JP2708539B2 - Resin composition and molded product thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a low melting polyamide resin of more than 40% by weight and less than 95% by weight and a vinylidene chloride resin of less than 60% by weight and 5% by weight.
The present invention relates to a polyamide resin composition comprising the above. Further, a molded product such as a film, a sheet or a container comprising the resin composition having improved mechanical properties and improved gas barrier properties under high humidity, particularly a stretch molded product having improved gas barrier properties and transparency. It is.

Conventional technology Conventionally, polyamide resins have excellent properties such as toughness, heat resistance, cold resistance, oil resistance, and transparency. It is industrially used as a resin in the field of melt extrusion moldings. (JP-A-60-105448, JP-B-59-37931).
However, the polyamide resin has a large oxygen permeability coefficient under high humidity, and its use range is limited.

Since the polyamide resin is a hydrophilic resin in its structure, it absorbs moisture in the atmosphere under a high humidity atmosphere, is plasticized by the absorbed water molecules, and has a poor barrier property against oxygen and water. If the barrier property has humidity dependency, not only the humidity of the outside air but also the moisture content of the content itself must be considered, so the polyamide resin has insufficient gas barrier properties especially when packaging content with a high moisture content. Becomes

In general, as a method for reducing the oxygen permeability coefficient of a polyamide resin, there is a method of mixing a saponified product of ethylene-vinyl acetate copolymer (Japanese Patent Laid-Open No. 62-7776). There are problems such as generation of cross-linking glue during melt extrusion.

Disadvantages of conventionally known polyamide resins, namely, a problem that oxygen gas barrier property under high humidity atmosphere is poor, a problem that moisture permeability under high humidity atmosphere is large,
In order to solve these problems by mixing with other resins, it is desired to improve the moldability, the oxygen gas barrier property, and the problem that the low-temperature impact strength cannot be maintained at the same time to reach a practically satisfactory level. .

Attempts have been made to solve this problem by laminating another resin layer on the polyamide resin layer (U.S. Pat. No. 4,112,182, JP-A-62-273849). It has the disadvantage of becoming complicated.

The present inventors have intensively studied to obtain a polyamide resin composition having improved gas barrier properties under high humidity, and as a result, a resin composition having a specific ratio of a polyamide resin and vinylidene chloride is a novel one, Further, they have found that they have properties that are practically satisfactory, and furthermore, molded articles obtained from this resin composition, particularly stretch molded articles in which vinylidene chloride resin is dispersed as flat dispersed particles in polyamide resin, have excellent gas barrier properties. The inventors have found that they have improved transparency, and have arrived at the present invention based on this finding.

Means for Solving the Problems The resin composition constituting the stretch molded product of the present invention has a crystalline melting point.
It is composed of a polyamide resin having a low melting point of 210 ° C. or less and a vinylidene chloride resin (hereinafter abbreviated as PVDC).

As the polyamide resin, a low melting point polyamide resin having a crystal melting point of 210 ° C. or lower, preferably 200 ° C. or lower, more preferably 190 ° C. or lower is used. In the present invention, the crystal melting point of the polyamide resin is the maximum value of the melting curve obtained by heating a sample of 8 to 10 mg at a heating rate of 20 ° C./min using a differential scanning calorimeter (TA-3000 manufactured by Mettler). Shown at the indicated temperature. As the low-melting polyamide resin, for example, any one of an aliphatic (C _{4 to} C ₁₂ ) polyamide, an alicyclic polyamide, and an aromatic polyamide or a mixture thereof is used. Examples of a monomer constituting the polyamide resin, for example, the number of carbon atoms C ₆ -C
₁₂ linear ω-aminocarboxylic acids and their lactams, adipic acid, sebacic acid, dodecanedicarboxylic acid, heptadecanedicarboxylic acid, hexamethylene diamine, isophthalic acid, bis- (4-aminocyclohexyl) -methane, 2,2 -Bis- (4'-aminocyclohexyl) -propane, terephthalic acid or its dimethyl ester, 1,6-diamino-2,2,4-trimethylhexane, 1,6
-Diamino-2,4,4-trimethyl-hexane, 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane and the like are preferable, and polymers and copolymers formed therefrom are used. Of these, nylon 6-66, nylon 6-69, nylon 6-11, nylon 11, nylon
12, nylon 6-12, nylon 6-66-610, nylon 6-66-610-612 and the like are preferred.

