JPH06305101A - Multilayer polymer alloy sheet for high moistureproof medicine packaging - Google Patents

Abstract

PURPOSE:To provide a multilayer polymer alloy sheet for high moistureproof medicine packaging which has eminently balanced properties and a good appearance and moldability in processing by laminating polymer alloy layers in which the outer and inner layers have a higher compounding ratio of high density polyethylene than the intermediate layer. CONSTITUTION:In a multilayer polymer alloy sheet for high moistureproof medicine packaging, the outer, intermediate, and inner layers are made of a polymer alloy in which amorphous polyolefin with a heat distortion temperature of 100 deg.C or less and high density polyethylene are compounded. The outer and inner layers have a higher compounding ratio of high density olyethylene than the intermediate layer, and the three layers are laminated. The refractive indices of the outer and inner layers are the same; the refractive index of the intermediate layer is close to those of the outer and inner layers. Since two types of polyolefin are combined, the polymers of three layers have good compatibility. The laminated sheet has a good balance in properties such as processability, rigidity, scratch resistance, impact resistance, moisture proof, transparency, oil resistance, and chemical resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer alloy multilayer sheet for packaging highly moisture-proof chemicals which can be used as a sheet or a film by extrusion molding or the like. More specifically, it is obtained by laminating a polymer alloy having a different ratio of a specific amorphous polyolefin and a specific high-density polyethylene having excellent compatibility with the outer layer, the inner layer, and the intermediate layer, the balance of physical properties and appearance, moldability, The present invention relates to a novel polymer alloy multilayer sheet for packaging highly moisture-proof chemicals, which is excellent in moisture resistance, transparency, impact resistance, oil resistance, and chemical resistance.

[0002]

2. Description of the Related Art Amorphous polyolefin has excellent properties such as transparency, moisture resistance, electrical properties, mechanical strength, moldability and dimensional stability, but it is extremely brittle and is manufactured by extrusion molding or the like. The sheet or film described above lacks impact resistance in practical use, and it is desired that the sheet or film be toughened without impairing the characteristics of the amorphous polyolefin. Further, the amorphous polyolefin has poor oil resistance because it is amorphous, and needs to be improved for use in applications such as foods requiring oil resistance. To improve these drawbacks, JP-A-4-272937 discloses a method of forming a composite sheet in which a crystalline polymer and a hydride of a ring-opening polymer of dicyclopentadiene having a high glass transition point are combined. However, although the composite sheet of the present invention is excellent in impact resistance, it is a sheet rich in crystalline resin having poor moldability and poor moisture resistance, and
A hydride of a ring-opening polymer of dicyclopentadiene, which is difficult to form and has a high glass transition point, was combined, and it was difficult to use as a highly moisture-proof chemicals packaging sheet. or,
In the polymer alloy composite sheet of the amorphous polyolefin (A) and the high density polyethylene (B), the high density polyethylene is used, so that the transparency and the moisture resistance are insufficient.

[0003]

According to the present invention, the outer layer, the inner layer and the intermediate layer are formed by laminating a polymer alloy in which an amorphous polyolefin having a heat distortion temperature of 100 ° C. or less and a high density polyethylene are mixed in different ratios. Workability, rigidity, scratch resistance, impact resistance, oil resistance, chemical resistance, water resistance,
It is an object of the present invention to provide a novel polymer alloy multilayer sheet for packaging highly moisture-proof chemicals, which has an extremely good balance of physical properties such as moisture resistance and transparency, and which has excellent appearance and moldability during molding processing of films, sheets and the like. It is a thing.

[0004]

The present invention provides a polymer alloy in which an outer layer, an inner layer, and an intermediate layer are blended with amorphous polyolefin (A) having a heat distortion temperature of 100 ° C. or less and high-density polyethylene (B) in different ratios. It relates to a polymer alloy multilayer sheet for packaging highly moisture-proof chemicals, characterized in that the outer layer and the inner layer have a blending ratio of the amorphous polyolefin (A) and the high-density polyethylene (B) of 70% by weight. %: 30% by weight to 40% by weight: 60% by weight, and the compounding ratio of the amorphous polyolefin (A) and the high-density polyethylene (B) in the intermediate layer is 95% by weight: 5% by weight to 7%
0% by weight: 30% by weight, the density of the high-density polyethylene (B) is 0.940 or more, and the amorphous polyolefin (A) is hydrogen of a copolymer of dicyclopentadiene and ethylene and / or butadiene. It is a polymer alloy multilayer sheet for packaging highly moisture-proof chemicals as an additive.

