross mass is the toluene of 1 mass %, prepares sample solution, using the obtained sample solution, implements gas phase color
Spectrum measurement, it is 0.5 times of peak below of the peak area at the peak from toluene that extracting, which has peak area, by the peak at the peak of extraction
The summation of area is set as area A, will be originated from the peak of extraction in the short time side appearance of the retention time than cyclohexanol
The summation of the peak area at the peak of ingredient is set as area B, will by value that formula below (1) is found out as area ratio AR,
Formula (1): area ratio AR (%)=(area B/area A) × 100.
2. fluoro-containing copolymer composition according to claim 1, wherein the content of the fluoroolefins unit is relative to described
Whole units that fluoropolymer is included are 30~70 moles of %,
The content of the cyclohexyl vinyl ether unit is 10~50 relative to whole units that the fluoropolymer is included
Mole %.
3. fluoro-containing copolymer composition according to claim 1 or 2, wherein the area ratio AR is 0.1~1.5%.
4. fluoro-containing copolymer composition described in any one of claim 1 to 3, wherein the fluoroolefins unit is four
Vinyl fluoride unit or chlorotrifluoroethylene unit.
5. fluoro-containing copolymer composition according to any one of claims 1 to 4, wherein fluoropolymer also includes tool
The unit of crosslinking property group.
6. fluoro-containing copolymer composition according to claim 5, wherein the unit with crosslinkable groups be with
The unit of hydroxyl.
7. fluoro-containing copolymer composition described according to claim 1~any one of 6, wherein fluoropolymer also includes base
In except fluoroolefins, cyclohexyl vinyl ether and with the monomer of crosslinkable groups in addition to the 4th monomer unit.
8. fluoro-containing copolymer composition according to claim 7, wherein the unit based on the 4th monomer is based on not
The unit of monomer with fluorine atom.
9. a kind of fluoropolymer-containing manufacturing method, which is characterized in that it makes the list comprising fluoroolefins and cyclohexyl vinyl ether
Body mixture polymerize to manufacture fluoropolymer, wherein purifies to cyclohexyl vinyl ether, cyclohexyl vinyl ether is made
In contain, boiling point than the compound of cyclohexanol low boiling point following the area ratios be 0.15% cyclohexyl vinyl ether below,
The cyclohexyl vinyl ether after purification is used for the polymerization,
The area ratio: in the measurement of the cyclohexyl vinyl ether based on gas-chromatography, in obtained gas-chromatography be originated from than
The peak area of the summation of the peak area at the peak for the ingredient that the short time side of the retention time of cyclohexanol occurs relative to whole peaks
The ratio of summation.
10. fluoropolymer-containing manufacturing method according to claim 9, wherein in the presence of solvent or decentralized medium
It polymerize the monomer mixture.
11. a kind of fluoropolymer-containing manufacturing method, which is characterized in that it makes the list comprising fluoroolefins and cyclohexyl vinyl ether
Body mixture polymerize in the presence of radical polymerization initiator, alkali carbonate and polymer solvent to manufacture fluoropolymer
Object, wherein polymer solvent is molten for the mixing of the organic solvent of the alcohol of carbon number 1~6 and 20 DEG C higher than the boiling point of the alcohol of boiling point or more
Agent is removed from the alkali carbonate that vacuum distillation is removed the alcohol in reaction mixture after polymerization and is precipitated, and
Be more than the alcohol vacuum distillation remove in usually used temperature and degree of decompression and the organic solvent be not depressurized distillation and go
The vacuum distillation removal that the alcohol is carried out under conditions of removing, obtains the fluoropolymer for being dissolved in the organic solvent.
12. fluoropolymer-containing manufacturing method according to claim 11, wherein the organic solvent is with 110 DEG C
The organic solvent of above boiling point, the alcohol are ethyl alcohol, carry out second under 65 DEG C or more of temperature, 45Torr degree of decompression below
The vacuum distillation of alcohol removes.
13. fluoropolymer-containing manufacturing method according to claim 11 or 12, wherein the cyclohexyl vinyl ether contains
Have compound of the boiling point than cyclohexanol low boiling point, and following the area ratios of the compound be 0.15% hereinafter,
The area ratio: in the measurement of the cyclohexyl vinyl ether based on gas-chromatography, in obtained gas-chromatography be originated from than
The peak area of the summation of the peak area at the peak for the ingredient that the short time side of the retention time of cyclohexanol occurs relative to whole peaks
The ratio of summation.