Polyamide resin with a crystalline melting point of 210 ° C or higher has a higher processing temperature during melt extrusion of the resin composition mixed with PVDC and PV
DC is easily decomposed, and good processing becomes difficult.

The glass transition temperature (Tg) of the polyamide resin is preferably 55 ° C. or lower, more preferably 47 ° C. or lower. The glass transition temperature is
According to DIN53445, a viscoelasticity measuring instrument TPA-1 manufactured by Resca Corporation
It was measured using type 0. The sample used was a polyamide resin press sheet that was slowly cooled and crystallized.

The PVDC used in the present invention is a copolymer mainly containing vinylidene chloride, preferably 65 to 98% by weight of vinylidene chloride and at least one monomer copolymerizable therewith with 2 to 35% by weight. Is used. Examples of copolymerizable monomers include vinyl chloride, acrylonitrile, alkyl acrylate (1 to 18 carbon atoms of alkyl group), alkyl methacrylate (1 to 18 carbon atoms of alkyl group), acrylic Those selected from acids, methacrylic acid and the like are preferred. 65% by weight of vinylidene chloride
If the amount is smaller, it becomes rubbery at room temperature and the gas barrier property is inferior. On the other hand, if the content is more than 98% by weight, the melting point becomes high and the composition is easily thermally decomposed, so that stable melt extrusion processing becomes difficult.

In the resin composition constituting the stretch molded product of the present invention, melt extrusion is usually performed alone, and PVDC containing 90 to 98% by weight of vinylidene chloride having excellent gas barrier properties, which is difficult to stretch, is also mixed with a large amount of polyamide resin. It can be easily melt-extruded and stretched to obtain a stretch molded product. Mixing ratio of low melting polyamide resin and PVDC is 40 for polyamide resin.
More than 95% by weight, preferably 45 to 90% by weight, more preferably 50 to 85% by weight, and PVDC is less than 60% by weight, 5% by weight or more, preferably 10 to 55% by weight. Is 15 to 50% by weight. When the amount of the polyamide resin is less than 40% by weight, the low-temperature impact strength is slightly lowered, and when the polyamide resin is used at an extremely low temperature, an inappropriate case occurs. PVDC is 5
If the content is less than 10% by weight, the gas barrier property is inferior, and it becomes difficult to store the contents for a long time.

The polyamide resin used in the present invention is more than 40% by weight, and 95% by weight or less, PVDC less than 60% by weight, and a resin composition of 5% by weight or more as long as the objects and effects of the present invention are not impaired, polyethylene, polypropylene, Modified polyolefins such as ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and their maleic acid grafts, ionomers and the like Inorganic and organic additives such as thermoplastic resins, elastomers and inorganic fillers and pigments can be added.

In addition, a small amount of a plasticizer, a stabilizer, a lubricant, an antioxidant, and the like can be added as needed. The resin composition thus obtained is used for a molded product, preferably a sheet, a film or a container. The molded product is polyamide resin 40
More than 95% by weight, less than 95% by weight, less than 60% by weight of PVDC, and at least one layer composed of the resin composition of 5% by weight or more, and other resin layers within a range not hindering the object of the present invention. Is also possible.

In the case of a single layer, a composition obtained by blending a polyamide resin and PVDC is melt-extruded by an extruder according to a conventional method, and is formed into a sheet, film or container by T-die molding, blow molding, inflation molding, or the like. it can. In the case of a multilayer, it is melt-extruded using a plurality of extruders and molded using a die for the multilayer.

Further, a sheet or film made of another resin may be bonded to a sheet, film or container having a layer made of a composition of a polyamide resin and PVDC.

The molded product obtained from the resin composition constituting the stretch molded product of the present invention has excellent low-temperature impact properties, practical oxygen gas barrier properties under high humidity, and moisture permeability.

The molded article preferably has an oxygen permeability coefficient of 2.0 × 10 ⁻¹¹ cc · cm / cm ² · sec · cmHg at 30 ° C. and 100% RH and a thickness of 30 μm at 40 ° C. and 90% RH. moisture permeability of preferably not more than 150g / m ² · day, brittle temperature Tb of
The value is preferably 10 ° C. or less.

