JP2016150953A - Molded article, food container body and food container lid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article combining moldability at low temperature with high gas permeability, and a food container and a food container lid.SOLUTION: The molded article is provided that contains a thermoplastic resin (A) and a thermoplastic resin (B) which is an olefin polymer and other than the thermoplastic resin (A), the content of the thermoplastic resin (A) being 2 pts.mass to 80 pts.mass and the content of the thermoplastic resin (B) being 20 pts.mass to 98 pts.mass based on total 100 pts.mass of the thermoplastic resin (A) and the thermoplastic resin (B). The thermoplastic resin (A) is copolymer having 60 mol% to 99 mol% of a constitutional unit (4MP1 unit) derived from 4-methyl-1-pentene and 1 mol% to 40 mol% of a constitutional unit (AO unit) derived from α-olefin having 2 to 20 carbon atoms and other than 4MP1, the total of the 4MP1 unit and the AO unit being 100 mol%, and the thermoplastic resin (A) has a melting point measured by a differential scanning calorimeter which is 199°C or less or practically not observed . The food container and the food container lid are also provided.SELECTED DRAWING: None

Description

  The present invention relates to a molded body, a food container body, and a food container lid.

Olefin polymers containing 4-methyl-1-pentene are superior to polyethylene and polypropylene in gas permeability, heat resistance, transparency, lightness, steam resistance, releasability, electrical properties, etc. . Therefore, olefin polymers containing 4-methyl-1-pentene are used in food containers, secondary materials for electronic / information materials, laboratory equipment, office supplies, cross-linking process members, release films, electronic / information material films, It is used in various fields such as food packaging and synthetic paper.
For example, 4-methyl-1-pentene polymer has a bulky functional group, and therefore has a lower density than other thermoplastic olefin resins. For this reason, the film containing 4-methyl-1-pentene polymer has high gas permeability, such as oxygen gas and carbon dioxide, and development is progressing as gas permeable films, such as packaging materials, such as fresh food ( For example, see Patent Document 1).
Further, as a technique related to the above, 4-methyl-1-pentene (co) polymer that can be injection blow molded, has excellent transparency and heat resistance, and gives a molded article with excellent mechanical properties has been proposed. (For example, refer to Patent Document 2).
Moreover, a film containing 4-methyl-1-pentene (co) polymer and a thermoplastic elastomer has been proposed as a packaging film having high gas permeability and heat sealability (for example, (See Patent Document 3).

Japanese Patent Laid-Open No. 11-301691 JP 2012-097208 A JP 2012-201392 A

However, since 4-methyl-1-pentene polymer has a high melting point, it needs to be molded at a higher temperature than polyolefin such as polyethylene and polypropylene. Therefore, when producing a molded body using a composition containing 4-methyl-1-pentene polymer and polyethylene or polypropylene, poor appearance tends to occur.
By the way, although the molded object described in patent document 2 is excellent in gas permeability, since it is mainly formed with the 4-methyl-1-pentene polymer whose melting | fusing point is 200 degreeC or more, it is necessary to shape | mold at high temperature. is there. When molding at high temperature, 4-methyl-1-pentene polymer is easily decomposed during molding, so the molecular weight of 4-methyl-1-pentene polymer is reduced, resulting in a decrease in mechanical strength and stickiness due to low molecular weight. Etc. are likely to occur.
Moreover, since the film described in patent document 3 contains the thermoplastic elastomer whose melting | fusing point in a film is 100 degrees C or less, thermoplastic elastomers are easy to adhere | attach and heat seal property is favorable. However, since the film also contains 4-methyl-1-pentene (co) polymer having a high melting point, when the film is molded at a low temperature, the moldability tends to be inferior.
Therefore, a material excellent in moldability at low temperature and gas permeability has been desired.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the molded object which has the moldability in low temperature, and high gas permeability.

  Specific means for solving the above problems include the following aspects.

<1> 60 to 99 mol% of structural units derived from 4-methyl-1-pentene and structural units derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene From 1 mol% to 40 mol% and derived from a structural unit derived from the 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms other than the 4-methyl-1-pentene. Thermoplastic whose structural unit is a copolymer having a total of 100 mol%, and whose melting point T _m measured by a differential scanning calorimeter (DSC) is 199 ° C. or lower or is substantially not observed A resin (A) and a thermoplastic resin (B) other than the thermoplastic resin (A), which is an olefin polymer, and the thermoplastic resin (A) and the thermoplastic resin (B). For a total of 100 parts by mass The content of the thermoplastic resin (A) is 2 parts by mass or more and 80 parts by mass or less, and the content of the thermoplastic resin (B) is 20 parts by mass or more and 98 parts by mass or less. Molded body.

<2> The molded article according to <1>, wherein the thermoplastic resin (B) is at least one polymer selected from the group consisting of an ethylene polymer and a propylene polymer.
<3> The molded article according to <1> or <2>, wherein the thermoplastic resin (A) has a melting point _Tm of 100 ° C. or higher and 180 ° C. or lower or is not substantially observed.
<4> The melting point _{T m} of a the thermoplastic resin (A) is either less than 100 ° C. or higher 165 ° C., or not substantially observed, shaped according to any one of <1> to <3> body.
<5> The molded article according to any one of <1> to <4>, wherein the α-olefin is propylene, and the thermoplastic resin (B) is a propylene-based polymer.

<6> The molded product according to any one of <1> to <5>, which is used in at least one of the food container main body and the food container lid.
<7> A food container main body including the molded body according to any one of <1> to <5>.
<8> A lid for a food container comprising the molded product according to any one of <1> to <5>.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object which has the moldability in low temperature and high gas permeability is provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, a plurality of substances present in the composition unless otherwise specified. Means the total amount.

