JP3150039B2 - Multilayer sheet for chemical packaging - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel chemical packaging sheet which can be used as a chemical packaging sheet or a film which requires transparency by extrusion or the like. More specifically, a new sheet with excellent physical balance, appearance, transparency, moldability, moisture resistance, and impact resistance, obtained by combining a specific amorphous polyolefin with excellent compatibility and a specific elastomer. Yes,
The present invention relates to a multi-layer sheet for packaging chemicals generally used for packaging solid medicines called PTP.

[0002]

2. Description of the Related Art In the field of pharmaceutical packaging, a sheet made of polyvinyl chloride (hereinafter abbreviated as PVC) resin is conventionally used as a PTP packaging sheet generally used for packaging solid preparations. PVC resin sheet is PT
It is an excellent sheet that almost satisfies the characteristics required for P packaging, but has poor moisture-proof properties. For example, a method of supplementing the moisture resistance by a method such as pillow packaging has been adopted. However, these methods increase man-hours and increase costs. Also, a sheet made of polypropylene (hereinafter abbreviated as PP) resin is used because of its better moisture-proof property than PVC resin, but PP has a narrow molding temperature range and thus has poor moldability, At present, the preparations that require extremely high moisture-proof properties are insufficient in moisture-proof properties, and at present, the usable range is considerably limited. Amorphous polyolefins have excellent mechanical strength, moldability, transparency, and dimensional stability, and have particularly excellent moisture-proof properties, but they are very brittle, and sheets made by extrusion molding or the like Films have a practical lack of impact resistance. Amorphous polyolefins also have the disadvantage of poor oil resistance because of their non-crystallinity, and the formation of fine cracks when sebum or the like adheres to the sheet surface under stress. To improve the disadvantages of this amorphous polyolefin,
Various studies have been carried out, but none of the properties of the amorphous polyolefin were impaired and none were toughened, and the characteristics of the amorphous polyolefin, especially excellent transparency, moisture resistance and moldability, were not impaired. It is desired to be strengthened.
In addition, not only moisture but also oxygen gas or the like impairs the medicinal properties of many preparations, and a sheet having a gas barrier property for oxygen and the like has been desired. Resin sheets are not enough.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a method for blending an amorphous polyolefin (A) and a styrene-based elastomer (B) to reduce the dispersion particle size, thereby achieving a balance of physical properties, appearance, transparency, and the like. It excels in moldability, moisture resistance, and impact resistance, and also excels in moldability of films and sheets.
Further, by laminating a resin layer made of polypropylene (C) on at least one side, oil resistance is good and there is no problem such as stress crack due to sebum and the like, and a resin layer made of polyvinylidene chloride (D) is laminated. Accordingly, it is an object of the present invention to provide a novel multilayer sheet for packaging chemicals having excellent oxygen gas barrier properties.

[0004]

In general, when two or more resins are combined, in order to obtain a resin having good transparency, a resin having a similar refractive index of each resin should be selected. It is necessary to select a suitable combination of resins and to disperse the dispersed particle diameter as finely as possible. However, the combination of resins is rarely compatible with each other, and in most cases, the obtained blend has inferior properties to any of the polymers in most cases. Therefore, as a result of various investigations, it was found that a combination of the specific amorphous polyolefin (A) and the specific elastomer (B) having a very close refractive index at normal temperature and having good compatibility with the specific amorphous polyolefin (A) reduced the dispersed particle diameter. By dispersing, it becomes possible to toughen without deteriorating the characteristics of amorphous polyolefin, especially excellent transparency, moisture proofing property and moldability, and balance of physical properties, appearance, transparency, moldability, moisture proofing property, A new polymer alloy sheet with excellent impact resistance is obtained, and an outer layer made of polypropylene (C) is further laminated, resulting in excellent oil resistance and chemical resistance, and a resin layer composed of polyvinylidene chloride (D) laminated. As a result, it has been found that a novel multilayer sheet for chemical packaging excellent in oxygen gas barrier properties can be obtained, and the present invention has been completed.

