JP6146430B2 - Blister packaging - Google Patents

Description

The present invention relates to blister packaging.

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.

Conventionally, as a form for packaging foods, cosmetics, pharmaceuticals, etc., a bottom material made of a plastic molded body in which a concave portion for storing contents is formed in a normal blister pack, and a concave portion for storing contents in the bottom material A so-called press-through pack (PTP) of a type using an aluminum foil that can be pressed and broken is widely used.

Patent Document 1 discloses a fluororesin composition containing polychlorotrifluoroethylene [PCTFE] (A) and a fluororesin (B), and the fluororesin (B) includes tetrafluoroethylene [TFE], ethylene. Total monomer units derived from at least one monomer selected from the group consisting of [Et], vinylidene fluoride [VdF], hexafluoropropylene [HFP] and perfluoro (alkyl vinyl ether) [PAVE] 90 to 100 mol%, the monomer unit derived from the fluorine-containing monomer is 40 mol% or more, the melting point is 80 to 270 ° C, the PCTFE (A) and the fluororesin (B) There is disclosed a fluororesin composition characterized by being 0.1 to 50% by mass of the total mass of Beam that is disclosed to be made.

In Patent Document 2, a) a polymer base layer and b) a fluoropolymer layer containing PCTFE or the like adhered to the polymer base layer via a first intermediate adhesive tie layer, and c) a second intermediate adhesive tie layer. A blister package comprising a multilayer film comprising a support layer adhered to the fluoropolymer layer via d) and a metal foil layer adhered to the support layer via a third intermediate adhesive tie layer; Improvement of low water vapor permeability is achieved.

Patent Document 3 discloses a blister packaging having a lid made by laminating an ethylene acrylic acid homopolymer layer and an oriented PCTFE layer on a polyvinyl chloride container.

JP 2008-189775 A JP-T-2005-523188 Special table 2009-504524 gazette

In blister packaging, the bottom material provided with recesses (cavities) for containing the contents is prepared by vacuum forming or the like, and the recesses for containing the contents in the bottom material are covered with a cover material such as aluminum foil. Sealed and created.

Therefore, when the bottom material is composed of a laminated body, the laminated body is required to have interlayer adhesiveness that does not peel when being formed. Further, since the bottom material and the lid material are bonded by heat sealing, it is also required that the both are firmly bonded by heat sealing.

However, although PCTFE used in Patent Documents 1 to 3 shows very good low water vapor permeability, in order to obtain sufficient interlayer adhesion and heat sealability, the surface of PCTFE is subjected to discharge treatment or adhesion. It was necessary to adhere through the agent.

In view of the current situation, the present invention is excellent in low water vapor permeability and transparency, and each layer constituting the bottom material, and the bottom material and the lid material are strong even without using a surface treatment or an adhesive. The object is to provide a blister packaging that is adhered to.

The present inventors have found that the above problems can be solved at once by forming at least one of the layers constituting the bottom material with a fluorine-containing polymer having a specific composition, and have completed the present invention.

That is, the present invention is a blister package comprising a bottom material in which a recess for containing contents is formed and a lid material bonded to a flange portion of the bottom material, wherein the bottom material includes at least A blister package comprising a fluorine-containing polymer layer formed from a fluorine-containing copolymer having a fluorine olefin unit and a vinyl alcohol unit.

The fluorine-containing olefin is preferably tetrafluoroethylene.

The content of fluorine-containing olefin units in the fluorine-containing copolymer is preferably 40 mol% or more.

It is preferable that the alternating rate of the fluorine-containing olefin unit and the vinyl alcohol unit in the fluorine-containing copolymer is 94% or less.

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 lid member preferably includes an aluminum foil layer.

Since the blister package of the present invention has the above-described configuration, it is excellent in low water vapor permeability and transparency, and excellent in adhesion with other materials without being surface-treated.

FIG. 1 is a schematic cross-sectional view of a first structure of a blister pack. FIG. 2 is a schematic cross-sectional view of a second structure of the blister package. FIG. 3 is a schematic cross-sectional view of a third structure of the blister package. FIG. 4 is a schematic cross-sectional view of a fourth structure of the blister package. FIG. 5 is a schematic cross-sectional view of a fifth structure of the blister package. FIG. 6 is a schematic cross-sectional view of a sixth structure of the blister package.

Hereinafter, the present invention will be specifically described.