[Molded body]
In the molded product of the present invention, the structural unit derived from 4-methyl-1-pentene is 60 mol% or more and 99 mol% or less, and an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene. The structural unit derived from 1 mol% to 40 mol%, the structural unit derived from the 4-methyl-1-pentene, and α- having 2 to 20 carbon atoms other than the 4-methyl-1-pentene. a copolymer with structural units derived from the olefin is 100 mol% in total, and, if the melting point T _m, as measured by differential scanning calorimetry (DSC) is 199 ° C. or less, or substantially observed Thermoplastic resin (A), and thermoplastic resin (B) other than the thermoplastic resin (A), which is an olefin polymer, the thermoplastic resin (A) and the thermoplastic resin (B ) 100 quality with The resin composition in which the content of the thermoplastic resin (A) is 2 parts by mass or more and 80 parts by mass or less and the content of the thermoplastic resin (B) is 20 parts by mass or more and 98 parts by mass or less with respect to parts. It is the molded object containing a thing.

  Since 4-methyl-1-pentene polymer has a bulky functional group and has a lower density than other thermoplastic olefin resins, 4-methyl-1-pentene polymer contains oxygen gas, carbon dioxide gas, etc. It is suitable for gas permeable food containers such as fresh food trays. However, 4-methyl-1-pentene polymer has a higher melting point and lower moldability than polyolefins such as polyethylene and polypropylene. Therefore, in the technique described in Patent Document 2, a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin other than 4-methyl-1-pentene are copolymerized, and 4-methyl The injection blow molding is made possible by forming a -1-pentene polymer.

  In the process of proceeding with the study of the material of the molded product, the present inventors, in the 4-methyl-1-pentene polymer, other than structural units derived from 4-methyl-1-pentene and 4-methyl-1-pentene. It has been found that there is a case where moldability at low temperatures may not be obtained while maintaining gas permeability only by changing the composition ratio with the structural unit derived from α-olefin.

  In the technique described in Patent Document 3, in a film containing 4-methyl-1-pentene polymer and a thermoplastic elastomer having a low melting point in a predetermined ratio, high gas permeability and heat sealability are obtained. Both are compatible. However, although the film is excellent in heat-sealability, it also contains a 4-methyl-1-pentene polymer having a high melting point. Therefore, when the film is molded at a low temperature, it is inferior in moldability and maintains gas permeability. However, moldability at low temperatures may not be obtained.

In the present invention, the resin composition includes a specific thermoplastic resin (A) containing a large amount of 4-methyl-1-pentene in the skeleton and a thermoplastic resin (B) that is an olefin polymer at a specific ratio. In this manner, a molded body having both low temperature moldability and high gas permeability is realized.
Although the action mechanism of the present invention is not clear, the present inventor presumes as follows.
Molding containing a resin composition in which a specific thermoplastic resin (A) containing a large amount of 4-methyl-1-pentene in the skeleton and a thermoplastic resin (B) that is an olefin polymer are mixed at a specific ratio. When the body is molded, it is considered that the thermoplastic resin (A) responsible for gas permeability in the molded body and the thermoplastic resin (B) responsible for moldability at low temperatures are appropriately dispersed.
Thereby, since high gas permeability is maintained and moldability at low temperature is obtained, it is considered that a molded body having both high gas permeability and moldability at low temperature can be realized.
Moreover, in addition to the structural unit derived from 4-methyl-1-pentene, the thermoplastic resin (A) has a structural unit derived from an α-olefin having 2 to 20 carbon atoms. Since the melting point of a certain thermoplastic resin (A) is lowered, it is considered that molding at a low temperature is possible.

  Hereinafter, the components contained in the molded article of the present invention will be described.

<Resin composition>
The resin composition in the present invention is a composition containing a thermoplastic resin (A) and a thermoplastic resin (B). That is, in the resin composition of the present invention, a structural unit derived from 4-methyl-1-pentene (hereinafter sometimes referred to as “4MP1 unit”) is 60 mol% or more and 99 mol% or less, and 4-methyl. 1 to 40 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than -1-pentene (hereinafter sometimes referred to as “AO unit”), and the above 4MP1 unit And a copolymer having a total of 100 mol% of the AO units (hereinafter sometimes referred to as “4MP1-based copolymer”), and measured by a differential scanning calorimeter (DSC). A thermoplastic resin (A) having a melting point _Tm of 199 ° C. or lower or substantially not observed, and a thermoplastic resin (B) other than the thermoplastic resin (A), which is an olefin polymer. Is a mixture containing .

[Thermoplastic resin (A)]
The thermoplastic resin (A) has 4MP1 units of 60 mol% or more and 99 mol% or less and AO units of 1 mol% or more and 40 mol% or less, and the 4MP1 units and the AO units are 100 mol% in total. a copolymer is, and, if the melting point T _m, as measured by differential scanning calorimetry (DSC) is 199 ° C. or less, or substantially not observed thermoplastic resin.

The 4MP1 copolymer in the present invention has 4MP1 units of 60 mol% or more and 99 mol% or less, preferably 65 mol% or more and 98 mol% or less, preferably 65 mol% or more and 97 mol% or less. It is more preferable to have it.
When the 4MP1 unit contained in the 4MP1 copolymer is 60 mol% or more, a molded article having high gas permeability can be obtained. In addition, a molded article having good gas permeability of a gas component having a large molecular weight is obtained. Moreover, when the 4MP1 unit contained in the 4MP1 copolymer in the present invention is 99 mol% or less, a molded product having good mechanical properties of the molded product can be obtained.