[0005] The present invention, difference in refractive index of each at room temperature is within 0.03, intermediate layer formed by blending an amorphous polyolefin (A) and the styrene elastomer (B), polyps propylene (C) and an oxygen gas barrier layer made of polyvinylidene chloride resin (D) were formed as follows: outer layer / oxygen gas barrier layer / intermediate layer / oxygen gas barrier layer /
A multilayer sheet for chemical packaging characterized by being laminated in the order of outer layer, or outer layer / oxygen gas barrier layer / intermediate layer / outer layer, preferably comprising an amorphous polyolefin (A) and a styrene-based elastomer (B). 2. The multi-layer sheet for chemical packaging according to claim 1, wherein the compounding ratio is 99% by weight: 1% by weight to 80% by weight: 20% by weight. The method for producing the multilayer sheet in the present invention is not particularly limited, but is a co-extrusion method in which a resin is melt-extruded with several extruders and guided to a multilayer die or a feed block to form a sheet, or each layer is formed. The method is a combination of a dry lamination method in which a single-layered sheet or film to be bonded using an appropriate adhesive, a method of forming the polyvinylidene chloride resin layer (D) by coating, and a combination of these methods. When a multilayer sheet is formed by a co-extrusion method, it is preferable to provide an appropriate adhesive resin layer between the resin layers.

The amorphous polyolefin (A) used in the present invention is a polymer having a cyclic olefin structure, and can be said to be an amorphous polyolefin based on its structure and properties. Examples of the amorphous polyolefin include an amorphous polymer represented by the following general formula. (Where n is a positive integer of 1 or more, m is a positive integer of 1 or more, R ₁ is a hydrogen atom, a halogen atom, CH ₃ CH
Represents _two groups or a C ₆ H ₄ R ₂ group, wherein R ₂ represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. X represents an addition reaction product of cyclopentadiene or a derivative thereof with norbornadiene or a derivative thereof or a hydrogenated product thereof, or an addition reaction product of dicyclopentadiene or a derivative thereof with ethylene. )

The general formula of the hydrogenated product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the addition product of dicyclopentadiene or its derivative with ethylene is shown below.

Embedded image (Where n is a positive integer of 1 or more, and R _{1 to} R
₁₂ each independently represent a hydrogen atom, a halogen atom, and atoms or groups selected from hydrocarbon groups, R ₉ to R
₁₂ may combine with each other to form a monocyclic or polycyclic ring. )

