JP2000234030A - Ptp package film and ptp package sealing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide PTP(press through pack) package films excellent in gas barrier properties, easy openability, flexibility and the like, and PTP package sealing members excellent in easy openability and capable of having a constitution easy in thermal disposal after use. SOLUTION: This PTP package film is composed of a film comprising a liquid crystalline polymer which shows optical anisotrophy on melting and having a ratio of the maximum value of the transmitted microwave intensity, measured by irradiation with a microwave perpendicular to the film surface by the microwave method, to the minimum value of greater than 1.2. A laminated film comprises a layer composed of a film comprising a liquid crystalline polymer which shows optical anisotrophy on melting and having a ratio of the maximum value of the transmitted microwave intensity, measured by irradiation with a microwave perpendicular to the film surface by the microwave method, to the minimum value of greater than 1.2 and a layer composed of a thermoplastic resin (provided that the liquid crystalline polymer is excluded). PTP package sealing members are composed of these PTP package films.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a press-through package for tablets, capsules, troches and the like.
Film suitable for pack (PTP) package, and PT
The present invention relates to a P package sealing member.

[0002]

2. Description of the Related Art A blister film of a PTP package is
In general, a plastic film or aluminum foil can be closely adhered to a predetermined mold and obtained by a hot press or vacuum compression method, or can be obtained by molding by a blister molding method. A PTP package can be obtained by putting contents such as a troche and sealing the blister film with a sealing member such as an aluminum foil or a laminated film of a sealant and an aluminum foil. However, at present, such a PTP package does not always sufficiently satisfy the requirements from the market.

[0003] For example, when an olefin resin such as polyethylene or polypropylene is used as a film for a PTP package, it has been pointed out from the market that the gas barrier performance is poor and the contents are easily deteriorated. It has been pointed out that when a vinyl copolymer or the like is used for the package, the gas barrier property deteriorates particularly under high humidity. Polyvinyl chloride or polyvinylidene chloride does not have sufficient gas barrier properties and has a problem of combustion gas at the time of disposal. When such a thermoplastic resin film is used as a sealing member, it may be difficult to open the PTP package.

[0004] When aluminum foil is used as a sealing member of a PTP package, the PTP package has good openability, but on the other hand, pinholes are liable to occur in the aluminum foil, so that the contents are deteriorated. Markets have pointed out problems such as difficult processing and heavy processing.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a film for a PTP package excellent in gas barrier property, easy opening property, flexibility, etc., and excellent easy opening property. An object of the present invention is to provide a sealing member for a PTP package that can easily be configured to be incinerated after finishing.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention comprises a liquid crystalline polymer that exhibits optical anisotropy when melted, and the maximum and minimum values of the transmitted microwave intensity measured when microwaves are irradiated perpendicularly to the film surface by the microwave method. Of a PTP package comprising a film having a ratio of greater than 1.2, and a liquid crystalline polymer exhibiting optical anisotropy when melted, and irradiated with a microwave perpendicular to the film surface by a microwave method. A layer composed of a film having a ratio of the maximum value to the minimum value of the transmitted microwave intensity measured at that time greater than 1.2 and a layer composed of a thermoplastic resin (excluding the liquid crystal polymer) are laminated. The present invention relates to a film for a PTP package comprising a laminated film. In addition, the present invention provides the PTP
The present invention relates to a PTP package sealing member made of a package film.

[0007]

Next, the present invention will be described in more detail. Various liquid crystalline polymers exhibiting optical anisotropy upon melting used in the present invention are known, such as wholly aromatic or semi-aromatic polyesters, polyesterimides, polyesteramides, and resin compositions containing them. Things. In the present invention, as the liquid crystal polymer, a liquid crystal polyester or a composition using a liquid crystal polyester as one component is preferably used.From the viewpoint of moldability and performance of the obtained film,
In the present invention, it is more preferable to use a liquid crystal polyester resin composition having (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase.

The liquid crystal polyester referred to here is a polyester called a thermotropic liquid crystal polymer.
Specifically, (1) A compound obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. (2) Those obtained by reacting a combination of different aromatic hydroxycarboxylic acids. (3) Those obtained by reacting an aromatic dicarboxylic acid with a nucleus-substituted aromatic diol. (4) Those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. And those forming an anisotropic melt at a temperature of 400 ° C. or less are preferred. In addition, instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester derivatives thereof may be used.

The repeating structural units of the liquid crystal polyester include the following repeating structural units derived from an aromatic dicarboxylic acid, the following repeating structural units derived from an aromatic diol,
Examples of the repeating structural unit derived from an aromatic hydroxycarboxylic acid include, but are not limited to, these.