The blister packaging of the present invention is a blister packaging comprising a bottom material in which a recess for containing contents is formed, and a lid material bonded to a flange portion (flat portion) of the bottom material, The bottom material includes a fluorine-containing polymer layer formed from a fluorine-containing copolymer having at least a fluorine-containing olefin unit and a vinyl alcohol unit.

The fluorine-containing copolymer has a fluorine-containing olefin unit and a vinyl alcohol unit (—CH ₂ —CH (OH) —).

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 preferably has a fluorine-containing olefin unit content of 40 mol% or more in the fluorine-containing copolymer, the fluorine-containing olefin unit is from 40 mol% to 80 mol%, and vinyl alcohol. More preferably, the unit is 20 mol% or more and 60 mol% or less. When the content of each monomer unit of the fluorine-containing copolymer is in such a range, the blister package obtained has low water vapor permeability and excellent adhesion to other materials. 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. It is particularly preferred that 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 ratio of fluorine-containing olefin units and vinyl alcohol units of 94% or less. When the alternating rate is in such a range, an effect of excellent flexibility as a film can be obtained. More preferably, it is 90% or less, More preferably, it is 80% or less. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. If the alternating rate is too low, the heat resistance may decrease, which is not preferable.

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 in 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 estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

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 preferable that the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit. Furthermore, it is also preferable that the copolymer is a fluorine-containing olefin / vinyl alcohol / vinyl ester monomer copolymer substantially consisting only of a fluorine-containing olefin unit, a vinyl alcohol unit and a vinyl ester monomer unit.

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, and vinyl versatate are preferable. More preferred are vinyl acetate monomer units, vinyl stearate monomer units, and vinyl propionate monomer units, still more preferred are vinyl acetate monomer units and vinyl stearate monomer units, and even more preferred are vinyl acetate monomer units. is there.

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 within such a range, the resulting blister package has excellent low water vapor permeability and adhesion to other materials. 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 94% or less. Is preferred. When the alternating rate is in such a range, an effect of excellent flexibility as a film can be obtained. More preferably, it is 90% or less, More preferably, it is 80% or less. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. If the alternating rate is too low, the heat resistance may decrease, which is not preferable.

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 numbers of V in A, B, and C are the vinyl alcohol unit (—CH ₂ —CH (OH) —) and vinyl ester monomer unit (—CH ₂ —CH (O (C═O) R) measured by ¹ H-NMR. It is calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of (-). The estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

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%.

In the present specification, the content of each monomer unit constituting the fluorine-containing copolymer can be calculated by appropriately combining NMR, FT-IR, and elemental analysis depending on the type of monomer.

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 20,000-2,000,000, Most preferably, it is 30,000-1,000,000.
The weight average molecular weight can be determined by gel permeation chromatography (GPC).

As described later, the fluorine-containing copolymer can be produced by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. That is, it is also preferable that the fluorine-containing copolymer is a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit.

Below, the manufacturing method of the said fluorine-containing copolymer is demonstrated.
Usually, the fluorine-containing copolymer 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. As a method for polymerizing the fluorine-containing copolymer, it is preferable to carry out the polymerization under a condition in which the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept substantially 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 stearate, vinyl propionate, vinyl versatate are preferred because they are easily available 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. However, it is preferable to produce by solution polymerization or suspension polymerization, but not limited thereto.

In emulsion polymerization, solution polymerization, or suspension polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant, a dispersant, 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 t-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 represented by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP), t- Alkyl peroxyesters such as butyl peroxypivalate and water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt, sodium salt, etc. Etc. can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

Examples of the dispersant used in suspension polymerization include partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and other water-soluble cellulose ethers used in ordinary suspension polymerization, and acrylic acid polymers. And water-soluble polymers such as gelatin. The ratio of water / monomer is usually 1.5 / 1 to 3/1 by weight, and the dispersant is used in an amount of 0.01 to 0.1 part with respect to 100 parts of monomer. If necessary, a pH buffer such as polyphosphate can be used.

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 the above-mentioned fluorine-containing copolymer 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 described above. The range may be within the range, specifically 50% or more is preferable, 60% or more is more preferable, and 70% or more is 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 is a vinyl ether monomer (CH ₂ = CH-OR) (hereinafter simply referred to as a vinyl ether monomer) in which a fluorine-containing olefin and a protecting group (R) that can be converted to vinyl alcohol by a deprotection reaction are bonded. To obtain a fluorinated olefin / vinyl ether copolymer, and deprotecting the fluorinated olefin / vinyl ether copolymer to obtain a fluorinated olefin / vinyl alcohol copolymer. It can also be obtained by a production method comprising steps.