The hydrogenated product of the addition product of cyclopentadiene or its derivative with norbornadiene or its derivative or the addition product of dicyclopentadiene or its derivative with ethylene is, for example, tetracyclo-3-dodecene, 8-methyltetracyclo-3
-Dodecene, 8-ethyltetracyclo-3-dodecene,
8-propyltetracyclo-3-dodecene, 8-butyltetracyclo-3-dodecene, 8-isobutyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-
Dodecene, 8-stearyltetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene,
2,10-dimethyltetracyclo-3-dodecene, 8,
9-dimethyltetracyclo-3-dodecene, 8-ethyl-9-methyltetracyclo-3-dodecene, 11,12
-Dimethyltetracyclo-3-dodecene, 2,7,9-
Trimethyltetracyclo-3-dodecene, 9-ethyl-
2,7-dimethyltetracyclo-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo-3-dodecene, 9,11,12-trimethyltetracyclo-3-dodecene, 9-ethyl-11,12- Dimethyltetracyclo-3-dodecene, 9-isobutyl-11,12-dimethyltetracyclo-3-dodecene, 5,8,9,10-
Tetramethyltetracyclo-3-dodecene, 8-ethylidenetetracyclo-3-dodecene, 8-ethylidene-9
-Methyltetracyclo-3-dodecene, 8-ethylidene-9-ethyltetracyclo-3-dodecene, 8-ethylidene-9-isopropyltetracyclo-3-dodecene,
8-ethylidene-9-butyltetracyclo-3-dodecene, 8-n-propylidenetetracyclo-3-dodecene, 8-n-propylidene-9-methyltetracyclo-
3-dodecene, 8-n-propylidene-9-ethyltetracyclo-3-dodecene, 8-n-propylidene-9-
Isopropyltetracyclo-3-dodecene, 8-n-propylidene-9-butyltetracyclo-3-dodecene,
8-isopropylidenetetracyclo-3-dodecene, 8
-Isopropylidene-9-methyltetracyclo-3-dodecene, 8-isopropylidene-9-ethyltetracyclo-3-dodecene, 8-isopropylidene-9-isopropyltetracyclo-3-dodecene, 8-isopropylidene-9 -Butyltetracyclo-3-dodecene, 8-chlorotetracyclo-3-dodecene, 8-bromotetracyclo-3-dodecene, 8-fluorotetracyclo-3-
Dodecene, 8,9-dichlorotetracyclo-3-dodecene, hexacyclo-4-heptadecene, 12-methylhexacyclo-4-heptadecene, 12-ethylhexacyclo-4-heptadecene, 12-isobutylhexacyclo-4-heptadecene, 1,6,10-trimethyl-1
2-isobutylhexacyclo-4-heptadecene, octacyclo-5-docosene, 15-methyloctacyclo-
5-docosene, 15-ethyloctacyclo-5-docosene, pentacyclo-4-hexadecene, 1,3-dimethylpentacyclo-4-hexadecene, 1,6-dimethylpentacyclo-4-hexadecene, 15,16-dimethylpentane Cyclo-4-hexadecene, heptacyclo-5
-Eicosene, heptacyclo-5-heneicosene, pentacyclo-4-pentadecene, 1,3-dimethylpentacyclo-4-pentadecene, 1,6-dimethylpentacyclo-4-pentadecene, 14,15-dimethylpentacyclo-4-pentadecene , Pentacyclo-4,10
-Pentadecadiene and the like.

An addition reaction product of the above cyclopentadiene or a derivative thereof with norbornadiene or a derivative thereof,
Or reacting with an addition reaction product of dicyclopentadiene or a derivative thereof with ethylene is one or more unsaturated monomers selected from ethylene, butadiene, or a styrene derivative; For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-ethylstyrene, m-ethylstyrene, p -Ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like are used. These can also be used as a mixture of two or more.

Another example of the amorphous polyolefin (A) is a hydrogenated product of a ring-opened polymer comprising tetracyclo-3-dodecene or a derivative thereof and bicyclohept-2-ene or a derivative thereof. The following general formulas can also be used.

Embedded image (Where n is 0 or a positive integer of 1 or more, m is a positive integer of 1 or more, and R _{1 to} R ₄ are a hydrogen atom or a hydrocarbon group.)

Examples of the above-mentioned tetracyclo-3-dodecene or derivatives thereof include tetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene,
2,10-dimethyltetracyclo-3-dodecene, 1
1,12-dimethyltetracyclo-3-dodecene, 2,
7,9-trimethyltetracyclo-3-dodecene, 9-
Ethyl-2,7-dimethyltetracyclo-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo-
3-dodecene, 9,11,12-trimethyltetracyclo-3-dodecene, 9-ethyl-11,12-dimethyltetracyclo-3-dodecene, 9-isobutyl-11,
12-dimethyltetracyclo-3-dodecene, 5,8,
9,10-tetramethyltetracyclo-3-dodecene,
8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, 8-propyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-dodecene, 8-stearyltetracyclo-3-dodecene,
8,9-dimethyltetracyclo-3-dodecene, 8-methyl-9-ethyltetracyclo-3-dodecene, 8-cyclohexyltetracyclo-3-dodecene, 8-isobutyltetracyclo-3-dodecene, 8-butyltetra Cyclo-3-dodecene, 8-ethylidenetetracyclo-3
-Dodecene, 8-ethylidene-9-methyltetracyclo-3-dodecene, 8-ethylidene-9-ethyltetracyclo-3-dodecene, 8-ethylidene-9-isopropyltetracyclo-3-dodecene, 8-ethylidene-9 −
Butyltetracyclo-3-dodecene, 8-n-propylidenetetracyclo-3-dodecene, 8-n-propylidene-9-methyltetracyclo-3-dodecene, 8-n-
Propylidene-9-ethyltetracyclo-3-dodecene, 8-n-propylidene-9-isopropyltetracyclo-3-dodecene, 8-n-propylidene-9-butyltetracyclo-3-dodecene, 8-isopropylidenetetracyclo -3-dodecene, 8-isopropylidene-
9-methyltetracyclo-3-dodecene, 8-isopropylidene-9-ethyltetracyclo-3-dodecene, 8
-Isopropylidene-9-isopropyltetracyclo-
3-dodecene, 8-isopropylidene-9-butyltetracyclo-3-dodecene and the like.