A repeating structural unit derived from an aromatic dicarboxylic acid:

[0011]

A repeating structural unit derived from an aromatic diol:

[0013]

A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and workability is And more preferably at least 30 mol% or more of such a repeating structural unit. Specifically, the combination of repeating structural units is preferably any one of the following (I) to (VI).

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

The production methods of the liquid crystal polyesters (I) to (VI) are described, for example, in JP-B-47-47870, JP-B-63-3888, JP-B-63-3891, and JP-B-56-18016. JP-A-2-515
No. 23, and the like. Of these, a combination of (I), (II) or (IV) is preferable, and a combination of (I) or (II) is more preferable.

In the field where high heat resistance is required in the present invention, the liquid crystal polyester of the component (A) contains 30 to 80 mol% of the following repeating unit (a ') and 0 to 100% of the repeating unit (b'). 10 mol%, repeating unit (c ') is 1
A liquid crystal polyester having 0 to 25 mol% and a repeating unit (d ') of 10 to 35 mol% is preferably used.

[0024] (In the formula, Ar is a divalent aromatic group.)

In the field where the disposal of the film for the PTP package or the sealing member of the PTP package of the present invention is required, such as incineration after use, from the viewpoint of environmental problems, each of the above is required. Among the preferable combinations in the field, a liquid crystal polyester formed by a combination consisting of elements of only carbon, hydrogen and oxygen is particularly preferably used.

The component (B) used in the liquid crystal polyester resin composition is a copolymer having a functional group reactive with the liquid crystal polyester. The functional group reactive with the liquid crystal polyester is not particularly limited as long as it has reactivity with the liquid crystal polyester, and specific examples include an oxazolyl group, an epoxy group, and an amino group. Preferably, it is an epoxy group. The epoxy group or the like may be present as a part of another functional group, and such an example includes a glycidyl group.

In the copolymer (B), the method for introducing such a functional group into the copolymer is not particularly limited, and it can be carried out by a known method. For example, at the stage of synthesizing the copolymer, it is possible to introduce the monomer having the functional group by copolymerization, or it is also possible to graft copolymerize the monomer having the functional group to the copolymer. It is.

As the monomer having a functional group reactive with the liquid crystal polyester, and particularly as the monomer containing a glycidyl group, unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether are preferably used.

Specifically, the unsaturated carboxylic acid glycidyl ester includes, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester,
Glycidyl p-styrenecarboxylate and the like can be mentioned. As unsaturated glycidyl ethers,
For example, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, styrene-p-glycidyl ether and the like are exemplified.

The unsaturated carboxylic acid glycidyl ester is preferably of the general formula Wherein R is a hydrocarbon group having an ethylenically unsaturated bond and having 2 to 13 carbon atoms. The unsaturated glycidyl ether is preferably a compound represented by the general formula: (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or It is. ).

The copolymer (B) having a functional group reactive with the liquid crystal polyester preferably contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. It is a copolymer containing.

The copolymer (B) having a functional group reactive with the liquid crystal polyester may be a thermoplastic resin or a rubber, or a mixture of a thermoplastic resin and a rubber. You may. Rubber is preferred because of its higher thermal stability and flexibility.

More preferably, the copolymer (B) having a functional group reactive with the liquid crystal polyester is
A copolymer having a heat of fusion of crystal of less than 3 J / g. The copolymer (B) preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30 and more preferably 4 to 30.
25 are particularly preferred. The Mooney viscosity here refers to a value measured using a large rotor at 100 ° C. according to JIS K6300.

The rubber referred to here is a polymer substance having rubber elasticity at room temperature according to a new edition of Polymer Dictionary (edited by the Society of Polymer Science, published in 1988, Asakura Shoten).
Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer (including SEBS rubber or SBS rubber, etc.), and graft copolymer), or The hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber,
Isobutylene-isoprene copolymer, acrylate-ethylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer rubber, styrene-isoprene copolymer Rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluoro rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-non-conjugated diene copolymer rubber, thiol rubber, polysulfide Examples include rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide, etc.), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and the like. Among them, an acrylate-ethylene copolymer is preferably used, and a (meth) acrylate-ethylene copolymer rubber is more preferred.

These rubber-like substances can be produced by any production method (eg, emulsion polymerization method, solution polymerization method, etc.) and any catalyst (eg, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst, etc.). It may be something.

