JPS5938897B2 - Sheet or film made of thermoplastic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sheet or film suitable for plastic processing of plastic cups, etc., and more specifically, it has excellent gas barrier properties against oxygen, carbon dioxide, etc., mechanical strength,
The present invention relates to a sheet or film suitable for manufacturing molded containers that has a desirable combination of hardness, interlayer adhesion and transparency.

In the present specification, plastic working means a cold or warm processing method of a resin using plastic deformation of the resin, and includes so-called draw molding.

Stretching of a sheet or film includes drawing, ironing, vacuum forming, stretching in addition to normal stretching.
This concept also includes pressure forming, etc. Conventionally, a polyolefin, particularly a thermoplastic resin such as polypropylene, is formed into a sheet or film, and then this sheet or film is processed into, for example, KUNSTSTOFFE-Bd.19.
75・H. As stated in lO, 666/69,
It is known to perform plastic working such as drawing at a relatively low temperature, such as below the melting temperature of the resin, to produce a biaxially stretched cup-shaped molded container.

Molded products produced by this plastic processing have greater mechanical strength, hardness, and
It has excellent creep resistance and transparency, but it also has gas barrier properties for filling and storing liquid foods, dry foods, medicines, liquid cosmetics, aerosol contents, carbonated drinks, beer, etc. However, it is still not fully satisfactory for use in pressure-resistant containers. That is, even though resins such as the polyolefins described above have excellent biaxial stretchability and are particularly excellent in transparency and mechanical strength, they have a drawback that they have relatively high permeability to gases such as oxygen or carbon dioxide gas. On the other hand, it is practically impossible to apply this plastic processing technology to thermoplastic resins that have excellent gas barrier properties (gas permeability resistance) against oxygen or carbon dioxide gas, etc. in terms of stretchability. .

For example, ethylene-vinyl alcohol copolymer (saponified ethylene monovinyl acetate copolymer) and various copolyamides have been known as melt-extrudable thermoplastic resins with excellent gas barrier properties. However, these thermoplastic resins with excellent gas barrier properties generally have a low elongation rate, or local stretching occurs during plastic processing, making it difficult to obtain satisfactory molded products. The present inventors have found that even in thermoplastic resins with excellent gas barrier properties, which are impossible or difficult to plastically process such as biaxial stretching molding, the solubility index (Sp value) described in detail below is 9.5. The difference in solubility index (ΔS
p value) is 4.5 or less, and when combined to form a sheet or film made of a resin blend,
This sheet or film can be plastically processed, and the film or sheet of the resin blend exhibits a significantly smaller gas permeability coefficient than the arithmetic average gas permeability coefficient of each resin through plastic processing, and is transparent. strength, strength,
It has been found that a molded container with excellent properties such as creep resistance can be provided.

That is, an object of the present invention is to provide a molded container by plastic working which has an excellent combination of gas barrier properties against oxygen, carbon dioxide, etc., and physical properties such as transparency, strength, creep resistance, and hardness. The purpose is to provide sheets or films. Another object of the present invention is to provide a sheet or film for producing a molded container by plastic processing from a thermoplastic resin having high gas barrier properties that is difficult or impossible to biaxially stretch mold.

Still another object of the present invention is to provide a sheet particularly suitable for providing gas barrier or pressure resistant plastic containers for liquid foods, dry foods, medicines, liquid cosmetics, aerosol contents, carbonated drinks, beer, etc. or provide film.

According to the present invention, the sheet 5 or film is made of a thermoplastic resin, and the sheet or film has a solubility index (Sp) of 9.5 or more and has a plurality of types of melt-extrudable thermoplastic resins. at least one layer of a resin-based blend and a moisture permeability of 100 at temperatures below 50°C.
×10-129・CT! L/(177f・1hsec-
CTnHg or less, the plurality of thermoplastic resins in the blend have an oxygen permeability coefficient of 5 x 10-11 cc. CfL/(1-J mo
Vi-Sec- (7 nHg or less and the difference in solubility index (ΔSp) between each resin is selected to be 4.5 or less, and the blend has an arithmetic average elongation rate (ε) of
A sheet or film is provided that is characterized by having a higher elongation rate than the above.

According to the present invention, there is further provided a sheet or film made of a thermoplastic resin, the sheet or film comprising:
At least one layer of a blend mainly composed of a plurality of thermoplastic resins having a solubility index (Sp) of 9.5 or more and capable of being melt extruded, at a temperature of 23° C. and at a temperature of 7×10 dy
Under the stress of ne/Crll, the sum of the initial 2 elastic modulus (Eg) and delayed elastic modulus (E1) is 1 x 1010 dyne/Cll.
The steady flow viscosity (η00) is 1×1017p
0ise or more and delay time (TR) is 6×106se
and at least one layer consisting of a thermoplastic resin, the blend having a plurality of types of thermoplastic resins, at least one of which has an oxygen permeability coefficient of 5 x 10- 11cC-CTn/CTIL-Se
C-CmHg or less and the difference in solubility index (ΔSp) between each resin is selected to be 45 or less, and the blend has a higher elongation rate than its arithmetic average elongation rate (ε). A sheet or film having the above characteristics is provided.

The present invention will be explained in detail below.

Blended resin The sheet or film for plastic processing of the present invention may have a layer of a blend mainly composed of a plurality of thermoplastic resins that have a solubility index of 9.5 or more and can be melt-extruded. , is important for the mechanical properties and gas barrier properties of the final formed container.

As used herein, solubility index (SOIutility)
parameter. For example, J. B.R.A.
As defined in "POlymer HandbOOk8 Chapter 4" edited by NDRUP et al. (published by JOhm Wiley & SOOns, Inc., 1967), it is defined as the % power of the cohesive energy density (Cat/Cc).

This solubility index is closely related to the strength of hydrogen bonds in thermoplastic resins, including hydroxyl groups, amide groups, ester groups,
Thermoplastic polymers containing polar groups such as nitrile groups or chlorine atoms in the polymer main chain or side chains generally have a relatively Shows a large solubility index. The Sp values of typical thermoplastic resins are as follows:
It is as shown in the table.

According to Table 1, it can be seen that polymers containing polar groups such as polyvinyl alcohol and polyacrylonitrile have large solubility indices. However, these polyvinyl alcohol and polyacrylonitrile cannot be melt extruded, and therefore they must be modified into a melt extrudable copolymer form before use for the purpose of the present invention. The solubility index (Sp value) of a copolymer can also be approximately determined as an arithmetic mean value from the Sp values of homopolymers of each monomer constituting the copolymer.

For example, the Sp value of an ethylene-vinyl alcohol copolymer is the following formula, where E8 is the Sp value of polyethylene,
EM is the mole fraction of ethylene in the copolymer, 8P is the Sp value of polyvinyl alcohol, and VM is the mole fraction of vinyl alcohol in the copolymer. can.

As shown in Table 2 below, the Sp value of ethylene-vinyl alcohol determined by the above-mentioned approximate formula is in good agreement with the measured values of copolymers with various vinyl alcohol (VA)/ethylene (Et) molar composition ratios. We are doing so.

Similarly, the Sp value of a copolymer of an ethylenically unsaturated nitrile monomer and another comonomer is determined by the following formula, where Asp is the Sp value of a homopolymer made of ethylenically unsaturated nitrile. AM is the molar fraction of ethylenically unsaturated nitrile contained in the copolymer, Spn is the Sp value of the homopolymer consisting of the comonomer alone, and Mn is the mole fraction of ethylenically unsaturated nitrile contained in the copolymer. n is a number greater than or equal to 1, and is a number equal to the type of copolymer contained in the copolymer.