The 4MP1 copolymer in the present invention has an AO unit of 1 mol% to 40 mol%, preferably 2 mol% to 35 mol%, preferably 3 mol% to 35 mol%. It is more preferable to have it.
When AO units 4MP1 copolymer in the present invention has in the above range, the melting point T _m of a thermoplastic resin as measured by differential scanning calorimetry (DSC) (A), to 199 ° C. or less, or substantially Can be adjusted so that it is not observed. Therefore, when producing a molded product containing the thermoplastic resin (A), the melting point is higher than that of a conventionally used 4-methyl-1-pentene polymer, particularly a 4-methyl-1-pentene homopolymer. Can be lowered.

  Examples of the α-olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, and functionalized vinyl compounds. .

  Examples of the linear or branched α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene, etc., a linear α-olefin having 2 to 20 carbon atoms (preferably 2 to 10); 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene Etc., preferably a branched α-olefin having 5 to 20 carbon atoms (more preferably 5 to 10 carbon atoms).

  Examples of the cyclic olefin include compounds having 4 to 20 carbon atoms (preferably 5 to 15) such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylnorbornene, and vinylcyclohexane. .

  As an aromatic vinyl compound, styrene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene And mono- or polyalkyl styrene.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples thereof include compounds having 4 to 20 carbon atoms (preferably 4 to 10) such as octadiene.

  Examples of the non-conjugated polyene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl- 1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyl Riden-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2 Compounds having 5 to 20 carbon atoms (preferably 5 to 10) such as 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned. It is done.

  Examples of functionalized vinyl compounds include hydroxyl group-containing olefins; halogenated olefins; acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8- Unsaturated carboxylic acids such as nonenic acid and 9-decenoic acid; unsaturated amines such as allylamine, 5-hexeneamine and 6-heptenamine; (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride, Unsaturated acid anhydrides such as acid anhydrides of the above unsaturated carboxylic acids; Halides of the above unsaturated carboxylic acids; 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, - and unsaturated epoxy compounds such as epoxy-1-undecene and the like.

The hydroxyl group-containing olefin is not particularly limited as long as it is an olefin compound having a hydroxyl group, but is preferably a terminal hydroxylated olefin compound.
Examples of the terminal hydroxylated olefin compound include vinyl alcohol, allyl alcohol, hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, and hydroxyl-1-decene. , Hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene, hydroxyl-1-octadecene, hydroxyl-1-eicosene, etc., having 4 to 20 carbon atoms (preferably 2-10) Linear hydroxylated α-olefin; hydroxylated 3-methyl-1-butene, hydroxylated 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated 3-ethyl- 1-pentene, hydroxylated-4,4-dimethyl-1-pentene, hydroxyl-4-methyl-1-hexene, hydroxylated-4,4-dimethyl-1-hexene, hydroxyl-4-ethyl-1- Hexene, hydroxy acid Preferably, such 3-ethyl-1-hexene, and the like branched hydroxide α- olefin having 5 to 20 carbon atoms (more preferably 5 to 10).

  Examples of the halogenated olefin include halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, C 4-20 (preferably 4-10) linear halogenated α-, such as halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1-eicosene Olefin; halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4 , 4-Dimethyl-1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogen 4-ethyl-1-hexene, (more preferably 5 to 10) 5 to 20 carbon atoms, such as halogenated-3-ethyl-1-hexene, and the like branched halogenated α- olefins.

The 4MP1-based copolymer in the present invention may contain only one type of AO unit or two or more types.
Examples of the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene include ethylene, propylene, 1-butene, from the viewpoint of controlling the copolymerizability and physical properties of the obtained copolymer, particularly the melting point. At least one selected from the group consisting of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hexadecene, and 1-octadecene is preferable, propylene, 1-butene, At least one selected from the group consisting of 1-hexene and 1-octene is more preferable, at least one selected from the group consisting of propylene and 1-butene is more preferable, and propylene is particularly preferable.

  The content (mol%) of 4MP1 unit and AO unit possessed by the 4MP1 copolymer in the present invention can be measured by the following method.

~conditions~
Measuring apparatus: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm

  The 4MP1 copolymer in the present invention is a copolymer in which the 4MP1 unit and the AO unit are 100 mol% in total. That is, the 4MP1 copolymer in the present invention does not contain other structural units other than the 4MP1 unit and the AO unit.

The 4MP1 copolymer in the present invention preferably has an intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent of 0.5 dl / g to 5.0 dl / g, 0.5 dl / g to More preferably, it is 4.0 dl / g. When the intrinsic viscosity [η] of the 4MP1 copolymer in the present invention is within the above range, the low-molecular weight material is small and the stickiness of the molded product is reduced, which is advantageous in terms of moldability.
The intrinsic viscosity [η] of the 4MP1 copolymer is a value measured by the following method using an Ubbelohde viscometer.
After dissolving about 20 mg of 4MP1 copolymer in 25 ml of decalin, the specific viscosity ηsp is measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin is added to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner as described above. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

Weight average molecular weight of 4MP1 copolymer in the present invention (Mw) of, from the viewpoint of moldability, is preferably from ^{1 × 10 4 ~2 × 10 6} , a 1 × ¹⁰ 4 ~1 × ^{10 6} Is more preferable.
In addition, the molecular weight distribution (Mw / Mn) of the 4MP1 copolymer in the present invention is preferably 1.0 to 3.5 from the viewpoint of stickiness and appearance of the molded body, and 1.1 to 3.0. It is more preferable that

  The weight average molecular weight (Mw) of the 4MP1 copolymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are as follows. It is a value calculated by a standard polystyrene conversion method using a graph (GPC).

