JPH04117441A - Resin composition and laminate - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. excellent in gas barrier properties, flexibility, etc., at a high humidity by mixing a specific ethylene-vinyl alcohol copolymer having specified properties with an olefin resin in a specified wt. ratio. CONSTITUTION:An ethylene-vinyl alcohol copolymer having an ethylene content of 20-65mol% and a syndiotacticity expressed by diad content of 55mol% or higher is compounded with an olefin resin (e.g. an ethylene-vinyl acetate copolymer) in a wt. ratio of the former to the latter of (93:7) to (60:40) to give a resin compsn. A laminate contg. at least one resin layer comprising the compsn. is useful as a container excellent in falling impact resistance, a tube excellent in air bag prevention, a bag-in-box excellent in flex resistance, a film excellent in skin packaging properties, etc.

Description

[Detailed Description of the Invention] 8-1 The present invention has excellent gas barrier properties, especially under high humidity conditions, and has excellent properties such as drop impact resistance, bending resistance, air bag prevention properties, and suitability for skin-back packaging. The present invention relates to a resin composition having excellent flexibility and a laminate including at least one layer of the resin composition.

B, 'O' Ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH)
) is usually obtained by copolymerizing and converting ethylene and vinyl acetate, and has gas barrier properties, oil resistance, solvent resistance,
Because of its excellent fragrance retention, it is used in various gas barrier films, gas barrier layers of gas barrier containers, etc. However, multilayer films, multilayer containers, etc. that use EVOH as a gas barrier layer often have problems due to the high rigidity of EVOH. For example, when a multilayer film or multilayer container filled with contents breaks or breaks when dropped,
Problems such as being easily broken, pinholes occurring in the multilayer film filled with contents due to bending and vibration during transportation, airbags in multilayer tubes, and wrinkles during skin-back packaging. can be mentioned. Therefore, a method has been proposed to improve these drawbacks by blending EVOH with a flexible olefin resin. For example, it has been shown that blending EVOI (with ethylene-carboxylic acid vinyl ester copolymer or ethylene-acrylic acid ester copolymer) improves the bending resistance (JP-A-61-2
20839) and EVOHi: α, 13-Non! It is known that blending ethylene-carboxylic anhydride-modified ethylene-carboxylic 5-vinyl ester copolymer and ethylene-acrylic bonito ester copolymer improves the i-impact properties of EVOH (Japanese Patent Laid-Open No. 61-83035). ing. However, although these methods improve the bending resistance and impact resistance of EXOH, they have the drawback of significant deterioration in barrier properties, especially gas barrier properties q under high humidity conditions.

Problems to be Solved by C Ming The present invention has high gas barrier properties, especially under high humidity conditions 1, and flexibility such as drop impact resistance, bending resistance, air bag prevention, and suitability for skin pack packaging. The present invention provides a resin composition and a laminate having excellent properties.

D. In order to obtain
, consisting of an EV OH (A) whose syndiotacticity is 55 mol % or more in terms of diad and an olefin resin (B), and the weight ratio of (A) and (B) is 93; 7 to 60. :4(l) has better gas barrier properties, especially gas barrier properties under high humidity conditions, than conventional compositions consisting of EVOH and olefin resin.
It is a flexible resin composition with extremely high properties, and a laminate containing a small amount of this resin composition has excellent flexibility such as drop impact resistance, bending resistance, air bag prevention property, and suitability for skin pack packaging. The present inventors have discovered that this is extremely useful as an excellent laminate, and have completed the present invention.

In the present invention, it is important that the content of the ethylene component is 20 to 65 mol%. If the content of the ethylene component is less than 20 mol%, the gas barrier properties of the resin composition will be significantly impaired under high humidity conditions, and the compatibility with polyolefins will be poor, and molded products with good appearance will not be produced. I can't get it.

On the other hand, if it is larger than 65 mol%, the gas barrier of the composition
The properties are significantly impaired regardless of the relative humidity. A more preferable range of the content of the ethylene component is 25 to 60 mol%, more preferably 25 to 50 mol%.