14. a kind of fluorine resin coating, it includes fluoro-containing copolymer compositions according to any one of claims 1 to 8.
15. a kind of coated article is formed on the article with article and the fluorine resin coating as described in claim 14
Film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016139553 | 2016-07-14 | ||
| JP2016-139553 | 2016-07-14 | ||
| PCT/JP2017/025504 WO2018012577A1 (en) | 2016-07-14 | 2017-07-13 | Fluorine-containing polymer composition, fluorine resin coating, coated article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109476785A true CN109476785A (en) | 2019-03-15 |
| CN109476785B CN109476785B (en) | 2021-08-20 |
Family
ID=60952125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780043675.6A Active CN109476785B (en) | 2016-07-14 | 2017-07-13 | Fluorine-containing polymer composition, fluorine resin coating material, and coated article |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6927216B2 (en) |
| CN (1) | CN109476785B (en) |
| WO (1) | WO2018012577A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115702225A (en) * | 2020-06-25 | 2023-02-14 | Ａｇｃ株式会社 | Paint and method for producing paint, and coated article and method for producing coated article |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345057A (en) * | 1980-08-08 | 1982-08-17 | Asahi Glass Company, Ltd. | Curable fluorocopolymer |
| JPS61174210A (en) * | 1985-01-29 | 1986-08-05 | Asahi Glass Co Ltd | Production of fluorine-containing copolymer |
| JPH10109952A (en) * | 1996-10-02 | 1998-04-28 | Maruzen Petrochem Co Ltd | Separation of cyclohexyl vinyl ether |
| JPH10158208A (en) * | 1996-11-25 | 1998-06-16 | Maruzen Petrochem Co Ltd | Separation and recovery of cyclohexyl vinyl ether |
| CN1553943A (en) * | 2001-09-27 | 2004-12-08 | ������������ʽ���� | Composition for fluororesin powder coating material |
| CN1629230A (en) * | 2003-12-15 | 2005-06-22 | 上海三爱富新材料股份有限公司 | Soluble fluorine-containing paint resin and method for preparing same |
| US20100249465A1 (en) * | 2009-03-26 | 2010-09-30 | Maruzen Petrochemical Co., Ltd. | Process for production of high-purity vinyl ether |
| CN102325802A (en) * | 2009-02-23 | 2012-01-18 | 旭硝子株式会社 | Method for producing fluoroolefin copolymer solution and method for producing paint composition |
| CN103582670A (en) * | 2011-05-30 | 2014-02-12 | 旭硝子株式会社 | Fluorine-containing copolymer composition and method for producing same |
| CN104704013A (en) * | 2012-10-03 | 2015-06-10 | 旭硝子株式会社 | Method for producing fluorine-containing copolymer solution, and coating composition |
| TW201527386A (en) * | 2013-11-13 | 2015-07-16 | Asahi Glass Co Ltd | Fluoroolefin-copolymer-containing solution composition, method for producing same, and coating material composition |
| CN105637030A (en) * | 2013-10-17 | 2016-06-01 | 旭硝子株式会社 | Fluoroolefin-copolymer-containing solution composition, method for producing same, and coating material composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6753418B2 (en) * | 2016-01-14 | 2020-09-09 | Ａｇｃ株式会社 | Fluororesin-containing solution, method for producing fluororesin-containing solution, paint composition and painted article |
-
2017
- 2017-07-13 CN CN201780043675.6A patent/CN109476785B/en active Active
- 2017-07-13 JP JP2018527656A patent/JP6927216B2/en active Active
- 2017-07-13 WO PCT/JP2017/025504 patent/WO2018012577A1/en active Application Filing
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345057A (en) * | 1980-08-08 | 1982-08-17 | Asahi Glass Company, Ltd. | Curable fluorocopolymer |
| JPS61174210A (en) * | 1985-01-29 | 1986-08-05 | Asahi Glass Co Ltd | Production of fluorine-containing copolymer |
| JPH10109952A (en) * | 1996-10-02 | 1998-04-28 | Maruzen Petrochem Co Ltd | Separation of cyclohexyl vinyl ether |
| JPH10158208A (en) * | 1996-11-25 | 1998-06-16 | Maruzen Petrochem Co Ltd | Separation and recovery of cyclohexyl vinyl ether |