~conditions~
Measuring device: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated type, manufactured by Waters)
Column: 2 GMH6-HT (manufactured by Tosoh Corp.) and 2 GMH6-HTL (manufactured by Tosoh Corp.) connected in series Eluent: o-dichlorobenzene Column temperature: 140 ° C
Flow rate: 1.0 mL / min

The melt flow rate (MFR) of the 4MP1 copolymer in the present invention is preferably from 0.1 g / 10 min to 100 g / 10 min from the viewpoint of fluidity during molding, and preferably 0.5 g / 10 min. It is more preferably ˜50 g / 10 min, and further preferably 0.5 g / 10 min to 30 g / 10 min.
Further, when the melt flow rate of the 4MP1 copolymer is within the above range, the moldability is more excellent.
The melt flow rate (MFR) of the 4MP1 copolymer is a value measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238.

Density of 4MP1 copolymer in the present invention, from the viewpoint of gas ^{permeability,} is preferably ^{820kg / m 3 ~870kg / m 3} , more preferably ^{830kg / m 3 ~850kg / m 3} .
Further, when the density of the 4MP1 copolymer is 820 kg / m ³ or more, the mechanical strength becomes good and problems such as breakage hardly occur in the obtained molded body. When the density of the 4MP1 copolymer is 870 kg / m ³ or less, a molded product having higher gas permeability can be obtained.
The density of the 4MP1-based copolymer is a value measured according to JIS K7112 (1999) (density gradient tube method).

The melting point (T _m ) of the 4MP1 copolymer in the present invention is 199 ° C. or lower or is not substantially observed. When the melting point (T _m ) of the 4MP1 copolymer is 199 ° C. or lower or is not substantially observed, molding at a low temperature becomes possible. The melting point (T _m ) of the 4MP1 copolymer is preferably 100 ° C. or higher and 180 ° C. or lower, or is not substantially observed. More preferably, it is 100 ° C. or higher and lower than 165 ° C. or is not substantially observed.
“The melting point (T _m ) is not substantially observed” means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 ° C. to 200 ° C.

The melting point (T _m ) of the 4MP1 copolymer is a value measured by the following method using a differential scanning calorimetry (DSC).
About 5 mg of 4MP1 copolymer is sealed in a measurement aluminum pan of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Inc. and heated from room temperature to 200 ° C. at 10 ° C./min. In order to completely melt the 4MP1-based copolymer, it is held at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating is performed to 200 ° C. at 10 ° C./min, and the peak temperature (° C.) at the second heating is defined as the melting point (T _m ) of the copolymer. When a plurality of peaks are detected, the peak detected on the highest temperature side is adopted.

  The thermoplastic resin (A) in the present invention may be polymerized using a polymerization catalyst. As a polymerization catalyst that can be used in the present invention, a conventionally known catalyst such as a magnesium-supported titanium catalyst, WO 01/53369 pamphlet, WO 01/27124 pamphlet, and JP-A-3-19396. Or a metallocene catalyst described in JP-A-02-41303 is preferable. As a method for producing a 4MP1 copolymer in the present invention, for example, methods described in International Publication No. 01/27124, International Publication No. 14/050817, etc. can be employed.

[Thermoplastic resin (B)]
The thermoplastic resin (B) in the present invention can be selected from olefin polymers (however, excluding the above-mentioned thermoplastic resin (A)).
The thermoplastic resin (B) is preferably at least one polymer selected from the group consisting of ethylene polymers and propylene polymers.

  The ethylene polymer may be a homopolymer of ethylene or a copolymer (copolymer) of ethylene and another monomer. For example, it is produced by a conventionally known method. Low density polyethylene, medium density polyethylene, high density polyethylene, high pressure method low density polyethylene, and the like. Examples of the ethylene polymer also include an ethylene polymer elastomer.

When the ethylene polymer is a copolymer, the copolymer is at least one selected from the group consisting of ethylene and an α-olefin having 3 to 10 carbon atoms from the viewpoint of mechanical strength and impact resistance. And a copolymer of at least one monomer selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. More preferably, it is a copolymer.
The proportion of structural units derived from ethylene in the ethylene polymer is preferably 50 mol% to 100 mol%, assuming that all the structural units in the ethylene polymer are 100 mol%, and 60 mol%. It is more preferably ˜99.9 mol%, and further preferably 80 mol% to 99.5 mol%. When the ratio of the structural unit derived from ethylene in the ethylene polymer is within the above range, the mechanical strength and impact resistance are excellent.

  The propylene polymer may be a homopolymer of propylene (homopolymer) or a copolymer (copolymer) of propylene and another monomer. For example, an isotactic propylene polymer, Examples thereof include a syndiotactic propylene polymer, a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / ethylene / 1-butene copolymer, and a mixture thereof. The isotactic propylene polymer may be a homopropylene polymer, a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene), and a propylene block. A copolymer may also be used. Examples of the propylene polymer include a propylene polymer elastomer.

When the propylene-based polymer is a copolymer, the copolymer is composed of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) from the viewpoint of mechanical strength and moldability. It is preferably a copolymer with at least one monomer selected from the group.
The proportion of the structural units derived from propylene in the propylene-based polymer is preferably 50 mol% to 100 mol%, assuming that all the structural units in the propylene-based polymer are 100 mol%, and 60 mol%. It is more preferably ˜99.9 mol%, and further preferably 70 mol% to 99.5 mol%. When the proportion of the structural unit derived from propylene in the propylene-based polymer is within the above range, the mechanical strength and moldability are excellent.

When the thermoplastic resin (B) is a propylene polymer, the α-olefin in the 4-methyl-1-pentene copolymer is preferably propylene.
When the thermoplastic resin (B) is a propylene-based polymer and the α-olefin in the 4-methyl-1-pentene-based copolymer is propylene, the compatibility is improved, and thus the transparency of the molded body is improved.