In general, the polymer alloys of the outer layer, the inner layer and the intermediate layer should be selected such that each resin has almost the same refractive index in order to obtain good transparency when two or more resins are combined. It is conceivable to disperse the particle size microscopically. In the case of the present invention, as the resin for the outer layer and the resin for the inner layer, two kinds of resins having almost the same refractive index and good moisture resistance, oil resistance, chemical resistance, and excellent compatibility as they are the same polyolefin resin are used. As a resin for the intermediate layer, a polymer alloy combining two types of resins, which have almost the same refractive index, good moisture resistance, transparency, and moldability, and also have excellent compatibility due to the same polyolefin resin. Only by laminating them, the balance of physical properties such as moldability, rigidity, scratch resistance, impact resistance, moisture resistance, transparency, oil resistance, chemical resistance, etc. is very good, and the film, sheet etc. It was found that a novel polymer alloy multilayer sheet for packaging highly moisture-proof chemicals having excellent appearance and moldability was obtained, and the present invention was completed. The amorphous polyolefin (A) having a heat distortion temperature of 100 ° C. or lower used in the present invention is a polymer having a cyclic olefin structure, and can be said to be an amorphous polyolefin due to its structure and properties. Examples of the amorphous polyolefin having a heat distortion temperature of 100 ° C. or lower include the following. For example, there is a ring-opening polymer of dicyclopentadiene represented by the general formula (1) or a hydrogenated product thereof, and this ring-opening polymer uses dicyclopentadiene or a derivative thereof as a monomer,
It can be produced by a known ring-opening polymerization method of a cyclic olefin. Further, the hydrogenated product of this ring-opening polymer can also be obtained by utilizing a usual hydrogenation reaction method. In the case of the present invention, the polymer may be used alone, but a copolymer of dicyclopentadiene and ethylene or butadiene is more preferable.

[0006]

[Chemical 1]

Further, at least one compound selected from the group consisting of unsaturated monomers represented by the general formula (2) or the general formula (3) can be given. These are easily manufactured by condensing cyclopentadiene and corresponding olefins, and cyclic olefins by the Diels-Alder reaction. (In the formula, n and m are both 0 or a positive integer, l is an integer of 3 or more, and R ₁ to R ₁₀ each represent a hydrogen atom, a halogen atom or a carbon-hydrogen group.) And also General formula (4)
(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
Represents a C _{1 to} C ₂₀ hydrocarbon group. ) And (5) (R ₃
To R ₆ are hydrogen atoms or C composed of R ₃ and R _4.
Shows an alkylidene group having ₁ -C _10. ), A ring-opening polymer of a tetracyclododecene derivative or a hydrogenated product thereof. Further, norbornadiene and the general formula (6) (in the formula, R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom). It is a copolymer with the styrene derivative represented.

[0008]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

As the norbornadiene as described above,
Unsubstituted norbornadiene or substituted norbornadiene is used. Specifically, the following norbornadiene compounds are used. Norbornadiene, 5-methylnorbornadiene, 5-ethylnorbornadiene, 5-
Phenylnorbornadiene, 1- (or 4-, or 7-) methylnorbornadiene, 1- (or 2-, or 3-, 4-, or 7-) dimethylnorbornadiene. Examples of the styrene derivative include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-ethylstyrene and m. -Ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like are used. In addition, these can also be used as a mixture of 2 or more types.

The high density polyethylene (B) used in the present invention has a density of 0.94 to 0.98 (g / ml), and among them, 0.96 to 0.98 (g / ml) is preferably used.
Further, the water vapor permeability is 1.0 (g / m ² · 24 hr / 0.1 mm) or less, and a low one is preferably used. Regarding the refractive index, those having similar refractive indices are preferably used depending on the amorphous polyolefin to be combined. In the outer layer and the inner layer of the polymer alloy multilayer sheet for highly moisture-proof chemical packaging according to the present invention,
70-40% by weight, preferably 55-45% by weight, of the amorphous polyolefin (A) having a heat distortion temperature of 100 ° C. or less,
High-density polyethylene (B) must be blended in the range of 30 to 60% by weight, preferably 45 to 55% by weight.
Further, in the intermediate layer, the amorphous polyolefin (A) having a heat distortion temperature of 100 ° C. or less is 95 to 65% by weight, preferably 85 to 75% by weight, and the high density polyethylene (B) is 5 to 35%.
It should be blended in an amount of preferably 15 to 25% by weight. Further, if necessary, a compatibilizer, an additive such as a dye / pigment, a stabilizer, etc. within a range that does not impair the basic properties.
A plasticizer, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a filler, an elastomer for imparting flexibility, and the like can also be added. The method for producing the polymer alloy multilayer sheet for highly moisture-proof chemical packaging according to the present invention is not particularly specified, but a laminated sheet is produced by a coextrusion method, an extrusion laminating method, a dry laminating method or the like, and a vacuum forming method or a pressure forming method is used. It can be molded by a molding method such as a molding method.