Further, the Sp values of commercially available polyamides are as shown in Table 3, for example, and they are all 9.
It has an Sp value in the range of 5 to 13.6.

According to the present invention, at least one of the above-mentioned thermoplastic polymers having an Sp value of 9.5 or more and capable of being melt extruded,
Preferably, both thermoplastic resins have an oxygen permeability coefficient of 5×10
-11cc-d-Sec-CTILHg (measured at 37°C and O%RH) or less, and the difference in solubility index (ΔSp value) between each resin is 4.5 or less, and the combination is This is important in relation to plastic workability such as biaxial stretch formability and gas permeation resistance.

Table 4 below shows the oxygen permeability coefficients (PO2) of typical thermoplastic resins.

From Table 4 above, it is clear that ethylene-vinyl alcohol copolymer (saponified ethylene monovinyl acetate copolymer) has outstanding gas permeation resistance among various thermoplastic resins, Therefore, in the present invention, it is desirable to use an ethylene-vinyl alcohol copolymer as one of the thermoplastic resin components constituting the blend. It is generally desirable that the ethylene-vinyl alcohol copolymer has a vinyl alcohol content in the range of 50 to 75 mol%, or in other words, an ethylene content in the range of 25 to 50 mol%. That is, if the amount of vinyl alcohol contained in the copolymer is less than 50 mol%, it is not preferable because the permeability to gases such as oxygen is greater than that of copolymers within the above range. When the vinyl alcohol content in the copolymer exceeds 75 mol%, the hydrophilicity of the copolymer becomes large and water vapor permeability increases, and the influence of humidity on oxygen permeability tends to become large. It is likewise undesirable for purposes of the present invention since its melt-formability is reduced. This ethylene-vinyl alcohol copolymer is described, for example, in U.S. Pat.
As described in No. 419,654, by saponifying a copolymer of ethylene and a vinyl ester of a lower fatty acid such as vinyl formate, vinyl acetate, or vinyl propionate, especially an ethylene monovinyl acetate copolymer. can get.

The degree of saponification of this ethylene-vinyl ester copolymer is
The ethylene-vinyl alcohol copolymer used in the sheet or film of the present invention has an important effect on the oxygen permeability of the final molded container, and the ethylene-vinyl alcohol copolymer contains at least 96% of the vinyl ester in the ethylene-vinyl ester copolymer. More preferably 9
It is a copolymer obtained by saponifying 9% or more, that is, the amount of residual vinyl ester per vinyl group in the copolymer is 4 mol% or less, more preferably 1 mol% or less. It is desirable from the viewpoint of gas permeability resistance. This ethylene-vinyl alcohol copolymer may contain propylene, butene, or 1, isobutylene, hexene-1, and other copolymerizable olefins having 3 to 6 carbon atoms may be contained as a copolymerization component. The molecular weight of this ethylene-vinyl alcohol copolymer is not particularly limited, as long as it has a molecular weight sufficient to form a film.

Intrinsic viscosity of ethylene-vinyl alcohol copolymer [η]
is measured, for example, at a temperature of 30°C in a mixed solvent of 85% by weight of phenol and 15% of water. It is desirable to use an ethylene-vinyl alcohol copolymer in the range of .171/9. Other examples of thermoplastic polymers with high gas barrier properties that satisfy the above-mentioned solubility index include various homopolyamides, copolyamides, and blends thereof.

Such polyamides include, for example, homopolyamides, copolyamides, or blends thereof having the following amide repeating units: can be mentioned.

From the viewpoint of gas barrier properties against oxygen, carbon dioxide gas, etc., homopolyamides, copolyamides, or these polyamides in which the number of amide groups per 100 carbon atoms in the polyamide is in the range of 3 to 30, particularly 4 to 25. Preferably, a blend is used. Examples of suitable homopolyamides are and the like.

Examples of suitable copolyamides include prolactam/laurinlactam copolymer, prolactam/hexamethylene diammonium adipate copolymer, lauryl lactam/hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate/ Examples include hexamethylene diammonium sebacate copolymer, ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, and prolactam/hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer.

These homopolyamides and copolyamides can also be used in the form of so-called blends, for example blends of polycaprolactam and polyhexamethylene adipamide, blends of polycaprolactam and polyprolactam/hexamethylene diammonium adipate copolymer. Any of these can be used for the purposes of the present invention.

Although they are slightly inferior in moldability compared to the above-mentioned aliphatic polyamides, they are disclosed in, for example, Japanese Patent Publications No. 50-1156, Japanese Patent Publication No. 5751-1982, Japanese Patent Publication No. 5753-1983, and Japanese Patent Publication No. 10196-1982. , Japanese Patent Publication No. 50-29
metaxylylene diamine, or a mixed xylylene diamine containing metaxylylene diamine and para-xylylene diamine in an amount of 30% or less of the total amount, as described in Publication No. 697, etc.; α
, ω-1 aliphatic dicarboxylic acid in the molecular chain at least 70 mol% can also be used as a blend with the ethylene-vinyl alcohol copolymer.

The molecular weight of these polyamides can generally be used without any particular restriction as long as it is within the range that allows film forming ability.
Dissolve 1 gram of polymer in 100 CC of 98% sulfuric acid,
Relative viscosity (ηRel) when measured at 20°C is 1.8
It is generally desirable that the value be in the range of 3.5 to 3.5.

Polyamides with a relative viscosity of less than 1.8 are combined with other resins to form a film or sheet, and when this is then subjected to plastic processing such as biaxial stretching, it gives a molded product with excellent mechanical strength. Polyamides having a relative viscosity higher than the above range generally appear to have poor melt moldability. As can be seen from Table 4, compared to the above-mentioned ethylene-vinyl alcohol copolymers and polyamides, thermoplastic polymers are useful for forming films or sheets made of blends, although they have inferior gas permeation resistance. As the coalescing material, aromatic polyester can be mentioned.

Such aromatic polyesters include, for example, polyesters consisting of repeating units of the formula or formula in which R3 is a linear alkylene group and R4 is an aromatic hydrocarbon group, in particular polyethylene terephthalate, polybutylene terephthalate, ethylene/ Butylene terephthalate copolymer, ethylene terephthalate/isophthalate copolymer, polyoxyethylene benzoate, etc. are used.

Melt extrusion is possible, and the above-mentioned Sp value and PO2
Examples of thermoplastic polymers that satisfy the following include so-called high nitrile content thermoplastic polymers.

Such resins include nitrile group-containing ethylenically unsaturated monomers such as acrylonitrile, methacrylonitrile, or mixtures thereof, in an amount of 40 to 97% of the total polymer.
mol%, preferably 60 to 86 mol%, and as a copolymerization component, conjugated diene hydrocarbons such as butadiene and isoprene; esters of ethylenically unsaturated carboxylic acids such as methyl methacrylate and ethyl acrylate; methyl vinyl ether, etc. Vinyl ether; monomers such as monovinyl aromatic hydrocarbons such as styrene and vinyltoluene,
Thermoplastic copolymers containing a large amount of the remaining thermoplastic copolymers may be used singly or in combination of two or more. Chlorine-containing thermoplastic polymers such as polyvinyl chloride, polyvinylidene chloride, vinylidene chloride copolymers, and internally plasticized vinyl chloride resins have problems with their thermal stability and melt moldability. It can be used for the purpose of the present invention under the condition that an organotin stabilizer, a metal soap stabilizer, a plasticizer, a lubricant, etc. which are known per se are added.