In the present invention, the copolymer (B)
Is a rubber having a functional group reactive with the liquid crystal polyester in the rubber as described above. In such a rubber, a method for introducing a functional group reactive with the liquid crystal polyester into the rubber is not particularly limited, and can be performed by a known method. For example, it is possible to introduce the monomer having the functional group by copolymerization at the stage of synthesizing the rubber, or it is also possible to graft copolymerize the monomer having the functional group to the rubber.

As specific examples of the copolymer (B) having a functional group reactive with the liquid crystal polyester, rubbers having an epoxy group include (meth) acrylate-ethylene- (unsaturated glycidyl carboxylate and And / or unsaturated glycidyl ether) copolymer rubber.

Here, the (meth) acrylic acid ester is
An ester obtained from acrylic acid or methacrylic acid and an alcohol. Alcohols have 1 carbon atom
~ 8 alcohols are preferred. Specific examples of (meth) acrylates include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, ter
Examples thereof include t-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. As the (meth) acrylic acid ester, one kind thereof may be used alone, or two or more kinds may be used in combination.

Preferably, the content of (meth) acrylate units is more than 40% by weight and less than 97% by weight, more preferably 45 to 70% by weight, and the ethylene unit is 3% by weight to 5% by weight.
0% by weight, more preferably 10 to 49% by weight, 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ether unit and / or unsaturated glycidyl ether unit,
More preferably, it is 0.5 to 20% by weight. If the ratio is outside the above range, the thermal stability and mechanical properties of a molded product such as a film or sheet obtained from the composition may be insufficient, which is not preferable.

The copolymer rubber can be produced by a conventional method, for example, bulk polymerization, emulsion polymerization, solution polymerization or the like using a free radical initiator. Typical polymerization methods are described in JP-B-46-45085 and JP-B-6-45085.
No. 1-127709, pressure of 500 k in the presence of a polymerization initiator generating free radicals
g / cm ² or more and a temperature of 40 to 300 ° C.

Other rubbers that can be used in the above copolymer (B) include acrylic rubber having a functional group reactive with liquid crystal polyester and vinyl aromatic carbon having a functional group reactive with liquid crystal polyester. A hydrogen compound-conjugated diene compound block copolymer rubber can also be exemplified.

The acrylic rubber mentioned here is preferably represented by the general formula (1) (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cyanoalkyl group.), A general formula (2) (Wherein, R ² is an alkylene group having 1 to 12 carbon atoms, R ³
Represents an alkyl group having 1 to 12 carbon atoms. ) And general formula (3) (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ^{5 is} an alkylene group having 3 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n is an integer of 1 to 20) .)) At least one monomer selected from the compounds represented by formula (1).

Specific examples of the alkyl acrylate represented by the general formula (1) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Examples thereof include butyl acrylate, pentyl acrylate, hexyl acrylate, actyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, and cyanoethyl acrylate.

The alkoxyalkyl acrylate represented by the general formula (2) includes, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate and the like. One or more of these can be used as the main component of the acrylic rubber.

As a constituent component of the acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the above general formulas (1) to (3), if necessary. Can be used. Examples of such unsaturated monomers include styrene, α-methylstyrene,
Acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinylnaphthalene, N-methylolacrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and the like. .

The preferred constituent ratio of the acrylic rubber having a functional group reactive with the liquid crystal polyester is at least one monomer selected from the compounds represented by the above general formulas (1) to (3). 0 to 99.9% by weight, 0.1 to 30.0% by weight of unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether, selected from the compounds represented by the above general formulas (1) to (3). Unsaturated monomer copolymerizable with at least one monomer 0.0
３30.0% by weight. When the constituent ratio of the acrylic rubber is within the above range, the heat resistance, impact resistance, and molding processability of a molded article such as a film or sheet obtained from the composition are favorable, which is preferable.

The method for producing the acrylic rubber is not particularly limited. For example, JP-A-59-113010, JP-A-62-64809, and JP-A-3-160008
Or a well-known polymerization method described in WO95 / 04764 or the like, and can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator. .

The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with the liquid crystal polyester is preferably (a)
Epoxidation of a rubber obtained by epoxidizing a block copolymer consisting of a sequence mainly composed of a vinyl aromatic hydrocarbon compound and (b) a sequence mainly composed of a conjugated diene compound, or epoxidation of a hydrogenated product of the block copolymer This is the rubber obtained.

The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or a hydrogenated product thereof can be produced by a known method.
798 and JP-A-59-133203.