Examples of bicyclohept-2-ene or derivatives thereof include bicyclohept-2-ene, 6
-Methylbicyclohept-2-ene, 5,6-dimethylbicyclohept-2-ene, 1-methylbicyclohept-2-ene, 6-ethylbicyclohept-2-ene, 6
-N-butylbicyclohept-2-ene, 6-isobutylbicyclohept-2-ene, 7-methylbicyclohept-2-ene and the like.

[0013] The amorphous polyolefin (A) is 70 to 1
It has a heat deformation temperature in the range of 70 ° C, and it is possible to select the most suitable one depending on the application to be used. In applications requiring vacuum moldability such as PTP packaging sheets, the heat denaturation temperature is It is preferable to use one having a temperature of 100 ° C. or lower.

Next, the styrene-based elastomer (B) used in the present invention refers to a polymer material that is elastic at room temperature. Specific examples thereof include butadiene-styrene copolymers (including random copolymers, block copolymers, and graft copolymers) and hydrogenated products thereof, styrene-butadiene-styrene copolymer (SBS), Hydrogenated styrene-butadiene-styrene copolymer (SEBS),
Isoprene-styrene copolymer, hydrogenated styrene-isoprene copolymer (SEP), styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-
Styrene copolymer (SEPS) and the like. Among them, in the present invention, styrene-based elastomers which have good compatibility with the amorphous polyolefin (A) and are preferably used are SEBS, SEP, SEPS, hydrogenated styrene-butadiene-olefin crystal block copolymer (SEBC).
The preferred styrene content is 10 to 80% by weight, more preferably 30 to 70% by weight, and more preferably 40 to 70% by weight. Also, by melting and kneading two or more of these styrene-based elastomers having good compatibility with each other, it is possible to disperse both very finely,
By making them completely compatible at substantially the molecular level, it becomes possible to produce a novel elastomer having a difference in refractive index from the amorphous polyolefin of 0.01 or less, preferably no difference in refractive index. Furthermore, by using this elastomer, it has become possible to obtain a novel polymer alloy which is excellent in transparency and has improved defects (particularly impact resistance) of the amorphous polyolefin (A).

In the polymer alloy sheet for chemical packaging according to the present invention, the mixing ratio of the amorphous polyolefin (A) and the styrene-based elastomer (B) is 99% by weight: 1% by weight to 80% by weight: 20% by weight. . When the content of the amorphous polyolefin (A) is less than 80% by weight, the moldability, moisture resistance and rigidity are not sufficient, and when it is more than 99% by weight, favorable properties in impact resistance cannot be obtained. Further, when the moisture-proof property is further emphasized, the mixing ratio of the amorphous polyolefin (A) and the styrene-based elastomer (B) is preferably 99% by weight to 1% by weight to 90% by weight, and more preferably 10% by weight. Is 99% by weight: 1% by weight to 95% by weight: 5% by weight. Further, the difference between the refractive indexes at room temperature must be within 0.03, more preferably within 0.02, and more preferably within 0.01. Further, amorphous polyolefin (A) and styrene-based elastomer (B)
Is melted and kneaded with, for example, a biaxial kneader to finely disperse the styrene-based elastomer (B) in the amorphous polyolefin (A), thereby further improving transparency and impact resistance. Preferably, a very good polymer alloy sheet can be obtained by setting the dispersed particle size to 0.3 μm or less, which is the limit that can be visually confirmed (that is, the wavelength of visible light).