In a preferred embodiment of the present invention, PO2 is 5X10-11
Hereinafter, a plurality of resins, particularly 4.3 x 10-11 or less, are blended together to form a blend.

Thus, in this aspect of the present invention, at least two of the ethylene-vinyl alcohol copolymers, polyamides, aromatic polyesters, high nitrile resins, or chlorine-containing polymers have the aforementioned ΔSp value of 4.5 or less. Combine them to make a blend. In the present invention,
A more preferred combination of thermoplastic resins is a combination of ethylene-vinyl alcohol copolymer (a) and polyamide (b). The film or sheet made of this blend of ethylene-vinyl alcohol copolymer and polyamide exhibits an outstanding biaxially stretched form, and the formed stretch-molded container is resistant to oxygen, carbon dioxide, etc. It also has outstanding gas permeability, transparency, creep resistance, hardness, and other mechanical strengths. Furthermore, (a) and (b)
), the combination that can most significantly exhibit the above-mentioned performances is a combination with an ethylene content of 25 to 50 mol%.
, ethylene containing 1 mol% or less of vinyl acetate
Vinyl alcohol copolymer and prolactam concentration is 8
It is a copolyamide consisting of 5 to 95 mol% of prolactam/hexamethylene diammonium adipate copolymer. Suitable examples of combinations of thermoplastic resins other than those mentioned above are combinations of ethylene-vinyl alcohol copolymers and the above-mentioned aromatic polyesters, and combinations of polyamides and aromatic polyesters or high nitrile resins.

Of course, these high gas barrier thermoplastic resins include, for example, blends of ethylene-vinyl alcohol copolymer/polyamide/hynitrile resin or blends of ethylene-vinyl alcohol copolymer/polyamide/aromatic polyester. , it is also possible to use a combination of three or more types.

In another aspect of the invention, PO2 is 5 x 10-11
The following resin (A) and a thermoplastic resin (B) whose PO2 is greater than 5×10 −11 but whose solubility index (Sp) is 9.5 or more are used as a blend. As the resin (A), those already detailed are widely used, while as the resin (B), for example, acrylic resins such as polymethyl methacrylate and polyethyl acrylate; polycarbonate resin (Sp value: 10.1), etc. are used. be done.

In the present invention, it is important that the plurality of types of thermoplastic resins be blended in such a proportion that a blend having an elongation rate higher than their arithmetic average elongation rate (ε) is formed. be.

In this specification, the elongation rate (ε) is expressed by the following formula BO. In the formula, Lt represents the breaking length in the extrusion direction of the sheet or film or in the direction perpendicular to it, and LO represents the breaking length in the direction in which the break occurs first. The arithmetic average elongation rate (ε) is a value expressed by ε, which represents the initial length in the direction corresponding to .

is the elongation rate of a sheet obtained by extruding the thermoplastic resin contained in the blend alone, Xn is the weight fraction of the thermoplastic resin contained in the blend, and n is 2
The value defined above is equal to the number of types of thermoplastic resin contained in the blend.

In the present invention, a blend is obtained by combining a plurality of types of thermoplastic polymers in a quantitative ratio that exhibits a higher elongation rate than the arithmetic average elongation rate (ε) of the above formula (8). In the present invention, when a plurality of types of thermoplastic resins are combined so as to satisfy the above-mentioned requirements, an unexpected improvement in the stretch formability of the sheet or film is achieved, as shown in Example 7 of Example 1 described below. It will be readily apparent upon reference to the table and accompanying drawings, FIG. 1.

That is, the unstretched sheet molded from ethylene-vinyl alcohol copolymer and the unstretched sheet molded from 6/6,6 copolymerized nylon were heated at a temperature of 120°C and 30C7rL.
When simultaneously biaxially stretched at the stretching speed of Anin, each
% and an elongation rate of 130%. On the other hand, according to the present invention, when the above-mentioned ethylene-vinyl alcohol copolymer and 6/6,6 copolymerized nylon are blended at a certain ratio and made into a film, this film is prepared under similar conditions. When biaxially stretched, this film exhibits an elongation rate (solid line in Figure 1) that is significantly greater than its arithmetic mean elongation rate (ε) (dotted line in Figure 1), and, for example, the nylon/ethylene- For a blend with a vinyl alcohol copolymer weight ratio of 60/40, 230%
It shows an abnormally high growth rate reaching . As described above, according to the present invention, even a thermoplastic resin that itself has poor biaxial stretchability can be made into a film or sheet by blending multiple types of resin so as to satisfy the above-mentioned requirements. , the biaxial stretching formability is significantly improved.
The reason why the biaxial stretching formability of the sheet or film is significantly improved in the present invention is not yet fully clear.

However, as is clear from the fact that all the thermoplastic resins used in the present invention have a high solubility index,
Considering that these resins have polar groups that form strong hydrogen bonds between polymer chains and are soluble in highly polar solvents, the blend of the present invention has a plurality of One of the reasons may be that the different thermoplastic resins mutually act to plasticize the resins. Further, according to the present invention, gas barrier properties are significantly improved by blending multiple types of thermoplastic resins to form a film or sheet. This fact becomes immediately clear, for example, by referring to Table 8 of Example 2, which will be described later. The oxygen permeability coefficient (PO2) of ethylene-vinyl alcohol copolymer is 10-13
While that of nylon is on the order of 10-
of the order of 12, and the nylons are about 10
Showing twice as much PO2. In contrast, a blend of nylon and ethylene-vinyl alcohol copolymer exhibits an oxygen permeability coefficient that is significantly lower than the arithmetic mean value of the oxygen permeability coefficients of both, and this tendency is consistent with the biaxial stretching of blends of both nylon and ethylene-vinyl alcohol copolymers. This increases further. The specific blending ratio of the plurality of thermoplastic polymers used varies considerably depending on the type of resin and the stretching ratio for manufacturing the stretch-molded container, but in the present invention, thermoplastic polymers with a small oxygen permeability coefficient are used. resin,
For example, for the ethylene-vinyl alcohol copolymer (4), a resin having a larger oxygen permeability coefficient, such as polyamide or polyester (B), is added to the ethylene-vinyl alcohol copolymer (4).
At the weight ratio of ▼, the elongation rate of the blend is equal to the arithmetic average elongation rate (ε
) is preferably blended within a range that is greater than .

Blends used in the films and sheets of the present invention include:
Within a range that does not impair the biaxial stretch formability and gas permeation resistance mentioned above, generally within a range of 40% by weight or less per blend,
Polymers with a solubility index of less than 9.5 - e.g. low,
Polyolefin polystyrene or styrene copolymer such as medium or high density polyethylene, polypropylene, ethylene-propylene copolymer: ethylene-butadiene rubber, ethylene-propylene-diene rubber, polybutadiene, butadiene-styrene rubber, butadiene-acrylonitrile rubber, One or more of elastomers such as isoprene and polyisobutylene; ethylene monovinyl acetate copolymers; and ionomers may also be blended.

In the present invention, the blend described above is used in the form of multiple layers to form a sheet or film.

Multilayer structure In one embodiment of the present invention, at least one layer of the aforementioned blend and a moisture permeability of 100 x 10-12 g (7n/CTil-Se
Formed into a sheet or film as a laminated structure having at least one layer of a thermoplastic resin having an adhesive strength of at least c.CffLHg of at least 209/?
A multilayer stretched molded product having the above properties and having even more excellent gas barrier properties is obtained.

