JP5796646B2 - Fluorine-containing laminate - Google Patents

Description

The present invention relates to a fluorine-containing laminate.

A fluorine-containing laminate in which a layer containing a fluorine-containing polymer and other layers are laminated is widely used due to properties such as heat resistance and chemical resistance derived from fluorine atoms. Expansion to various uses is being attempted depending on the type of other layers to be used.

As a method for adhering a fluoropolymer and another material for producing a fluoropolymer laminate, 1) the surface of the substrate is physically roughened by sand fraster treatment or the like and adhered to the fluoropolymer. 2) Method of surface treatment such as sodium etching, plasma treatment, photochemical treatment, etc. on fluorine-containing polymer and bonding to other materials 3) Method of bonding using adhesive It is being considered. However, the methods 1) and 2) require processing steps, are complicated in process, and have low productivity. Moreover, the kind and shape of a base material will be limited. In the first place, the adhesive strength was insufficient, and problems in appearance (coloring and scratches) of the obtained laminate were likely to occur.

Regarding the method 3), various studies have been made on adhesives. General hydrocarbon-based adhesives have insufficient adhesion and insufficient heat resistance in themselves, and are generally used in adhesive processing conditions for fluoropolymers that require molding and processing at high temperatures. Unbearable, causing peeling or coloring due to decomposition. And the laminate using such an adhesive also has insufficient heat resistance, chemical resistance, and water resistance of the adhesive layer, so that the adhesive force cannot be maintained due to temperature change or environmental change, and reliability is improved. It was lacking.

On the other hand, studies have been made on adhesion using an adhesive and an adhesive composition using a fluorine-containing polymer having a functional group.

For example, a fluorine-containing polymer obtained by graft polymerization of a hydrocarbon-based monomer having a carboxyl group, carboxylic anhydride residue, epoxy group, or hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane. Reports using polymers as adhesives (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6) and hydrocarbon-based single molecules containing functional groups such as hydroxyl alkyl vinyl ether An adhesive composition of a fluorine-containing copolymer obtained by copolymerizing a monomer with tetrafluoroethylene or chlorotrifluoroethylene and an isocyanate curing agent is cured, and polyvinyl chloride and corona discharge treated ETFE (ethylene- Reports used for adhesives with tetrafluoroethylene copolymers (for example, Patent Document 7) It has been made.

Also reported are adhesives and adhesive compositions that use a fluorinated polymer having a functional group obtained by copolymerizing a sulfonic acid or a derivative thereof or a perfluorovinyl ether compound containing a carboxylic acid or a derivative thereof with a fluorine-containing monomer. Has been. Patent Document 8 describes a laminate in which a fluoropolymer having a functional group introduced by copolymerizing perfluorovinyl ether having a sulfonic acid group, a carboxylic acid group, or a derivative thereof with tetrafluoroethylene or the like is used as an adhesive. Has been. This is a laminate using a metal surface treated with an epoxy resin or the like when laminated with an inorganic material such as metal.

Patent Document 9 describes adhesion between a terpolymer having a sulfonic acid group, a terpolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), and a metal.

Patent Document 10 describes adhesion between a novel hydroxyl group-containing monomer, a terpolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), and a metal.

Preparation of a refractive index image comprising a fluoromonomer, vinyl acetate, vinyltrimethylsilyl, optionally a vinyl alcohol, and a binder, monomer, and photoinitiator that is a copolymer comprising about 3 to 23% by weight fluorine. And a laminated structure made of glass are disclosed (for example, see Patent Document 11).

In addition, a hydrophilic porous fluororesin material in which a copolymer of a fluorine-containing monomer and a hydrophilic group-containing monomer is attached in the pores of the porous fluororesin material (see, for example, Patent Document 12), or such hydrophilicity An electrochemical reactor separator made of a porous fluororesin material (see, for example, Patent Document 13) is disclosed.

JP-A-7-18035 Japanese Patent Application Laid-Open No. 7-259592 Japanese Patent Laid-Open No. 7-25594 JP 7-173230 A JP-A-7-173446 JP-A-7-173447 Japanese Unexamined Patent Publication No. 7-228848 US Pat. No. 4,916,020 JP 7-145362 A JP 2005-170049 A Japanese Patent Laid-Open No. 7-210065 JP-A-4-139237 JP-A-7-192716

The adhesive or adhesive composition using a fluoropolymer obtained by graft polymerization or copolymerization of a hydrocarbon-based functional group monomer disclosed in Patent Documents 1 to 6 has insufficient heat resistance and high temperature with a fluororesin. During processing at high temperatures or when used at high temperatures, decomposition, foaming, etc. occur, resulting in decreased adhesive strength, peeling, or coloring. In the adhesive composition described in Patent Document 7, the fluororesin requires corona discharge treatment.

The adhesive made of a fluorinated polymer introduced with a sulfonic acid group or a carboxylic acid group disclosed in Patent Document 9 has insufficient adhesion to metal, and the functional group is strongly acidic. There is a problem of corroding the metal in the. In addition, a perfluorovinyl ether-based functional group-containing monomer as disclosed in Patent Document 9 has a property of lowering the glass transition temperature of the polymer, and when introduced into the polymer to sufficiently increase the adhesion, However, there was a disadvantage that the remarkably decreased. In addition, the glass transition point is lowered and the permeability is deteriorated. As a result, although they are in close contact, there is a problem that water vapor permeates and the laminated metal is corroded.

In addition, carboxylic acids are generally easily decomposed at high temperatures, and are liable to cause adhesion failure, foaming, coloring, peeling, etc. during processing and use at high temperatures.

In addition, when a laminate using these adhesives is used as an electrical material, these functional groups are introduced into the fluoropolymer, so that there is a problem that the electrical insulation is greatly reduced because of the ionic nature. .

The ternary copolymer disclosed in Patent Document 10 has a low functional group concentration and insufficient adhesion.

The copolymer containing fluorine disclosed in Patent Document 11 has a low fluorine content and insufficient heat resistance.

Thus, although a fluorine-containing laminated body has been examined, there has not yet been a sufficient material as a material that achieves both heat resistance, adhesiveness, and low permeability.

Incidentally, the hydrophilic porous fluororesin material disclosed in Patent Documents 12 and 13 is obtained by adhering a copolymer of a fluorine-containing monomer and a hydrophilic group-containing monomer in the pores of the porous fluororesin material, It cannot be said to be a laminate of a copolymer of a monomer and a hydrophilic group-containing monomer and a layer of a porous fluororesin material, and the adhesion method disclosed in the examples can hardly exhibit adhesion. It is.

The present invention provides a fluorine-containing laminate excellent in heat resistance, low permeability and adhesion.