[0011]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. A 0.30 mm T-die sheet was used for measuring the sheet characteristics, and the light transmittance and the HAZE were A
According to STM-D1003, the water vapor transmission rate is JIS-Z020
Condition A based on No. 8, temperature 40 ℃, relative humidity 90%
And the appearance was visually evaluated. For oil resistance, a sheet of 5 mm square and a thickness of about 300 μ
-Evaluation for appearance change (swelling, etc.), degree of softening, change in transparency, etc. after immersion in heptane and leaving at 23 ° C for 3 days,
The thing which did not change was made into ◯, the thing which changed a little was made into Δ, and the thing changed was shown as x. The DuPont 50% breaking impact test is JIS-
Based on K5400, ie tip R = 1/4 inch, 30
It is the result of measuring the drop height at which the breakage of the sheet is 50% from the result of dropping 20 times by changing the drop height of the 0 g weight into steps of 5 cm and dropping the sheet. The results of each characteristic value are shown in Table 1.

As the component (A), Apel APL650
9 [APO; heat distortion temperature 72 ° C (ASTM D648
18.6 Kg / cm ² ) manufactured by Mitsui Petrochemical Co., Ltd.] is used as the component (B).
080 V [HDPE; density 0.961 g / cm ³ (JI
SK6760) manufactured by Showa Denko KK] was used. Example 1 Outer layer = 10 μ / middle layer = 280 μ / inner layer = 10 μm in total 3
In the case of a laminated body of 00μ, the compounding ratio of the outer layer and the inner layer is (A) component 5
0% by weight, 50% by weight of the component (B), and 80% by weight of the component (A) and 20% by weight of the component (B) were used as the compounding ratio of the intermediate layer. Example 2 Outer layer = 10 μm / middle layer = 280 μ / inner layer = 10 μm in total 3
In the case of a laminated body of 00 μ, the compounding ratio of the outer layer and the inner layer is the same as in Example 1, and the compounding ratio of the intermediate layer is 60% by weight of the component (A),
The component (B) used was 40% by weight. (Example 3) Outer layer = 10 μ / middle layer = 280 μ / inner layer = 10 μm in total 3
In the case of a laminated body of 00 μ, the compounding ratio of the outer layer and the inner layer is (A) component 7
0% by weight, 30% by weight of the component (B), and the compounding ratio of the intermediate layer were the same as those in Example 1. Example 4 Outer layer = 10 μ / middle layer = 280 μ / inner layer = 10 μm in total 3
In the case of a laminated body of 00 μ, the compounding ratios of the outer layer and the inner layer were the same as in Example 3, and the compounding ratio of the intermediate layer was the same as in Example 2.

(Comparative Example) As the component (A), APEL AP
L6509 [APO; manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used. As the component (B), Ace Polyethylene HD F6
080 V [HDPE; density 0.961 g / cm ³ (JI
SK6760) manufactured by Showa Denko KK] was used. (Comparative Example 1) Component (A) 300μ single layer sheet (Comparative Example 2) Component (A) 70% by weight, component (B) 30% by weight 300μ polymer alloy single layer sheet (Comparative Example 3) (A) component 50 %, Component (B) 50% by Weight 300μ Polymer Alloy Alloy Single Layer Sheet

[0014]

[0015]

EFFECTS OF THE INVENTION The polymer alloy multilayer sheet for packaging highly moisture-proof chemicals according to the present invention is easily processed into a film, a sheet, etc. by a processing method used for a usual thermoplastic sheet, for example, extrusion molding. The balance of physical properties such as properties, rigidity, scratch resistance, impact resistance, oil resistance, chemical resistance, water resistance, transparency, and moisture resistance is extremely good, and the appearance of films and sheets during molding is excellent. Give the product.

Claims (4)

[Claims] 1. The outer layer, the inner layer and the intermediate layer have a heat distortion temperature of 1.
Consisting of a polymer alloy in which an amorphous polyolefin (A) at a temperature of 00 ° C. or lower and a high-density polyethylene (B) are blended,
A polymer alloy multi-layer sheet for highly moisture-proof chemical packaging, characterized in that the outer layer and the inner layer are laminated with a polymer alloy having a higher blending ratio of high-density polyethylene than that of the intermediate layer. 2. The outer layer and the inner layer have a blending ratio of the amorphous polyolefin (A) and the high-density polyethylene (B) of 70% by weight: 30% by weight to 40% by weight: 60% by weight, and the intermediate layer is amorphous. The polymer alloy multilayer for highly moisture-proof chemical packaging according to claim 1, wherein the compounding ratio of the water-soluble polyolefin (A) and the high-density polyethylene (B) is 95% by weight: 5% by weight to 70% by weight: 30% by weight. Sheet. 3. The high density polyethylene (B) has a density of 0.9.
40 or more, The polymer alloy multilayer sheet for highly moisture-proof chemical | medical agent packaging of Claim 1 or 2 characterized by the above-mentioned. 4. The highly moisture-proof chemical packaging according to claim 1, 2 or 3, wherein the amorphous polyolefin (A) is a hydrogenated product of a copolymer of dicyclopentadiene and ethylene and / or butadiene. Polymer alloy multilayer sheet.