As the aromatic hydrocarbon compound, for example,
Styrene, vinyltoluene, divinylbenzene, α-methylstyrene, p-methylstyrene, vinylnaphthalene and the like can be mentioned, among which styrene is preferable.
Examples of the conjugated diene compound include butadiene, isoprene, pyrrylene, 1,3-pentadiene, 3-butyl-1,3-octadiene and the like, butadiene or isoprene is preferred.

The rubber used as the copolymer (B) is preferably (meth) acrylate-ethylene-
(Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is used.

The rubber used as the copolymer (B) can be vulcanized as required and used as a vulcanized rubber. The above (meth) acrylic acid ester-ethylene-
Vulcanization of the (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is achieved by using a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, and the like. It is not limited.

As a specific example of the copolymer (B) having a functional group reactive with the liquid crystal polyester, the thermoplastic resin having an epoxy group includes (a) 50 to 99% by weight of ethylene units, (b) ) 0.1 to 30% by weight, preferably 0.5 to 20% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units.
% By weight, and (c) an epoxy group-containing ethylene copolymer having an ethylenically unsaturated ester compound unit of 0 to 50% by weight.

Examples of the ethylenically unsaturated ester compound (c) include vinyl carboxylate such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Esters, α, β-unsaturated carboxylic acid alkyl esters, and the like. Particularly, vinyl acetate, methyl acrylate and ethyl acrylate are preferred.

Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units and glycidyl methacrylate units, and a methyl acrylate unit. Copolymers composed of glycidyl methacrylate units and ethyl acrylate units, and copolymers composed of ethylene units, glycidyl methacrylate units and vinyl acetate units are exemplified.

The epoxy group-containing ethylene copolymer has a melt index (hereinafter sometimes referred to as MFR. JI.
SK6760, 190 ° C, 2.16 kg load) is preferably 0.5 to 100 g / 10 min, more preferably 2 to 100 g / 10 min.
５０50 g / 10 min. The melt index may be outside this range, but the melt index is 100 g
If it exceeds / 10 minutes, it is not preferable in view of the mechanical properties of the composition, and if it is less than 0.5 g / 10 minutes, the compatibility with the liquid crystal polyester of the component (A) may be inferior.

[0057] Also, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the flexural rigidity is outside this range, the molding processability and mechanical properties of the composition may be insufficient, which is not preferable.

The epoxy group-containing ethylene copolymer is usually prepared by reacting an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high-pressure radical polymerization method in which copolymerization is carried out in the presence. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt-grafted and copolymerized in an extruder.

The above liquid crystal polyester resin composition is
A resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase. If the liquid crystal polyester is not in the continuous phase, the gas barrier properties and heat resistance of the film made of the liquid crystal polyester resin composition may be significantly reduced, which is not preferable.

The details of the mechanism of such a resin composition of a copolymer having a functional group and a liquid crystal polyester are unknown, but the resin composition between the component (A) and the component (B) of the composition is not clear. It is considered that a reaction occurs, and the component (A) forms a continuous phase, and the component (B) is finely dispersed, thereby improving the moldability of the composition.

One embodiment of the above liquid crystal polyester resin composition comprises (A) 56.0 to 99.9 liquid crystal polyester.
44% by weight, preferably 65.0 to 99.9% by weight, more preferably 70 to 98% by weight, and (B) a copolymer having a functional group reactive with a liquid crystal polyester.
The resin composition contains 0 to 0.1% by weight, preferably 35.0 to 0.1% by weight, and more preferably 30 to 2% by weight. If the content of the component (A) is less than 56.0% by weight, the gas barrier properties and heat resistance of a molded article such as a film or sheet obtained from the composition may be undesirably reduced. On the other hand, if the content of the component (A) exceeds 99.9% by weight, the molding processability of the composition may be reduced, and the composition is expensive, which is not preferable.

As a method for producing such a liquid crystal polyester resin composition, a known method can be used. For example, there is a method in which each component is mixed in a solution state and the solvent is evaporated or precipitated in the solvent. From an industrial point of view, a method of kneading each component of the above composition in a molten state is preferred. For the melt kneading, kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders which are generally used can be used. In particular, a biaxial high kneader is preferred. During melt-kneading, the cylinder set temperature of the kneading device is 20
The temperature is preferably in the range of 0 to 360 ° C, more preferably 23 ° C.
0-350 ° C.

At the time of kneading, the respective components may be previously mixed uniformly using a device such as a tumbler or a Henschel mixer, or if necessary, the mixing may be omitted, and each component may be separately supplied to the kneading device. Methods can also be used.