In the present invention, the polypropylene resin layer (C) contains a propylene homopolymer and ethylene-
Appropriate propylene copolymers or blends thereof are used. Further, an appropriate amount of a crystal nucleating agent, a petroleum resin or the like may be added. When the lamination method is dry lamination or the like, a film or sheet generally produced from these resins, which is not stretched, is preferable.

When the polyvinylidene chloride resin layer (D) in the present invention is laminated by co-extrusion, 60 to 97 parts by weight of vinylidene chloride and unsaturated monomer such as vinyl chloride, alkyl acrylate, acrylic acid and acrylonitrile are used. And a blend of known plasticizers and stabilizers, if necessary. In the case of lamination by coating, an aqueous dispersion obtained by emulsifying and copolymerizing vinylidene chloride as a main component, methacrylic acid, acrylonitrile and / or methyl methacrylate is coated by an air knife coating method, a gravure coating method, or the like. A method of applying by a roll coating method or the like is used. The kind of the emulsifier, the polymerization initiator, the surfactant and the like used in the preparation of the aqueous dispersion of polyvinylidene chloride is not particularly limited. However, if a large amount remains in the dried coating film, the barrier property is reduced. Therefore, it is preferable that the amount used is as small as possible, and it is preferable to remove as much as possible by performing a dialysis treatment following the emulsion polymerization. Alternatively, a method in which a copolymer of vinylidene chloride and acrylonitrile or the like is dissolved in a solvent such as methyl ethyl ketone or tetrahydrofuran to form a coating film in the same manner as described above is also used. Further, a method of laminating a film made of polyvinylidene chloride resin by a method such as dry lamination is also used.

If necessary, additives such as dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants and fillers may be added to each resin layer as long as the basic properties are not impaired. Etc. can also be added. The overall thickness of the sheet of the present invention is not particularly limited,
0.5 mm, particularly 0.25 to 0.40 mm
Is suitable as the thickness of the PTP packaging material. Although the thickness of each layer is not particularly limited, the thickness of the intermediate layer formed by mixing the amorphous polyolefin (A) and the styrene-based elastomer (B) and the thickness of the oxygen gas barrier layer formed of the polyvinylidene chloride resin (D) about,
It is necessary to design the required thickness according to the required moisture-proof property and gas barrier property. In addition, polypropylene resin (C)
0.005 to 0.03 m for the thickness of the outer layer made of
m is appropriate. If the thickness is smaller than this, the mechanical suitability of the PTP molding machine is deteriorated. If the thickness is larger, the thickness of the intermediate layer and the oxygen gas barrier layer is reduced, and the required moisture proof property and gas barrier property may not be obtained. .

[0019]

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. In the examples and comparative examples, the components of the amorphous polyolefin (A) and the styrene-based elastomer (B) used for compounding to obtain the polymer alloy resin are shown below. [Amorphous polyolefin (A)] APO APL-6509T [manufactured by Mitsui Petrochemical Industries, Ltd .; nD =
1.5353] [Styrene-based elastomer (B)] SEPS Septon 2104 [manufactured by Kuraray Co., Ltd .; nD = 1.544]
5] SEPS Septon 2002 [manufactured by Kuraray Co., Ltd .; nD = 1.505]
4] SEBS Tuftec H1041 [manufactured by Asahi Kasei Corporation; nD = 1.
5011] SEBS Tuftec H1071 [manufactured by Asahi Kasei Corporation; nD = 1.
4958] S-1; nD = 1.331 Septon 2104 [manufactured by Kuraray Co., Ltd .; nD = 1.544]
5] and Septon 2002 [manufactured by Kuraray Co., Ltd .; nD = 1.5
054] was mixed at 76% by weight: 24% by weight, melt-kneaded with a twin-screw kneader, and substantially completely compatible were pelletized to produce a novel elastomer. -S-2; nD = 1.5300 Septon 2104 [manufactured by Kuraray Co., Ltd .; nD = 1.544
5] and Tuftec H1041 [manufactured by Asahi Kasei Corporation; nD
= 1.5011] was mixed at 80% by weight: 20% by weight, melt-kneaded by a twin-screw kneader, and substantially completely compatible were pelletized to produce a novel elastomer. -S-3; nD = 1.4958 Septon 2002 [manufactured by Kuraray Co., Ltd .; nD = 1.505
4] and Tuftec H1071 [manufactured by Asahi Kasei Corporation; nD
= 1.4958] in a ratio of 50% by weight: 50% by weight, melt-kneaded with a twin-screw kneader, and substantially completely compatible to form a pellet to produce a novel elastomer.