Further, the obtained stretched product such as a film, sheet or container is subjected to PVDC in a layer composed of polyamide resin and PVDC.
So that the dispersed particles have a flat shape that is long in at least one stretching direction and the flatness of the cross section of the dispersed particles (long axis of the cross section of the dispersed particles / short axis of the cross section of the dispersed particles) is 2 or more. It is stretched. The stretch ratio may be any stretch ratio that satisfies these conditions, but is preferably 4 times or more, more preferably 6 times or more in area stretch ratio. Also,
There is no particular limitation on the ratio of the stretching ratio in the vertical direction and the horizontal direction,
It may be uniaxial stretching or biaxial stretching.

The area stretching ratio means a longitudinal stretching ratio × a transverse stretching ratio.
By performing such a stretching treatment, the properties of the molded product are further improved, and the oxygen permeability coefficient at 30 ° C. and 100% RH is 3/4 or less as compared with the case where the film is not stretched. Has a cloudiness of 3/4 or less as compared with the case where it is not stretched. If the area stretching ratio is 4 or more, good results can be obtained, but it is preferable that the vertical and horizontal stretching ratios are the same.

The reason why the oxygen permeability coefficient becomes very small by performing the above-described stretching treatment on the resin composition layer constituting the stretch-formed product of the present invention is not yet sufficiently clear, but the shape of the dispersed particles is large. You may be involved. In general, the physical properties of polymer blends depend on the size of the dispersed particles,
It greatly depends on the shape and the arrangement. For example, the gas permeability coefficient is such that the polymer serving as the barrier material is dispersed in another resin in a flat shape such as a disk or a flake, and the major axis thereof is the surface of a film, sheet, container, or the like. In the case where the polymers are arranged in parallel to the direction, the size of the polymer serving as the barrier material is smaller than the case where the polymers are spherically dispersed in another resin.
What is important in this case is the flatness of the dispersed particles. When the flatness of the cross section of the dispersed particles is defined as the long axis of the cross section of the dispersed particles / the short axis of the cross section of the dispersed particles, the effect of reducing the transmission coefficient is small when the flatness is small, but the transmission is small when the flatness is large. The effect of reducing the coefficient is very large.

In the layer comprising a mixture of PVDC and polyamide of the present invention, PVDC has a function as a barrier material,
By stretching the cross section of the dispersed particles so as to increase the flatness, the oxygen gas barrier property is improved. In particular, by stretching so that the flatness of the cross section is 2 or more, the oxygen gas barrier property is significantly improved even when the amount of PVDC is small. The stretched film of the present invention has an oxygen transmission coefficient at 30 ° C. and 100% RH of 2.0 × 10 ⁻¹¹ cc · cm / cm ² · sec · cmHg or less, preferably 1.5 × 10 ⁻¹¹ cc · cm / cm ² · sec · cmHg or less.

Further, the reason why the transparency is greatly improved by stretching the mixture layer of the present invention is not sufficiently clear yet, but it is considered that the shape of the dispersed particles is greatly involved in this as well. . That is, it is considered that this is because the manner of scattering light changes as the shape of the dispersed particles changes. In particular, when the flatness of the dispersed particles is 2 or more, a remarkable effect is produced, and a molded product having a thickness of 30 μm and a haze of 40% or less can be easily obtained.

Those having a haze of more than 40% are not preferred in the field where transparency is required, especially in the field where the contents of the package are required to be easily seen.

According to the present invention, a molded article having excellent low-temperature impact strength can be obtained. The low-temperature impact strength was evaluated by measuring the brittle temperature (Tb). The Tb value is practically preferably 10 ° C. or less, more preferably 5 ° C. or less, and most preferably 0 ° C. or less. In the composition of the present invention, sheets, films and containers having extremely low Tb value can be obtained.

This means that molded articles composed of a mixture of PVDC and polyamide have the common sense of conventional polyamides, that is, the disadvantage that the gas barrier properties under high humidity are insufficient, and the common sense of PVDC, that is, low-temperature impact strength. Breaking down the conventional wisdom that it must be dealt with by lamination with other resins in order to compensate for the insufficiency of insufficiency, and that a single-layer molded product can sufficiently compensate for these insufficiencies. Is shown. In the present invention, a known arbitrary method of performing cold or warm by utilizing plastic deformation of a resin is used for stretching, and in addition to stretching by ordinary stretching, drawing, ironing, vacuum forming, and pressure forming. , Sheet blow molding, compression molding and the like. Further, the same effect can be obtained in the stretching that can flatten the dispersed particles even in the stretching in the fluid state.