In the copolymer having a fluorinated olefin unit and a vinyl alcohol unit, the present inventors are a hydrocarbon-based functional group monomer unit, but have a heat resistance equal to or higher than that of a fluorinated functional group monomer unit. It was found to have And when the content rate of the fluorine-containing olefin unit in the copolymer which has a fluorine-containing olefin unit and a vinyl alcohol unit shall be 40 mol% or more, it will consist of a layer which consists of such a copolymer, and a layer different from the said layer. It has been found that the heat resistance, low permeability and adhesion of the fluorine-containing laminate are significantly improved.

That is, the present invention is a fluorine-containing laminate comprising a layer (A) comprising a fluorine-containing copolymer and a layer (B) different from the layer (A), wherein the fluorine-containing copolymer comprises A fluorine-containing laminate comprising a fluorine-olefin unit and a vinyl alcohol unit, wherein the fluorine-containing copolymer has a fluorine-containing olefin unit content of 40 mol% or more.

The fluorine-containing olefin is preferably tetrafluoroethylene.

The fluorine-containing copolymer preferably has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit.

The fluorine-containing copolymer is preferably a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit.

The layer (B) is preferably made of an organic material.

The layer (B) is preferably made of a non-fluorine polymer.

The layer (B) is preferably made of an inorganic material.

Since the fluorine-containing laminate of the present invention has the above-described configuration, it is excellent in heat resistance, low permeability and adhesion.

The present invention is described in detail below.
The fluorine-containing laminate of the present invention is composed of a layer (A) composed of a fluorine-containing copolymer and a layer (B) different from the layer (A). As long as the layer (A) and the layer (B) are included, other layers may be included. Further, each of the layer (A) and the layer (B) may be a single layer, or may be the same or different two or more layers.
Furthermore, the layer (A) may contain other components as long as it contains the fluorine-containing copolymer in the present invention.

The fluorine-containing copolymer has a fluorine-containing olefin unit and a vinyl alcohol unit (—CH ₂ —CH (OH) —), and the content of the fluorine-containing olefin unit in the fluorine-containing copolymer is 40 mol% or more. There is something. Since the fluorine-containing laminate of the present invention includes a layer of a fluorine-containing copolymer having such characteristics, it is excellent in heat resistance, low permeability and adhesion.

The said fluorine-containing olefin unit represents the polymerization unit based on a fluorine-containing olefin. The fluorine-containing olefin is a monomer having a fluorine atom.

Examples of the fluorine-containing olefin include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, CH ₂ = CZ. ¹ (CF ₂ ) _n1 Z ² (wherein Z ¹ is H, F or Cl, Z ² is H, F or Cl, and n1 is an integer of 1 to 10), CF ₂ = CF-ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms) and CF ₂ = CF-OCH ₂ -rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the It is preferably be at least one kind of fluorine-containing olefin.

Examples of the monomer represented by CH ₂ = CZ ¹ (CF ₂ ) _n1 Z ² include CH ₂ = CFCF ₃ , CH ₂ = CHCF ₃ , CH ₂ = CFCHF ₂ and CH ₂ = CClCF ₃ .

Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), etc. Among them, PMVE PEVE or PPVE is more preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

As said fluorine-containing olefin, at least 1 sort (s) selected from the group which consists of TFE, CTFE, and HFP is more preferable, and TFE is still more preferable.

The fluorine-containing copolymer has a vinyl alcohol unit. Vinyl alcohol is a hydrocarbon functional group monomer, but is a hydroxyl group-containing vinyl ether monomer such as 4-hydroxybutyl vinyl ether or 2 The present inventors have found for the first time that the heat resistance is remarkably higher than that of hydroxyethyl vinyl ether and the like, and the heat resistance is equal to or higher than that of fluorine-based functional group monomers.

The fluorine-containing copolymer has a fluorine-containing olefin unit content of 40 mol% or more in the fluorine-containing copolymer, but the fluorine-containing olefin unit is 40 mol% or more and 80 mol% or less, and the vinyl alcohol unit is It is preferable that it is 20 mol% or more and 60 mol% or less. When the content of each monomer unit of the fluorinated copolymer in the present invention is in such a range, the resulting fluorinated laminate is excellent in heat resistance, low permeability and adhesion. As the content of each monomer unit, the fluorine-containing olefin unit is 45 mol% or more and 75 mol% or less, the vinyl alcohol unit is more preferably 25 mol% or more and 55 mol% or less, and the fluorine-containing olefin unit is 50 mol% or less. More preferably, the content is from mol% to 70 mol%, and the vinyl alcohol unit is from 30 mol% to 50 mol%.

The fluorine-containing copolymer preferably has an alternating rate of fluorine-containing olefin units and vinyl alcohol units of 30% or more. When the alternating rate is in such a range, the heat resistance of the fluorine-containing copolymer is further improved. More preferably, it is 35% or more, and still more preferably 40% or more. Even more preferably, it is 70% or more, and particularly preferably 90% or more. The upper limit of the alternating rate is 100%.

The alternating rate of the fluorinated olefin unit and the vinyl alcohol unit was determined by performing ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone is dissolved, and calculating from the following formula: It can be calculated as the alternating rate of chaining.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of V bonded to two T like T- (T: fluorine-containing olefin unit, V: vinyl alcohol unit)
The number of V units of A, B, and C is calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of the vinyl alcohol unit (—CH ₂ —CH (OH) —) of ¹ H-NMR measurement.

The fluorine-containing copolymer is further represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). It may have a vinyl ester monomer unit. Thus, it is also one of the preferred embodiments of the present invention that the fluorinated copolymer in the present invention has a fluorinated olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit. Furthermore, it is a fluorine-containing olefin / vinyl alcohol / vinyl ester monomer copolymer consisting essentially of a fluorine-containing olefin unit, a vinyl alcohol unit and a vinyl ester monomer unit. One.

The vinyl ester monomer unit is a monomer represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). Although it is a unit, as R in the said formula, a C1-C11 alkyl group is preferable and a C1-C5 alkyl group is more preferable. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.

Examples of the vinyl ester monomer unit include monomer units derived from the following vinyl esters.
Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valelate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, vinyl pelargonate, vinyl caprate, Vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova-10 (Showa Shell Sekiyu KK) )), Vinyl benzoate, vinyl versatate.
Among these, monomer units derived from vinyl acetate, vinyl propionate, vinyl versatate, and vinyl stearate are preferable. More preferred are vinyl acetate monomer units, vinyl propionate monomer units, and vinyl stearate monomer units, and even more preferred are vinyl acetate monomer units.