In the liquid crystalline polymer used in the present invention, an inorganic filler is used if desired. Such inorganic fillers include calcium carbonate, talc, clay,
Examples thereof include silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flake, glass fiber, carbon fiber, alumina fiber, silica-alumina fiber, aluminum borate whisker, and potassium titanate fiber.

The liquid crystalline polymer used in the present invention may further contain, if necessary, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, a rust inhibitor, a crosslinking agent. Agent, foaming agent, fluorescent agent, surface smoothing agent, surface gloss improving agent,
Various additives such as a release improver such as a fluororesin can be used in the manufacturing process or in the subsequent processing process.

In order to obtain a film from the above liquid crystalline polymer, for example, a method in which a molten liquid crystalline polymer is extruded from a T-die, and is wound up while stretching, and a method in which the molten liquid crystalline polymer is extruded from a cylindrical die. Inflation film-forming method, in which dry air is blown into a cylindrical resin while being stretched and rolled while forming, or a method in which a sheet obtained by injection molding or extrusion is further uniaxially stretched to obtain an oriented film. However, the present invention is not limited to these methods.

The film for a PTP package of the present invention is composed of such a liquid crystalline polymer, and has a maximum value and a minimum value of the transmitted microwave intensity measured when the film surface is irradiated with microwaves perpendicularly by a microwave method. Is a film for a PTP package comprising a film having a ratio of more than 1.2. A film having a ratio of the transmitted microwave intensity of more than 1.2 is particularly excellent in easy-opening property, and is preferable. The ratio of the transmitted microwave intensities is more preferably greater than 1.4.

The method of irradiating a microwave perpendicular to the film surface by the microwave method here is to irradiate the microwave in a direction perpendicular to the film surface using a microwave molecular orientation meter, and to irradiate the microwave with the film. It can be obtained as (a maximum value of the transmitted microwave intensity) / (a minimum value of the transmitted microwave), which is a value reflecting the interaction with the constituting polar molecule, as a scale indicating the molecular orientation of the film. (Maximum value of transmitted microwave intensity) / (Minimum value of transmitted microwave) in PTP package film of the present invention
When the value is within the above range, the tearability of the film is good, which is preferable.

The film for a PTP package of the present invention is composed of such a liquid crystalline polymer, and has a maximum value and a minimum value of the transmitted microwave intensity measured when the film surface is irradiated with microwaves perpendicularly by a microwave method. Is 1.
A laminated film formed by laminating a layer made of a film larger than 2 and a layer made of a thermoplastic resin (excluding the liquid crystalline polymer) can also be used. The ratio of the transmitted microwave intensities is more preferably greater than 1.4. In such a laminated film, an adhesive layer may be interposed between the layers.

The thermoplastic resin (excluding the liquid crystalline polymer) used herein is not particularly limited, but includes polyolefin, polystyrene, polycarbonate, polyester, polyacetal, polyamide, polyphenylene ether, polyether sulfone, ethylene -It is preferable to contain at least one selected from a vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, a fluororesin, and an acrylic resin. Among them, those containing at least one of polyolefin, polyester, and polyamide are preferable.

As the polyolefin used herein, a homopolymer or copolymer of an olefin having 2 to 20 carbon atoms, a diolefin or the like can be used. Olefins, specific examples of diolefins, ethylene, propylene,
Butene-1, pentene-1, hexene-1, heptene-
1, octene-1, nonene-1, decene-1, hexadecene-1, eicosene-1,4-methylpentene-1,
5-methyl-2-pentene-1 and the like are exemplified. Specific examples of such polyolefins include low density polyethylene, high density polyethylene, polypropylene, poly-1-
Butene, poly-4-methylpentene-1, ethylene / butene-1 copolymer, ethylene / 4-methylpentene-1
Copolymers, ethylene / hexene-1 copolymer, propylene / ethylene copolymer, propylene / butene-1 copolymer and the like can be mentioned.

Further, the polyester mentioned here includes
For example, a polycondensate of a divalent carboxylic acid and a dihydric alcohol can be mentioned. In this case, a polycondensate of an aromatic dicarboxylic acid and an alkylene glycol is preferable. Specific examples of such polyester include polyethylene terephthalate and polybutylene terephthalate.

Examples of the polyamide include a polycondensate of a divalent carboxylic acid and a divalent amine and a polycondensate of an aminocarboxylic acid. Specific examples of such a polyamide include polyamide 6 , Polyamide 12, polyamide 11, polyamide 6-6, polyamide 6-12,
Polyamide MXD6 and the like.

Among these thermoplastic resins, polyolefins are preferred. As the polyolefin, polyethylene is more preferable, and low density polyethylene is more preferable.