Further, the sheet or film of the present invention can be formed into a pouch-shaped (bag) -shaped container by laminating the opposite edges. For bonding, an epoxy-based or isocyanate-based adhesive may be used, or bonding may be performed by heat sealing or high-frequency sealing.

Effect of the Invention The resin composition constituting the stretch molded product of the present invention has a crystalline melting point.
Exceeding 40% by weight of low melting polyamide resin of 210 ° C or less, 95%
Since the polyamide resin composition comprises less than 5% by weight and less than 60% by weight of PVDC and less than 5% by weight of PVDC, it is possible to obtain a molded product excellent in gas barrier properties and high-temperature impact strength under high humidity, particularly a film, sheet or container. it can.

Further, by having at least one layer containing the resin composition as a main component and stretching the cross-sectional flatness of PVDC as dispersed particles to be 2 or more, further improved gas barrier property and improved. A transparent film, sheet, container or the like.

Therefore, it is suitable for packaging materials such as foods that are easily denatured by oxygen gas, for example, beverages such as ham, sausage, livestock meat, juice, and cider. These foods and beverages often require refrigeration or freezing during production, distribution, and storage, and therefore require low-temperature impact strength. However, the molded article of the present invention has excellent low-temperature impact strength, so that the product breaks. The ratio becomes very small, and the yield and workability are greatly improved. Further, in a molded product stretched to 4 times or more in area stretching ratio, transparency is improved, the contents of the product can be seen, and the commercial value is extremely high.

 Hereinafter, the present invention will be described in detail with reference to examples.

 The measuring method of each property of the molded product is as follows.

-Oxygen permeability coefficient According to ASTM D3985-81, use MOCON OXTRAN-100 manufactured by Modern Control Co., at 30 ° C, 100%
It was measured under the condition of RH.

Moisture Permeability The moisture permeability of a 30 μm-thick film was measured at 40 ° C. and 90% RH according to the method described in JIS z0208.

-Crystal melting point The crystal melting point of the polyamide was measured with a Mettler DSC TA3000 according to ASTM D3418.

Haze (HAZE) The haze (HAZE) of the molded product was measured with a # 80 COLOR MEASURING SYSTEM manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM 1003, and the value converted to a thickness of 30 μm was shown.

・ Measurement method of flatness of dispersed particles Ultra-thin sections were prepared so that the cross section of a sheet, film, or container could be observed, photographed with a transmission electron microscope 100CX of JEOL Ltd. Flatness was determined.

Here, the major axis of the cross section of the dispersed particles is the length of the sheet or film and the container in the stretching direction in the direction of the largest stretching ratio. The minor axis of the cross section of the dispersed particles is the thickness of the thickest part of the dispersed particles. The major axis of the cross section of the dispersed particles and the minor axis of the cross section of the dispersed particles are the average values of the 20 dispersed particles.

・ Measurement of film embrittlement temperature Measurement was performed by the Kureha Chemical Method. Measurement temperature (room temperature ~
-30 ° C), 3mm diameter with hemispherical tip (1.5mm radius)
A shock was applied to the measurement film at a speed of 1 m / sec by a cylindrical punch (punch).
No was observed.

Generally, phenomena involving destruction have a large statistical variation, so in order to determine the embrittlement temperature more precisely, the number of measurements under one temperature condition is set to n = 20, and the temperature at which 20 do not break at all is determined.
When the total of the destruction rate (%) at each temperature during the measurement at intervals of 5 ° C between the maximum temperature (Th (° C)) at which all 20 pieces break and S is the film embrittlement temperature, It was calculated by the following equation.

