JP3365846B2 - Method for producing fluoropolymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fluoropolymer composition containing a dye and a method for producing the same.

[0002]

Conventionally, Te tetrafluoroethylene resin, a perfluoro (ethylene-propylene) resin, perfluoroalkoxy resin, bi two isopropylidene fluoride resin, an ethylene - tetrafluoroethylene resin, fluoride such as click Rollo trifluoroethylene resin Resins have excellent chemical resistance, low dielectric properties, low surface energy, non-adhesiveness, weather resistance and the like, and are therefore used in various applications where general-purpose plastics cannot be used. Various cases dispersing the dye in a resin to impart optical functionality, such as UV-absorbing these fluororesin, is usually how kneading the dye in the molten state of the resin at high temperature is performed However, it is difficult to uniformly disperse the dye. Further, since many fluororesins have crystallinity, they scatter light and have low transparency, and there is a drawback that the light absorption performance of the dye cannot be sufficiently exhibited.

A polymer having a fluorinated alicyclic structure is
It has excellent transparency and is soluble in solvents (Japanese Patent Laid-Open No. 63-
238111, JP-A-63-238115). However, since the solvents described in these inventions do not dissolve the dye, they cannot be uniformly dispersed even in a solution state.

[0004]

DISCLOSURE OF THE INVENTION According to the present invention, the dye is uniformly dispersed in a solution state, and after removing the solvent, the dye is evenly dispersed in the fluoropolymer, which is excellent in light absorption. It is intended to provide a fluororesin composition.

[0005]

Means for Solving the Problems Based on the recognition of the above-mentioned problems, the present inventor has conducted extensive studies and found that a polymer having a fluorine-containing alicyclic structure is represented by the general formula Rf-Rh (where Rf is the number of carbon atoms). 6 to 12 perfluoroalkyl group, Rh is a block compound represented by C1 to C4 alkyl or alkenyl group), and the dye is dissolved and dispersed in the solvent, or the dispersibility is further improved. dye by after dissolving the dye in a hydrocarbon solvent mixable with these solvents, and, prepare dye-containing fluorine resin solution by Rukoto be mixed together and the solvent is removed by an appropriate processing method to It was found that a fluorine-containing polymer composition containing uniformly was obtained.

Further, by selecting a dye having a functional group reactive with the functional group present in the polymer having a fluorinated alicyclic structure, the dispersion of the dye in the polymer is enhanced, and the functional group It was found that more dye than the chemical equivalent was dispersed.

Furthermore, the present inventors have protic fluorinated solvent such as fluorinated alcohol, by dissolving various dyes and found that dissolve in the aprotic fluorine-containing solvent, a fluorine-containing dye is uniformly dispersed It was found to give a polymer solution.

Thus, the present invention has been completed based on the above findings, and a polymer having a fluorine- containing alicyclic structure is represented by the general formula Rf-Rh (where Rf is a carbon number of 6 to 1).
2 perfluoroalkyl group, Rh is an alkyl group having 1 to 4 carbon atoms.
In a polymer having a fluorine-containing alicyclic structure, which comprises dispersing the dye in a solution prepared by dissolving the block compound represented by a block compound represented by an alkyl group or an alkenyl group) and then removing the solvent. A method for producing a fluorine-containing polymer composition in which a dye is dispersed, and a solution obtained by dissolving a polymer having a fluorine-containing alicyclic structure in an aprotic fluorine-containing solvent, in a protic fluorine-containing solvent. A method for producing a fluoropolymer composition in which a dye is dispersed in a polymer having a fluorine-containing alicyclic structure, which comprises removing a solvent after mixing a solution in which the dye is dispersed in Newly provided.

[0009] As the polymer having a fluorinated aliphatic ring structure, those obtainable by polymerization of a monomer having a fluorinated cyclic structures or a fluorine-containing monomer having at least two polymerizable double bonds by cyclic polymerization A polymer having a ring structure in the obtained main chain is suitable.

Polymers having a ring structure in the main chain obtained by polymerizing a monomer having a fluorine-containing ring structure are, for example, perfluoro (2,2-dimethyl-1,3-dioxole) [hereinafter, PDD] and the like. mono with a fluorine-containing ring structure
Mer was homopolymerized or obtained by copolymerizing a radical polymerizable monomer, such as those monomers and tetrafluoroethylene (JP-B 63-18964 Patent Publication).