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 integral value of protons derived from a t-butyl group (—C (CH ₃ ) ₃ ) in the vicinity of 1.0 to 1.3 ppm before and after deprotection, 2.2 It can be measured by quantifying the integral value of protons derived from 2.7 ppm of 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 t-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 94% or less. When the alternating rate is in such a range, an effect of high solvent solubility can be obtained. More preferably, it is 90% or less, and particularly preferably 80%. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40%. If the alternating rate is too low, the heat resistance may decrease, which is not preferable.

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 in A, B, and C is bonded to the tertiary carbon of the vinyl alcohol unit (—CH ₂ —CH (OH) —) and the vinyl ether unit (—CH ₂ —CH (OR)) of ¹ H-NMR measurement. It is calculated from the intensity ratio of H of the main chain. The estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

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, solution polymerization, or suspension polymerization, it is not this limitation.

In the above emulsion polymerization, solution polymerization or suspension polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant, a dispersant 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, t-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 represented by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP), t- Alkyl peroxyesters such as butyl peroxypivalate and water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt, sodium salt, etc. Etc. 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 dispersant used in suspension polymerization include partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and other water-soluble cellulose ethers used in ordinary suspension polymerization, and acrylic acid polymers. And water-soluble polymers such as gelatin. The ratio of water / monomer is usually 1.5 / 1 to 3/1 by weight, and the dispersant is used in an amount of 0.01 to 0.1 part with respect to 100 parts of monomer. If necessary, a pH buffer such as polyphosphate can be used.

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 above-mentioned fluorine-containing copolymer by deprotecting the copolymer having the above-mentioned fluorine-containing olefin unit and vinyl ether monomer unit is the content of each monomer unit of the above-mentioned fluorine-containing copolymer. Is within the range described above, specifically 50% or more is preferable, 60% or more is more preferable, and 70% or more is 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 integral value of protons derived from the t-butyl group (—C (CH ₃ ) ₃ ) is E The integrated value of protons derived from the main chain methylene group (—CH ₂ —CH—) corresponds to D + E. From the above two values, D is obtained.

The fluorine-containing polymer layer can be obtained from a paint containing the fluorine-containing copolymer or a powder of the fluorine-containing copolymer. The paint can be prepared in a conventional manner in the form of solvent-type paint, water-type paint, powder-type paint, and the like. Among these, the form of a solvent-type paint is preferable from the viewpoint of easy film formation and good drying properties. That is, it is preferable that the paint further contains a solvent. By including a solvent, thin film coating becomes easier and the resulting coating film can be made thinner.

The solvent is preferably an organic solvent, esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; tetrahydrofuran Cyclic ethers such as dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; glycols such as propylene glycol methyl ether and ethyl cellosolve Ethers; diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane n- dodecane, aliphatic hydrocarbons such as mineral spirit; a mixed solvent, and the like.
Of these, esters are preferable, and butyl acetate is particularly preferable.

When the coating material is a solvent-based coating material, the concentration of the fluorine-containing copolymer with respect to the total amount of the coating material of 100% by mass is preferably 5 to 95% by mass, and more preferably 10 to 70% by mass.

It is also preferable that the coating material contains 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 chemically curing reactive group in the fluorine-containing copolymer in the present invention. The composition can be cured usually at 0 to 200 ° C. for several minutes to 10 days.

Moreover, the said coating material 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, and 5.0 × 10 ^{−5 with} respect to 100 parts by weight of the fluorinated copolymer in the present invention. About -1.0 * 10 < ^-3 > weight part is more preferable.

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 act as a crosslinking agent for the paint 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 coating material 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.

Furthermore, various additives can be blended with the coating material according to required characteristics within a range not impairing the effects of the present invention. Examples of the additive include pigments, pigment dispersants, antifoaming agents, leveling agents, ultraviolet absorbers, light stabilizers, thickeners, adhesion improvers, matting agents, and the like.

The bottom material sheet forming the bottom material may have a single-layer structure composed only of a coating film obtained from the paint, or a multilayer structure composed of a coating film obtained from the paint and another material layer. May be. The coating film obtained from the above-mentioned paint has a single layer structure from the viewpoint of simplification of the blister packaging process in addition to exhibiting sufficient low water vapor permeability and transparency alone and firmly adhering to the lid material. Is preferred.

The single-layered bottom material sheet includes, for example, (1) peeling a coating film obtained by applying and drying on a base material from the base material, for example, by throwing it into water. It can be produced by the method (cast film formation).