Next, it is extremely important that the syndiotacticity is 55 mol% or more in order for the resin composition of the present invention to exhibit high barrier properties. syndiotactic city
If the amount is less than 55 mol %, the gas barrier properties will be impaired, as is clear from the examples below. The upper limit of syndiotacticity is not particularly limited, but is 65 mol%, more preferably 70 mol%, from a manufacturing standpoint. Here, the ``Nndiotacticity'' is ``H-NMR (1) 4.0~
It is calculated from the integrated intensity ratio of the hydrogen peaks of the hydroxyl groups present at 4.7 ppm.

Furthermore, in the present invention, the melt index of EVOH (value measured under the conditions of temperature 190 ° C. and load 2160 g;
MI) is not particularly limited, but is 0.1 to 50.
g/10 minutes is preferred, and more preferably 0.5-2
It is 0g.

In the present invention, the ethylene-vinyl alcohol copolymer is produced, for example, by the following method.

That is, it is a method of copolymerizing ethylene and a vinyl ester represented by formula (1), and saponifying the resulting copolymer.

(1) CH,=H=O R'--R3 Here, R' and R' are hydrogen, f2 indicates a hydrocarbon group, and R3 indicates a hydrocarbon group, but as a hydrocarbon group,
Lower alkyl groups such as methyl, ethyl, propyl, butyl, t-butyl; aryl groups such as phenyl; cycloalkyl groups such as cyclohexyl group having 1-18 carbon atoms
hydrocarbon groups.

Among these, R', R'', and R3 are all preferably lower alkyl groups, particularly methyl groups.In other words, as a vinyl ester component, vinyl pivalate in which R', R'', and R3 are all methyl groups is preferable. Most preferably.

Ethylene-vinyl ester copolymerization is carried out by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and can be carried out in bulk or by solution polymerization in the presence of a solvent at a temperature of a °C to In °C, preferably 30 °C to 60℃
It is preferable to carry out under the following conditions. Polymerization rate is 20~
80%, preferably 30 to 60%, and during solution polymerization, the solvent concentration is 50% or less, preferably 30% or less.

The solvent used for solution polymerization is preferably an alcohol, usually methanol, ethanol, propatool, t
- Lower alcohols such as butanol are preferred. These solvents can be used alone or in combination of two or more. For the copolymerization operation, either a batch method or a continuous method can be used, or a flow system operation using a stirring and mixing type polymerization tank is preferable.

The ethylene content of the ethylene-vinyl ester copolymer is determined by the vinyl ester present in the system and the amount of ethylene dissolved in the solution, and the latter depends on the ethylene pressure and temperature in the system. It is well known that when polymerization is carried out in a batch manner, the copolymerization composition changes with the polymerization rate according to the copolymerization reactivity ratio. In order to obtain a copolymer having a uniform copolymer composition, it is more desirable to employ a semi-batch method in which the polymer is added. An example of a method for calculating the amount added at this time is R, J, Hanna (Industrial
andEngineering Chemistry
Vol. 49, 208 (1957)). In the case of a continuous method, a completely mixed one-stage flow system reaction system in which the stirring mixing tank is used as a copolymerization reaction tank is suitable, and in the case of a multi-stage flow system reaction system of two or more stages, the same method as above is preferred. For this reason, it is more preferable to carry out the reaction while adding monomers to the second and subsequent copolymerization tanks so that the monomer composition in each stage of the copolymerization tank remains constant.

A radical polymerization initiator is used in the copolymerization reaction,
For example, 2.2"-azobis-(4-methokino-2,4-
dimethylvaleronitrile), nitriles such as 2.4.4-trimethylvaleronitrile, 2.2"-azobis-isobutyronitrile, di-n-propyl peroxycarbonate, his-4-t-butylcyclohexyl peroxydi Examples include carbonates such as carbonate, bis-2-ethylhexyl quinone carbonate, and peroxides such as acetylene chlorohexane sulfonyl peroxide, benzoyl peroxide, and lauroyl peroxide.