Further, a polymer having a ring structure in its main chain obtained by cyclopolymerization of a fluorine-containing monomer having at least two polymerizable double bonds is, for example, perfluoro (allyl vinyl ether) or perfluoro (butene). butenyl vinyl ether) monomers, such as by polymerizing cyclization, or their mode
Copolymerizing a radical polymerizable monomer such as Nomar tetrafluoroethylene obtained (JP 63-238
111, JP-A-63-238115).

Further, by copolymerizing a monomer and perfluoro (allyl vinyl ether) or perfluoro (butenyl vinyl ether) fluoromonomer having at least two polymerizable double bonds, such as having a fluorinated cyclic structure of the PDD such It may be a polymer obtained by

The polymer having a fluorinated alicyclic structure is
A polymer having a ring structure in the main chain is suitable. Ring structure 2
Those containing 0% by weight or more are particularly preferable in terms of transparency, mechanical properties and the like.

[0014]

Usually, a polymer having a fluorinated alicyclic structure has a functional group such as a carboxylic acid group derived from an initiator, a chain transfer agent or the like at its terminal. Various functional groups can be introduced into the polymer by converting the carboxylic acid group into an ester or further into an amino group. Further, in order to increase the introduced amount of these functional groups to enhance the effect of the present invention, a small amount of CF ₂ ═CFO (CF ₂ ) ₃ COOCH ₃ ,
_{CF 2 = CFOCF 2 CF (CF} 3) O (CF 2) 3 C
OOCH ₃ , CF ₂ = CFO (CF ₂ ) ₃ CH ₂ NH
₂ , CF ₂ ═CFOCF ₂ CF (CF ₃ ) SO ₂ F, etc. may be copolymerized.

As the functional group in the polymer, --COX (X
Is OH or OR. R is an alkyl group having 1 to 3 carbon atoms. ), —SO ₂ Y (Y is F, Cl, OH or OR.
R is an alkyl group having 1 to 3 carbon atoms. ), -NH ₂ or-
OH and the like. These of -COX or -SO ₂ Y is reacted with amino groups in the dye, -NH ₂ in the polymer are reacted sulfonic acid groups in the dye, a carboxylic acid group, a phosphoric acid group. In the present invention, as a solvent comprising a specific block compounds, one general formula Rf-Rh (although, Rf is a carbon number 6-1
2 perfluoroalkyl group, Rh is Ru is adopted blocked compound represented by the alkyl or alkenyl group) having 1 to 4 carbon atoms.

[0017] is insufficient solubility of carbon number less than 6 and the polymer of Rf, the number of carbon atoms in R f is Ru unsuitable Dare as solid at the solvent at 12 larger than normal temperature.

[0018] Solubility of the carbon atoms of R h is greater than 4 and polymer you decrease. By appropriately selecting the Rf group and the Rh group in the above range, the boiling point and the viscosity can be selected in a wide range, a composition can be prepared according to the coating conditions and the drying conditions, and a uniform transparent coating film having an arbitrary film thickness can be prepared. Is obtained.

In the present invention, Rf-Rh (provided that Rf
Is a perfluoroalkyl group having 6 to 12 carbon atoms, Rh is an alkyl or alkenyl group having 1 to 4 carbon atoms, and Rh is not particularly limited as long as it has 1 to 4 carbon atoms.
_{CH 3, -CH 2 CH 3,} -CH = CH 2, -CH 2 C
_{H = CH 2, -CH = CHCH} 3, -C (CH 3) = C
_{H 2, -CH 2 CH 2 CH} 3, -CH 2 CH 2 CH = C
_{H 2, -CH 2 CH = CHCH} 3, -CH = CHCH 2
CH _3, or the like -CH ₂ CH ₂ CH ₂ CH ₃ is Ru is illustrated.
Rf-Rh can be synthesized , for example, as shown in Chemical formula 1 and Chemical formula 2.

[0020]

[Chemical 1]

[0021]

[Chemical 2]

[0022] That is, (2) is obtained by reacting in the presence of a radical initiator (1) and ethylene. This and
Selectively ethylene when comes pressure is 3~8kg / cm ² G
Giving 1 mole adduct, pressure is 20~25kg / cm ²
When G, a 2-mol addition product of ethylene is given as a main product. (3) is obtained quantitatively by heating under stirring in the presence phase transfer catalyst and (2) with a basic aqueous solution.
(4) is obtained by hydrogenation, for example in the hydrogenation reaction in the presence of a catalyst such as Raney nickel (3).

[0023] (5), in the presence of a radical initiator (1)
It is obtained by reacting propylene with propylene. (6) is obtained quantitatively by heating under stirring in the presence a phase transfer catalyst (5) and a basic aqueous solution. (7) is obtained by hydrogenation, for example in the hydrogenation reaction in the presence of a catalyst such as Raney nickel (6).