The method for applying the paint is not particularly limited, and a conventionally known method may be employed depending on the form of the paint. For drying, a conventionally known method may be employed.

In the case of a single layer structure, the thickness of the coating film obtained from the paint is preferably 5 to 1000 μm from the viewpoint of chemical resistance and moisture resistance. More preferably, it is 7-500 micrometers, More preferably, it is 10-250 micrometers.

The multi-layered bottom material sheet can be manufactured by (2) a method of forming a coating film by applying the paint to at least one surface of another material layer and drying as necessary. .

Further, the above-mentioned multi-layered bottom material sheet can be appropriately selected according to (3) the type, form and shape of the constituent material of the bottom material. For example, the above-mentioned fluorine-containing copolymer can be used to contain fluorine. An adhesive film is prepared, laminated with a film of another material, and laminated by heat activation by heating, or the above-mentioned fluorine-containing copolymer is dispersed in an aqueous or organic solvent dispersion or organic on a film of another material. It can also be produced by a coating method such as a solvent-soluble material or powder, and a method of applying and heat-activating by heating, an insert molding method or the like. Moreover, when laminating | stacking the said fluorine-containing copolymer and the thermoplastic polymer which can be melt-molded, a coextrusion method etc. are employable.

In the case of a multilayer structure, the thickness of the coating film obtained from the paint is preferably 5 to 1000 μm from the viewpoint of chemical resistance and moisture resistance. More preferably, it is 7-500 micrometers, More preferably, it is 10-100 micrometers.

Other material layers in the multilayer structure include, for example, materials such as polyamide, polyester, and polyolefin, such as polyethylene [PE] and polypropylene [PP], poly (vinyl chloride) [PVC], poly Examples include vinylidene chloride [PVdC], cyclic olefin copolymer [COC], polystyrene [PS], acrylic resin, polyamide, polyolefin, cyclic olefin copolymer [COC], polyester, poly (vinyl chloride) [PVC]. It is preferable to include a material selected from the group consisting of polyvinylidene chloride [PVdC], polystyrene and acrylic resin, and polyester and poly (vinyl chloride) [PVC] are most preferable. Examples of the polyethylene include low-density polyethylene [LDPE], linear low-density polyethylene [LLDPE], linear medium-density polyethylene [LMDPE], linear and very low-density polyethylene [VLDPE], linear ultra-low-density polyethylene [ ULDPE] and high-density polyethylene [HDPE], and low-density polyethylene is preferred. Examples of the polyester include polyethylene terephthalate [PET] and glycol-modified polyethylene terephthalate [PETG]. The cyclic olefin copolymer [COC] is preferably a copolymer of ethylene and norbornene.

The polyamide is preferably a polyamide homopolymer or copolymer. Polyamide homopolymers include poly (4-aminobutyric acid) [nylon 4], poly (6-aminohexanoic acid) [nylon 6, or poly (caprolactam)], poly (7-aminoheptanoic acid) [nylon 7], Poly (8-aminooctanoic acid) [nylon 8], poly (9-aminononanoic acid) [nylon 9], poly (10-aminodecanoic acid) [nylon 10], poly (11-aminoundecanoic acid) [nylon 11], And poly (12-aminododecanoic acid) [nylon 12]. Polyamide copolymers include nylon 4,6, poly (hexamethylene adipamide) [nylon 6,6], poly (hexamethylene sebacamide) [nylon 6,10], poly (heptamethylene pimelamide) [Nylon 7,7], poly (octamethylene suberamide) [nylon 8, 8], poly (hexamethylene azelamide) [nylon 6, 9], poly (nonamethylene azelamide) [nylon 9, 9], poly (Decamethylene Azelamide) [Nylon 10,9], Poly (tetramethylenediamine-co-oxalic acid) [Nylon 4,2], n-dodecanedioic acid and hexamethylenediamine polyamide [Nylon 6,12], Dodeca Examples include methylenediamine and polyamide of n-dodecanedioic acid [nylon 12, 12]. Other useful polyamide copolymers include caprolactam / hexamethylene adipamide copolymer [nylon 6,6 / 6], hexamethylene adipamide / caprolactam copolymer [nylon 6 / 6,6], Methylene adipamide / hexamethylene azelaamide copolymer [nylon trimethyl 6, 2/6, 2], hexamethylene adipamide-hexamethylene-azelayamide caprolactam copolymer [nylon 6, 6/6, 9 / 6], poly (tetramethylenediamine-co-isophthalic acid) [nylon 4, I], polyhexamethylene isophthalamide [nylon 6,1], hexamethylene adipamide / hexamethylene-isophthalamide [nylon 6, 6 / 6I], hexamethylene adipamide / hexamethylene terephthalamide Nylon 6,6 / 6T], poly (2,2,2-trimethylhexamethylene terephthalamide), poly (m-xylylene adipamide) [MXD6], poly (p-xylylene adipamide), poly ( Hexamethylene terephthalamide), poly (dodecamethylene terephthalamide), polyamide 6T / 6I, polyamide 6 / MXDT / I, polyamide MXDI, and the like. Also included are other nylons not specifically described herein, as well as combinations of those described herein. Among these, as polyamide, nylon 6, nylon 6,6, nylon 6 / 6,6 or a mixture thereof is more preferable, and nylon 6 is still more preferable.