The r dicopolymer thus obtained is then subjected to a saponification reaction.

In general, vinyl esters with a high group in the side chain as represented by formula (1), such as vinyl pivalate, are susceptible to hydrolysis due to their steric hindrance, and in copolymers with ethylene. The alkaline saponification method under the conditions used for ordinary ethylene-vinyl acetate copolymers does not result in sufficient saponification. It is preferable to saponify the mixture under the following conditions.

First of all, it is important to perform saponification in the absence of oxygen or in the presence of an antioxidant, and furthermore, the molar ratio of the amount of basic substance used/the amount of vinyl ester units contained is 0.1.
~10, and it is further important to set the saponification temperature to 60°C or higher.

A typical method for performing oxygen in the absence of oxygen is by replacing it with an inert gas (nitrogen, etc.). In addition, the antioxidant is not particularly limited as long as it does not adversely affect the saponification reaction and does not lose its antioxidant effect in the saponification system.For example, the compound shown below (IRGANOX 1010 (manufactured by Nippon Ciba Geigy))
Hindered phenolic antioxidants such as 8 (manufactured by Nippon Ciba Geigy), phenolic antioxidants such as hydroquinone, SAN OL L S-770
Typical examples include hindered amine antioxidants such as (manufactured by Nippon Ciba Geigy).

The saponification reaction is carried out in the presence of a basic substance, and either a transesterification reaction or a direct saponification reaction can be selected depending on the type and concentration of the basic substance and the type of solvent. Examples of basic substances include strong bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide,
Examples include metal alkoxides such as potassium ethoxylate and potassium t-butoxide. The molar ratio of the amount of basic substance used/vinyl ester unit content is expressed as a molar ratio to the 2-vinyl ester units contained in the copolymer, and is O1 to 10, preferably 0.5 to 3. . This value varies depending on the target degree of saponification, degree of polymerization, solvent, type of basic substance, etc. - If the value is less than 0.1, the degree of saponification will not increase, and if it is greater than 10, the degree of polymerization will increase during the saponification reaction. A decline or significant occurrence occurs. The amount of the basic substance to be used will depend on the amount of the basic substance used when the monomer unit other than the copolymer contains a group that reacts with a basic substance (for example, a calfoquine group) or when the antioxidant reacts with a basic substance. It is set to compensate for the amount consumed.

Saponification temperature: 60°C or higher, preferably 60-14°C
The temperature is 0°C, more preferably 80 to 120°C.

The saponification reaction time is appropriately set depending on the target saponification degree, polymer concentration, solvent, basic substance, temperature, etc. After the saponification is completed, it is preferable to immediately neutralize the basic substance remaining in the reaction system with an acid. Types of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid, as well as formic acid, acetic acid, ammonium, and e.

Examples include organic acids such as aromatic acid, but organic acids are preferred;
Acetic acid is most preferred. If the basic substance remaining in the reaction system is not neutralized after saponification, the degree of polymerization of the copolymer will decrease.

The solvent used during saponification is capable of dissolving or swelling the ethylene-vinyl ester copolymer, and desirably one capable of dissolving the basic substance and the saponified polymer.

Two solvents that have these properties include cyclic ethers such as tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; sulfoxides such as dimethyl sulfoxide; amides such as dimethylformamide; toluene,
Examples include aromatic hydrocarbons such as benzene, alcohols such as methanol, ethanol, t-butanol, n-propanol, 1so-propanol, 5ee-butanol, and soclohexanol, particularly tetrahydrofuran, methyl ethyl ketone, and t-butanol. etc. are suitable. These can be used alone or in combination of two or more.

The concentration of the ethylene-vinyl ester copolymer in the solvent solution in the saponification system is appropriately determined depending on the degree of polymerization of the copolymer, but is usually between 3 and 70% by weight. .