When the moisture permeability of the blend material is high, or when the gas permeability of oxygen and the like increases in a high humidity atmosphere, it is practically necessary to protect the blend material layer with a resin having a low moisture permeability.

For example, if the contents to be packaged in the final container are dry, it is necessary to protect the blended substance from the outside of the container, that is, from the outside air, and if the contents to be packaged by the container are hydrated. It is necessary to protect the blended material both from the outside of the container, ie, from outside air, and from the inside of the container. According to a preferred embodiment of the present invention, the blend material having excellent gas barrier properties has a moisture permeability of 100×10-129.
By laminating layers of thermoplastic resin having CTn/C7ll-Sec-0fnHg or less, high barrier properties can be significantly improved. Table 5 below shows moisture permeability values for various thermoplastic resins for reference.

The adhesive strength of a multilayer sheet or film generally tends to be considerably reduced by stretching.

The reason for this is thought to be that during stretch molding, different stresses are generated at the interfaces of each layer depending on the viscoelastic properties of the resin in each layer, and stress that causes the interfaces to peel off is generated. In a cup formed from the above-mentioned laminated sheet or film by normal thermoforming, it is at least 70 f! It is necessary for practical purposes, such as drop tests, to have a T-peel peel strength (adhesive strength) of /CTrL or higher. However, the adhesive strength of a cup formed from the above-mentioned laminated sheet or film by the drawing process described below is lower than that of a normal thermoformed cup made from the same laminated sheet or film for the reasons mentioned above. The adhesive strength required for practical purposes such as drop tests is at least 20f! / I found that it is good to have more than 100 cm. The reason for this is still not completely clear, but stretch molding significantly improves the viscoelastic properties of the inner and outer layer resin, for example, the elastic modulus increases significantly, so the amount of deformation for the same stress is small. This is thought to be due to the fact that when a force such as a fall or vibration is applied to the cup, the force applied perpendicularly to the laminated interface, ie, the peeling force, becomes smaller. Detailed data are shown in Reference Example 2 described later. As the moisture-resistant resin layer, low, medium or high density polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, polypentene-1, poly-4-methylbenzene-
or a copolymer of an olefin and an ethylenically unsaturated monomer containing a carbonyl group, such as ethylene monovinyl acetate copolymer, ionomer, ethylene-acrylic acid ester copolymer, maleic acid-modified polypropylene, Acrylic acid grafted polyethylene and the like are preferably used.

The carbonyl group concentration of the copolymer is 120 to 800 m
It is preferably in the range of eq/100g of polymer. In addition to the above-mentioned polyolefins or copolymers of olefins and ethylenically unsaturated monomers containing carbonyl groups, polyfluorinated ethylenes such as polyethylene trifluoride and polytetrafluoroethylene, although they have some drawbacks in moldability. Resins can also be used as the moisture-resistant resin layer. Furthermore, in another aspect of the present invention, at least one layer of the blend as described above is combined with initial elastic modulus (Eg) and delayed elastic modulus ( At least a thermoplastic resin having a sum of E1) of 1 x 101 ratio dyne/Cd or more, a steady flow viscosity (η00) of 1 x 1017 p0ise or more, and a delay time (TR) of 6 x 106 sec or less. A film for multilayer stretching, which is formed into a sheet or film as a laminated structure having one layer and an adhesive strength between each layer of at least 209/(1-JmoV! or more), and has even better creep resistance. In general, when a stress S is applied to a viscoelastic material such as a thermoplastic polymer for a time t, it behaves like a viscoelastic material when t is short, and as t increases, it behaves like an elastic material. In addition, the system behaves viscoelastically due to the influence of viscosity, and viscous flow occurs where t is sufficiently large.

These viscoelastic behaviors are Eg, El, η mentioned above. and various characteristics of TR. When a molded container is used as a pressure-resistant container such as a carbonated beverage container or an aerosol container, the material composing the container wall must not only have excellent gas barrier properties but also a suitable material that can withstand the pressure of the contents. A combination of hardness and creep resistance and impact resistance is required.

According to a preferred embodiment of the present invention, the blend layer having excellent gas barrier properties is laminated with a layer of a thermoplastic resin having viscoelastic properties within the above-mentioned range. Compared to the above, the creep resistance and hardness required for pressure containers are significantly improved, and the multilayer structure also improves impact resistance.

Among the above-mentioned viscoelastic properties, the sum of the initial elastic modulus and delayed elastic modulus (Eg+E1) is related to the hardness of the container.
Under the condition of
It is important that it is 1010 dyne/Crll or more.

In addition, the working flow viscosity (η00) and the delay time (TR) are related to creep resistance, and in the present invention, from the standpoint of preventing creep, ηo is 1×1017p0jse.
Above, especially above 5×1017p0ise, TR is 6×1
It is important that the time is less than 0.06sec, particularly 3×106sec or less. Table 6 below shows viscoelastic property values for various thermoplastic resins for reference.

In Table 6, PE (HD) is high-density polyethylene, IsO-
PP is isotactic polypropylene, FEP is fluorinated ethylene-propylene copolymer, PS is polystyrene, PVC is polyvinyl chloride, HNR is acrylonitrile-styrene-butadiene resin with an acrylonitrile content of 62 mol%, PTFE is polytetrafluorocarbon Ethylene, PCTFE is polychlorotrifluoroethylene, ABS
is an acrylonitrile-butadiene-styrene copolymer (
Styrene content: 51 mol%), PMMA represents polymethyl methacrylate, and PET represents polyethylene terephthalate.

In the present invention, as creep-resistant thermoplastic resins, among the thermoplastic resins listed in Table 6 above, those whose viscoelastic parameters are within the range specified in the present invention, in order of importance, polyethylene Preferably used are terephthalate, polybutylene terephthalate, polycarbonate, ABS resin, polyacetal, nylons, polymethyl methacrylate, isotactic polypropylene, polystyrene resin, and the like. In the case of sheets or films for producing pressure containers, thermoplastic resins whose viscoelastic parameters have low pressure and temperature dependence are most preferred; for this purpose, polyethylene terephthalate, polyethylene terephthalate,
Polycarbonate, optical polypropylene, polystyrene, etc. are most suitable.

In the present invention, the blend layer with excellent gas permeability resistance and the thermoplastic resin with excellent moisture resistance or creep resistance are:
It can be laminated with a variety of bonding methods and multilayer configurations.

For example, if the blend layer itself contains a thermoplastic resin having a carbonyl group in the main chain or side chain, such as polyamide, the blend layer itself may be more resistant to thermoplastic resins with excellent moisture resistance or creep resistance. Since they generally exhibit excellent thermal adhesion properties, laminated structures can be obtained directly by co-melt extrusion without the use of special adhesive means.
Of course, there may be cases where the above-mentioned carbonyl group-containing thermoplastic polymer is not contained in the blend layer or the moisture-resistant or creep-resistant thermoplastic resin layer, or even if it is contained, the delamination resistance between both layers may be reduced. In order to further improve
Free carboxylic acid, carboxylic acid salt, carboxylic acid ester, carboxylic acid amide, carboxylic acid anhydride, carbonic acid ester, urethane, urea, etc. in either or both of the blend layer or the moisture-resistant or creep-resistant resin layer adjacent to each other. The carbonyl group based on the functional group of polymer 100f
! 0.5 to 15 parts by weight per 100 parts by weight of the resin blend or moisture-resistant or creep-resistant resin. It is desirable to mix the amount.