When the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit, the content of each monomer unit is 40 mol% or more and 80 mol% or less of the fluorine-containing olefin unit. The vinyl alcohol unit is preferably more than 0 mol% and less than 60 mol%, and the vinyl ester monomer unit is preferably more than 0 mol% and less than 60 mol%. When the content of each monomer unit is in such a range, the resulting fluorine-containing laminate is excellent in heat resistance, low permeability and adhesion. As the content of each monomer unit, the fluorine-containing olefin unit is from 45 mol% to 75 mol%, the vinyl alcohol unit is from 5 mol% to 50 mol%, and the vinyl ester monomer unit is from 5 mol% to 50 mol%. More preferably, the fluorine-containing olefin unit is 50 mol% or more and 70 mol% or less, the vinyl alcohol unit is 10 mol% or more and 40 mol% or less, and the vinyl ester monomer unit is 10 mol% or more. More preferably, it is 40 mol% or less.

When the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit, the alternating rate of the fluorine-containing olefin unit, the vinyl alcohol unit, and the vinyl ester monomer unit is 30% or more. Is preferred. When the alternating rate is in such a range, the heat resistance of the fluorine-containing copolymer is further improved. More preferably, it is 35% or more, and still more preferably 40% or more. Even more preferably, it is 70% or more, and particularly preferably 90% or more. The upper limit of the alternating rate is 100%.

The alternating rate of the fluorinated olefin unit, the vinyl alcohol unit, and the vinyl ester monomer unit is determined by performing ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone is dissolved, It can be calculated as an alternating rate of three chains from the following formula.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of Vs bonded to two Ts such as T- (T: fluorinated olefin unit, V: vinyl alcohol unit or vinyl ester monomer unit)
The number of V units of A, B, and C is the vinyl alcohol unit (—CH ₂ —CH (OH) —) and vinyl ester monomer unit (—CH ₂ —CH (O (C═O)) of ¹ H-NMR measurement. Calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of R)-).

The said fluorine-containing copolymer may have other monomer units other than a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit in the range which does not impair the effect of this invention.

As said other monomer, as a monomer which does not contain a fluorine atom (however, except vinyl alcohol and a vinyl ester monomer), for example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, Preference is given to at least one fluorine-free ethylenic monomer selected from the group consisting of vinylidene chloride, vinyl ether monomers and unsaturated carboxylic acids.

The total content of the other monomer units is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, based on all monomer units of the fluorine-containing copolymer, More preferably, it is 30 mol%.

The weight average molecular weight of the fluorine-containing copolymer is not particularly limited, but is preferably 9,000 or more, and more preferably 10,000 or more. More preferably, it is 30,000 to 2,000,000, and particularly preferably 50,000 to 1,000,000.
The weight average molecular weight can be determined by gel permeation chromatography (GPC).

As will be described later, the fluorine-containing copolymer can be produced by hydroxylating (saponifying) a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. That is, the fluorine-containing copolymer in the present invention is a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. One.

Below, the manufacturing method of the fluorine-containing copolymer in this invention is demonstrated.
Usually, the fluorine-containing copolymer in the present invention is produced by copolymerizing a fluorine-containing olefin such as tetrafluoroethylene and a vinyl ester monomer such as vinyl acetate, and then hydroxylating the obtained copolymer. can do. When the alternating ratio of the fluorine-containing copolymer is 30% or more, it is preferable to carry out the polymerization under the condition that the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept almost constant. That is, the above-mentioned fluorine-containing copolymer is polymerized under a condition in which the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept almost constant to obtain a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. It is preferably obtained by a production method comprising a step and a step of obtaining a copolymer having a fluorine-containing olefin unit and a vinyl alcohol unit by hydroxylating the obtained copolymer.

Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, pelargon. Vinyl acetate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova 10 (manufactured by Showa Shell Sekiyu KK), vinyl benzoate, vinyl versatate, etc. Among them, vinyl acetate, vinyl propionate, vinyl versatate, and vinyl stearate are easy to obtain and inexpensive. Preferably used.
As said vinyl ester monomer, 1 type of these may be used and 2 or more types may be mixed and used.

Examples of the method of copolymerizing the fluorinated olefin and the vinyl ester monomer include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like, and emulsion polymerization is easy because it is industrially easy to implement. Or it is preferable to manufacture by solution polymerization, but it is not this limitation.

In emulsion polymerization or solution polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant and the like can be used, and those usually used can be used.

The solvent used in the solution polymerization is preferably a solvent capable of dissolving the fluorine-containing olefin, the vinyl ester monomer, and the fluorine-containing copolymer to be synthesized. For example, n-butyl acetate, t-butyl acetate, ethyl acetate Esters such as methyl acetate and propyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Methanol and ethanol Alcohols such as tert-butanol and isopropanol; cyclic ethers such as tetrahydrofuran and dioxane; fluorine-containing solvents such as HCFC-225; dimethyl sulfoxide, dimethylformamide, and mixtures thereof.
Examples of the solvent used in the emulsion polymerization include water, a mixed solvent of water and alcohol, and the like.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

As the surfactant, a commonly used surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used. Moreover, you may use a fluorine-containing surfactant.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
The amount of the chain transfer agent added may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.001 to 10% by mass relative to the polymerization solvent.

The polymerization temperature may be in a range where the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 100 ° C.

The polymerization pressure may be in a range in which the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 10 MPaG.

Hydroxylation of an acetate group derived from vinyl acetate is well known in the art, and can be performed by a conventionally known method such as alcoholysis or hydrolysis using an acid or base. Of these, hydrolysis using a base is generally called saponification. In this specification, however, hydroxylation of a vinyl ester monomer is hereinafter called saponification regardless of the method. By this saponification, the acetate group (—OCOCH ₃ ) is converted into a hydroxyl group (—OH). Similarly, other vinyl ester monomers can be saponified by a conventionally known method to obtain a hydroxyl group.

The degree of saponification in the case of obtaining a fluorine-containing copolymer in the present invention by saponifying a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit is the content of each monomer unit of the fluorine-containing copolymer in the present invention. It is sufficient that the rate is within the above-mentioned range, specifically, 50% or more is preferable, 60% or more is more preferable, and 70% or more is still more preferable.

The saponification degree is calculated from the following equation by IR measurement or ¹ H-NMR measurement of the fluorine-containing copolymer.
Saponification degree (%) = D / (D + E) × 100
D: number of vinyl alcohol units in the fluorinated copolymer E: number of vinyl ester monomer units in the fluorinated copolymer

The fluorine-containing copolymer in the present invention is also a vinyl ether monomer (CH ₂ = CH-OR) (hereinafter simply referred to as a fluorine-containing olefin and a protective group (R) that can be converted to vinyl alcohol by a deprotection reaction). And a fluorine-containing olefin / vinyl alcohol copolymer by deprotecting the fluorine-containing olefin / vinyl ether copolymer. By the process of obtaining, a copolymer having a fluorine-containing olefin unit and a vinyl alcohol unit can be obtained.