EVO) (obtained by saponification using this method)
) The degree of saponification of the vinyl ester acid component represented by the formula is 90 mol % or more, preferably 98 mol % or more, and optimally 99 mol % or more. The higher the degree of saponification, the better the thermal stability and the better the gas barrier properties. In addition, the EVOH may be an α-olefin such as propylene or isobutyne, an olefinic unsaturated monomer containing silicon, or an unsaturated carboxyl group such as acrylic acid, methacrylic acid, or maleic acid, as long as the purpose of the present invention is not impaired. There is no problem in containing an acid or a salt thereof, or an ester thereof, or a comonomer other than ethylene and the above formula (1) such as vinyl acetate as a copolymerization component.

In the present invention, as the olefin resin, polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, propylene butene-1 copolymer, polybentene-1, copolymers mainly composed of these olefins, such as ethylene Ethylene-vinyl acetate copolymer with a content of 70 to 95 mol%, preferably 80 to 95 mol%, its saponified product, ethylene-acrylic acid ester copolymer, ionically crosslinked olefin copolymer, etc. Alternatively, a mixture of two or more of these is exemplified. Among these, polyethylene, ethylene-vinyl acetate copolymers, or saponified products thereof are particularly preferably used. The olefin resin may be modified with an epoxy group-containing monomer such as glycidyl methacrylate, a silicon-containing monomer such as vinyltrimethoxysilane, triethoxysilane, etc. to an amount of about 5 mol % or less.

The resin composition of the present invention is a mixture of EvoH (A) and an olefin resin (B), but it is important that the weight ratio of (A) and (B) is 93.7 to 60:40. be. If the blending ratio of olefin resin (B) is less than 7% by weight, flexibility such as drop impact resistance and bending resistance is poor. On the other hand, if it exceeds 40% by weight, the gas barrier properties will be significantly impaired and the appearance of the molded product will be poor.

In the present invention, the method of mixing E''t・OH (A) and 1 m of olefin resin (B) includes a method using a Banbury mixer, a single screw or twin screw extruder, a Brabender blast mill, etc. Each resin may be directly supplied to various molding machines and molded while being kneaded by the molding machine.In addition, when mixing these resins, plasticizers, lubricants, fillers, antioxidants, antistatic agents, and colorants may be added. , various resins, etc. may be added without impairing the effects of the present invention.

The resin composition of the present invention is preferably used in a laminate [
). Examples of resins to be laminated with the resin composition of the present invention include olefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer, thermoplastic polyesters such as polyethylene terephthalate, 6-nylon, 6-nylon, and 6-nylon. Preferred are polyamides such as .6-nylon, polystyrene, polyvinyl chloride, polycarbonate, ordinary EVOH (obtained by saponifying ethylene-vinyl acetate copolymer), polyvinyl alcohol, or a mixture of two or more of these.

Among these, particularly preferred are low moisture permeable plastic resins, especially polyethylene, polypropylene, ethylene-
These are propylene copolymers, thermoplastic polyesters, polystyrene, and polycarbonates.

The layer structure of the laminate is: resin composition of the present invention/thermoplastic resin, thermoplastic resin/resin composition of the present invention/thermoplastic resin,
Thermoplastic resin/resin composition of the present invention/thermoplastic resin/resin composition of the present invention/thermoplastic resin, etc., and the resin composition of the present invention and the thermoplastic resin may each be a single layer, In some cases, it may be multi-layered. Further, if necessary, an adhesive resin may be placed between each layer of the laminate, and the adhesive resin may be any material such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene, etc. - A product obtained by modifying an acrylic ester or the like with an ethylenically unsaturated acid or an acid anhydride thereof, and especially a product obtained by blending an unmodified polymer with a maleic anhydride modified product or a maleic anhydride modified product, More suitably used.

The resin composition of the present invention can be formed into a film, sheet, tube, bottle, etc. as a laminate, and there is no particular restriction on the thickness structure of each layer. The thickness is preferably 2Hμ or less, more preferably 2Hμ or less.