Tb = Th + ΔT {(S / 100) − (1/2)} Tb; Film embrittlement temperature (° C) Th; Maximum temperature (° C) at which all 20 measurement samples are destroyed ΔT; Measurement temperature interval (5 (° C.)) S: Sum of destruction rates at each temperature from the lowest temperature to Th at which all 20 measurement samples do not break down Example 1 (Reference Example) and Examples 2 to 4 Nylon 6 having a crystal melting point of 130 ° C. -12 (copolymer of nylon 6 and nylon 12, copolymer ratio 50/50 by weight)
After dry-blending Grilon CF 6S (Tg = 30 ° C) and vinylidene chloride / vinyl chloride copolymer (copolymerization ratio 80/20% by weight) in a weight ratio of 80/20 by CHEMI AG, extruder It was melt-kneaded. This kneaded product was melt-pressed at a temperature of 175 ° C. by a conventional method using a tabletop press (Shinto Kinzoku Kogyosho Co., Ltd., Model AYSR 5) and then rapidly cooled with a 5 ° C. cooling plate to obtain a press sheet. This press sheet was stretched by a biaxial stretching machine at an area stretching ratio as shown in Table 1. The stretching ratio was the same in the longitudinal and transverse directions. Table 1 shows the oxygen permeability coefficient, moisture permeability, haze, embrittlement temperature, and flatness of the dispersed particles of the obtained unstretched and stretched films. It can be seen that both unstretched and stretched films have excellent gas barrier properties and low-temperature impact strength. When the area stretching ratio is 4 times or more, the flatness of the dispersed particles becomes 2 or more, and the oxygen transmission coefficient at 30 ° C. and 100% RH is further improved by the unstretched film (Example 1 [Reference Example]). It is 3/4 or less compared to the case of. Also, the degree of haze is improved and becomes 3/4 or less as compared with the case of an unstretched film.

Example 5 (Reference Example) and Examples 6 and 7 The same Gyllon CF as in Examples 2 to 4 as a polyamide resin
After dry-blending vinylidene chloride / vinylidene chloride copolymer (copolymerization ratio 80/20% by weight) at 60/40 (weight ratio) as 6S, PVDC, press sheets were produced in the same manner as in Examples 2 to 4. The press sheet was stretched by a biaxial stretching machine at an area ratio as shown in Table 1. The stretching ratio was the same in the longitudinal and transverse directions. Table 1 shows the properties of the obtained unstretched and stretched films.

Example 8 Polyamide resin used in Examples 2 to 4 and 6 to 7
Using PVDC, the mixing ratio was changed to 41/59 (weight ratio), and otherwise the same operation was performed to obtain a press sheet. This press sheet was stretched by an area magnification of 14.8 times with a biaxial stretching machine. The stretching ratio was the same in the longitudinal and transverse directions. Table 1 shows the properties of the obtained stretched film.

Example 9 (Reference Example) and Examples 10 to 13 As the polyamide, the same glilon CF 6 as in Examples 2 to 4 was used.
S, PVDC using vinylidene chloride / methyl acrylate copolymer (copolymerization ratio 95/5 wt%), mixing ratio 90/10
(Weight ratio), and a press sheet was obtained in the same manner as in Examples 2 to 4. This press sheet is subjected to a second stretching by a biaxial stretching machine.
The film was stretched at the same ratio in the vertical and horizontal directions at the area magnification as shown in the table.
The properties of the obtained unstretched film and stretched film are changed to the second
It is shown in the table.

Comparative Examples 1 to 5 The same Gyllon CF as in Examples 2 to 4 as a polyamide resin
Press sheets were prepared in the same manner as in Examples 2 to 4, using 6S and a vinylidene chloride / vinyl chloride copolymer (copolymerization ratio: 80/20% by weight) alone. This press sheet was stretched by a biaxial stretching machine at an area ratio as shown in Table 3 at the same ratio vertically and horizontally. The properties of the obtained unstretched film and stretched film are shown in Table 3.

6-12 nylon has a very good embrittlement temperature,
Insufficient oxygen gas barrier properties. On the other hand, the VD / VC copolymer has excellent oxygen gas barrier properties, but has a high embrittlement temperature and insufficient low-temperature impact strength. That is, it is understood that all films are very unbalanced as a packaging material. Further, in any of the films, the oxygen gas barrier property was hardly improved by stretching.