A method for copolymerizing the fluorinated olefin and the vinyl ether monomer and a method for deprotecting the fluorinated olefin / vinyl ether copolymer are well known in the art. It can be carried out. By deprotecting the fluorinated olefin / vinyl ether copolymer, the protecting group alkoxy group is converted to a hydroxyl group, and a fluorinated olefin / vinyl alcohol copolymer is obtained.

The fluorine-containing olefin / vinyl ether copolymer obtained by copolymerizing the fluorine-containing olefin and the vinyl ether monomer is a molar ratio of the fluorine-containing olefin and the vinyl ether monomer (fluorine-containing olefin) / (vinyl ether unit The (mer) is preferably (40-60) / (60-40), and more preferably (45-55) / (55-45). When the molar ratio is in the above range and the deprotection is in the range described later, a fluorinated copolymer in which the molar ratio of each polymer unit is in the above range can be produced.

The deprotection of the fluorinated olefin / vinyl ether copolymer is preferably performed so that the degree of deprotection is 1 to 100%, and more preferably 30 to 100%.

The degree of deprotection is determined by ¹ H-NMR, the integrated value of protons derived from an acetyl group (CH ₃ C (═O) O—) near 2.1 ppm before and after deprotection, and 0.8 to 1.8 ppm. It can be measured by quantifying the integral value of protons derived from the main chain methylene group (—CH ₂ —CH—).
¹ H-NMR: GEMINI-300 manufactured by Varian

The vinyl ether monomer preferably does not contain a fluorine atom. The vinyl ether monomer is not particularly limited as long as it is deprotected, but tertiary butyl vinyl ether is preferable from the viewpoint of availability.

When the said fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ether unit, it is preferable that the alternating rate of a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ether unit is 30% or more. When the alternating rate is in such a range, the heat resistance of the fluorine-containing copolymer is further improved. More preferably, it is 35% or more, and still more preferably 40% or more. Even more preferably, it is 70% or more, and particularly preferably 90% or more. The upper limit of the alternating rate is 100%.

The alternating rate of the fluorinated olefin unit, the vinyl alcohol unit and the vinyl ether unit was measured by ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone was dissolved. It can be calculated as an alternating rate of three chains from the equation.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of Vs bonded to two Ts such as T- (T: fluorine-containing olefin unit, V: vinyl alcohol unit or vinyl ether unit)
The number of V units of A, B, and C is the tertiary carbon of vinyl alcohol unit (—CH ₂ —CH (OH) —) and vinyl ether unit (—CH ₂ —CH (OR)) measured by ¹ H-NMR. Calculated from the strength ratio of H of the main chain to be bonded.

Examples of the method for copolymerizing the fluorine-containing olefin and the vinyl ether monomer include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and the like, which are industrially easy to implement. Although it is preferable to manufacture by emulsion polymerization or solution polymerization, it is not this limitation.

In the emulsion polymerization or solution polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant and the like can be used, and those usually used can be used.

The solvent used in the solution polymerization is preferably a solvent capable of dissolving the fluorine-containing olefin, the vinyl ether monomer, and the fluorine-containing copolymer to be synthesized. For example, n-butyl acetate, t-butyl acetate, Esters such as ethyl acetate, methyl acetate and propyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Methanol Alcohols such as ethanol, tert-butanol and isopropanol; cyclic ethers such as tetrahydrofuran and dioxane; fluorine-containing solvents such as HCFC-225; dimethyl sulfoxide, dimethylformamide, and mixtures thereof.
Examples of the solvent used in the emulsion polymerization include water, a mixed solvent of water and alcohol, and the like.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

As the surfactant, a commonly used surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used. Moreover, you may use a fluorine-containing surfactant.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
The amount of the chain transfer agent added may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.001 to 10% by mass relative to the polymerization solvent.

The polymerization temperature may be in a range in which the composition ratio during the reaction of the fluorinated olefin and the vinyl ether monomer is substantially constant, and may be 0 to 100 ° C.

The polymerization pressure may be in a range where the composition ratio during the reaction of the fluorinated olefin and the vinyl ether monomer is substantially constant, and may be 0 to 10 MPaG.

The deprotection of the vinyl ether monomer can be performed by a conventionally known method such as acid, heat or light. By this deprotection, the leaving group (for example, —C (CH ₃ ) ₃ ) can be replaced with hydrogen to obtain a hydroxyl group.

The degree of deprotection in the case of obtaining the fluorine-containing copolymer in the present invention by deprotecting the copolymer having the above-mentioned fluorine-containing olefin unit and vinyl ether monomer unit is determined according to each monomer of the fluorine-containing copolymer in the present invention. The unit content may be in the range as described above, specifically 50% or more is preferable, 60% or more is more preferable, and 70% or more is still more preferable.

The degree of deprotection is calculated from the following formula by IR measurement of the fluorine-containing copolymer or the above-mentioned ¹ H-NMR measurement.
Deprotection degree (%) = D / (D + E) × 100
D: Number of vinyl alcohol units in the fluorinated copolymer E: Number of vinyl ether monomer units in the fluorinated copolymer

The fluorine-containing laminate of the present invention includes a layer (B) different from the layer (A) made of a fluorine-containing copolymer. The constituent material of the layer (B) can be appropriately selected according to the use of the fluorine-containing laminate of the present invention. For example, synthetic polymer materials such as synthetic resin, synthetic rubber, synthetic fiber, and synthetic leather And organic materials such as natural rubber, natural fiber, wood, paper, leather and the like, or composite materials thereof, and inorganic materials such as metal materials and nonmetal inorganic materials. That is, it is also one preferred embodiment of the present invention that the layer (B) in the present invention is made of an organic material. Moreover, it is also one of the suitable embodiment of this invention that the layer (B) in this invention consists of inorganic materials.

The organic material is preferably a non-fluorine polymer. That is, it is also one preferred embodiment of the present invention that the layer (B) in the present invention is made of a non-fluorine polymer.
Examples of the non-fluorine polymer include polyester, polyamide, polyphenylene sulfide, acrylic, vinyl acetate, polyolefin, vinyl chloride, polycarbonate, styrene, polyurethane, acrylonitrile butadiene styrene copolymer (ABS), polyimide, and polyamideimide. , Polyether polyetherketone (PEEK), polyethersulfone (PES), polysulfone, polyetherphenyl oxide (PPO), polyaramide, polyacetal, polyetherimide, silicone resin, epoxy resin, phenol resin, amino resin, unsaturated Examples include polyester and cellophane.