The Rf group is a linear or branched perfluoroalkyl group having 6 to 12 carbon atoms, and examples thereof include the following. _{CF 3 (CF 2) n -} (n = 5~11), (CF 3) 2
CF (CF ₂ ) _m − (m = 3 to 9), CF ₃ CF ₂ CF
_{(CF 3) (CF 2)} j - (j = 2~8), (CF 3 C
_{F 2) 2 CF (CF 2} ) k - (k = 1~7).

As the protic fluorine-containing solvent in the present invention , trifluoroethanol, 2,2,3,3,3-
Pentafluoro-1-propanol, 2- (perfluorobutyl) ethanol, 2- (perfluorohexyl)
Ethanol, 2- (perfluorooctyl) ethanol, 2- (perfluorodecyl) ethanol, 2- (perfluoro-3-methylbutyl) ethanol, 1H, 1
H, 3H-tetrafluoro-1-propanol, 1H,
1H, 5H-octafluoro-1-pentanol, 1
H, 1H, 7H-dodecafluoro-1-heptanol,
1H, 1H, 9H-hexadecafluoro-1-nonanol, 2H-hexafluoro-2-propanol, 1H,
Fluorine-containing alcohols such as 1H, 3H-hexafluoro-2-butanol can be exemplified.

Further, trifluoroacetic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid,
Fluorine-containing carboxylic acids such as perfluorodecanoic acid, 3H-tetrafluoropropanoic acid, 5H-octafluoropentanoic acid, 7H-dodecafluoroheptanoic acid, 9H-hexadecafluorononanoic acid, amides of these fluorine-containing carboxylic acids, and trifluoromethane. Examples thereof include fluorinated sulfonic acids such as sulfonic acid and heptadecafluorooctane sulfonic acid.

[0027] These protic fluorine-containing solvent may be used alone <br/> or in combination, can be used a wide range of compounds in addition to these.

Examples of the aprotic solvent for dissolving the polymer having a fluorinated aliphatic ring structure, can be exemplified fluorine-containing compounds other than block the aforementioned compound below together with examples of the block compound.

For example, perfluorobenzene, pentafluorobenzene, 1,3-bis (trifluoromethyl)
Benzene, polyfluoroaromatic compounds such as 1,4-bis (trifluoromethyl) benzene, perfluorotributylamine, polyfluorotrialkylamine compounds such as perfluorotripropylamine, perfluorodecalin, perfluorocyclohexane, perfluoro −
Examples include polyfluorocycloalkane compounds such as 1,3,5-trimethylcyclohexane, polyfluoro cyclic ether compounds such as perfluoro-2-butyltetrahydrofuran, and fluorine-containing low molecular weight polyethers.

Further, perfluorohexane, perfluorooctane, perfluorodecane, perfluorododecane, perfluoro-2,7-dimethyloctane, 1,
1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloro-2,2,2-trifluoroethane, 1,3-dichloro-1,1,2,2,3- Pentafluoropropane, 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane, 1,1,
3,4-tetrachloro-1,2,2,3,4,4-hexafluorobutane, perfluoro-1,2-dimethylhexane, perfluoro-1,3-dimethylhexane, 2
H, 3H-perfluoropentane, 1H-perfluorohexane, 1H-perfluorooctane, 1H-perfluorodecane, 1H, 1H, 1H, 2H, 2H-perfluorohexane, 1H, 1H, 1H, 2H, 2H- Perfluorooctane, 1H, 1H, 1H, 2H, 2H-perfluorodecane, 3H, 4H-perfluoro-2-methylpentane, 2H, 3H-perfluoro-2-methylpentane, 1H-1,1-dichloroper Examples include polyfluoroalkane compounds such as fluoropropane and 1H-1,3-dichloroperfluoropropane.

[0031] These aprotic solvents can be used alone or in combination, a wide range of compounds can be used <br/> In addition to these.

The dye used in the present invention is not particularly limited. Those containing an amino group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group in the molecule are preferable for increasing the content of the dye in the polymer. Generally, a benzophenone derivative, an acridine derivative, a quinoline derivative, an isoquinoline derivative, and a benzothiazole derivative used as a UV absorber are exemplified. Moreover, the spiropyran derivative used as a photochromic material is also illustrated. Furthermore, porphyrin derivatives and quinizarin derivatives used as photochemical hole burning (PHB) are also exemplified. In order to further increase the content, a perfluoroalkyl group (straight chain or branched chain having 6 to 12 carbon atoms) may be introduced into these dye molecules.