The thickness of the other material layer is usually about 50 to 250 μm. Further, when moisture resistance is particularly required, a SiOx vapor-deposited PET sheet is preferable. The thickness is usually about 10 to 20 μm.

As the lid member, one having a heat-sealable resin layer is preferable because the contained contents can be sealed by heat sealing. The heat-sealable resin layer is not particularly limited as long as the heat-sealing resin layer is a layer that is fused to the surface of the bottom material in which the contents are accommodated. For example, low-density polyethylene [LDPE], medium-density polyethylene [ MDPE], high density polyethylene [HDPE], linear low density polyethylene [LLDPE], ethylene vinyl acetate copolymer [EVA], polypropylene [PP], ethylene / acrylic acid copolymer [EAA], ethylene / methacrylic acid Copolymer [EMA], ethylene / methyl acrylate copolymer [EMAA], ethylene / ethyl acrylate copolymer [EEA], ethylene / methyl methacrylic acid copolymer [EMMA], ionomer [IO], etc. Examples include a seed or a layer containing two or more.

Moreover, it is preferable that a lid | cover material contains metal layers, such as metal vapor deposition film layers, such as an aluminum layer, and a metal foil layer, from the point that low water vapor permeability is favorable, and it is more preferable that an aluminum foil layer is included.

The blister packaging of the present invention can be produced by the following production method using the bottom material and the lid material.
The blister packaging of the present invention is a blister packaging comprising a bottom material in which a recess for accommodating contents is formed and a lid material bonded to the flange portion of the bottom material.
The blister packaging forms a predetermined number of recesses in the bottom material sheet, and then stores the contents such as tablets in each of the formed recesses, and uses a molding filling sealing machine for blister packaging to flange the bottom material It can be manufactured by heat sealing the lid to the part.

As a method for forming the concave portion of the bottom material sheet, there are the following forming methods.
・ Hot and compressed air forming method: A bottom sheet is sandwiched between a lower mold having holes for supplying high-temperature and high-pressure air and an upper mold having pocket-shaped recesses, and air is supplied while being softened by heating to form recesses. Method.
・ Preheater flat pressure forming method: After heating and softening the bottom sheet, it is sandwiched between a lower mold with holes to which high-pressure air is supplied and an upper mold with pocket-shaped recesses, and air is supplied to make recesses How to form.
Drum-type vacuum forming method: A method of forming a recess by vacuuming the recess of a drum having a pocket-shaped recess after partially heating and softening the bottom material sheet with a heating drum.
Pin molding method: A method in which a bottom material sheet is heat-softened and then crimped with a pocket-shaped uneven mold.
・ Preheater plug-assisted pressure forming method: After heating and softening the bottom material sheet, it is sandwiched between a lower mold having holes to which high-pressure air is supplied and an upper mold having pocket-shaped recesses, and air is supplied to provide recesses. A method of assisting molding by raising and lowering a convex plug during molding.
Among these, the preheater plug assist pressure forming method, which is a heating vacuum forming method, is preferable in that the thickness of the bottom material after forming can be obtained uniformly.

The blister packaging of the present invention comprises a bottom material in which a bottom material sheet is formed with a recess by a method such as vacuum or pressure forming, and a lid material. The bottom material has a contour that is almost matched to the shape of the contents, and has a concave portion that accommodates the content, and a flange portion that is formed around the concave portion. It is fixed. In order to package with such a bottom material, the contents are sealed between the recess of the bottom material and the lid material, and the flange portion and the lid material are fixed by a fixing means such as heat seal and packaged.