Examples of such carbonyl group-containing polymers are disclosed in JP-A-49
-39678, in particular, ionomers (Surlyn A manufactured by Dupont), maleic anhydride-modified polypropylene, ethylene-acrylate copolymers, polyalkylene oxide/polyester block copolymers, etc. of the present invention. used for the purpose of

The blend layer and the moisture-resistant or creep-resistant resin can have any multilayer configuration as long as they are provided in an adjoining relationship; for example, 1. Asymmetric two-layer blend layer/moisture-resistant or creep-resistant resin; symmetrical three-layer structure: moisture-resistant or creep-resistant resin layer / blend layer / moisture-resistant or creep-resistant resin layer, blend layer / moisture-resistant or creep-resistant resin layer / blend layer, etc. It is possible to have a layered structure.

Moreover, instead of blending the carbonyl group-containing polymer in either or both of the adjoining blend layer and the moisture-resistant or creep-resistant resin layer, a carbonyl group-containing polymer may be added between the blend layer and the moisture-resistant or creep-resistant resin layer. , an adhesive layer made of the carbonyl group-containing thermoplastic resin described above is interposed, so that, for example, an asymmetrical three-layer structure: moisture-resistant or creep-resistant resin layer/carbonyl-containing adhesive layer/blend layer, symmetrical five-layer structure. It can have a multilayer structure such as a moisture-resistant or creep-resistant resin layer/a carbonyl adhesive layer/a blend layer/a carbonyl-containing adhesive layer/a moisture-resistant or creep-resistant resin layer.

Also, in the multilayer structure described above, the blend layer may be 80 to 0.5% of the total thickness of the final molded structure, especially 5%.
It is desirable that the amount is 0 to 2%.

Method for Forming Sheet or Film The sheet or film of the present invention is formed from a multilayer structure of the above-mentioned bread product and a water-resistant or creep-resistant thermoplastic resin. It can be manufactured by any means known per se.

For example, the sheet or film of the present invention can be manufactured by any method such as T-die molding or inflation molding. The molding conditions for this sheet or film are not particularly limited; for example, in the case of a molded structure with a single layer made of a blend, dry-blended thermoplastic resins of multiple types or pre-prepared thermoplastic resins may be used. Multiple types of thermoplastic resins are kneaded into a compound, heated in a cylinder to a temperature of generally 180 to 350°C, and then passed through a T-die or a tubular die for blown film to form a sheet or a compound. Extrude into film shape.
The extrusion pressure varies depending on the type and combination of resins, the size of the extruder, etc., but generally speaking, it is between 2 and 10
Preferably, a pressure of 00 kg/Crl is used. As an extruder, a Dalmage type screw or a metering type screw can be used, and as a die, a conventionally commonly used fish tail die or manifold die (T die) can be used. ) and screw dies can be used, and both T dies and inflation dies are used for film forming. In addition, it goes without saying that the aforementioned blend can be formed into a sheet or film by injection molding, hot compression molding, roll molding, or the like. In order to co-extrude the aforementioned blend and a water-resistant or creep-resistant thermoplastic resin into a multilayer sheet or film, a number of extruders corresponding to the types of resin layers to be coextruded, such as an extruder for the blend and an extruder, are used. Using an extruder for extruding a water-resistant or creep-resistant resin or an extruder for extruding a carbonyl-containing adhesive layer, each resin stream is extruded through a multilayer die into a multilayer sheet or film. .

Furthermore, in multilayer injection molding, a number of injection molding machines corresponding to the types of resin layers are used, and a plurality of types of resin streams are injected into a mold cavity through a composite nozzle.

In the case of hot compression molding, for example, if the intermediate layer is the blended material and the inner and outer layers are water-resistant resins, fill the mold with the desired amount of each resin in the order of the water-resistant resin, the blended material, and the water-resistant resin. A laminated structure in the form of a sheet or film can be produced by heating at an appropriate temperature for an appropriate time and then applying pressure.
Applications The sheet or film of the present invention is useful as a material for plastic working.

The plastic processing conditions for a multilayer sheet or film of the above-mentioned blend and a water-resistant or creep-resistant resin vary depending on the composition of the resin blend used, but generally the resin constituting the sheet or film is If the resin is crystalline, stretching can be performed at a temperature within the range of crystallization temperature or melting point, and if the resin constituting the sheet or film is amorphous, it can be stretched at a temperature within the range of glass transition temperature or crystallization temperature. Temperatures within the range of initiation temperature or flow initiation temperature, for example, for resins with a relatively high degree of crystallinity such as polypropylene and poly-4-methylbenzene-1, below the melting point (melting temperature) of those resins. Within the temperature range, for resins with relatively low crystallinity such as polyethylene terephthalate, polyethylene terephthalate/isophthalate copolymer, or polybutylene terephthalate, the temperature range is from above the glass transition temperature to below the crystallization start temperature of those resins. Furthermore, for amorphous resins such as polyvinyl chloride, polyvinylidene chloride, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, or resins with extremely low crystallinity, the temperature may exceed the glass transition temperature of those resins. Stretch molding is preferably carried out within a range below the flow initiation temperature.

In addition, for resins with a relatively fast crystallization rate, such as polypropylene, polybutylene terephthalate, and polyethylene terephthalate, melt-molded sheets or films can be formed at temperatures ranging from 1°C/l to 5000°C/l]! , preferably 5°C/11 to 1200°C/I! If the molded container is rapidly cooled at a cooling rate of 11 and plastic working is performed under the above-mentioned conditions, the transparency of the molded container will be further improved. If a multilayer sheet or film containing a resin blend exhibits thermal behavior specific to each resin, it is natural that the reference should be that of the resin with a higher crystallization temperature or glass transition point. That's true. The stretchability of a sheet or film made of the blend of the present invention, or a sheet or film made of a multilayer structure of the blend and a water-resistant or creep-resistant resin, is determined by changing the load-elongation curve of the sheet or film at each temperature. It can also be determined by measurement. That is, the lower limit of the temperature at which stretch forming can be performed can be easily determined as the temperature at which so-called netting does not occur in the sheet or film. The effect of biaxial stretching of a sheet or film varies significantly depending on the composition of the blend, but in general, the length of a stretched sample is measured after being left in an atmosphere at 50 to 150°C for 10 to 15 minutes. The structure after biaxial stretching has a heat shrinkage rate (σ) of at least 5% defined by the following formula, where Ls is the length of the stretched product and Le is the equilibrium length after the shrinkage treatment. In particular, if the content is 7% or more, it can be said that the stretching orientation provides effects such as improved creep resistance, hardness, and transparency.

For this reason, it is generally desirable that the stretching ratio of the sheet or film be in the range of 1.1 to 20 times, particularly 1.5 to 5 times.

The stretching speed of the sheet or film varies depending on the type of resin, and may be within a speed range such that the above-mentioned stretching effect is produced in the molded product after stretching, but in particular, the stretching speed is 10%/ml.
It is preferably within the range of 6,000,000%/MTl. An example of stretch-molding a multilayer sheet or film of the above-mentioned blend and water-resistant or creep-resistant resin under the above-mentioned stretching conditions will be described with reference to FIGS. 2, 3, 4, and 5. . In FIG. 2, the sheet or film 1 of the present invention is heated to a predetermined temperature, then clamped with clamps 4 and 5, and placed into a mold 6 to a predetermined depth with a plug 2 as shown in FIGS. 3 and 4. After pressing, as shown in FIG. 5, the vacuum valve 7 is opened and the sheet or film 1 is brought into close contact with the inner surface of the mold 6 by vacuum suction.