The content of the dye in the polymer is 0.01 to 20% by weight. When it is less than this range, the light absorption performance of the dye is not sufficiently exhibited. Further, when the amount is large, it is extremely difficult to uniformly disperse the dye, and various properties of the polymer having a fluorinated alicyclic structure are impaired, which is not preferable.

In the present invention, the auxiliary solvent used for enhancing the solubility of the organic dye is one which dissolves the organic dye and mixes with the block compound represented by the above general formula Rf-Rh. There is no particular limitation. Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate,
Examples thereof include ethers such as tetrahydrofuran and diethyl ether, and chlorinated hydrocarbons such as chloroform and methylene chloride. These hydrocarbon-based cosolvents are 0 to the block compound represented by Rf-Rh above.
20% by weight is preferred. If added in excess of this, the polymer having a fluorinated alicyclic structure will not dissolve in these hydrocarbon solvents and the polymer will precipitate, which is not preferable. The solution prepared by dissolving the block compound of the present invention in the solvent is a dye of the general formula Rf-Rh (where Rf is a perfluoroalkyl group having 6 to 12 carbon atoms,
Rh preferably contains an auxiliary solvent which can be mixed with a solvent composed of a block compound represented by an alkyl or alkenyl group having 1 to 4 carbon atoms.

[0035]

EXAMPLES Next, examples of the present invention will be specifically described, but the description does not limit the present invention.

(Synthesis Example 1) 35 g of perfluoro ( butenyl vinyl ether ) ,
1,1,2-Trichlorotrifluoroethane (R11
3) 5 g, ion-exchanged water 150 g, and diisopropyl peroxydicarbonate 90 as a polymerization initiator.
mg was placed in a pressure-resistant glass autoclave having an internal volume of 200 ml. After substituting the system with nitrogen three times, suspension polymerization was carried out at 40 ° C. for 22 hours. As a result, 28 g of a polymer A containing a carboxylic acid group was obtained. Intrinsic viscosity of polymer A [η]
Was 0.50 dl / g at 30 ° C. in perfluoro (2-butyltetrahydrofuran). The glass transition point of the polymer A is 180 ° C., and it is a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature was 465 ° C., and the light transmittance was 95% or higher.

(Synthesis Example 2) 8 g of perfluoro ( butenyl vinyl ether ) , PD
2 g of D, 40 g of R113, and 0.1 g of diisopropyl peroxydicarbonate as a polymerization initiator,
It was placed in a pressure-resistant glass ampoule having an internal volume of 50 ml. After freezing and degassing the system three times, the system was shaken in a water bath at 40 ° C. for 20 hours. As a result, 6.7 g of a copolymer B containing a carboxylic acid group was obtained. The glass transition point of copolymer B was 157 ° C., and [η] was 0.30 dl / g. The PDD content was determined from the absorbance of the IR spectrum at 1930 cm ⁻¹ and found to be 12 mol%.

(Synthesis Example 3) PDD 65 mol% and tetrafluoroethylene 35 mol%
Was subjected to radical copolymerization to obtain a copolymer C having a glass transition point of 160 ° C. Copolymer C is colorless and transparent and has a refractive index of 1.
It was 31.

Example 1 One part (part by weight, hereinafter the same) of Polymer A was added to CF ₃ (CF
₂ ) It was dissolved in 10 parts of ₇ CH ₂ CH ₃ (boiling point 155 ° C.) to obtain a polymer solution. Next, 2 parts of chloroform and 0.02 part of 9-aminoacridine as a dye were mixed. The polymer solution was mixed with this solution and stirred at 50 ° C. for 3 hours to form a uniform solution. The solution thus prepared was cast on a glass plate and dried at 100 ° C. to give a thickness of 7
At 0 μm, a yellow film in which the dye was uniformly dispersed was obtained. When the absorption spectrum of ultraviolet / visible light of this film was measured, it was found that 90% or more of the light of 500 nm or more was transmitted and 100% of the ultraviolet light of 260 nm or less was absorbed as shown in FIG.

(Example 2) A film was prepared in the same manner as in Example 1 except that 0.01 part of 2-aminobenzothiazole was used as a dye. The absorption spectrum of this film is shown in FIG.