The method of molding the laminate of the present invention is not particularly limited, but
Examples include a coextrusion method, an extrusion lamination method, a dry lamination method, etc., and the coextrusion method is particularly preferred because it can exhibit the characteristics of the resin composition of the present invention.

The laminates obtained in this way can be used as containers with excellent drop impact resistance, tubes with excellent air bag prevention properties, bag-in-boxes with excellent bending resistance, films with excellent suitability for skin packs, etc. can be used.

Hereinafter, the present invention will be roughly explained in detail with reference to Examples.
The present invention is not limited in any way by this.

"Parts" or "%" in the examples are based on weight unless otherwise specified.

Example I E V OH (A) was produced under the conditions described below. Ethylene content: 32 mol%, degree of sulfurization: 997 mol%, non-geo-toughness: 61 mol%, Ml (190 mol%) °C, 21
60g) 1.8g/10min EVOH, vinyl acetate included as olefin resin (B) 28 weight! %, Ml(
190℃, 21Hg) 2.0g/10min of ethylene-
Using vinyl acetate copolymer, production of resin composition, film formation,
The film surface and various physical properties of the film-formed products were evaluated.

(1) Production of EVOH In a pressure-resistant polymerization tank, 100 parts by weight of vinyl pivalate, 1 tl of 23 parts of methanol, 1 part of 7.5 parts of ethanol, and 0.065 parts by weight of 2,2゛-azobisisobutyronitrile as a polymerization initiator. After replacing the oxygen in the tank with ethylene, the ethylene pressure was maintained at 25 kg/cm.
After polymerization was carried out at 60° C. for 5 hours with stirring, a polymerization inhibitor was added. The polymerization rate of vinyl pivalate was 50%. Next, unreacted ethylene was purged out of the tank, and unreacted vinyl pivalate was further distilled off at 60° C. under reduced pressure. Next, 30 parts by weight of ethylene-hinyl pivalate copolymer and 450 parts by weight of tetrahydrofuran were charged into a pressure-resistant saponification reactor and dissolved at 60° C. while blowing nitrogen.

Next, potassium hydroxide 78 weight! 225 parts and methanol! After removing oxygen, the solution was charged into a pressure-resistant saponification reactor, and a stirring reaction was carried out at 95°C for 75 minutes without blowing in nitrogen. Next, the saponified product was thoroughly washed with methanol and pure water, and dried in nitrogen at 80°C for 5 hours and then at 105°C for 15 hours. The analytical values of EVOH thus obtained are as described above. The ethylene content, degree of saponification, and syndiotacticity were determined using 'H-NMR using d6-dimethylsulfoquine (DSMO) as a solvent. Non-geo toughness is 40-4.7pp
It was calculated from the integrated intensity of the hydrogen peak of the hydroxyl group present in m.

(2) Production of resin composition and film formation 70 parts by weight of the above EVOH and 88 mol% ethylene content
30 parts by weight of the ethylene-vinyl acetate copolymer were triblended and formed into pellets at a temperature of 220° C. using a 30 mmφ bidirectional twin-screw extruder. Then, using this pellet, the extruder temperature was 180-220°C and the T-die temperature was 215°C, depending on the film forming method consisting of a 40 mmφ extruder and a T-die.
A film with a thickness of 20 μm was obtained by copying under the following conditions.

(3) Evaluation of film surface and various physical properties The film surface was evaluated by visual inspection for streaks and matte finish, and ranked into three grades A to C shown in Table 1.

Table 1 Lube Stiffness is calculated by measuring the repulsive force at 20°C when a film with a width of 15 mm is bent into a loop shape of 60 mm in length using a Lube Stiffness Tester manufactured by Toyo Seiki Co., Ltd. and compressed until the diameter of the loop becomes 20 av. , 65% RH. Lube stiffness is important as a measure of air bag prevention properties, and it is considered that the smaller the lube stiffness is, the better the air bag prevention properties are.