Example 14 EMS having a crystal melting point of nylon 6-12 having a melting point of 130 ° C. (copolymer of nylon 6 and nylon 12, copolymerization ratio of 50/50 by weight)
CHEMI AG Grillon CA6 (Tg = 30 ° C) and vinylidene chloride / methyl acrylate copolymer (vinylidene chloride content: 95% by weight) are mixed at a weight ratio of 80/20, and this mixture is cyclically mixed. In a kneading extruder with a die (40φ, L / D = 24)
The resin was melt-extruded at a resin temperature of 175 ° C and quenched with water at 15 ° C to obtain a cylindrical parison. Immediately after heating this cylindrical parison in hot water at 50 ° C, air is injected into the parison, and inflation is performed three times in the vertical axis direction and four times in the horizontal axis direction by air pressure. A stretched film having a thickness of 30 μm was obtained. Table 4 shows the results of examining the inflation stretching stability and the occurrence of brown to black decomposition products having a size of 0.25 mm ² or more during the production of the stretched film. Further, Table 4 also shows the measurement results of the oxygen permeability coefficient and the film embrittlement temperature of the film.

Polyamide resin and PVDC constituting the stretch molded product of the present invention
The mixture had stable inflation stretchability and suppressed generation of PVDC decomposition products, and simultaneously satisfied the oxygen permeability coefficient and the low-temperature impact strength.

Comparative Examples 6, 7 The same glilon CA6 as in Example 14 as a polyamide, PVDC
, A vinylidene chloride / methyl acrylate copolymer (vinylidene chloride content: 95% by weight) was used alone, and a stretched film was obtained in the same manner as in Example 14. Table 4 shows the results of examining the inflation stretching stability and the state of occurrence of brown to black decomposition products having a size of 0.25 mm ² or more during the production of these films. Further, Table 4 also shows the measurement results of the oxygen permeability coefficient and the film embrittlement temperature of the film.

The polyamide film of Comparative Example 6 has a high oxygen permeability coefficient, and the PVDC film of Comparative Example 7 has poor extrusion processability and poor low-temperature impact strength.

Examples 15 and 16 6-66 having a crystal melting point of 153 ° C. as a low melting point polyamide resin
-610 nylon copolymer (Toray Amilan CM4000, Tg = 32
° C) and a vinylidene chloride / vinyl chloride copolymer (vinylidene chloride content; 80% by weight) resin in a weight ratio of 80/20, 60 /
The resin was mixed at a ratio of 40, and the mixed resin was melt-extruded at a resin temperature of 170 ° C. by a kneading extruder equipped with an annular die, and rapidly cooled with water at 15 ° C. to obtain a cylindrical shape. After contacting the barison with a heating roll at 50 ° C., air was immediately injected into the parison and the air pressure was applied to determine the vertical axis (MD) / horizontal axis (TD) = 2.5 / 2.
The film was blown and stretched 5 times to obtain a stretched film having a thickness of 30 µm. The gas barrier property and the film embrittlement temperature of this film were measured, and the results are shown in Table 5. This shows that the stretched film made of the resin composition of the present invention has both excellent gas barrier properties and a low film embrittlement temperature.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08J 5/18 CEU C08J 5/18 CFG CFG C08L 27/08 C08L 27/08 77/00 77/00 B65D 1 / 00 A // (C08L 27/08 77:00) (C08L 77/00 27:08) B29K 27:00 77:00 B29L 7:00

Claims (6)

(57) [Claims] 1. A vinylidene chloride resin having a crystalline melting point of not more than 40% by weight and not more than 95% by weight of a low melting point polyamide resin having a melting point of 210 ° C. or less.
A stretch molded article having at least one resin composition layer consisting of less than 60% by weight and 5% by weight or more. 2. The stretch molded article according to claim 1, wherein the stretch molded article is a film, a sheet or a container. 3. The dispersion particles of the vinylidene chloride resin exhibit a flat shape that is long in at least one stretching direction, and the flatness of the cross section of the dispersion particles (the long axis of the cross section of the dispersion particles / the short axis of the cross section of the dispersion particles). Is 2 or more. 4. An oxygen permeability coefficient at 30 ° C. and 100% RH of 1.5
× 10 ^-11 cc · cm / cm ² · sec · cmHg or less (3)
The stretch molded article as described above. 5. The stretch molded product according to claim 3, wherein the molded product having a thickness of 30 μm has a haze of 40% or less. 6. The stretch-formed product according to claim 3, wherein the stretch-formed product is a film, a sheet or a container.