This molding method is often used for molding simple containers using thin sheets, and is generally called plug assist molding. Stretch forming described in this specification refers to the above-mentioned vacuum forming, as well as air pressure forming, sheet blow molding, drawing forming, drawing/ironing forming, compression forming, and other special forming processes from thick sheet pieces. front and back·
It is clear that this also refers to high-energy forming such as front-back extrusion and explosive forming.

Furthermore, the sheet-based film of the present invention is biaxially stretched by means known per se to form a biaxially stretched film,
A pouch-like container can be made by pasting opposing edge portions of a sheet made of this biaxially stretched film.

Epoxy or isocyanate adhesives may be used to bond the biaxially stretched films, and the moisture-resistant or creep-resistant resin layer provided on the innermost surface may be heat-resistant, such as polyethylene or polypropylene. If it has sealability, opposing edge portions can be bonded together by heat sealing. According to the present invention, a combination of a plurality of types of thermoplastic resins satisfying the above-mentioned requirements, most preferably an ethylene-vinyl alcohol copolymer and a polyamide, is molded into a sheet or a film, so that either one of the thermoplastic resins can be formed into a sheet or a film. Biaxial stretching molding, which would be impossible or difficult with resin alone, becomes possible, and the stretching ratio during molding can be significantly improved.

Therefore, by using the sheet or film for plastic processing of the present invention, it is possible to improve the stretching ratio, thereby significantly improving the creep resistance, mechanical strength, hardness, etc. of products such as final containers. Furthermore, as a result, it is possible to make the container thinner and lighter, and to significantly reduce the amount of resin used. In addition, when the material of the present invention is used, the resin used as a blend itself has significantly excellent gas permeation resistance, and furthermore, this gas permeation resistance is further significantly improved by biaxial stretching molding. As a result, a remarkable advantage is that excellent gas barrier properties are maintained even when the container walls are made significantly thinner than conventional gas barrier plastic containers.
The stretch-molded container using the material of the present invention generally has a basis weight (volume per unit g of resin) of 0.01 to 5 d1/9, particularly 0.05 to 2 d1/9, although it differs depending on its use. and the thickness of the container wall can be in the range of 0.02 to 5 Lm, especially 0.05 to 31 Lm,
Within these ranges, a desirable combination of gas barrier properties, mechanical strength, creep resistance, hardness and transparency can be achieved.

The stretch-molded container using the material of the present invention is further comprised of a blend of a plurality of thermoplastic resins mentioned above and is biaxially stretched, so that when the layers of the blend have the same thickness, Compared to the unstretched material, it has an oxygen permeability of 1 or less, especially 1 or less, a carbon dioxide gas permeability of 1 or less, especially 1 or less, and a water vapor permeability of 1 or less, especially - or less.

For example, in the case of low-malt beer such as beer and soft drinks saturated with carbon dioxide gas, the trace amount of oxygen that penetrates through the plastic container wall has a significant effect on the flavor, but if the material of the present invention is used, the aroma will be greatly affected. As a result, the shelf life of these beverages can be significantly improved. Furthermore, the molded container using the material of the present invention has extremely excellent barrier properties against carbon dioxide gas, and the drop in gas pressure of the contents can be maintained at a significantly lower level than in conventional plastic containers. Thus,
The stretch-molded container formed from the material of the present invention can be used for liquid or paste foods and beverages, such as low-malt beer such as beer,
Alcoholic beverages, including fruit liquors such as alcoholic beverages, whiskey, shochu and grape wine, and various cocktails such as Ginfuise; cola,
Various carbonated drinks including cider juice, plain soda, etc.; Straight juices such as lemon juice, orange juice, plum juice, budo juice, strawberry juice, etc.; Fruit juice drinks including processed fruit juice drinks such as Necta juice: tomato juice, various vegetable juices Cannabis juice drinks containing sugar; synthetic drinks and vitamin-enriched drinks containing synthetic fruit juice made with sugars such as sugar or fructose, citric acid, coloring agents, flavorings, etc., or vitamins added as necessary; lactic acid bacteria Beverages; seasonings such as mustard oil, sauce, vinegar, mirin, dressing, mayonnaise, ketchup, edible oil, soybean paste, lard, ketchup; condiments such as tofu, jam, butter, marcarin; liquid medicines, Pesticides, cosmetics, cosmetics, detergents; Also, ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as normal hexane and normal heptane; alicyclic hydrocarbons such as cyclohexane; aromatic compounds such as benzene, toluene, and xylene. Hydrocarbons; chlorine-containing compounds such as carbon tetrachloride, ethane tetrachloride, and ethylene tetrachloride; or various higher fatty acids;
Gasoline, kerosene, petroleum benzine, heavy oil, thinner, grease, silicone oil, light oil, machine oil; Useful as a container.

Example 1 Ethylene content is 25 mol%, vinyl acetate content is 0.
5 mol%, vinyl alcohol content 74.5 mol%,
Sp value is 11.3 (Cat/CC)%, intrinsic viscosity is 0.
121/f! , an ethylene vinyl alcohol copolymer (E) with a melting point of 182°C as determined by differential thermal analysis (DTA method) at a heating rate of 10/C/ml, and an Sp value of 12.7 (
Polycaprolactam (N1) with a relative viscosity of 1.9 and a melting point of 219°C by the DTA method, S
Prolactam/hexamethylene diammonium adipate copolymer (N2) with a p value of 12.8 (d/Cc)%, a relative viscosity of 3.3, a caprolactam concentration of 91 mol%, and a melting point of 193°C by the above DTA method. , Sp value is 10.7
(Cat/Cc)%, the intrinsic viscosity at 30°C in a mixed solvent with a weight ratio of phenol/tetrachloroethane of 50/50 is 0.101/9, and the melting point by the DTA method is 2.
Polyethylene terephthalate (PET) at 56°C, Psychopacz 8930 (Sp value =
11.7 (C (1t/CC)%, the glass transition point measured by the DAT method is 107°C, hereinafter referred to as AS), XT8 polymer manufactured by American Cyanamid Co., Ltd. (Sp value = 9.8
(01!./CC)%, the glass transition point is 102°C,
(hereinafter referred to as XT), Surlyn 8-A manufactured by DuPont, USA
(Ionomer Sp value = 7.9 (Cat/CC)%, the melting point is 104°C, hereinafter referred to as Su), density is 0.95
9/CC, the melting point is 142°C, and the Sp value is 7.9 ((X
! t/CC)% high density polyethylene (HD), the density is 0.929/Cc, the melting point is 108°C, and the Sp value is 8.
1(R4/Cc)% low density polyethylene (LD), density 0.90f! /Cc, isotactic polypropylene (PP) with a melting point of 154°C and an Sp value of 7.9 (Ca!, /Cc) 3A, a melt index of 6.0
9/101, the glass transition point is 92°C, and the Sp value is 8.
Attractive polystyrene (PS) of 6 ((:
Using an extruder with an effective length of 1,100 mm, a sheet with a width of 150 mm and a wall thickness of 0.5 mm was formed.

For comparison, a sheet of each resin alone (thickness is 0.511
) was also molded using the same extruder. A simultaneous biaxial stretching test was conducted on each of these sheets using a biaxial stretching machine manufactured by Iwamoto Seisakusho Co., Ltd.