Next, the blister packaging of the present invention will be described with reference to the drawings.
In the first structure shown in FIG. 1, the blister packaging of the present invention is composed of a bottom material 7 and a lid material 6 and contains the contents 2. In the first structure, the bottom material 7 is composed only of the fluoropolymer layer 3, and the lid material 6 is composed only of the metal layer 1.

In the blister packaging having the first structure, for example, first, a bottom material sheet made of only the fluorine-containing polymer layer 3 is formed by the method (1) described above. The contents 2 can be accommodated in the recess 9 of the bottom material 7 formed from the above-mentioned bottom material sheet, and the lid material 6 made of the metal layer 1 can be overlapped and fixed to the flange portion 8 by heat sealing. .

In the second structure shown in FIG. 2, the bottom material 7 is composed of the fluoropolymer layer 3 and the other material layer 4, and the lid material 6 is composed of the metal layer 1, and the fluoropolymer layer 3 and the metal layer 1 are directly connected to each other. It is provided to touch. The other material layers 4 are as described above.

In the blister packaging having the second structure, for example, first, a bottom sheet made of the fluoropolymer layer 3 and the other material layer 4 is formed by the method (2) described above. The contents 2 can be accommodated in the recess 9 of the bottom material 7 formed from the above-mentioned bottom material sheet, and the lid material 6 made of the metal layer 1 can be overlapped and fixed to the flange portion 8 by heat sealing. .

In the third structure shown in FIG. 3, the bottom material 7 is composed of the fluoropolymer layer 3 and the other material layer 4, and the lid material 6 is composed of only the metal layer 1, and the other material layer 4 and the metal layer 1 are separated from each other. It is provided so that it may touch directly.

In the blister packaging having the third structure, for example, first, a bottom material sheet composed of the fluoropolymer layer 3 and the other material layer 4 is formed by the method (2) described above. The contents 2 can be accommodated in the recess 9 of the bottom material 7 formed from the above-mentioned bottom material sheet, and the lid material 6 made of the metal layer 1 can be overlapped and fixed to the flange portion 8 by heat sealing. .

In the fourth structure shown in FIG. 4, the bottom material 7 is composed only of the fluoropolymer layer 3, and the cover material 6 is composed of the metal layer 1 and the heat-sealable resin layer 5. Are provided so as to be in direct contact with each other. The heat-sealable resin layer is as described above.

In the blister packaging having the fourth structure, for example, first, a bottom material sheet made of only the fluorine-containing polymer layer 3 is formed by the method (1) described above. The contents 2 are accommodated in the concave portion 9 of the bottom material 7 formed from the bottom material sheet, the lid material 6 is obtained by previously laminating the heat sealable resin layer 5 on the metal layer 1, and the heat sealable resin layer 5 can be manufactured by stacking them with the bottom material 7 side and fixing them to the flange portion 8 by heat sealing.

In the fifth structure shown in FIG. 5, the bottom material 7 is composed of the fluoropolymer layer 3 and other material layers 4, and the lid material 6 is composed of the metal layer 1 and the heat-sealable resin layer 5. And the heat-sealable resin layer 5 are provided in direct contact with each other.

In the blister packaging having the fifth structure, for example, first, a bottom sheet made of the fluoropolymer layer 3 and the other material layer 4 is formed by the method (2) described above. The contents 2 are accommodated in the concave portion 9 of the bottom material 7 formed from the bottom material sheet, the lid material 6 is obtained by previously laminating the heat sealable resin layer 5 on the metal layer 1, and the heat sealable resin layer 5 can be manufactured by stacking them with the bottom material 7 side and fixing them to the flange portion 8 by heat sealing.

In the sixth structure shown in FIG. 6, the bottom material 7 is composed of the fluoropolymer layer 3 and the other material layer 4, and the lid material 6 is composed of the metal layer 1 and the heat-sealable resin layer 5. And the heat-sealable resin layer 5 are provided in direct contact with each other.

In the blister packaging having the sixth structure, for example, first, a bottom sheet made of the fluoropolymer layer 3 and the other material layer 4 is formed by the method (2) described above. The contents 2 are accommodated in the concave portion 9 of the bottom material 7 formed from the bottom material sheet, the lid material 6 is obtained by previously laminating the heat sealable resin layer 5 on the metal layer 1, and the heat sealable resin layer 5 can be manufactured by stacking them with the bottom material 7 side and fixing them to the flange portion 8 by heat sealing.

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

Each numerical value of the examples was measured by the following method.