Examples of the metal material include metals such as aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten, and cobalt; carbon steel, Ni steel, Cr steel , Ni-Cr steel, Cr-Mo steel, stainless steel, silicon steel, permalloy alloy steel; Al-Cl, Al-Mg, Al-Si, Al-Cu-Ni-Mg, Al-Si-Cu-Ni -Aluminum alloys such as Mg; copper alloys such as brass, bronze (bronze), silicon bronze, silicon brass, white and nickel bronze; nickel manganese (D nickel), nickel-aluminum (Z nickel), nickel-silicon, monel metal , Constantan, Nichrome Inconel, Hastelloy and other nickel alloys; Metal oxides; Metal hydroxides; Gold such as carbonates and sulfates Salts and the like.

Examples of the non-metallic inorganic materials include glass-based materials such as crystallized glass, foamed glass, heat ray reflective glass, heat ray absorbing glass, and multilayer glass; ceramic base materials such as tiles, large ceramic plates, ceramic panels, and bricks Natural stones such as granite and marble; concrete base materials such as high-strength concrete, glass fiber reinforced concrete (GRC), carbon fiber reinforced concrete (CFRC), lightweight cellular foam concrete (ALC), composite ALC; extruded cement, composite Cement-based substrates such as molded cements; other asbestos slate, enamel steel plates, single crystal silicon, polycrystalline silicon, amorphous silicon, clays, boron-based, carbon-based materials and the like.

The layer (A) comprising the fluorinated copolymer in the present invention can be obtained by curing the composition containing the fluorinated copolymer in the present invention.

When hardening the said composition, it can harden | cure by making the said composition contain a crosslinking agent.

The crosslinking agent is a compound that crosslinks by reacting with the hydroxyl group of the vinyl alcohol of the fluorine-containing copolymer. For example, isocyanates, amino resins, acid anhydrides, polyepoxy compounds, isocyanate group-containing silane compounds are usually used. Used.

Specific examples of the isocyanates include, for example, 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene. Diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and blocked isocyanates However, it is not limited to these.

Specific examples of the amino resins include urea resins, melamine resins, benzoguanamine resins, glycoluril resins, methylolated melamine resins obtained by methylolating melamine, and methylolated melamines with alcohols such as methanol, ethanol, and butanol. Examples include etherified alkyl etherified melamine resins, but are not limited thereto.

Specific examples of the acid anhydrides include, but are not limited to, phthalic anhydride, pyromellitic anhydride, meritic anhydride, and the like.

As the polyepoxy compound and the isocyanate group-containing silane compound, for example, those described in JP-A-2-232250 and JP-A-2-232251 can be used. As a suitable example, for example,

Etc.

The compounding amount of the crosslinking agent is 0.1 to 5 equivalents, preferably 0.5 to 1.5 equivalents, with respect to 1 equivalent of the chemical curing reactive group in the fluorine-containing copolymer. The composition can be cured usually at 0 to 200 ° C. for several minutes to 10 days.

Moreover, the said composition can add a hardening accelerator as what accelerates | stimulates this hardening.

Examples of the curing accelerator include organic tin compounds, acidic phosphate esters, reaction products of acidic phosphate esters and amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, organic titanate compounds, and amine compounds. And lead octylate.

Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate, dibutyltin phthalate, tin octylate, tin naphthenate, and dibutyltin methoxide.

The acidic phosphate ester is

A phosphate ester containing a moiety, for example

(Wherein, b represents 1 or 2, and R ⁸ represents an organic residue). In particular

Etc.

Examples of the organic titanate compound include titanic acid esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

Furthermore, specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylene diene. Amine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), etc. Low molecular weight polyamide resins obtained from excess polyamines and polybasic acids, excess polyamines and epoxy compounds Such as the reaction product, and the like.

The said hardening accelerator may use 1 type and may use 2 or more types together. The blending ratio of the curing accelerator is preferably about 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻² parts by weight with respect to 100 parts by weight of the copolymer, and 5.0 × 10 ^{−5 to} 1.0 × 10. More preferred is about ^-3 parts by weight.

Moreover, you may add the additive for contact | adherence improvement, such as a silane coupling agent, in order to improve adhesiveness. Specific examples of such silane coupling agents include tetraalkoxysilanes (for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane), trialkoxysilanes (for example, methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methyl Captopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, etc.) It is done. Moreover, what condensed one type of these silane coupling agents or two or more types of mixtures can also be used. They work as a crosslinking agent for the composition and contribute to improving the strength and heat resistance of the cured product.
Of these, tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and condensates thereof are preferable.

As a compounding quantity in the said composition of the said silane coupling agent, it can adjust in 0-99 mass% with respect to 100 mass% of fluorine-containing copolymers in this invention.

Appropriate reinforcing agents, fillers, stabilizers, UV absorbers, pigments, pigment dispersants, leveling agents, antifoaming agents, anti-gelling agents, antioxidants, hydrophilicity as long as the properties of the fluorinated copolymer are not impaired It is also possible to add other appropriate additives such as an agent. Such additives can improve thermal stability, surface hardness, wear resistance, weather resistance, chargeability, and the like.

Although it can set suitably as thickness of the fluorine-containing laminated body of this invention according to a use, it is preferable that it is 5-10000 micrometers, for example, More preferably, it is 25-4000 micrometers.

As a manufacturing method of the fluorine-containing laminated body of this invention, although it can select suitably according to the kind, form, and shape of the constituent material of a layer (B), For example, using the fluorine-containing copolymer in this invention A method of laminating a fluorine-containing adhesive film with a substrate made of an organic material film or an inorganic material and laminating by heat activation by heating, or on a substrate made of an organic material film or an inorganic material. The fluorine-containing copolymer can be in the form of a coating material such as aqueous or organic solvent dispersion, organic solvent soluble material, powder, etc., and can be applied and thermally activated by heating, insert molding method, etc. . Moreover, when laminating the fluorine-containing copolymer and melt-moldable thermoplastic polymer in the present invention, a coextrusion method or the like can be employed.
However, when the fluorine-containing laminate of the present invention is produced by immersing the constituent material of the layer (B) in the solution containing the fluorine-containing copolymer in the present invention and impregnating the fluorine-containing copolymer, the layer (A ) And the layer (B) have insufficient adhesion, the fluorine-containing laminate of the present invention is obtained by adding the constituent material of the layer (B) to the solution containing the fluorine-containing copolymer of the present invention. It was not obtained by dipping and impregnating the fluorine-containing copolymer.

Moreover, the one where the adhesiveness between the layers of the fluorine-containing laminated body of this invention is high is preferable. As one of the adhesion indexes, it can be evaluated by a cross cellophane tape peeling test method described in JIS K5400.
An evaluation score of JIS is preferably 8 or more. More preferably, it is 10 points.

The fluorine-containing copolymer in the present invention is excellent in heat resistance, low permeability and adhesion, but also has excellent transparency, so it has transparency and good adhesion to aluminum. And the permeation of water vapor can be suppressed. From these characteristics, the fluorine-containing laminate of the present invention can be suitably used as a medicine package or a blister package.
In addition, the fluorine-containing copolymer in the present invention can be spin-coated. Therefore, in addition to high adhesion and low water vapor permeability, high adhesion and low water vapor permeability can be realized by laminating with an inorganic material by spin coating. From these characteristics, the fluorine-containing laminate of the present invention can be suitably used as an organic EL sealing material.