The melt flow rate (MFR) of the thermoplastic resin (B) in the present invention is preferably 0.1 g / 10 min to 100 g / 10 min from the viewpoint of moldability of the molded body and mechanical properties of the molded body. More preferably, it is 5g / 10min-50g / 10min.
The melt flow rate (MFR) of the thermoplastic resin (B) is a value measured according to ASTM D1238. Specifically, the ethylene polymer has a value measured at 190 ° C. with a load of 2.16 kg, and the propylene polymer has a value measured at 230 ° C. with a load of 2.16 kg. .

The density of the thermoplastic resin (B) in the present invention, light weight, and from the viewpoint of dispersibility when formed into a 4-methyl-1-pentene copolymer ^{composition, 820kg / m 3 ~960kg / m} 3 it is ^preferably, and more preferably ^{830kg / m 3 ~940kg / m 3} .
The density of the thermoplastic resin (B) is a value measured according to JIS K7112 (1999) (density gradient tube method).

The content of the thermoplastic resin (A) in the molded body of the present invention is 2 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass in total of the thermoplastic resin (A) and the thermoplastic resin (B). It is preferably 5 parts by mass or more and 75 parts by mass or less, and more preferably 5 parts by mass or more and 49 parts by mass or less.
The content of the thermoplastic resin (A) in the molded body of the present invention is high by being 2 parts by mass or more with respect to 100 parts by mass in total of the thermoplastic resin (A) and the thermoplastic resin (B). A molded body having gas permeability can be obtained. Moreover, when content of the thermoplastic resin (A) in the molded object of this invention is 80 mass parts or less with respect to a total of 100 mass parts of a thermoplastic resin (A) and a thermoplastic resin (B). Molding at a low temperature is possible.

The content of the thermoplastic resin (B) in the molded body of the present invention is 20 parts by mass or more and 98 parts by mass or less with respect to 100 parts by mass in total of the thermoplastic resin (A) and the thermoplastic resin (B). 25 parts by mass or more and 95 parts by mass or less is preferable, and 51 parts by mass or more and 95 parts by mass or less are more preferable.
The content of the thermoplastic resin (B) in the molded body of the present invention is 20 parts by mass or more with respect to a total of 100 parts by mass of the thermoplastic resin (A) and the thermoplastic resin (B). Can be formed. Moreover, when content of the thermoplastic resin (B) in the molded object of this invention is 98 mass parts or less with respect to a total of 100 mass parts of a thermoplastic resin (A) and a thermoplastic resin (B). A molded body having high gas permeability can be obtained.

[Other ingredients]
The molded body of the present invention may contain other components such as resins and additives other than the above-described thermoplastic resin (A) and thermoplastic resin (B) within a range not impairing the object of the present invention. .
Examples of the additive include a heat resistance stabilizer, a weather resistance stabilizer, a rust inhibitor, a copper damage stabilizer, and an antistatic agent. It is preferable that content of an additive is 0.0001 mass part-10 mass parts with respect to 100 mass parts of resin compositions which form the molded object of this invention.

In the present invention, as described above, the specific thermoplastic resin (A) containing a large amount of 4-methyl-1-pentene in the skeleton and the thermoplastic resin (B) that is an olefin polymer are in a specific ratio. In this manner, a molded body having both high gas permeability and low temperature moldability is realized.
When a specific thermoplastic resin (A) containing a large amount of 4-methyl-1-pentene in the skeleton and a thermoplastic resin (B) that is an olefin polymer are mixed at a specific ratio, and a molded body is molded, It is considered that the thermoplastic resin (A) responsible for gas permeability and the thermoplastic resin (B) responsible for moldability at low temperatures are appropriately dispersed in the molded body. As a result, high gas permeability is maintained, and moldability at low temperatures is also obtained. As a result, a molded body having both high gas permeability and moldability at low temperatures can be realized.

[Method for producing molded article]
An example of the manufacturing method of the molded object of this invention is demonstrated. The molded body of the present invention can be produced, for example, by the following method. However, the present invention is not limited to this.
First, the thermoplastic resin (A) and the thermoplastic resin (B) are mixed (for example, melt blended with a dry blend, a single screw, a twin screw extruder, a mixer, or the like). In addition, it is preferable that the thermoplastic resin (A) and the thermoplastic resin (B) are appropriately kneaded by dry blending or the like, rather than uniformly mixed by melt kneading or the like.

Subsequently, the obtained mixture is shape | molded and a molded object is obtained.
The method for molding the molded body of the present invention is not particularly limited. For example, deep drawing such as press molding, injection molding, blow molding, extrusion molding, inflation molding and sheet processing after vacuum molding, pressure molding, vacuum pressure molding, etc. A known molding method such as a method for performing the above can be employed, and various molded products can be produced.

The preferable conditions etc. which shape | mold the molded object of this invention below are described.
When the molded body is molded by injection molding, a general injection molding method can be used, and further, a gas injection molding method, an injection press molding method, an injection blow molding method, or the like can be employed.
The cylinder temperature at the time of injection molding is preferably equal to or higher than the _Tm or flow start temperature of the thermoplastic resin (A), more preferably 160 ° C to 300 ° C, and further preferably 170 ° C to 250 ° C.
If the molding temperature is equal to or higher than _Tm or the flow start temperature, for example, the load at the time of injection is maintained in an appropriate range, and a sufficient amount of resin is filled into the mold or the like. Therefore, the occurrence of so-called “short shot” can be suppressed, and the moldability is excellent. On the other hand, if the molding temperature is 300 ° C. or less, the mechanical strength is reduced due to the decrease in the molecular weight due to the decomposition of the thermoplastic resin (A), the stickiness due to the generation of low molecular weight, and the appearances such as burrs derived from the crosslinked product Generation | occurrence | production of a defect etc. can be suppressed.
It is preferable that the mold temperature at the time of molding is equal to or lower than the _{Tm of the} thermoplastic resin (A) or the flow start temperature. As mold temperature, _Tm- 40 degreeC is more preferable, 10 to 70 degreeC is further more preferable, and 20 to 60 degreeC is especially preferable.

In the case of extruding the thermoplastic resin (A), the extrusion temperature is preferably equal to or higher than the melting point (T _m ) or flow start temperature of the thermoplastic resin (A), more preferably 160 ° C to 300 ° C, More preferably, it is the range of 170 to 250 degreeC.
When the molding temperature is _{equal to} or higher than _Tm or the flow start temperature, for example, the load during extrusion is maintained in an appropriate range, and the moldability is excellent. On the other hand, if the molding temperature is 300 ° C. or lower, the appearance of mechanical strength decreases due to the decrease in molecular weight due to decomposition of the thermoplastic resin (A), stickiness due to the generation of low molecular weight substances, and irregularities derived from cross-linked products. Generation | occurrence | production of a defect etc. can be suppressed.

Although the thickness of the molded object of this invention is not specifically limited, 50 micrometers or more are preferable, 150 micrometers-3 mm are more preferable, 300 micrometers-3 mm are further more preferable.
When the thickness of the molded body of the present invention is 50 μm or more, the molded body has excellent mechanical strength, and when the thickness of the molded body is 3 mm or less, it is possible to reduce the weight of the molded body and control gas permeability. .

[Use of molded body]
As the molded product of the present invention, food containers such as fresh food, agricultural / horticultural containers, blister pack containers, press-through pack containers, fluid containers, tableware, container lids, packing, office supplies, daily necessities, optical parts , Agricultural / horticultural materials, toys, resin parts for electrical appliances, resin parts for automobiles, and the like.
The form of the food container, agricultural / horticultural container, blister pack container, and press-through pack container is not particularly limited, but is deeply drawn to a depth of 2 mm or more in order to accommodate food, articles, medicines, etc. Preferably it is.
Although the thickness of a container is not specifically limited, From the point of mechanical strength, thickness is 50 micrometers or more, More preferably, they are 150 micrometers-3 mm, More preferably, they are 300 micrometers-3 mm.

Examples of food containers include food container bodies and food container lids, and specific examples include fresh food trays, instant food containers, fast food containers, lunch boxes and the like.
Specific examples of the agricultural / horticultural containers include seedling pots.
Food containers and agricultural / horticultural containers can be formed mainly by injection molding.
Since the molded article of the present invention has excellent gas permeability, it is preferably used for food containers among the above containers, and more preferably used for food container bodies or food container lids.

Specific examples of blister pack containers include packaging containers for various product groups such as office supplies, toys, and dry batteries in addition to food.
Specific examples of press-through pack containers include pharmaceutical containers.
A blister pack container or a press-through pack container can be produced by forming a resin composition into a sheet and then using the sheet by deep drawing such as vacuum forming, pressure forming, or vacuum / pressure forming.

[Laminated molded product]
The laminated molded body of the present invention can be molded as a molded body having at least one layer containing the resin composition contained in the molded body of the present invention.
The laminated molded body of the present invention has a layer containing the resin composition contained in the molded body of the present invention, which has both high gas permeability and low temperature moldability, and therefore has high gas permeability and low temperature. Also has moldability.

The laminated molded product of the present invention may be a molded product obtained by laminating two or more layers of the resin composition of the present invention, and within the range not impairing the object of the present invention, the resin composition of the present invention, What laminated | stacked other resin compositions other than a resin composition may be sufficient.
As the other resin composition, a molded body formed of a material having gas permeability and moldability at a low temperature is preferable. For example, a base material for adjusting mechanical strength, moldability, and the like, and controlling the gas transmission amount Gas permeable material and the like.

[Production method of laminated molded body]
The method for producing the laminated molded body of the present invention is not particularly limited. For example, the thermoplastic resin (A) or the thermoplastic resin (B) contained in the molded body of the present invention and the configuration of other molded bodies. A method in which the components are bonded together by mixing in the vicinity of the interface to form a laminated molded body is preferable. Examples of such a method include a co-extrusion method in which a melted resin is laminated, a heat fusion method in which a preformed resin molding is heat-sealed, and the like. Laminated melted resin is laminated in that it can form a laminated molded body having higher interlayer adhesion with the molded body and less delamination between the molded body of the present invention and other molded bodies. More preferred is the coextrusion method.

  The thickness of the laminated molded body of the present invention is preferably 50 μm or more, more preferably 150 μm to 3 mm, and still more preferably 300 μm to 3 mm in terms of easy handling.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.
In the examples, various physical properties of the copolymer were measured by the following methods.

〔composition〕
The content (mol%) of 4-methyl-1-pentene and propylene (C3 α-olefin) in the copolymer was measured by ¹³ C-NMR. The measurement conditions are as follows.

~Measurement condition~
Measuring apparatus: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the copolymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device.
Specifically, about 20 mg of the powdery copolymer was dissolved in 25 ml of decalin, and then the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner as described above. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) of the copolymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC: Gel). It calculated by the standard polystyrene conversion method using Permeation Chromatography). The measurement conditions are as follows.

~Measurement condition~
Measuring device: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated type, manufactured by Waters)
Column: 2 GMH6-HT (manufactured by Tosoh Corp.) and 2 GMH6-HTL (manufactured by Tosoh Corp.) connected in series Eluent: o-dichlorobenzene Column temperature: 140 ° C
Flow rate: 1.0 mL / min

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the copolymer was measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238. The unit is g / 10 min).

〔density〕
The density of the copolymer was measured according to JIS K7112 (1999) (density gradient tube method).

[Melting point ( _Tm )]
The melting point ( _Tm ) of the copolymer was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device.
About 5 mg of the copolymer was sealed in a measurement aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. In order to completely melt the copolymer, it was kept at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating was performed to 200 ° C. at 10 ° C./min. The peak temperature (° C.) at the second heating was defined as the melting point (T _m ) of the copolymer.

[Synthesis Example 1] Synthesis of Copolymer A-1 In a stainless steel (SUS) autoclave with a stirring blade with a capacity of 1.5 L, which was sufficiently purged with nitrogen, 300 ml of n-hexane (in a dry nitrogen atmosphere on activated alumina). Dried) and 450 ml of 4-methyl-1-pentene were charged at 23 ° C. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.
Next, the autoclave was heated until the internal temperature reached 60 ° C., and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-dioxide) prepared in advance in terms of aluminum (Al) were prepared. 0.34 ml of a toluene solution containing -t-butyl-fluorenyl) zirconium dichloride was pressed into the autoclave with nitrogen to start the polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.
Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to the atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.
Subsequently, the polymerization reaction product containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours to obtain 44.0 g of a powdery copolymer A-1.

Table 1 shows the measurement results of various physical properties of the obtained copolymer A-1.
The content of 4-methyl-1-pentene in the copolymer A-1 was 84.1 mol%, and the content of propylene was 15.9 mol%. Moreover, the density of the copolymer A-1 was 838 kg / m ³ . Copolymer A-1 has an intrinsic viscosity [η] of 1.5 dl / g, a weight average molecular weight (Mw) of 340,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow. The rate (MFR) was 11 g / 10 min. The melting point (T _m ) of copolymer A-1 was 132 ° C.

[Synthesis Example 2] Synthesis of Copolymer A-2 In a SUS autoclave with a 1.5 L stirring blade sufficiently purged with nitrogen, 300 ml of n-hexane (dried on activated alumina under a dry nitrogen atmosphere) ), And 450 ml of 4-methyl-1-pentene were charged at 23 ° C. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.
Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance were converted into Al. 0.34 ml of a toluene solution containing (butyl-fluorenyl) zirconium dichloride was pressed into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.
Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to the atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.
Subsequently, the polymerization reaction product containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours to obtain 36.9 g of a powdery copolymer A-2.

Table 1 shows the measurement results of various physical properties of the obtained copolymer A-2.
The content of 4-methyl-1-pentene in the copolymer A-2 was 72.5 mol%, and the content of propylene was 27.5 mol%. Moreover, the density of the copolymer A-2 was 839 kg / m ³ . Copolymer A-2 has an intrinsic viscosity [η] of 1.5 dl / g, a weight average molecular weight (Mw) of 337,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow. The rate (MFR) was 11 g / 10 min. The melting point ( _Tm ) of copolymer A-2 was not observed.

Synthesis Example 3 Synthesis of Copolymer A-3 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave equipped with a stirring blade having a capacity of 1.5 L, which had been sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.
Next, the autoclave was heated until the internal temperature reached 60 ° C., and pressurized with propylene so that the total pressure (gauge pressure) was 0.17 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.005 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance were converted into Al. 0.34 ml of a toluene solution containing (butyl-fluorenyl) zirconium dichloride was pressed into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.
Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to the atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.
Subsequently, the polymerization reaction product containing the obtained solvent was dried at 130 ° C. under reduced pressure for 12 hours to obtain 35.2 g of a powdery copolymer A-3.

Table 1 shows the measurement results of various physical properties of the obtained copolymer A-3.
The content of 4-methyl-1-pentene in the copolymer A-3 was 93.0 mol%, and the content of propylene was 7.0 mol%. Moreover, the density of the copolymer A-3 was 832 kg / m ³ . Copolymer A-3 has an intrinsic viscosity [η] of 1.6 dl / g, a weight average molecular weight (Mw) of 370,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow. The rate (MFR) was 4 g / 10 min. The melting point ( _Tm ) of copolymer A-3 was 178 ° C.

[Synthesis Example 4] Synthesis of Copolymer A-4 In Comparative Example 7 of International Publication No. 2006/054613, the copolymer was changed by changing the ratio of 4-methyl-1-pentene and 1-decene. A-4 was obtained.

Table 1 shows the measurement results of various physical properties of the obtained copolymer A-4.
The content of 4-methyl-1-pentene in the copolymer A-4 was 98.0 mol%, and the content of 1-decene was 2.0 mol%. Further, the density of the copolymer A-4 was 833 kg / m ³ . Copolymer A-4 had an intrinsic viscosity [η] of 2.4 dl / g and a melt flow rate (MFR) of 4 g / 10 min. The melting point ( _Tm ) of the copolymer A-4 was 238 ° C.

[Molded body]
<Example 1>
10 parts by mass of copolymer A-1 and a propylene-based polymer (B-1, Prime Polypro (registered trademark) J105G, propylene homopolymer, density: 900 kg / m ³ , MFR (230 ° C.): 9 g / 10 min, 90 parts by mass (manufactured by Prime Polymer Co., Ltd.) were mixed (dry blended). Subsequently, the obtained mixture was subjected to an injection molding machine IS-55 manufactured by Toshiba Machine Co., Ltd., with a cylinder temperature of 230 ° C., an injection filling speed = 50 cm ³ / sec to 65 cm ³ / sec, a screw rotation speed of 60 rpm, and a mold temperature. = A square plate (molded body) having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm at 20 to 60 ° C. was produced.