(Examples 1 to 6, and Comparative Examples 1 to 3) All components were dry-blended sufficiently at the compounding ratios shown in Table 1, melt-kneaded by a twin-screw kneader, pelletized, and then subjected to T-die. 0.2 to be an intermediate layer by extrusion
A sheet having a thickness of 25 mm was prepared. Regarding the refractive index in the table, the refractive index at 23 ° C. in a sheet state was measured by a digital refractometer RX-2000 [manufactured by Atago Co., Ltd.].

Table 1 Example Comparative Example 1 2 3 4 5 6 1 2 3 Blended (parts by weight) APO 95.0 95.0 98.5 95.0 81.0 95.0 100 95.0 95.0 SEPS 5.0 SEPS 5.0 SEBS 5.0 S-1 1.5 5.0 19.0 S-2 5.0 S-3 5.0 Refraction Rate difference (× 10 ^-2 ) 0.92 2.99 0.22 0.22 0.22 0.53 − 3.95 3.52

Polyvinylidene chloride (hereinafter abbreviated as PVDC) is applied to the corona-treated surface of an unstretched polypropylene (hereinafter abbreviated as CPP) film [CP unstretched polypropylene film EC manufactured by Tocelo Co., Ltd., 0.02 mm thick].
An aqueous dispersion of resin [Saran Latex L-509 manufactured by Asahi Kasei Kogyo Co., Ltd.]
It was applied to a thickness of 15 mm. After corona discharge treatment on both sides of the sheet as the intermediate layer, the P
A urethane-based adhesive [Dick Dry LX-75A / KW40 / manufactured by Dainippon Ink and Chemicals, Inc.]
Ethyl acetate compounding ratio 10: 1: 10.8]
The laminate was laminated on the intermediate layer by a dry laminating method to prepare a multilayer sheet having a total thickness of 0.3 mm and a CPP / PVDC / amorphous polyolefin-based intermediate layer / PVDC / CPP layer structure.

Example 7 As a method for applying a PVDC resin, Saran Resin F-216 manufactured by Asahi Kasei Kogyo Co., Ltd. was diluted with a solvent (tetrahydrofuran: methyl ethyl ketone = 75: 25% by weight) to a resin concentration of 20% by weight. Except for using the CP, a CP
P / PVDC / Amorphous polyolefin intermediate layer / PVD
A multilayer sheet having a C / CPP layer configuration was produced. (Example 8) A CPP film [CP unstretched polypropylene film manufactured by Tosero Co., Ltd., EC thickness 0.02 mm] and a PVDC film [Saran-UB thickness 0.015 mm manufactured by Asahi Kasei Kogyo Co., Ltd.] are bonded to a urethane-based adhesive [Dainippon] Dick Dry LX-75A / KW4 manufactured by Ink Chemical Industry Co., Ltd.
0 / ethyl acetate compounding ratio 10: 1: 10.8] by dry lamination. Apply the same urethane adhesive as above to the PVDC surface of this film,
It was laminated on the corona-treated surface of the intermediate layer having the same composition as in Example 4 to prepare a multilayer sheet having a total thickness of 0.3 mm and a layer configuration of CPP / PVDC / amorphous polyolefin-based intermediate layer / PVDC / CPP.