The stretching conditions were as follows: temperature was 120℃, initial length of sample was 80×
The shape was 8011 square, and the stretching speed was 30011 mm. The elongation rate (ε} was determined according to the formula (7) in the specification. In this test, the fracture occurred first in the direction perpendicular to the extrusion direction of the sheet. The results are shown in Table 7. 7th
The table shows that the Sp values are all 9.5 (C (1t/CC)% or more) and the difference in Sp values (ΔSp) is 4.5 (d/Cc)%.
For blend systems of resins within the range, the elongation rate (ε)
shows that both values are larger than the arithmetic average elongation rate (ε). Furthermore, it is known from Table 7 that this tendency is remarkable in the combination of ethylene/vinyl alcohol copolymer (EV) and polyamide resin (N1 and N2). In addition, the Sp value was 9.5 in the presence of EV and N2.
Adding a small amount of resin of (d/Cc)% or less, the elongation rate ε is E
It is known that this is not substantially different from the case of a two-component system of V and N2. Example 2 An ethylene-vinyl alcohol copolymer (EV) and a cap0lactam/hexamethylene diammonium adipate copolymer (nylon 6/6,6 copolymer, N2) having the physical properties described in Example 1 were used. A sheet with a width of 150 m and a wall thickness of 0.5 mm was molded using the same extruder and extrusion conditions as in Example 1, but with different mixing ratios (weight ratios).

Then, a simultaneous biaxial stretching test was conducted under the same conditions using a biaxial stretching machine and a simultaneous biaxial stretching machine under the same conditions as in Example 1. The results are shown in Figure 1. From FIG. 1, the elongation rate (
ε) is larger than the arithmetic average elongation rate (7) calculated from the elongation rates of each of E and N2 alone, and has a maximum value when the N2/EV mixing ratio (weight ratio) is around 60/40. It is known that Next, the samples of each composition were subjected to 100% simultaneous biaxial stretching under the same conditions as before using a biaxial stretching machine, and the corresponding unstretched samples of each composition were tested using a gas permeation tester. using a temperature of 37, 0% RH
The oxygen gas permeability coefficient (PO2) and the carbon dioxide gas permeability coefficient (PcO2) were measured under the humidity of 100 mL, and the water vapor permeability (QHO, converted to a thickness of 50 μm) of each sample was measured in accordance with JlSZ-0208. Furthermore, the heat shrinkage rate (σ) in the sheet extrusion direction (MD) and the direction perpendicular to it (TD) after leaving the 100% simultaneously stretched sample in an oven at a temperature of 140°C for 15 minutes was calculated using equation (9). I asked. The results are also shown in Table 8. From Table 8, we can see that it is impossible to measure the stretched product because E alone cannot stretch 100%, and that N2 alone cannot measure the stretched product.
By stretching to 00%, each of the permeability of oxygen, carbon dioxide, and water vapor (PO2, PCO, and QH2O) of the stretched product becomes higher than that of the unstretched product. It is known that barrier properties deteriorate.

On the other hand, in the mixed system of EV and N2, each permeability of the stretched product is smaller than the value of the unstretched product, and the heat shrinkage rate (b) is also higher than that of N2 alone, and the barrier properties are improved due to the stretching effect. It is known from Table 8 that Example 3 An inner and outer layer extruder with a built-in full-flight screw with a diameter of 657!1j and an effective length of 143011, and a melt channel branched into two flow paths, and an extruder with a diameter of 50 m.
A sheet having a width of 200111 and a wall thickness of 1.0 m1 was extruded using a combination of an extruder for intermediate layer equipped with a full-flight screw having an effective length of 110011 and a triple T die for multilayer.

The resins used for molding were as follows: (a) for the inner and outer layers, for the polyethylene terephthalate (PET) intermediate layer in Example 1;
The ethylene-vinyl alcohol copolymer alone in Example 1, (b) the prolactam/hexamethylene diammonium adipate copolymer (nylon 6/6,6 copolymer) alone in Example 1, and (c) the above Ethylene-
Using a mixture of vinyl alcohol copolymer and the nylon 6/6,6 copolymer in a weight ratio of 40/60, the outer layer:
The thickness ratio of the intermediate layer to the inner layer was 1:1:1 in both cases.
For comparison, the extruder for the inner and outer layers was used alone, the extruder for the PET was used alone, and the extruder for the intermediate layer was used alone for the ethylene-vinyl alcohol alone, the nylon 6/
Sheets of a single 6,6 copolymer and a blend having the blending ratio in (c) above were molded. The shape of the sheet was the same as above. Reference Example 1 The seven types of sheets in Example 3 were heated at 110°C for 5 minutes, and then molded with an inner diameter of 100°C using a mold at a temperature of 20°C.
mj height is 150" wall thickness is 0.611111 internal volume is 1
An attempt was made to form a cylindrical cup of 150CC with a basis weight of 0.22 to 0.29 d1/9 by the biaxial stretching vacuum forming method as shown in FIGS.

Hereinafter, a stretched laminated cup made of the PET and (a) will be described as A.
, PET and (b), B, PET.
A stretched laminated cup consisting of (C) and (c), D1 a stretched cup of PET alone, D1 a stretched cup of ethylene-vinyl alcohol alone, E1 a stretched cup of nylon 6/6,6 copolymer, F1 a stretched cup of the above blend. It is written as G. on the other hand,
For comparison, the extruder and cup mold described above were used,
Seven types of cylindrical laminated cups, single cups, and blend cups having the same shapes as those described above were molded by a known thermoforming method (molten sheet vacuum forming method).

Since these seven types of cups were formed by vacuum forming from molten sheets, it was confirmed from observation using polarized fluorescence that they were all unstretched cups. Hereinafter, an unstretched cup having the same resin and layer structure as above A is J1 a cup corresponding to above B is K1 a cup corresponding to above C is L1 a cup corresponding to above D is M1 a cup corresponding to above E is N1 The cup corresponding to the above F is written as P1, and the cup corresponding to the above G is written as Q. The moldability of these 14 types of cups (visual judgment by a panel of 5 people), the oxygen permeability (QO2) of the cups by a method similar to the bottle oxygen permeability measurement method described in JP-A-50-49379. , 10 per 3 cups of each type
Moisture reduction rate (Lw = 1
00XCL0-Lt]/LO, where L.

(initial moisture content, 10009, Lt means average moisture weight after 7 days), 1200f for 10 cups of each type! of saline solution and placed in an atmosphere at -1°C for 30 minutes.
After leaving it for day and night and taking it out, immediately heat it at a temperature of 20℃ for 1 hour.
．． Drop strength when dropped from a height of 2m onto a concrete surface so that the bottom of the cup hits the concrete surface (FB = 100 x [1
0-F1]/10, where F1 means the number of cups broken in the first drop test), each type of cup was filled with 10009 Coca-Cola 8 (trade name), and 2
After being left at a temperature of 5℃ for 48 hours, the change in carbon dioxide pressure is defined as (LcO2=100XCP0-Pt)/PO, where P. is the initial pressure of carbon dioxide, in this case about 3kg/C.
fl, Pt means carbon dioxide pressure after 48 hours)
and deformation (defined as Df = 100. ) were measured respectively. In addition, the cup wall surface should be 50 mm in the height direction (MD) and 5 mm in the perpendicular direction (TD).
After cutting off the sample and leaving it in an oven at 130°C for 15 minutes, the heat shrinkage rates in the MD and TD directions were determined based on equation (9). The results are shown in Table 9. From Table 9, it is clear that ethylene-vinyl alcohol copolymer (8
) is known to be impossible to perform such biaxial stretching.