<Example 2 to Example 6, Comparative Example 1, Comparative Example 3>
Except having changed the raw material of a molded object into the kind and compounding ratio of the thermoplastic resin which are shown in Table 2, according to the method similar to Example 1, the molded object of Example 2- Example 6, Comparative Example 1, and Comparative Example 3 Was made.

<Comparative example 2>
In the same manner as in Example 1, except that only a propylene polymer (B-1, Prime Polypro (registered trademark) J105G, manufactured by Prime Polymer Co., Ltd.) was used as a raw material (100 parts by mass). The molded body of Example 2 was obtained.

[Evaluation]
The molded body of Examples 1 to 6 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 2 below.

1. Formability (injection molding at a molding temperature of 230 ° C)
The injection molded articles of Examples 1 to 6 and Comparative Examples 1 to 3 were visually observed and evaluated according to the following evaluation criteria.

-Evaluation criteria-
A: The surface of the molded body was observed with the naked eye, the appearance was poor such as short shots due to unfilling and flow marks due to melting unevenness, and the dimensional change due to post-shrinkage after molding was not noticeable, and the cross section of the molded body was cut. Sometimes injection molding is possible without the occurrence of looseness derived from unmelted material.
B: The surface of the molded body was visually observed, and appearance changes such as short shots caused by unfilling and flow marks due to melting unevenness, dimensional changes due to post-shrinkage after molding occurred, and the cross section of the molded body was cut. Sometimes injection molding is not possible without the occurrence of blisters derived from unmelted material.

2. Gas permeability Oxygen permeability (oxygen permeability coefficient, unit: cm ³ · mm / (m ² · 24h · atm)), water vapor permeability (water vapor permeability coefficient, unit: g · mm / (m ² · 24h) )) And carbon dioxide permeability (carbon dioxide permeability coefficient, unit: cm ³ · mm / (m ² · 24 h · atm)) were measured by the following methods.
A molded body having a thickness of 2 mm cut into a shape having a length of 30 mm and a width of 30 mm was used as a test piece.
Oxygen permeability and carbon dioxide permeability are in accordance with JIS K7126-1 (2006), using a differential pressure method gas permeability measuring device (manufactured by Toyo Seiki Seisakusho) with a test temperature of 23 ° C. and a test humidity of 0% RH. Under the conditions, the measurement area of the molded body was set to 5 cm ² for measurement. As for the measurement area of the molded body, prepare two aluminum masks with adhesive made by Modern Kotrol Co., Ltd. with a hole of 25 mm in diameter at the center, and sandwich the molded object to be measured with these two masks. Laminated and adjusted. Specifically, the molded body is arranged so that the hole in the central portion overlaps with two masks.
The water vapor permeability is based on JIS K7129B (2008), and using a MOCON water vapor excess rate measuring device (manufactured by Hitachi High-Tech), the measurement area of the molded product is 50 cm at a test temperature of 40 ° C. and a test humidity of 90% RH. ² and measured.

~ Explanation of Table 2 ~
B-1 Prime Polypro (registered trademark) J105G, homopolymer of propylene, density: 900 kg / m ³ , MFR (230 ° C.): 9 g / 10 min, manufactured by Prime Polymer Co., Ltd. B-2 Prime Polypro (registered trademark) J3021GR, Random copolymer of propylene and ethylene, density: 900 kg / m ³ , MFR (230 ° C.): 33 g / 10 min, manufactured by Prime Polymer Co., Ltd. B-3 Evolue (registered trademark) SP2540, random copolymer of ethylene and hexene, density : 924 kg / m ³ , MFR (190 ° C.): 3.8 g / 10 min, manufactured by Prime Polymer Co., Ltd.

  As shown in Table 2, the molded body of the present invention had high permeability to at least one gas among oxygen, carbon dioxide, and water vapor, and moldability at low temperature (Examples 1 to 5). (See Example 6).

  Since the molded article of the present invention has both high gas permeability and low temperature moldability, it is suitably used as a packaging material. In particular, the molded article of the present invention is suitable as a food container body, a food container lid, and the like because it has excellent moldability at low temperatures.

Claims (8)

The structural unit derived from 4-methyl-1-pentene is 60 mol% or more and 99 mol% or less, and the structural unit derived from α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 1 mol. % To 40 mol% and a structural unit derived from the 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than the 4-methyl-1-pentene , And a thermoplastic resin having a melting point T _m measured by a differential scanning calorimeter (DSC) of 199 ° C. or lower or substantially not observed (A )When,
A thermoplastic resin (B) other than the thermoplastic resin (A), which is an olefin polymer;
Including
Content of the thermoplastic resin (A) is 2 parts by mass or more and 80 parts by mass or less with respect to a total of 100 parts by mass of the thermoplastic resin (A) and the thermoplastic resin (B), and the thermoplastics The molded object containing the resin composition whose content of resin (B) is 20 to 98 mass parts.   The molded article according to claim 1, wherein the thermoplastic resin (B) is at least one polymer selected from the group consisting of an ethylene polymer and a propylene polymer. The molded article according to claim 1 or 2, wherein the thermoplastic resin (A) has a melting point _Tm of 100 ° C or higher and 180 ° C or lower or is not substantially observed. The melting point T _m is either a 165 below ° C. 100 ° C. or higher, or not substantially observed, the molded body according to any one of claims 1 to 3 of the thermoplastic resin (A).   The molded article according to any one of claims 1 to 4, wherein the α-olefin is propylene, and the thermoplastic resin (B) is a propylene-based polymer.   The molded article according to any one of claims 1 to 5, which is used for at least one of a food container main body and a food container lid.   The food container main body containing the molded object of any one of Claims 1-5.   The lid | cover for food containers containing the molded object of any one of Claims 1-5.