(Example 9) A 0.3 mm thick multilayer sheet having a layer structure of outer layer / adhesive layer / oxygen gas barrier layer / adhesive layer / intermediate layer / adhesive layer / oxygen gas barrier layer / adhesive layer / outer layer was co-extruded. It was produced by the method. The thickness of each layer is
20/3/15/3/218/3/315/3/20 μm
And The following resin materials were used for forming each layer. -Outer layer Polypropylene resin [Mitsui Polypro JHH-G manufactured by Mitsui Toatsu Chemicals, Inc.]-Intermediate layer Polymer alloy material of the same material and composition as in Example 4-Oxygen gas barrier layer PVDC resin (vinylidene chloride 92% by weight and acrylic (Copolymer of 8% by weight of acid) Adhesive layer APL-6509T, Septon 2104 and Septon 20
02 and melt-kneaded at a ratio of 50:38:12 ・ Adhesive layer Acid-modified polypropylene resin [Admer QF-500 manufactured by Mitsui Petrochemical Co., Ltd.]

(Comparative Example 4) A polymer alloy material having the same material and the same composition as in Example 4 was melt-extruded from a T-die to 0.3 m.
A single-layer sheet having a thickness of m was prepared. (Comparative Example 5) A single-layer sheet (0.2) obtained by melt-extruding a polymer alloy material having the same material and the same composition as in Example 4 from a T-die.
55 mm) as an intermediate layer, the same CPP film as in Example 1 was used as an outer layer, and a multilayer sheet having a total layer thickness of 0.3 mm having an outer layer / intermediate layer / outer layer structure was dry-laminated in the same manner as in Example 1. Produced by

The sheets of Examples 1 to 9 and Comparative Examples 1 to 5 were evaluated by the following methods. (Light transmittance and HAZE) Measured according to ASTM-D1003. (Moisture resistance) Measured under condition B, that is, at a temperature of 40 ° C. and a relative humidity of 90% based on JIS-Z0208. (Oxygen permeability) It was measured by the B method (isobaric method) based on JIS-K-7126. (Tensile test) Measured according to ASTM-D638. (Appearance) Judged visually. (Oil resistance) A 5 mm square sheet was immersed in n-heptane and evaluated for changes in appearance (swelling, etc.), degree of softening, changes in transparency, etc., after standing at 23 ° C. for 3 days. ○,
The changed thing was evaluated as x. (Stress crack resistance) Sheet 1 is 40mm x 15mm
And set it in an arch shape on a U-shaped jig shown in Fig. 1, and put “sebum” on the top of the arch (marked with ▼).
Was applied, and changes in the sheet were visually observed. The sample having no change was marked with "O", and the sample with cracks was marked with "X". (DuPont Impact Test) Measured at 23 ° C. and −20 ° C. by a method according to JIS-K-7211. The above evaluation results are shown in Tables 2 and 3.

Table 2 Example 1 2 3 4 5 6 7 Light transmittance (%) 89 87 90 90 90 89 89 HAZE (%) 7 8 5 6 6 6 6 Moisture permeability (g / m ² · 24Hr · 0.3 mm) 0.24 0.25 0.22 0.24 0.27 0.25 0.24 Oxygen permeability (cm ³ / m ² · 24Hr · atm) 1.3 1.2 1.3 1.3 1.2 1.2 1.4 Tensile strength MD 4.6 4.4 4.8 4.8 4.3 4.7 4.9 (kgf / cm ² ) TD 4.6 4.5 4.7 4.9 4.3 4.8 4.8 ○ ○ ○ ○ ○ ○ ○ Oil resistance ○ ○ ○ ○ ○ ○ ○ Stress crack resistance ○ ○ ○ ○ ○ ○ ○ Dupont impact value 23 ℃ 26 35 17 25 40 26 27 (kgf ・ cm) -20 ℃ 6 10 4 7 10 8 7