The bending resistance was evaluated using a GELBOLLEX tester manufactured by Rigaku Kogyo Co., Ltd. A 12-inch x 8-inch film was shaped into a cylinder with a diameter of 3.5 inches. The gripping distance is 1 inch, the first 3.5 inches of the stroke is a twist of 440 degrees, and the next 2.5 inches are linear horizontal motion. Repeated reciprocating motion at a speed of 40 times/minute. , 20℃, 65
This was done by calculating the number of pinholes in the film after repeating it 300 times under %RH conditions.

Young's modulus was measured at 20° C. and 65% RH according to ASTM D-81112-67. Young's modulus is important in relation to skin pack suitability. That is,
For skin pack packaging that involves a stretching process, a material with a low Young's modulus that can be stretched with a smaller force is suitable.

Oxygen gas permeation II1. (OTR) was measured using OX-TRAN 10-50A manufactured by Modern Control Co., Ltd. (1, 20°C, 65% RH and 100% RH conditions).

The evaluation results for the above items are shown in Table 2. The film formed from the resin composition has a good film surface and is excellent in lube stiffness, bending resistance, flexibility expressed by Young's modulus, and gas barrier properties.

Comparative Example 1 Ethylene content 32 mol%, saponification degree 99.7 mol%,
Syndiotacticity - 61 mol%, Ml (190°C
, 2160 g) A film was formed in the same manner as in Example 1 except that 1.8 g/10 min of EV OH alone was used, and the film surface and various physical properties of the film were evaluated. The results are shown in Table 2. Although the film surface and gas barrier properties were good, the flexibility was extremely poor.

Comparative Example 2 Ethylene content 32 mol% as E V OH (A),
Saponification degree 99.5 mol%, non-geotufted tea 5
2 mol%, Ml (190°C, 2tsOg) 1.6g/
A film was formed in the same manner as in Example 1 except that a saponified ethylene-vinyl acetate copolymer was used, and the film surface and various physical properties of the film were evaluated. The results are shown in Table 2. Although the film surface and flexibility are good, high humidity (100%R) I
) The gas barrier properties under these conditions are poor.

Example 2 EV OH (A) and ethylene-
Using vinyl acetate copolymer (B), the mixing ratio is (A) (B)
)-80:20 (weight ratio; the same applies hereinafter) A pellet-shaped resin composition was produced in the same manner as in Example 1, and then a film was formed, and the film surface and various physical properties of the film were evaluated. The results are shown in Table 2. f2 has excellent film surface, flexibility, and gas barrier properties.

Comparative Example 3 Using EVOH (containing) and ethylene-vinyl acetate copolymer (B) described in Example 1, the mixing ratio was (A) (B)
= 95 + 5 and the rest is the same as in Example 1? A pellet-shaped resin composition was produced by straining, and then a film was formed, and the film surface and various physical properties of the film were evaluated. The results are shown in Table 2. Although the membrane surface and gas barrier properties are good, the flexibility is poor and poor.

Comparative Example 4 EV OH (A) and ethylene-
Vinyl acetate copolymer (B) was used, and the mixing ratio was (A) (B).
) = 50: 50 (1) A pellet-shaped resin composition was produced in the same manner as in Example (2), and then a film was formed, and the film surface and various physical properties of the film were evaluated. Second result
Shown in the table. Although the flexibility is good, the membrane surface and gas barrier properties are extremely poor.

Comparative Example 5 Ethylene content: 32 mol%, saponification degree: 852 mol%, syndiotacticity: Ethylene content: 32 mol%, saponification degree: 852 mol%, produced in the same manner as in Example 1 except that the saponification conditions were changed as E V OH (A)
61 mol%, Ml (190°C, 2160g) 2.3g
A pellet-shaped resin composition was produced in the same manner as in Example 1, except that EVOH for 10 minutes was used.
Shown in the table. Although the film surface and flexibility were poor, the gas barrier properties were poor.