Since the fluorinated copolymer in the present invention also has an antifogging effect and weather resistance, the fluorinated laminate of the present invention can also be suitably used as an agricultural vinyl film.
Furthermore, since the fluorine-containing copolymer in the present invention has a low dielectric constant, it can be laminated with high adhesion without using an adhesive on copper or aluminum, and has a low dielectric constant and high heat resistance. is there. From these characteristics, the fluorine-containing laminate of the present invention can be suitably used as a flexible printed board.

In addition, since the fluorine-containing copolymer in the present invention has high light resistance, the fluorine-containing laminate of the present invention is a back sheet for solar cells that makes use of a low water vapor transmission point, transparency, light resistance, low It can be suitably used for a solar cell front sheet utilizing water vapor permeation.

Furthermore, the fluorine-containing laminate of the present invention is suitably used for an optical laminate film such as antireflection utilizing the low refractive index, a gas barrier laminate film and a functional gas separation laminate film utilizing low permeability. be able to.

Next, the present invention will be described with reference to synthesis examples and examples, but the present invention is not limited to such synthesis examples and examples.

The measurement methods employed in this specification are summarized below.

(1) Fluorine content 10 mg of sample was burned by the oxygen flask combustion method, the decomposition gas was absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid was determined by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) ) To obtain (mass%).

(2) ¹⁹ F-NMR measurement NMR measurement apparatus: VARIAN-made GEMINI-300
¹⁹ F-NMR measurement conditions: 376 MHz (trichlorofluoromethane = 0 ppm)

(3) ¹ H-NMR measurement NMR measurement apparatus: VEMIRAN-made GEMINI-300
¹ H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

(4) Molecular weight and molecular weight distribution GPC HLC-8020 manufactured by Tosoh Corporation using gel permeation chromatography (GPC), one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802) The average molecular weight is calculated from the data measured by flowing tetrahydrofuran (THF) at a flow rate of 1 ml / min as a solvent using two GPC KF-806Ms connected in series.

(5) Glass transition temperature (Tg)
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature range from −50 ° C. to 200 ° C. was raised at a rate of 10 ° C./min (first run) -temperature fall-temperature rise (second run) The intermediate point of the endothermic curve in the second run was defined as Tg (° C.).

(6) Melting point (Tm)
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised (second run) at 10 ° C./min was defined as Tm (° C.). .

(7) IR analysis Measured at room temperature with a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer.

(8) Cross cellophane tape peel test The cross cellophane tape peel test of JIS K5600 evaluated. The coating film is cut with a grid knife at intervals of 1 mm with a knife, peeled off after applying cellophane tape, 10 points with no peeled part, 8 points with 0-5%, 5-15% 6 points, 15 to 35% of 4 points, 35 to 65% of 2 points, 65% or more of 0 points.

(9) Measurement of haze and total light transmittance The haze value and total light transmittance were measured according to ASTM D1003 using a haze meter (Hazeguard II manufactured by Toyo Seiki Co., Ltd.).

Synthesis example 1
In a 2.5 L stainless steel autoclave, 980 g of butyl acetate as a solvent and 17 g of vinyl acetate as a vinyl ester monomer are added, 6.2 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, and a flange is formed. The autoclave was replaced with vacuum and the bath temperature was raised to 60 ° C. With stirring, 93 g of tetrafluoroethylene was sealed as a fluorine olefin gas to start the reaction. At this time, the pressure in the tank was 0.74 MPa, and the stirring speed was 200 rpm.
Addition of vinyl acetate was started at the start of the reaction, and 93 g of vinyl acetate was added over 4 hours. During the reaction, tetrafluoroethylene was continuously supplied using a solenoid valve so that the ratio of vinyl acetate / tetrafluoroethylene was constant. The stirring speed was 200 rpm.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.740 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.720 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.

Four hours after the start of the reaction, the supply of tetrafluoroethylene and vinyl acetate was stopped. Thereafter, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and 1110 g of a butyl acetate solution of vinyl acetate / tetrafluoroethylene copolymer (solid content concentration 21.0% by mass) was obtained.
After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer A1.

The composition of the polymer A1 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from ¹ H-NMR, and the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.

Synthesis example 2
A 3 L stainless steel autoclave was charged with 1000 g of pure water, 23.2 g of vinyl acetate, Neocor P (76.4 mass% isopropyl alcohol solution of sodium dioctylsulfosuccinate: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nitrogen-substituted, and tetrafluoro Ethylene 37g was added and the inside of a tank was heated up to 80 degreeC. Thereafter, 30 g of tetrafluoroethylene was added. At this time, the pressure in the tank was 0.809 MPa. Under stirring, 22 g of a 1% by mass aqueous solution of ammonium persulfate (APS) was added to initiate the reaction. The addition of vinyl acetate was started at the start of the reaction, and 283 g of vinyl acetate was added over 6 hours. During the reaction, tetrafluoroethylene was continuously supplied using a solenoid valve so that the ratio of vinyl acetate / tetrafluoroethylene was constant. The stirring speed was 500 rpm.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.775 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.800 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.

Six hours after the start of the reaction, the supply of tetrafluoroethylene and vinyl acetate was stopped. Then, after reacting for 1 hour, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, thereby obtaining 1661 g of a vinyl acetate / tetrafluoroethylene copolymer emulsion (solid content concentration 38.5% by mass).

The resulting vinyl acetate / tetrafluoroethylene copolymer (Polymer A2) had a glass transition temperature of 40 ° C. and a particle size of 116 nm. The particle size was measured using a laser light scattering particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., trade name ELS-3000).

Synthesis example 3
Into a 3 L stainless steel autoclave, 1200 g of butyl acetate as a solvent and 140 g of vinyl acetate as a vinyl ester monomer were added, 7.2 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was replaced with vacuum, and the bath temperature was raised to 60 ° C. Under stirring, tetrafluoroethylene was sealed as a fluorine olefin gas to initiate the reaction. At this time, the pressure in the tank was 1.00 MPa, and the stirring speed was 500 rpm. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed. In 6 hours, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and the remaining gas was blown to complete the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer A3.

The composition of polymer A3 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from ¹ H-NMR, and the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.

Synthesis example 4
A 300 mL stainless steel autoclave is charged with 50 g of butyl acetate solvent and 10 g of vinyl stearate monomer, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. Then, 8.0 g of tetrafluoroethylene was encapsulated as a fluorine olefin gas, and 2.6 g of hexafluoropropylene was subsequently encapsulated, and the mixture was placed in a shaking thermostat at 60 ° C. to initiate the reaction. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 15 hours, and the remaining gas was blown to complete the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer B1.