Table 3 Example comparisons Example 8 9 1 2 3 4 5 light transmittance (%) 90 90 91 86 87 92 92 HAZE (%) 6 6 3 18 14 4 4 Moisture Permeability ^{(g / m 2 · 24Hr /} 0.3mm) 0.26 0.26 0.22 0.26 0.26 0.27 0.32 Oxygen permeability (cm ³ / m ² · 24Hr · atm) 1.3 1.4 1.3 1.3 1.4 95 84 Tensile strength MD 4.8 4.9 4.7 4.6 4.5 4.8 4.8 (kgf / cm ² ) TD 4.8 4.8 4.7 4.5 4.5 5.1 5.0 Appearance ○ ○ ○ ○ ○ ○ ○ Oil resistance ○ ○ ○ ○ ○ × ○ Stress cracking ○ ○ ○ ○ ○ × ○ Dupont impact value 23 ℃ 28 27 5 28 42 12 30 (kgf ・ cm) -20 ℃ 8 7 2 10 12 6 6

[0029]

The multilayer sheet according to the present invention can be easily processed into a sheet or the like by a processing method used for an ordinary thermoplastic sheet, for example, extrusion molding, dry lamination, etc., and has moisture-proof properties, transparency, rigidity, and the like. Scratch resistance, impact resistance,
The balance of physical properties such as chemical resistance and water resistance is extremely good, and the appearance and moldability of the film, sheet, etc. during molding processing are excellent, and the oil resistance is good and there is no problem such as stress crack due to sebum, etc. It is also a novel multilayer sheet with excellent oxygen gas barrier properties, and is most suitable for chemical packaging.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a method for measuring stress crack resistance when a sheet is set in a U-shaped jig in an arch shape.

Claims (6)

(57) [Claims] 1. A difference in refractive index of each at room temperature is within 0.03, intermediate layer formed by blending an amorphous polyolefin (A) and the styrene elastomer (B), polyps Ropi <br / > An outer layer made of ren (C) and an oxygen gas barrier layer made of polyvinylidene chloride resin (D) are formed by an outer layer / oxygen gas barrier layer / intermediate layer / oxygen gas barrier layer / outer layer or outer layer / oxygen gas barrier layer / intermediate A multilayer sheet for packaging medicine, characterized by being laminated in the order of layer / outer layer. 2. The compounding ratio of the amorphous polyolefin (A) and the styrene-based elastomer (B) is 99% by weight: 1.
The multi-layer sheet for chemical packaging according to claim 1, wherein the content is from 20% by weight to 80% by weight. 3. An amorphous polyolefin (A) comprising: an addition product of cyclopentadiene or a derivative thereof and norbornadiene or a derivative thereof; and one or more unsaturated monomers selected from ethylene, butadiene, and styrene derivatives. The multilayer sheet for chemical packaging according to claim 1 or 2, which is a copolymer with a body or a hydrogenated product thereof. 4. An amorphous polyolefin (A) comprising: an addition reaction product of dicyclopentadiene or a derivative thereof with ethylene; and one or more unsaturated monomers selected from ethylene, butadiene, and styrene derivatives. The multilayer sheet for chemical packaging according to claim 1 or 2, which is a copolymer of the above. 5. The amorphous polyolefin (A) is a hydrogenated product of a ring-opened polymer composed of tetracyclo-3-dodecene or a derivative thereof and bicyclohept-2-ene or a derivative thereof. 3. The multilayer sheet for chemical packaging according to 1 or 2. 6. The styrene elastomer (B) is a butadiene-styrene copolymer (random copolymer, block copolymer, graft copolymer) and a hydrogenated product thereof, a styrene-butadiene-styrene copolymer ( SBS), hydrogenated styrene-butadiene-styrene copolymer (SEB)
S), isoprene-styrene copolymer, hydrogenated styrene-
Amorphous polyolefin (A) is formed by two or more elastomers selected from isoprene copolymer (SEP), styrene-isoprene-styrene copolymer (SIS), and hydrogenated styrene-isoprene-styrene copolymer (SEPS). 3. The multilayer sheet for chemical packaging according to claim 1, wherein the multilayer sheet is prepared to have a refractive index equivalent to that of (1).