Example 3 Ethylene content: 32 mol%, saponification degree: 94.2 mol%, syndiotacticity: -61 mol%, produced in the same manner as in Example 1 except that the saponification conditions were changed as E V OH (A) , MI (190°C, 2160g) 2.1
A pellet-shaped resin composition was produced in the same manner as in PJ 2 using EVOH of g/10 minutes, and then a film was formed, and the film surface and various physical properties were evaluated. The results are shown in Table 2. The film surface, flexibility, and gas barrier properties were all good.

Example 4 As E V OH (A), the ethylene content 44 mol%, saponification degree 991 mol%, non-geotufting tea 60 mol%, Ml (190 ° C.,
2160g) 5.2g/10 min saponified ethylene-vinyl pivalate copolymer, olefin resin (B)
As ethylene content 89 mol%, saponification degree 95 mol%,
MI (190°C, 2160g) using partially saponified ethylene-vinyl acetate copolymer for 4.8g/10 minutes),
In the same manner as in Example 1, the mixing ratio was (A):(B)=
A pellet-shaped resin composition of 80:20 was produced and formed into a film, and the film surface and various physical properties of the film were evaluated. The results are shown in Table 2. The film surface, flexibility, and gas barrier properties are all good.

Comparative Example 6 E V OH (A) was produced according to Example 1 with an ethylene content of 68 mol%, a saponification degree of 99.6 mol%,
Non-geotufted tea 58 mol%, Ml (lil.

A pellet-shaped resin composition was prepared in the same manner as in Example 4, except that 13 g/10 minutes of saponified ethylene-vinyl pivalate copolymer was used, and then film formation was performed. To evaluate the film surface and various physical properties.

The results are shown in Table 2. Although the flexibility was good, the film surface and gas barrier properties were poor.

Example 6 E V OH (A) was prepared according to Example 1 with an ethylene content of 27 mol %, a saponification degree of 986 mol %, an ethylene/diotactic protein of 62 mol %, an MI (210° C.,
2160g) 3.5g/10 min saponified ethylene-vinyl pivalate copolymer, olefin resin (B)
as Ml (190°C, 2160g) 3. Og/1
A pellet-shaped resin composition was produced in the same manner as in Example 1 except that linear low-density polyethylene modified with 81 mol% of glyphnormethacrylate of 0 min was used, and then a film was formed. and various physical properties were evaluated. The results are shown in Table 2. The film surface, flexibility, and gas barrier properties were all good.

Comparative Example 7 EVOH (A) was produced according to Example I with an ethylene content of 19 mol%, a saponification degree of 985 mol%, a 7-unit content of 60 mol%, Ml (210°C, Hu
g) J, Dg/ A pellet-shaped resin composition was produced in the same manner as in Example 6 except that a 10-minute ethylene-hinyl pivalate copolymer was used, and then a film was formed. The film surface and various physical properties were evaluated. Second result
Shown in the table. The membrane surface, flexibility, and gas barrier properties under high M conditions (100% RH) were all poor.

Example 7 An intermediate layer with a thickness of 15μ made of the resin composition described in Example 1, and MT (190″) with a thickness of 30μ on each side of the intermediate layer.
C, 2160g) 2.1g/10 4-methyl-1
- Has a surface layer made of 3.2 mol% pentene-modified linear low-density polyethylene, with a thickness of 5μ between each layer, maleic anhydride-modified ethylene-acetic acid with a vinyl acetate content of 20% by weight and a maleic anhydride content of 05% by weight. A laminated film with a total thickness of 85 μm arranged through an adhesive resin layer made of a vinyl copolymer was manufactured by a coextrusion method using three extruders and a gouhet for three types and five layers. The laminated film is subjected to a Gelbolex test until no pinholes are observed, and the oxygen gas permeation rate (OTR) at each stage up to the generation of pinholes is measured using the gas permeation rate manufactured by Modern Control Co., Ltd. Using the measuring device I), 20°C, 65% R
Measured under conditions of H and 100% RH.

The measurement results are shown in Table 3. During the bending fatigue test process up to the occurrence of pinholes, there was almost no change in the amount of oxygen gas permeation. In addition, the occurrence of pinholes was not observed after 7,000 cycles of the bending fatigue test, and after 7,100 cycles of the bending fatigue test.
After the round trip, when I inspected the pinhole, did I find that one pinhole had already formed?=yy? h
rko. Second, the film has no streaks or matte finish, and has a good appearance.

Comparative Example 8 A laminate film of 3 types and 5 layers was produced in the same manner as in Example 7 except that the E V○H described in Comparative Example 1 alone was used for the intermediate layer, and a flex fatigue test and measurement of oxygen permeation amount were carried out. carried out.

The results are shown in Table 3. The bending fatigue resistance was poor, with more than 100 pinholes occurring after 1000 reciprocations.

Comparative Example 9 Using the resin composition described in Comparative Example 2 for the intermediate layer, a laminate film of 5 layers of 3 types was produced in the same manner as in Example 7,
A bending fatigue test and measurement of oxygen permeation were conducted. The results are shown in Table 3. Although the bending fatigue resistance is good,
Gas barrier properties under high humidity (100% RH) conditions are poor.

Example 8 An intermediate layer having a thickness of 50 μm made of the resin composition described in Example 4, and 70 parts by weight of an ethylene-vinyl acetate copolymer containing 115% by weight of vinyl acetate and 0.5 parts by weight of maleic anhydride on both sides of the intermediate layer. Weight% modified ethylene vinyl acetate copolymer 3
A container (capacity: 1 lB) having an inner and outer layer of 0 parts by weight and a thickness of 300 μm each was manufactured by a coextrusion/direct blow molding method using two extrusion type Gouy heads for two types and three layers. Fill the container with water LH and press it from a height of 1 m.
After being dropped several times, there was no breakage and good impact resistance was exhibited.

Comparative Example 10 A container having two types and three layers was manufactured in the same manner as in Example 8, except that the intermediate layer was made of only EVOH described in Example 4. The container broke during the first drop test and was rejected due to poor impact resistance.

Example 9 An intermediate layer with a thickness of 20 μm made of the resin composition described in Example 4 and a surface layer with a thickness of 150 μm each made of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 8% by weight were placed on both sides of the intermediate layer. Between each layer is a vinyl acetate-containing layer with a thickness of 15μ.
A laminated tube with a total thickness of 350μ arranged through an adhesive resin layer made of an ethylene-vinyl acetate copolymer modified with 0.5% by weight and 0.5% by weight of maleic anhydride was processed using three extruders.
Manufactured by coextrusion/direct blow molding using a die head for 3 types and 5 layers. The center of the body of the tube was cut to a width of 15 mm, and the repulsive force was measured when it was compressed by 10 mm using a lube stiffness tester.
It was 00mg.

Comparative Example 1 A laminated tube of 3 types and 5 layers was produced in the same manner as in Example 9, except that the intermediate layer was made of only the EVOH described in Example 4.

The repulsive force of the tube measured by a lube stiffness tester was 1500 mg76D, which was extremely large compared to Comparative Example 9.

Below is a blank space F. Effects of the Invention The resin composition of the present invention has gas barrier properties,
In particular, the laminate, which has remarkable gas barrier properties under high humidity conditions and is flexible, and which includes at least one layer of the resin composition, has excellent drop impact resistance and excellent air bag prevention properties. It is extremely useful as a tube with excellent bending resistance, f-niback-in-hocks, and a film with excellent skin-back suitability.

Patent applicant RiRashi Co., Ltd.

Claims (2)

[Claims] (1) Ethylene-vinyl alcohol copolymer (A) having an ethylene component content of 20 to 65 mol% and a syndiotacticity of 55 mol% or more in diad display.
and an olefin resin (B), and (A)
and (B) in a weight ratio of 93:7 to 60:40. (2) A laminate comprising at least one layer of the resin composition according to claim 1.