When laminating such a laminated film,
As the layer made of the thermoplastic resin does not significantly reduce the easy-opening property of the layer made of the liquid crystalline polymer, for example, the orientation direction of the unidirectionally oriented thermoplastic resin layer and the layer made of the liquid crystal polyester resin composition It is preferable to devise such a technique as to form a laminated body in a state where the orientation directions are almost the same. This is particularly desirable when such a laminated film is used as a sealing member for a PTP package.

The PTP package of the present invention usually comprises a blister film mainly for storing tablets and capsules,
It consists of a sealing member with a flat surface that seals it. The film for a PTP package of the present invention has excellent openability, and is particularly preferably used as a sealing member in a PTP package.

As the blister film in the PTP package of the present invention, the PTP package film of the present invention or a film made of another thermoplastic resin can be used according to the purpose. Here, when the film for a PTP package of the present invention is used as a blister film, when the film for a PTP package of the present invention is used as a sealing member, a PTP package excellent in gas barrier properties, easy-openability, and flexibility can be obtained. Can be obtained and even PTP
If a film made of the above liquid crystalline polymer is used as a film for a package, a PTP package having high heat resistance can be obtained. Further, for example, in a field where a gas barrier property is not so required, a film made of another thermoplastic resin is used as a blister film, and the PTP package film of the present invention is used as a sealing member to provide a PTP excellent in easy-opening property. A package can be obtained.

Examples of the other thermoplastic resins include polyolefins such as polyethylene, polypropylene and ethylene-α-olefin copolymer, polyesters such as polystyrene, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyacetals, polyamides and polyphenylenes. ether,
Examples thereof include polyether sulfone, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, fluororesin, and acrylic resin. Among them, polyethylene, polypropylene,
Vinyl chloride, vinylidene chloride, ethylene-vinyl alcohol copolymer, or polyethylene terephthalate is preferably used.

By using a material made of a combination of elements of only carbon, hydrogen, and oxygen as a material for the PTP package film, especially the material for the sealing member of the PTP package, it is possible to make the structure easy for the incineration treatment after use. Possible.

The method for forming the blister film portion of the PTP package in the present invention is not particularly limited, and the material film is heated and pressed by a predetermined mold, and the material film is evacuated to the concave portion of the drum. The pocket portion can be obtained by a well-known method such as a drum-type vacuum forming method in which pressure forming is performed while pressing, a plug-type forming method in which an uneven mold is pressed from above and below a film, and a pin forming method. The diameter, depth, number of pockets per unit area, and the like of the pockets can be determined according to the purpose.

The PTP package of the present invention is obtained by filling the contents such as capsules and tablets into the blister film obtained by the above-mentioned method, and then laminating the film of the sealing member and thermocompression bonding or ultrasonic bonding. It can be obtained by bonding the both by a well-known method such as using an adhesive or a solvent. The inside of the PTP package may be replaced with an inert gas such as nitrogen or argon. The adhesive between the sealing member and the blister film is not particularly limited, but an adhesive for dry lamination, an adhesive for melt extrusion, or a resin can be used according to the purpose.

The surface of the blister film or the surface of the sealing member can be subjected to a surface treatment as required. Such surface treatment methods include, for example, corona discharge treatment,
Examples include plasma processing, flame processing, sputtering processing, solvent processing, ultraviolet processing, infrared processing, ozone processing, and polishing processing.

The thickness of the PTP package sealing member of the present invention is not particularly limited, but is preferably 3 to 1000 μm, more preferably 3 to 500 μm. Further, the thickness of the blister film of the PTP package is not particularly limited,
A blister film having a strength capable of protecting the contents and having a sufficient gas barrier property is preferable, and a preferable thickness is 30 to 2000 μm, and more preferably 50 to 10 μm.
00 μm.

Next, an embodiment of the present invention will be described with reference to the drawings. In FIG. 1, reference numeral 1 denotes a film sealing member made of a liquid crystalline polymer having a ratio of the maximum value to the minimum value of the transmitted microwave intensity larger than 1.2, and 2 denotes a blister film made of a thermoplastic resin. Reference numeral 3 denotes contents such as tablets and capsules. The sealing member has excellent gas barrier properties, chemical resistance, flexibility, and the like, and is easy to open.

In FIG. 2, 1 is a sealing member made of the same liquid crystal polymer as in FIG. 1, 2 is a film made of a thermoplastic resin, 3 is a film made of a liquid crystal polymer or a thermoplastic resin, and 4 is a tablet or capsule. It is.