The same analysis as in Synthesis Example 1 was performed except that the melting point was measured instead of the glass transition temperature. The results are shown in Table 2.

Synthesis example 5
In a 300 mL stainless steel autoclave, 50 g of butyl acetate as a solvent and 10 g of vinyl acetate as a vinyl ester monomer were added, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was vacuum-replaced, 17 g of chlorotrifluoroethylene was sealed as a fluorine olefin gas, and the reaction was started by placing it in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 4 hours, the remaining gas was blown to terminate the reaction, and polymer B2 was obtained. The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis Example 6
(Synthesis of t-butyl vinyl ether / tetrafluoroethylene copolymer)
A 300 ml stainless steel autoclave is charged with 150 g of t-butanol, 26.7 g of t-butyl vinyl ether and 0.48 g of potassium carbonate, 0.46 g of a 70% isooctane solution of perbutyl PV as a catalyst is added, the flange is tightened, and the autoclave is vacuum-substituted. Then, 26.7 g of tetrafluoroethylene was sealed, and the reaction was started by placing it in a 60 ° C. shaking thermostat. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 3 hours, and the remaining gas was blown to complete the reaction.
After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain a t-butyl vinyl ether / tetrafluoroethylene copolymer (polymer C1).
The composition of the t-butyl vinyl ether / tetrafluoroethylene copolymer determined by elemental analysis of fluorine was 52/48 (molar ratio). The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis example 7 (saponification homogeneous system)
The TFE / vinyl acetate polymer A3 obtained in Synthesis Example 3 was uniformly dissolved in 10 g THF solvent so as to have a concentration of 10% by mass. Thereafter, a 0.6N NaOH solution was added to give an equivalent amount of vinyl acetate in the polymer, and after 30 minutes the polymer was reprecipitated in a large amount of water. After washing with 1N HCl, it was thoroughly washed with ion-exchanged water, and the reprecipitated polymer was suction filtered and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate from the relative intensity of the carbonyl peak by IR, 34% of TFE / vinyl alcohol / vinyl acetate polymer A3-34 was obtained. The results are summarized in Table 3.

Synthesis examples 8 to 10 (saponification homogeneous system)
By changing the saponification time of Synthesis Example 7, AFE-vinyl alcohol / vinyl acetate polymers A3-45, A3-86, and A3-96 were obtained. Table 3 summarizes.

Synthesis Examples 11 to 13 (saponification uniform system)
A saponification polymer, A1-98, B1-97 and Synthesis Example 7 were used in the same manner as in Synthesis Example 7, except that the saponification time of Synthesis Example 7 was 1 day and the polymers obtained in Synthesis Example 1 and Synthesis Examples 4-5 were used. B2-96 was obtained. The results are summarized in Table 3.

Synthesis Example 14
The emulsion of vinyl acetate / tetrafluoroethylene copolymer obtained in Synthesis Example 2 was freeze-coagulated, rinsed with pure water, and then dried, and the dried TFE / vinyl acetate polymer (Polymer A2) had a concentration of 10 g in 10 g THF solvent. It was uniformly dissolved so as to be mass%. After that, 0.6N NaOH solution was added so as to be equivalent to vinyl acetate in the polymer. After stirring for 24 hours, neutralized with 1N HCl, re-precipitated in a large amount of pure water, and washed well with ion-exchanged water. The re-precipitated polymer was filtered by suction and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate from the relative intensity of the carbonyl peak by IR, 96% TFE / vinyl alcohol / vinyl acetate polymer (A2-96) was obtained. The results are summarized in Table 3.

Synthesis Example 15 (deprotection step):
(Hydrolysis: Synthesis of vinyl alcohol / tetrafluoroethylene copolymer)
In a 100 ml eggplant flask, 2.63 g of t-butyl vinyl ether / tetrafluoroethylene copolymer (t-butyl vinyl ether / tetrafluoroethylene = 52/48 (molar ratio)) obtained in Synthesis Example 6 and 1,4-dioxane 1 .2ml, 4N HCl aqueous solution 50ml was put and heated and stirred at 80 ° C. After 2 hours, heating was stopped and the mixture was allowed to cool, and the precipitated polymer was washed 3 times with pure water. The polymer was dissolved in tetrahydrofuran (THF), reprecipitated in a solution of ethanol / water (50/50% by volume), and dried in vacuo to obtain a purified vinyl alcohol / tetrafluoroethylene copolymer (C1-95). ). The degree of deprotection was 95%. The results are summarized in Table 3.

Example 1
Polymer A2-96 obtained in Synthesis Example 14 was dissolved in a butyl acetate solvent so as to be 40% by mass. Then, it apply | coated on the aluminum plate using bar coating (# 10). After preliminary drying at room temperature for 30 minutes, the film was dried at 120 ° C. for 30 minutes in a blower dryer. As a result of measuring the film thickness after drying with a micrometer, it was 28 μm.
About the obtained coating film, the following item was evaluated. The evaluation results are shown in Table 4.

(Cross-cut adhesion test)
Evaluation was performed by a cross-celling cellophane tape peeling test of JIS K5600. The coating film is cut with a grid knife at intervals of 1 mm, and the cellophane tape is applied and then peeled off, 10 points without peeling, 8 points with 0-5%, 5-15% 6 points, 15 to 35% of 4 points, 35 to 65% of 2 points, 65% or more of 0 points.

Example 2
The adhesion to aluminum was evaluated in the same manner as in Example 1 except that the polymer A3-45 obtained in Synthesis Example 8 was used instead of the polymer A2-96 used in Example 1. The results are shown in Table 5.

Examples 3-5
In the same manner as in Example 2, the adhesion to aluminum was also evaluated for the polymers B1-97, B2-96, and C1-95. The results are shown in Table 5.

Example 6
2 parts of phenyltriethoxysilane were dissolved in 100 parts of the butyl acetate solution of the polymer prepared in Example 1. Then, it apply | coated on the slide glass plate using the bar coat (# 10). After preliminary drying at room temperature for 30 minutes, the film was dried at 120 ° C. for 30 minutes in a blower dryer. It was 32 micrometers as a result of measuring the film thickness after drying with a micrometer.
About the obtained coating film, the cross cellophane tape peeling test was done like Example 1. FIG. The evaluation results are shown in Table 6.

Comparative Example 1
Polymer A2 obtained in Synthesis Example 2 was dissolved in a butyl acetate solvent so as to be 40% by mass. Thereafter, 2 parts of phenyltriethoxysilane was dissolved in 100 parts of a solution prepared in the same manner as in Example 2. Then, it apply | coated on the slide glass plate using the bar coat (# 10). After preliminary drying at room temperature for 30 minutes, the film was dried at 120 ° C. for 30 minutes in a blower dryer. As a result of measuring the film thickness after drying with a micrometer, it was 38 μm. A cross cellophane tape peeling test was conducted in the same manner as in Example 1. The evaluation results are shown in Table 6.