[Measurement of composition and alternating rate of fluoropolymer by NMR (nuclear magnetic resonance method)]
^{For the 1} H-NMR (nuclear magnetic resonance method) measurement, JNM-EX270 (manufactured by JEOL: 270 MHz) was used. Heavy acetone was used as the solvent.

[ ¹⁹ F-NMR measurement]
¹⁹ F-NMR measurement conditions: 376 MHz (trichlorofluoromethane = 0 ppm)

[Molecular weight and molecular weight distribution]
By gel permeation chromatography (GPC), using Tosoh's GPC HLC-8020, Shodex columns (one GPC KF-801, one GPC KF-802, GPC KF-806M) The average molecular weight was calculated from data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min.
When the sample did not dissolve in THF, the average molecular weight was calculated by the following method. A high-performance liquid chromatograph manufactured by JASCO Corporation was used, and the analysis column set was one guard column (Shodex GPC KD-G [4.6 mm ID × 10 mm L]) and an analysis column (KD-806M [8. 0 mm ID × 300 mm L]) 3 were used. The measurement was carried out using N-methyl-2-pyrrolidone containing 10 mM LIBr as a mobile solvent, RI as a detector, and a polystyrene standard sample as a calibration curve sample, with a flow rate of 1 ml / min and a sample injection amount of 200 μL. A data station (ChromNAV) was used for data analysis.

[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.).

[Melting point (Tm)]
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature was increased (first run) -temperature-lowered (second run) at 10 ° C./min, and the maximum value in the heat of fusion curve in the second run. The temperature corresponding to is Tm (° C.).

[IR analysis]
The measurement was performed at room temperature using a Perkin Elmer Fourier transform infrared spectrophotometer 1760X.

[Fluorine content]
By burning 10 mg of sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) Determined (mass%).

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, 4.3 g of t-butyl peroxypivalate is added as a polymerization initiator, the flange is tightened, and the autoclave is evacuated. Substitution was carried out 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 0.740 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 so that the ratio of vinyl acetate / tetrafluoroethylene was constant.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.720 MPa, tetrafluoroethylene is supplied, and when 0.740 MPa is reached, the supply of tetrafluoroethylene is stopped and the supply and pressure of tetrafluoroethylene are controlled. However, vinyl acetate was added according to 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 using 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 so that the ratio of vinyl acetate / tetrafluoroethylene was constant.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.775 MPa, tetrafluoroethylene is supplied, and when 0.800 MPa is reached, the supply of tetrafluoroethylene is stopped and the supply and pressure of tetrafluoroethylene are controlled. However, vinyl acetate was added according to 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). The results are shown in Table 2.

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 are added, 5.0 g of t-butyl peroxypivalate is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. 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 using 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, 0.3 g of t-butyl peroxypivalate is added as a polymerization initiator, the flange is tightened, the autoclave is vacuum-substituted, and fluorine olefin gas is added. Then, 8.0 g of tetrafluoroethylene was sealed, and 2.6 g of hexafluoropropylene was subsequently sealed, and the reaction was started 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 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 and the composition of the polymer B1 was determined from the elemental analysis of fluorine and ¹⁹ F-NMR. The results are shown in Table 2.

Synthesis example 5
A 300 mL stainless steel autoclave is charged with 50 g of butyl acetate as a solvent and 10 g of vinyl acetate as a vinyl ester monomer, 0.3 g of t-butyl peroxypivalate is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. Then, 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)
In a 300 ml stainless steel autoclave, 150 g of t-butanol, 26.7 g of t-butyl vinyl ether and 0.48 g of potassium carbonate are charged as a solvent, 0.32 g of t-butyl peroxypivalate is added as a polymerization initiator, and the flange is tightened. The autoclave was replaced with vacuum, 26.7 g of tetrafluoroethylene was sealed, 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 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 (polymer C1) 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 a 50 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 (degree of saponification) from the relative intensity of the carbonyl peak by IR, TFE / vinyl alcohol / vinyl acetate polymer A3-34, which was 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. The results are summarized in Table 3.