FIGS. 1 and 2 are merely examples, and in the present invention, various forms of PT other than these forms are used.
A package for a P package is included in the present invention.

[0087]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples, and the present invention is not limited to these examples.

(1) Liquid crystal polyester of component (A) (i) 8.3 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 4 5,45 kg (20.2 mol) of 4,4'-diacetoxydiphenyl was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere, and polymerization was performed at 330 ° C. for 1 hour. The acetic acid gas produced as a by-product during this period was polymerized under strong stirring while being liquefied and collected and removed by a cooling tube. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system.
The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This is further heated at 280 ° C. in a rotary kiln under a nitrogen gas atmosphere.
For 3 hours, the flow start temperature becomes 324.
A wholly aromatic polyester comprising the following repeating structural units in the form of particles at a temperature of ° C was obtained. Here, the flow start temperature is determined using a Shimadzu flow tester CFT-500 manufactured by Shimadzu Corporation.
The resin heated and melted at a heating rate of 4 ° C./min is loaded with a load of 10
Under 0kgf / cm ² , inner diameter 1mm, length 10mm
When extruded from the nozzle, the melt viscosity is 48000
A temperature (° C.) indicating poise. Hereinafter, the liquid crystal polyester is abbreviated as A-1. The polymer is 340 under pressure
It showed optical anisotropy at a temperature of at least ° C. Liquid crystal polyester A-1
Are as follows.

[0089]

(2) Copolymer of Component (B) In the following, E represents ethylene, MA represents methyl acrylate, GMA represents glycidyl methacrylate, and VA represents vinyl acetate.

(I) According to the method described in Example 5 of JP-A-61-127709, MA / E / GMA = 5
9.0 / 38.7 / 2.3 (weight ratio), Mooney viscosity =
15 (here, Mooney viscosity is a value measured using a large rotor at 100 ° C. according to JIS K6300) was obtained. Hereinafter, the copolymer is referred to as b-1
It may be called.

(3) Method of measuring physical properties (i) Oxygen gas permeability: Measured at a temperature of 20 ° C. in accordance with JIS K7126 A method (differential pressure method). The unit is cc / m ² · 24 hr · 1 atm.

(Ii) Water vapor transmission rate: JIS Z0208
The measurement was performed under the conditions of a temperature of 40 ° C. and a relative humidity of 90% according to the (cup method). The unit is g / m ²・ 24hr ・ 1atm
It is.

(Iii) Flex resistance: The laminated material was cut out in the MD and TD directions of the liquid crystal polyester resin composition layer,
MIT bending tester manufactured by Toyo Seiki Co., Ltd.
Folding Endurance Tester
Using the MIT-D type, a bending test was performed based on JIS-p-8115 at a load of 1 kgf, a bending angle of 135 degrees, a bending surface curvature radius of 1 mm, and a bending speed of 175 times / min until the film or sheet was broken. The number of bendings was determined.

(Iv) Molecular orientation ratio: Shin Oji Paper Co., Ltd.
The microwave transmittance of the sample film was measured at a measurement frequency of 4 GHz using a microwave orientation evaluation device MOA-5001, and the ratio of maximum transmittance / minimum transmittance was determined as the molecular orientation ratio.

(V) Evaluation of easy opening property of film: MD
The film in the orientation direction was torn by hand along the MD, and the easy-opening property of the film was evaluated without notch according to the following criteria. ：: Can be easily torn linearly along the MD. ×: The tearing of the film is difficult, and even if it is torn, the crack does not run straight.

Example 1 85% by weight of A-1 and 15% by weight of b-1 were melted at a cylinder set temperature of 350 ° C. and a screw rotation speed of 200 rpm using a TEX-30 type twin screw extruder manufactured by Nippon Steel Corporation. The composition was obtained by kneading. The resulting composition pellets exhibited optical anisotropy at 340 ° C. or higher under pressure. A pellet of this composition is supplied to a single-screw extruder of 60 mmΦ equipped with a cylindrical die, and is melt-extruded at a cylinder set temperature of 350 ° C. and a screw rotation speed of 90 rpm to obtain a die diameter of
The molten resin was extruded upward from a cylindrical die having a lip interval of 1.0 mm and a die set temperature of 350 ° C., and dried air was pressed into the hollow portion of the cylindrical film to expand the cylindrical film, and then cooled. Thereafter, the film was wound through a nip roll at a winding speed of 68 m / min to perform inflation film formation. At this time, the blow ratio was 2.6, and the thickness of the obtained film was 27 μm. When the physical properties were measured, the result of the bending test was 100,000 times or more. The oxygen permeability was 0.4 cc / m ² · atm · 24 h, and the water vapor permeability was 0.5 g / m ² · atm · 24 h. In addition, the molecular orientation ratio was 1.7, and the easy-opening property evaluation of the film was ○. When this film is used as a blister film and a sealing member of a PTP package, a PTP package excellent in gas barrier properties, easy-openability, flexibility and heat resistance will be obtained. Further, since this film is made of a combination of elements of only carbon, hydrogen, and oxygen, it can be used as a sealing member of a PTP package excellent in easy-opening property, which does not generate a chlorine compound or ash even when incinerated.

[0098]

According to the present invention, there is provided a film for a PTP package excellent in gas barrier properties, easy-openability, flexibility and the like. For example, as a component of the film, carbon, hydrogen, by using a component consisting of only oxygen,
The utility value of the present invention is extremely large, for example, such that a film for a PTP package that can be easily incinerated after use can be obtained.

[Brief description of the drawings]

FIG. 1 is an example of an embodiment of a PTP package using the PTP package film of the present invention.

FIG. 1 is an example of an embodiment of a PTP package using the PTP package film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Film consisting of a liquid crystalline polymer 2 ... Film consisting of a thermoplastic resin 3 ... Tablets and capsules 4 ... Film consisting of a liquid crystalline polymer

Continued on the front page F term (reference) 3E067 AA11 AB82 BB14A BB15A BB16A BB25A CA04 CA16 CA24 EA06 EA11 FB04 GA19 4F071 AA12 AA13 AA33 AA42 AA43 AA48 AA75 AB03 AB21 AB24 AB26 AB28 AF30 CF01 CFB CF181 DA016 DE136 DE136 DE186 DE236 DG046 DJ006 DJ016 DJ036 DJ046 DK006 DL006 FA016 FA046 FA066 FD016 GB00 GF00 GG02

Claims (13)

[Claims] The present invention relates to a liquid crystal polymer which exhibits optical anisotropy when melted, and has a maximum value and a minimum value of transmitted microwave intensity measured when a microwave is irradiated perpendicularly to a film surface by a microwave method. A film having a ratio of greater than 1.2. 2. The maximum and minimum values of the transmitted microwave intensity measured when a film is irradiated with microwaves perpendicularly to a film surface by a microwave method. For a PTP package, comprising a laminated film formed by laminating a layer made of a film having a ratio of more than 1.2 and a layer made of a thermoplastic resin (excluding the liquid crystalline polymer). the film. 3. The thermoplastic resin is polyolefin, polystyrene, polycarbonate, polyester, polyacetal, polyamide, polyphenylene ether, polyether sulfone, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, fluorine. The film for a PTP package according to claim 2, wherein the film contains at least one selected from a resin and an acrylic resin. 4. A liquid crystalline polymer exhibiting optical anisotropy upon melting, wherein (A) a liquid crystalline polyester is a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystalline polyester is a dispersed phase. The film for a PTP package according to any one of claims 1 to 3, which is a liquid crystal polyester resin composition. 5. A liquid crystalline polymer exhibiting optical anisotropy when melted comprises (A) 56.0 to 99.9% by weight of a liquid crystalline polyester and (B) a copolymer having a functional group reactive with the liquid crystalline polyester. 2. A composition obtained by melt-kneading 44.0 to 0.1% by weight of a polymer.
4. The film for a PTP package according to any one of claims 3 to 3. 6. The film for a PTP package according to claim 4, wherein the functional group reactive with the liquid crystal polyester is an oxazolyl group, an epoxy group or an amino group. 7. A copolymer (B) having a functional group reactive with a liquid crystal polyester, wherein the copolymer (B) contains 0.1 to 30% by weight of an unsaturated glycidyl ester unit and / or an unsaturated glycidyl ether unit. The film for a PTP package according to claim 4, wherein the film is a polymer. 8. The film for a PTP package according to claim 4, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a rubber having an epoxy group. 9. The film for a PTP package according to claim 4, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a thermoplastic resin having an epoxy group. . 10. The liquid crystal polyester (A) according to claim 4, wherein the liquid crystal polyester (A) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid. The film for a PTP package according to the above. 11. The PTP package according to claim 4, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different aromatic hydroxycarboxylic acids. the film. 12. The ratio of the maximum value to the minimum value of the transmitted microwave intensity measured when the film surface is irradiated with microwaves perpendicularly by the microwave method, is greater than 1.4. A film for a PTP package according to any one of claims 1 to 11. 13. The PT according to claim 1,
A PTP package sealing member comprising a P package film.