Example 7
Polymer A1-98 obtained in Synthesis Example 11 was dissolved in a butyl acetate solvent so as to be 55% by mass. Thereafter, 12 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), which is an isocyanate curing agent, was added as a crosslinking agent to 100 parts of the solution to obtain a curable composition. This composition was applied onto various substrates using a bar coat (# 24). After coating, after preliminary drying at room temperature for 60 minutes, the metal and glass-based substrates were cured at 120 ° C. in an air blow dryer for 30 minutes. The other substrate was cured for 60 minutes at 100 ° C. in a blower dryer. Each sample was aged at 50 ° C. for an additional 2 days. The film thickness after curing was measured with a micrometer. The results are shown in Table 7. Further, a grid cellophane tape peeling test was conducted in the same manner as in Example 1. The results are shown in Table 7.

Example 8
In Example 7, the haze value and total light transmittance of the laminate applied to a transparent substrate were measured. The results are summarized in Table 7.

Example 9
Among the laminates produced in Example 7, the appearance of the laminate after being held for 96 hours in a blow dryer at 150 ° C. was visually evaluated for the laminate laminated on a highly heat-resistant base metal or glass. The results are summarized in Table 7.
○: No change △: Partially peeled ×: Mostly peeled or discolored

Example 10
A curable composition was obtained in the same manner as in Example 7 except that Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as the isocyanate curing agent. This composition was applied onto a glass substrate using a bar coat (# 24). A cross cellophane tape peeling test was conducted in the same manner as in Example 1. The results are shown in Table 8.

Example 11
3 parts of phenyltriethoxysilane was added as a silane coupling agent to 100 parts of the curable composition produced in Example 7. This composition was applied onto a glass substrate using a bar coat (# 24). A cross cellophane tape peeling test was conducted in the same manner as in Example 1. The results are shown in Table 8.

Example 12
1 g of each polymer obtained in Synthesis Examples 7, 9, and 10 was dissolved in a butyl acetate solvent to make a total of 5 g. Then, after filtering using a 0.45 μm PTFE filter, it was applied onto a 104 μm thick PET film (Lumirror manufactured by Toray Industries, Inc.) using a bar coat (# 24). After preliminary drying at room temperature for 1 hour, the film was dried for 1 day in a blower dryer at 60 ° C. to obtain a laminated film.

The film thickness of the entire laminated film after curing was measured at 10 points with a micrometer, the average value was obtained, and the thickness of the laminated polymer was determined from the difference from the PET film of the substrate. The results are summarized in Table 9.

Each of the produced laminated films was cut to a size of 100 mm × 100 mm, and Dr. based on JIS K7129 (A method). The water vapor permeability of the laminated film was measured using a water vapor permeability meter L80-5000 manufactured by Lyssy. Note that the surface side in direct contact with water vapor is PET, and the dry air side is the membrane of the present invention.
Further, a value obtained by dividing the obtained water vapor permeability value by the total thickness of the laminated film was defined as a water vapor transmission coefficient. The results are summarized in Table 9.

Comparative Example 2
The water vapor permeability of only the PET film of the substrate was measured. The results are summarized in Table 9.
Clearly, the laminated film showed a lower water vapor transmission coefficient than the PET single film.

Example 13
The polymer obtained in Synthesis Example 11 was dissolved in isopropyl alcohol so as to be 1% by mass. An ABS resin substrate (50 × 50 × 1 mm) and a PS resin substrate (50 × 50 × 1 mm) were dip-coated on the above resin solution. After preliminary drying at room temperature for 1 hour, the film was dried for 1 day in a blower dryer at 60 ° C. to obtain a laminated film. As a result of measuring the film thickness after drying with a micrometer, all the film thicknesses were 200 nm. The appearance was visually evaluated. The results are shown in Table 10.
○: Uniform coating has been achieved. Δ: Partially peeled. X: Most peeled. The coated surface was rubbed with a nail, and the adhesion was evaluated according to the following evaluation criteria. The results are shown in Table 10.
○: Cannot be easily peeled with nails △: Can be easily peeled with nails ×: Adhesion is not recognized

The fluorine-containing laminate of the present invention can be used for various applications, and in particular, solar cell front sheets, back sheets, medicine packages, blister package applications, organic EL encapsulant applications, agricultural vinyl film applications. Suitable for flexible printed circuit board applications, optical laminate film applications, gas barriers and gas separation laminate film applications.

Claims (6)

A fluorine-containing laminate comprising a layer (A) comprising a fluorine-containing copolymer and a layer (B) different from the layer (A),
The fluorine-containing laminate is produced by a method of applying a fluorine-containing copolymer coating to the layer (B),
The fluorine-containing copolymer has a fluorine-containing olefin unit and a vinyl alcohol unit,
The fluorine-containing olefin is at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene,
Der content of the fluorine-containing olefin units or 40 mol% in the fluorinated copolymer is,
The alternating rate of fluorine-containing olefin units and vinyl alcohol units in the fluorine-containing copolymer is 30% or more,
The fluorine-containing laminate , wherein the layer (B) is made of an inorganic material . The fluorine-containing laminate according to claim 1, wherein the fluorine-containing olefin is tetrafluoroethylene. The fluorine-containing laminate according to claim 1 or 2, wherein the fluorine-containing copolymer contains 40 to 80 mol% of a fluorine-containing olefin unit and 20 to 60 mol% of a vinyl alcohol unit. A fluorine-containing laminate comprising a layer (A) comprising a fluorine-containing copolymer and a layer (B) different from the layer (A),
The fluorine-containing laminate is produced by a method of applying a fluorine-containing copolymer coating to the layer (B),
The fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit and a vinyl ester monomer unit,
The fluorine-containing olefin is at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene,
The content of fluorine-containing olefin units in the fluorine-containing copolymer is 40 mol% or more,
The alternating rate of the fluorine-containing olefin unit and the vinyl alcohol unit and the vinyl ester monomer unit in the fluorine-containing copolymer is 30% or more,
The layer (B) is made of an inorganic material.
The fluorine-containing laminated body characterized by the above-mentioned . The fluorine-containing copolymer has a fluorine-containing olefin unit of 40 mol% or more and 80 mol% or less, a vinyl alcohol unit of more than 0 mol% and less than 60 mol%, and a vinyl ester monomer unit of more than 0 mol%. The fluorine-containing laminate according to claim 4, which is less than 60 mol%. The fluorine-containing laminate according to any one of claims 1 to 5 , wherein the fluorine-containing copolymer is a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit.