JP3004499B2 - High moisture proof sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet which is rolled and formed by a calendering method, and relates to a novel highly moisture-proof sheet for chemical packaging or food packaging. More specifically, it is a sheet made of a resin composition obtained by combining a specific amorphous polyolefin excellent in compatibility and a specific high-density polyethylene, and the resin composition further adheres to a calender roll and mixes air bubbles in the sheet. ,
The present invention relates to a novel highly moisture-proof sheet for chemical packaging or food packaging, which has no calendar surface stains, has good calendar processing, and is excellent in appearance, moisture resistance, transparency, and impact resistance of the produced sheet.

[0002]

2. Description of the Related Art Amorphous polyolefins have excellent transparency and moisture-proof properties. However, in a calendering method having high industrial productivity, adhesion to calender rolls during roll-forming film, There is a problem with the inclusion of air bubbles in the sheet, and the physical properties are low in impact resistance, so that it has not reached a practical level. It has been desired to solve these problems without impairing the properties of the amorphous polyolefin.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyolefin having excellent impact resistance, excellent appearance and good calendering without impairing the excellent transparency and moisture-proof properties of an amorphous polyolefin. An object of the present invention is to provide a highly moisture-proof sheet for packaging medicine or food obtained from a novel resin composition.

[0004]

According to the present invention, a compounding ratio of an amorphous olefin (A) having a heat distortion temperature of 100 ° C. or less and a high-density polyethylene (B) is 95% by weight: 5% by weight to 70% by weight.
% By weight: A resin composition containing 0.05 to 4.0 parts by weight of a fatty acid ester lubricant and 0.05 to 3.0 parts by weight of a fatty acid lubricant with respect to 100 parts by weight of a resin which is 30% by weight. It is a highly moisture-proof sheet roll-formed by a calendering method. In general, in order to obtain a resin having good transparency when two or more resins are combined, it is conceivable to select resins having almost the same refractive index and to disperse the dispersed particle diameter microscopically. In the case of the present invention, as the resin, the refractive index is almost the same and the moisture resistance is good, and two kinds of resins which are excellent in compatibility because of the same polyolefin resin are combined, and the heat deformation temperature which is excellent in the moisture resistance is 100. Only when the non-crystalline polyolefin (A) having a temperature of not more than ℃ is used as the sea component and the high density polyethylene (B) as the island component is finely dispersed, the impact resistance, moisture resistance and transparency are extremely good and the sheet By mixing two kinds of lubricants having different lubricating effects of fatty acid ester lubricant and fatty acid lubricant without mixing of air bubbles and excellent appearance, adhesion to calender rolls when rolled and formed by calendering method It has been found that a novel highly moisture-proof sheet for drug packaging or food packaging having good calendering processability with no stain on the calender roll surface can be obtained and complete the present invention. And it has reached.

In the present invention, the heat distortion temperature used is 100
The non-crystalline polyolefin (A) having a temperature of not more than ° C is a polymer having a cyclic olefin structure, and can be said to be a non-crystalline polyolefin from its structure and properties. If the heat deformation temperature of the component (A) is higher than 100 ° C., favorable properties in terms of moisture permeability cannot be obtained. Examples of the amorphous polyolefin having a heat distortion temperature of 100 ° C. or lower include the following. For example, a ring-opened polymer of dicyclopentadiene represented by the general formula (1) or a hydrogenated product thereof.

Embedded image This ring-opened polymer can be produced by a known ring-opening polymerization method of a cyclic olefin using dicyclopentadiene as a monomer. The hydrogenated product of the ring-opened polymer can also be obtained by using a usual hydrogenation reaction method. In the case of the present invention, a polymer alone may be used, but a copolymer of dicyclopentadiene and ethylene or butadiene is more preferable.

[0006] Further, at least one compound selected from the group consisting of unsaturated monomers represented by the general formula (2) or (3) is also included. These are easily produced by condensing cyclopentadiene with the corresponding olefin and cyclic olefin by a Diels-Alder reaction.

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Embedded image (In the formula, n and m are each 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 hydrocarbon group.)

[0007] and the general formula (4) (wherein, R1 represents a hydrogen atom or a methyl group, R2 is a hydrocarbon group of C ₁ -C _20.) And the general formula (5) (R ₃ ~ R ₆ represents a hydrogen atom or a C ₁ -C ₁₀ alkylidene group composed of R ₃ and R _4. ), A ring-opened polymer of a tetracyclododecene derivative or a hydrogenated product thereof. Can be
And a norbornadiene and a general formula (6) (wherein R ₁ and R ₂ 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 represented styrene derivative.

[0008]

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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-, or 4-, or 7-) dimethylnorbornadiene. Examples of the styrene derivatives include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-ethylstyrene, m-methylstyrene -Ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like are used. These can be used as a mixture of two or more kinds.

The high-density polyethylene (B) used in the present invention has a density of 0.94 to 0.98 (g / ml), among which 0.96 to 0.98 having a low moisture permeability.
(G / ml) is preferably used in a highly moisture-proof sheet. Fatty acid ester lubricant used in the present invention,
It is a compound formed by an ester bond between a long-chain fatty acid and an alcohol. Fatty acids include long-chain saturated and unsaturated monocarboxylic acids, dicarboxylic acids, and oxycarboxylic acids.As alcohols, monohydric alcohols such as butanol and octanol, ethylene glycol, glycerin,
There are polyhydric alcohols such as pentaerythritol and sorbitol, and many fatty acid esters are formed by a combination of an alcohol and an acid, but the combination is not particularly limited. The fatty acid lubricant used in the present invention is a long-chain saturated fatty acid, but does not particularly limit the number of long-chain carbon atoms. When the melting points of the fatty acid ester and the fatty acid lubricant used in the present invention are too low, workability is difficult.
C. to 70.degree. C. are preferably used.

In the highly moisture-proof sheet according to the present invention, the amorphous polyolefin (A) 7 having a heat distortion temperature of 100 ° C. or less
0 to 95% by weight, 5% by weight of high density polyethylene (B)
With respect to 100 parts by weight of the resin composed of 30% by weight, 0.05 to 4.0 parts by weight of the fatty acid ester lubricant and 0.0
It must be blended in the range of 5 to 3.0 parts by weight.
When the content of the component (A) is less than 70% by weight, transparency and moisture resistance are not sufficient, and when the content is more than 95% by weight,
Preferable properties in impact resistance cannot be obtained, and bubbles are mixed in the sheet during calendering. If the fatty acid ester lubricant is not added in an amount of 0.05 parts by weight or more to reduce the adhesive strength of the calendar roll, it is difficult to carry out calendering. If it is more than 4.0 parts by weight, the surface of the calendar roll becomes dirty. In addition, the surface properties of the sheet are impaired. The fatty acid lubricant has a calender roll cleaning effect, and if the amount is less than 0.05 parts by weight, the surface of the calender roll cannot be stained and the sheet surface property is impaired.
If the amount is more than 0 parts by weight, the surface of the calender roll is stained by the fatty acid lubricant, and the surface property of the sheet is impaired. The highly moisture-proof sheet according to the present invention is easily processed into a film, a sheet or the like by rolling and forming a film by a calendering method used for a normal thermoplastic resin sheet.

[0012]

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. Note that a 0.25 mm-thick sheet rolled and formed by an inverted L-type four calender was used for the characteristic measurement, the light transmittance and the haze were JIS-K-6714, and the humidity proof was JIS-Z0208. , That is, a measurement value at a temperature of 25 ° C. and a relative humidity of 90%. Also, 50
The% breaking energy is a result measured according to JIS-K-7211. Table 1 shows the results of the composition and each characteristic value of the example, and Table 2 shows the results of the composition and each characteristic value of the comparative example. (Examples 1 to 3) As the component (A), Apel APL6509 [APO
A heat distortion temperature of 72 ° C. (ASTM D648 18.6)
Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.]
As the component (B), Ace Poly HDF6080V
[HDPE; density 0.961 g / cm ³ (JIS K6
760) Showa Denko Co., Ltd.], Kaowax 220 [Kao Co., Ltd.] as a fatty acid ester lubricant, and stearic acid 250 [Shin Nippon Rika Co., Ltd.] as a fatty acid lubricant.
It was used.

(Comparative Examples 1 to 4) As the component (A), Apel APL6509 [APO;
STM D648 18.6 Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.], and as component (B), acepolyethylene HDF6080V [HDPE; density 0.961
g / cm ³ (JIS K6760, manufactured by Showa Denko KK) and Kaowax 2 as a fatty acid ester lubricant.
20 [Kao Corporation] Stearic acid 2 as fatty acid lubricant
50 [manufactured by Shin Nippon Rika Co., Ltd.] was used. (Comparative Example 5) As the component (A), Apel APL651 was used.
5 [APO; heat deformation temperature 125 ° C (ASTM D64
8 18.6 Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.
Ace Polyethylene HDF
6080 V [HDPE; density 0.961 g / cm ³ (J
IS K6760) manufactured by Showa Denko K.K., and as a fatty acid ester lubricant, Kaowax 220 [Kao
Co., Ltd.], and stearic acid 250 [manufactured by Shin Nippon Rika Co., Ltd.] was used as a fatty acid lubricant.

[0014]

[0015]

[0016]

The high moisture-proof sheet according to the present invention can be easily processed into a film, a sheet, etc. by rolling a specific resin composition by a calendering method used for a normal thermoplastic sheet. This gives a product with extremely good physical properties such as impact resistance, transparency and moisture resistance.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI // (C08L 65/00 23:06) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 65/00- 65/04 C08L 23/00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. An annular olefin having a heat distortion temperature of 100 ° C. or less.
95% by weight: 5% by weight to 70% by weight of the amorphous olefin (A) having a rubber structure and the high-density polyethylene (B).
% By weight: A resin composition containing 0.05 to 4.0 parts by weight of a fatty acid ester lubricant and 0.05 to 3.0 parts by weight of a fatty acid lubricant with respect to 100 parts by weight of a resin which is 30% by weight. And high moisture-proof sheet. 2. A highly moisture-proof sheet formed by rolling the resin composition according to claim 1 by calendering.