In addition, the unstretched 1 molded cup (J-Q) has a larger loss of carbon dioxide pressure and cup deformation than the biaxially stretched molded cup (A-G), and the copolymerized nylon and the ethylene-vinyl alcohol The three-layer laminated cup (C) with a blend of polymer as the middle layer and the polyethylene terephthalate resin as the inner and outer layers has barrier properties such as QO2, LcO2, and Lw due to the stretching effect, as known from σ. It is known from Table 9 that it has excellent mechanical properties such as deformation and strength. It is also known that the barrier properties of stretched products of the blends are improved due to the stretching effect. Example 4 The ethylene-vinyl alcohol copolymer and prolactam/prolactam copolymer in Example 1 were prepared using a multi-layer triple T die equipped with the inner and outer layer extruders and the middle layer extruder in Example 3.
Hexamethylene diammonium adipate copolymer (a mixture with nylon 6/6, 6 in a weight ratio of 40/60 was used as the intermediate layer, and as the inner and outer layers, (a) an ethylene content of about 1
0 wt% ethylene-propylene copolymer, (b) a maleic acid modified product of the ethylene-propylene copolymer of the above (a), (c) a maleic acid modified product of the ethylene-propylene copolymer of the above (a). A product with a higher degree of modification (maleic acid content) than the modified product in (b), and (d) a product in the above (a).
) of the ethylene-propylene copolymer modified with maleic acid, which has a higher degree of modification than the modified product of (c), and the thickness ratio of the outer layer: intermediate layer: inner layer is 1:1:1. is 2001! , a sheet having a wall thickness of 1.011 mm was extruded.

Reference Example 2 After heating the four types of sheets in Example 4 at 150°C for 20 minutes, using a mold at a temperature of 20°C, the inner diameter was 1.
An attempt was made to mold a cylindrical cup with a height of 150 mm, a wall thickness of 0.6 mm, and an internal volume of 1150 cc by the biaxial stretching vacuum forming method as shown in FIGS. 2, 3, 4, and 5.

Below, a stretched laminated cup consisting of a mixture of (a) and the above ethylene-vinyl alcohol copolymer and nylon 6/6,6 copolymer is used. A stretched laminated cup made of a mixture of 6,6 copolymer is 0B, (c), and a stretched laminated cup made of a mixture of ethylene-vinyl alcohol copolymer and nylon 6/6,6 copolymer is 0C, (d). ), ethylene-vinyl alcohol copolymer, and nylon 6/6,6
A stretched laminated cup made of a mixture with a copolymer is designated as OD. On the other hand, for comparison, four types of cylindrical laminated cups having the same shape as those described above were formed by a known thermoforming method (molten sheet vacuum forming method) using the extruder and cup mold described above. did.

Since these 4j types of cups were formed by vacuum forming from molten sheets, it was confirmed from observation using X-ray diffraction and polarized fluorescence that they were all unstretched cups. Ta. Hereinafter, an unstretched cup having the same resin and structure as the above 0A is DAl, a cup corresponding to the above 0B is DBL, a cup corresponding to the above 0C is DCl the above 0
The cup corresponding to D is written as DD. Three specimens of width 10 m and length 100 mI were cut from the body of each of these eight types of cups in the height direction of the cup, and peeled at a peeling rate of 100 in an atmosphere of room temperature (20°C) and 60% RH.
T-peel peel strength of m1/Min, 10 cups of each type were filled with 12009 saline solution, left in an atmosphere of -1℃ for 3 days and nights, taken out, and then immediately heated to 1.2m at a temperature of 20℃. The drop strength (FB; defined in Reference Example 1) was measured when the cup was dropped from a height of 100 to a concrete surface so that the bottom of the cup touched the concrete surface.

The results are shown in Table 10. From Table 10, the peel strength of the stretch-molded cup is 209/? It can be seen that FB becomes extremely small when the peel strength exceeds 709/Cln in the case of a normal thermoformed cup. In other words, stretch-molded cups have significantly lower adhesive strength such as drop strength that can withstand practical use than thermoformed cups.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the relationship between the composition ratio and elongation rate (%) of copolymerized nylon/ethylene-vinyl alcohol copolymer, and Figures 2, 3, 4, and 5 are FIG. 3 is an explanatory diagram for explaining the steps of a biaxial stretching molding method. 1...Resin, 2...Plug, 3...
...Chamber, 4...Outer clamp, 5...
...Inner clamp, 6...Mold, 7
...Vacuum valve.

Claims (1)

[Scope of Claims] 1 A sheet or film made of a thermoplastic resin, the sheet or film having a solubility index (S
p) of 9.5 or more and at least one layer of a blend mainly composed of multiple types of melt-extrudable thermoplastic resins, and a moisture permeability of 100 x 10^-^ at a temperature of 50°C or less.
1^2g・cm/cm^2・sec・cmHg or less and at least one layer consisting of a thermoplastic resin, and the plurality of types of thermoplastic resins in the blend are at least one of the Oxygen permeability coefficient of resin is 5×1
0^-^1^1cc・cm/cm^2・sec・cmH
g or less and the difference in solubility index between each resin (ΔSp)
is selected to be 4.5 or less, and the blend has a higher elongation rate than its arithmetic mean elongation rate (@ε@). 2. The sheet or film according to claim 1, wherein the moisture-resistant resin is a polyolefin or a copolymer of an olefin and a carbonyl group-containing ethylenically unsaturated monomer. 3. The sheet or film according to claim 1, wherein the sheet or film has a multilayer structure comprising an inner layer made of the moisture-resistant resin, an intermediate layer made of the blend, and an outer layer made of the moisture-resistant resin. 4. The moisture-resistant resin is a polyolefin, the layer of the blend and the layer of the polyolefin are provided in an adjacent positional relationship, and the blend or the polyolefin has 1
The sheet or film according to claim 1, wherein a thermoplastic polymer having a carbonyl group content of 120 to 1400 meq/100 g is blended in an amount of 0.5 to 15 parts by weight per 00 parts by weight. 5 A sheet or film made of a thermoplastic resin, the sheet or film having a solubility index (Sp)
is 9.5 or more and is melt-extrudable at least one layer of a blend mainly composed of multiple types of thermoplastic resins, at a temperature of 23 ° C. and under a stress of 7 × 10^7 dyne/cm^2. The sum of the initial elastic modulus (Eg) and delayed elastic modulus (E_1) is 1 x 10^1^0 dyne/cm^2 or more, and the steady flow viscosity (η∞) is 1 x 10^1^7 poise
or more, and the delay time (t_R) is 6×10^6se
and at least one layer made of a creep-resistant thermoplastic resin having a creep-resistant thermoplastic resin of less than or equal to 10^-^1^1cc/cm
/cm^2sec・cmHg or less, and the difference in solubility index (ΔSp) between each resin is selected to be 4.5 or less, and the blend has an arithmetic average elongation rate (@ε
A sheet or film characterized by having a higher elongation rate than @). 6 The creep-resistant thermoplastic resin is polyethylene terephthalate, polybutylene terephthalate, polycarbonate, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, polyacetal, polyamide, polymethyl methacrylate, polystyrene or polyarylate, polyphenylene oxide, iso The sheet or film according to claim 5, which is made of tactical polypropylene or polysulfone. 7. The sheet or film according to claim 5, wherein the sheet or film has a multilayer structure consisting of an inner layer made of the creep-resistant resin, an intermediate layer made of the blend, and an outer layer made of the creep-resistant resin. .