Example 3 A part of the copolymer B was added to CF ₃ (CF ₂ ) ₇ CH ₂ CH ₃
It was dissolved in 12 parts (boiling point 155 ° C.) to obtain a polymer solution. Next, 2 parts of chloroform, 2 parts of R113 and 0.02 part of 9-aminoacridine as a dye were mixed.
The polymer solution was mixed with this solution and stirred at 50 ° C. for 3 hours to form a uniform solution. The solution thus prepared was cast on a glass plate and dried at 120 ° C. to give a thickness of 70 μm.
As a result, a yellow film having a uniform pigment dispersion was obtained.

Example 4 Copolymer C was used in place of Copolymer B, and 9 was used as a dye.
In the same manner as in Example 3 except that 0.01 part of aminoacridine was mixed instead of 0.02 part, a film having a thickness of 80 μm and a yellow colorant dispersed therein was obtained.

(Comparative Example 1) Mixing was performed in the same manner as in Example 1 except that perfluorotributylamine was used in place of CF ₃ (CF ₂ ) ₇ CH ₂ CH ₃ to disperse a pigment. I couldn't.

[0044] (Comparative Example _{2) CF 3 (CF 2)} 7 except for using perfluoro (2-butyl tetrahydrofuran) in place of CH ₂ CH ₃ is
When mixed in the same manner as in Example 2, the dye was precipitated and could not be dispersed.

Example 5 For both the film obtained in Example 1 and the film of polymer A containing no dye for comparison, 248 nm
When spot-irradiated with the pulsed laser light of, the dye dispersed film is heated by 0.1 mm in diameter.
Could be punched, but the film that did not contain did not.

Example 6 1 part of the polymer A was dissolved in 10 parts of perfluoro (2-butyltetrahydrofuran) to obtain a polymer solution. Next, 0.02 parts of 9-aminoacridine as a dye was mixed with 2 parts of 2- (perfluorohexyl) ethanol to prepare a solution. The polymer solution was mixed with this solution to form a uniform solution. When the solution thus prepared was cast on a glass plate and dried at 100 ° C., a yellow film having a thickness of 70 μm and uniformly dispersed with a dye was obtained. The absorption spectrum of ultraviolet and visible light of this film is 50
It was found that 90% or more of light of 0 nm or more was transmitted and 100% of ultraviolet light of 260 nm or less was absorbed.

Example 7 A film was prepared in the same manner as in Example 6 except that 0.01 part of 2-aminobenzothiazole was used as a dye. Three
Absorption by dye is observed below 50 nm, 400 nm
Since the above visible light has a transmittance of 85% or more, it was confirmed that the dye was uniformly dispersed.

[0048]

The fluorine-containing polymer composition comprising a polymer having a fluorine-containing alicyclic structure in which the dye of the present invention is uniformly dispersed has chemical resistance, low dielectric constant, low surface energy, non-adhesiveness, Not only does it have the original property of a fluororesin that it is excellent in weather resistance, etc., but it also has the property of absorbing the light of a specific wavelength possessed by the dye, so it is useful as various optical functional materials.

[Brief description of drawings]

FIG. 1 is an ultraviolet and visible light absorption spectrum of the film of Example 1.

FIG. 2 is an ultraviolet / visible light absorption spectrum of the film of Example 2.

Continuation of front page (56) Reference JP-A-3-9344 (JP, A) JP-A-5-140400 (JP, A) JP-A-1-313566 (JP, A) JP-A-2-129254 (JP , A) JP-A-5-117481 (JP, A) Special Table 55-500988 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 27/12-27/20 C08L 29/10 C08L 37/00

Claims (4)

(57) [Claims] [Claim 1] An a polymer having a fluorinated aliphatic ring structure
General formula Rf-Rh (where Rf is a C 6-12 per carbon)
Fluoroalkyl group, Rh is an alkyl group having 1 to 4 carbon atoms.
Or a alkenyl group), the dye is dispersed in a solution prepared by dissolving the solvent in a solvent composed of a block compound, and the solvent is removed to obtain a polymer having a fluorinated alicyclic structure. A method for producing a fluoropolymer composition in which a dye is dispersed. 2. The production method according to claim 1 , wherein an auxiliary solvent other than the block compound is used together with the solvent comprising the block compound. 3. A solution prepared by dissolving a polymer having a fluorinated alicyclic structure in an aprotic fluorinated solvent is mixed with a solution prepared by dispersing a dye in the protic fluorinated solvent. A method for producing a fluoropolymer composition in which a dye is dispersed in a polymer having a fluoroaliphatic ring structure, which comprises removing the solvent. 4. The method according to claim 3 , wherein the protic fluorinated solvent is a fluorinated alcohol.