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. The TFE / vinyl acetate polymer (Polymer A2) had a concentration of 10 in 50 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. Then, the re-precipitated polymer was subjected to suction filtration, and dried with a dryer at 80 ° C. for 2 hours. As a result of calculating the hydrolysis rate (saponification degree) from the relative intensity of the carbonyl peak by IR, 96% of 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, 5.26 g of t-butyl vinyl ether / tetrafluoroethylene copolymer (polymer C1) obtained in Synthesis Example 6 (t-butyl vinyl ether / tetrafluoroethylene = 52/48 (molar ratio)), 1 , 4-dioxane 2.4 ml, 4N HCl aqueous solution 100 ml was added, and the mixture was 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 30 minutes pre-drying at room temperature, it was dried for 30 minutes in a blower dryer at 120 ° C. As a result of measuring the film thickness after drying with a micrometer, it was 28 μm.
About the obtained coating film, the adhesiveness with respect to aluminum was evaluated by the following method. The evaluation results are shown in Table 4.

(Adhesion)
Evaluation was performed by a cross-celling cellophane tape peeling test of JIS K5600. The coating film is cut in a grid pattern with a 1 mm interval with a cutter knife, peeled after attaching a cellophane tape, 10 points with no peeled portion, 8 points with more than 0% and less than 5%, 5 points Less than 15% scored 6 points, 15-35% scored 4 points, 35-65% scored 2 points, 65% or more scored 0 points.

Example 2
The adhesiveness 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.

Examples 6-8
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 6.

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 6.

Comparative Example 1
The water vapor permeability of only the PET film of the substrate was measured. The results are summarized in Table 6.
Clearly, the laminated film showed a lower water vapor transmission coefficient than the PET alone film.

Example 9
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 a 104 μm thick PET film (Lumirror manufactured by Toray Industries, Inc.) substrate using a bar coat (# 24). After the application, it was pre-dried at room temperature for 60 minutes and then cured at 100 ° C. for 60 minutes in a blower dryer. Thereafter, the film was further aged at 50 ° C. for 2 days. The film thickness after curing was measured with a micrometer. As a result, it was 15 μm. Similar to Example 1, the adhesion to the PET film was evaluated and was 10 points. Next, the haze value and total light transmittance of this laminate were measured according to ASTM D1003. As a result, the total light transmittance was 93.5, the haze value was 9.8, and the transparency was very high.

1: Metal layer 2: Contents 3: Fluoropolymer layer 4: Other material layer 5: Heat-sealable resin layer 6: Cover material 7: Bottom material 8: Flange 9: Recess

Claims (10)

A blister package comprising a bottom material in which a recess for containing contents is formed and a lid material bonded to a flange portion of the bottom material, the bottom material comprising at least a fluorine-containing olefin unit and vinyl alcohol Including a fluorine-containing polymer layer formed from a fluorine-containing copolymer having a unit, and the bottom material is composed of only the fluorine-containing polymer layer or the fluorine-containing polymer layer and other material layers, A blister package, wherein the fluorine-containing polymer layer and the lid member are heat-sealed so as to be in direct contact with each other. The blister package according to claim 1, wherein the fluorine-containing olefin is tetrafluoroethylene. The blister package according to claim 1 or 2, wherein a content of the fluorine-containing olefin unit in the fluorine-containing copolymer is 40 mol% or more. The blister package according to claim 1, 2, or 3, wherein the alternating rate of fluorine-containing olefin units and vinyl alcohol units in the fluorine-containing copolymer is 94% or less. The blister package according to claim 1, 2, 3, or 4, wherein the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit. The blister package according to claim 1, 2, 3, 4, or 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. The fluorine-containing copolymer is obtained by copolymerizing a fluorine-containing olefin and a vinyl ether monomer (CH ₂ ═CH—OR) to which a protecting group (R) that can be converted into vinyl alcohol by a deprotection reaction is bonded. Obtained by a production method comprising a step of obtaining an olefin / vinyl ether copolymer, and a step of obtaining a fluorine-containing olefin / vinyl alcohol copolymer by deprotecting the fluorine-containing olefin / vinyl ether copolymer,
The fluorine-containing olefin / vinyl ether copolymer is a molar ratio of the fluorine-containing olefin to the vinyl ether monomer (fluorine-containing olefin) / (vinyl ether monomer) is (40-60) / (60-40). Yes,
The method for producing a blister package according to claim 1, 2, 3 or 4, wherein the deprotection is performed so that the degree of deprotection is 1 to 100%. The fluorine-containing copolymer is a fluorine-containing olefin units is 70 mol% or less than 40 mol%, claim 1,2,3,4,5 or vinyl alcohol units is less than 60 mol% to 30 mol% 6. The blister packaging according to 6 . The cover material, according to claim 1, 2, 3, 4 comprising a metal layer, 6 or blister packaging 8 according. The cover material, according to claim 1,2,3,4,5,6 including aluminum foil layer, a blister pack 8 or 9, wherein.

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