| CN1553943A (en) * | 2001-09-27 | 2004-12-08 | ������������ʽ���� | Composition for fluororesin powder coating material |
| CN1629230A (en) * | 2003-12-15 | 2005-06-22 | 上海三爱富新材料股份有限公司 | Soluble fluorine-containing paint resin and method for preparing same |
| CN102325802A (en) * | 2009-02-23 | 2012-01-18 | 旭硝子株式会社 | Method for producing fluoroolefin copolymer solution and method for producing paint composition |
| US20100249465A1 (en) * | 2009-03-26 | 2010-09-30 | Maruzen Petrochemical Co., Ltd. | Process for production of high-purity vinyl ether |
| CN103582670A (en) * | 2011-05-30 | 2014-02-12 | 旭硝子株式会社 | Fluorine-containing copolymer composition and method for producing same |
| CN104704013A (en) * | 2012-10-03 | 2015-06-10 | 旭硝子株式会社 | Method for producing fluorine-containing copolymer solution, and coating composition |
| CN105637030A (en) * | 2013-10-17 | 2016-06-01 | 旭硝子株式会社 | Fluoroolefin-copolymer-containing solution composition, method for producing same, and coating material composition |
| TW201527386A (en) * | 2013-11-13 | 2015-07-16 | Asahi Glass Co Ltd | Fluoroolefin-copolymer-containing solution composition, method for producing same, and coating material composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115702225A (en) * | 2020-06-25 | 2023-02-14 | Ａｇｃ株式会社 | Paint and method for producing paint, and coated article and method for producing coated article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6927216B2 (en) | 2021-08-25 |
| CN109476785B (en) | 2021-08-20 |
| JPWO2018012577A1 (en) | 2019-06-13 |
| WO2018012577A1 (en) | 2018-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2716704B1 (en) | Fluorine-containing copolymer composition and method for producing same | |
| EP3233940B1 (en) | Photocrosslinkable block copolymers for hot-melt adhesives | |
| JP6753418B2 (en) | Fluororesin-containing solution, method for producing fluororesin-containing solution, paint composition and painted article | |
| KR102023226B1 (en) | Method for the preparation of styrenic fluoropolymers | |
| US20020197407A1 (en) | Reactive coalescents | |
| US8461251B2 (en) | Method for producing fluoroolefin copolymer solution and method for producing coating composition | |
| CN109476785A (en) | Fluoro-containing copolymer composition, fluorine resin coating, coated article | |
| WO2010112290A1 (en) | Polyfunctional (meth)acrylic polymer, coating composition, process for producing a coating and coated article | |
| DE69122953T2 (en) | INNOVATIVE FLUORINE AND THEREFORE COATING PRODUCT | |
| CN100366648C (en) | Tert fluoro water dispension resin containing phosphate and its preparing method | |
| CN104448098A (en) | Fluorine-containing copolymer composition and manufacturing method thereof | |
| EP1992647A1 (en) | Silane laquers based on aminosilanes and epoxyfunctional polyacrylates | |
| WO2010112288A1 (en) | Coating agent, method for producing a coating and coated object | |
| JPH11310672A (en) | Fluorine-containing copolymer solution having excellent storage stability | |
| CN116194539A (en) | Stain resistant latex resin | |
| JP2015067826A (en) | Method for producing fluorine-containing copolymer solution, method for producing coating material composition and fluorine-containing copolymer solution | |
| CN107236077A (en) | The preparation method of the high rigidity acrylic resin of resistance to gasoline | |
| WO2010127910A1 (en) | Coating agent, method for producing a coating agent and coated object | |
| MXPA98002588A (en) | Coalescentes reacti | |
| DE102009001217A1 (en) | Monomer mixture, useful for preparing a polymer, which is useful to prepare a coating composition, preferably lacquers and aqueous dispersion, comprises a carbonyl group containing monomer and another carbonyl group containing monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |