JP6774828B2 - container - Google Patents

Description

The present invention relates to sheets, films and containers.

Sustained-release containers are known that diffuse fragrances and gaseous substances such as pesticides and insect repellents in small amounts from the inside to the outside of the container at a relatively slow rate.

Patent Document 1 describes a sustained-release container that releases the gaseous substance little by little from a large number of pores provided in the container.

Further, Patent Document 2 describes a sustained-release container formed from a single layer of silicone rubber. According to Patent Document 2, rubber is more permeable to gas than plastic, and silicone rubber is particularly suitable as a material for a sustained-release container because it is permeable to various gases well.

On the other hand, since the 4-methyl-1-pentene polymer has a bulky functional group, the density is lower than that of other thermoplastic olefin films, so that the film containing the 4-methyl-1-pentene polymer can be produced. Highly permeable to gases such as oxygen gas and carbon dioxide. According to Patent Document 3, development of packaging bags for fresh foods and the like using 4-methyl-1-pentene polymer as a gas permeable film is underway.

However, 4-methyl-1-pentene polymer is known to have a high melting point and releasability, and therefore, a film mainly composed of 4-methyl-1-pentene polymer (hereinafter, "" 4-Methyl-1-pentene polymer film "is sometimes referred to as"), which requires a high heat-sealing temperature and low heat-sealing strength. In Patent Document 4, another thermoplastic resin, for example, an olefin, is applied to the 4-methyl-1-pentene polymer film by a method of imparting heat-sealing property to the 4-methyl-1-pentene polymer film. A method of using a multilayer film in which a film composed of a based polymer (hereinafter, sometimes referred to as an "olefin polymer film") is laminated into a packaging bag for fresh foods or the like is being studied.

Japanese Unexamined Patent Publication No. 2009-107071 Japanese Unexamined Patent Publication No. 8-155022 Japanese Unexamined Patent Publication No. 11-301691 Japanese Unexamined Patent Publication No. 2000-189051

The containers described in Patent Documents 1 to 4 are premised on the fact that gaseous substances diffuse uniformly from the inside to the outside of the container. However, if the air freshener continues to diffuse in a room where a person is absent for a long period of time, or if the insect repellent continues to diffuse until after returning from going out, these air fresheners and insect repellents will be wasted. Become.

Further, in the 4-methyl-1-pentene polymers described in Patent Documents 3 and 4, it is necessary to set a high heat seal temperature due to high heat resistance and releasability, and the heat seal strength is also low. In addition to this, unlike silicone rubber, it does not exhibit rubber elasticity that restores after stretching, so there is a problem that the amount of diffusion of fragrances and insect repellents cannot be controlled.

In view of the above problems, the present invention includes a thermoplastic porcelain composition capable of producing a container capable of controlling a state in which a gaseous substance is diffused from the inside to the outside of the container and a state in which the diffusion of the gaseous substance is suppressed. Its purpose is to provide sheets or films, and containers.

The present invention for solving the above problem relates to the following container.
[1] see contains a thermoplastic resin composition which satisfies the following (I) and (II),
(I) The ratio G'@ 15 ° C./G'@ 40 ° C. of the storage elastic modulus at 15 ° C. and the storage elastic modulus at 40 ° C., which is obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s, is 50 or more. (II) conforming to JIS K7126-1, under the conditions of test temperature 40 ° C. and a test humidity of 0% RH, the oxygen permeability (oxygen permeability, ^{unit: cm 3 · mm / (m} 2 · 24h · atm)) is , 500 or more
The thermoplastic resin composition is
Constituent unit (i) derived from 4-methyl-1-pentene and
Containing a structural unit (ii) derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene.
It may optionally contain a building block (iii) derived from a non-conjugated polyene.
4-Methyl-1-pentene / α-olefin copolymer
When the total of the constituent units (i), (ii) and (iii) is 100 mol%,
The constituent unit (i) is 55 to 90 mol%,
The constituent unit (ii) is 10 to 45 mol%,
Containing 0-10 mol% of building blocks (iii),
A composition containing a 4-methyl-1-pentene / α-olefin copolymer (A-1).
A container capable of changing its state between a state in which an internal gaseous substance is diffused to the outside and a state in which the diffusion of the gaseous substance is suppressed by a temperature change or expansion and deformation to the original shape.
[2] The temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the thermoplastic resin composition reaches a peak value is 20 ° C. or higher and 40 ° C. or lower, according to [1]. Described container .
[3] The peak value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the thermoplastic resin composition is 0.5 or more and 5.0 or less, [1] or [ a container according to 2].
[4] The description according to any one of [1] to [3], wherein the tensile elongation at break when the thermoplastic composition is stretched at a tensile speed of 200 mm / min in accordance with JIS K7127 is 400% or more. Container .
[5] The thermoplastic resin composition contains the thermoplastic resin (A) containing the 4-methyl-1-pentene / α-olefin copolymer (A-1 ) and the inorganic filler (B). The container according to any one of [1] to [4], which is the composition to be used.
[6] The thermoplastic resin composition, the 4-methyl-1-pentene · alpha-olefin copolymer (A-1) contained 50% by weight or less than 99 wt%, 1 an inorganic filler (B) The container according to any one of [1] to [5], which is a composition containing 50% by mass or more by mass .
[ 7 ] The container according to any one of [1] to [6], which comprises at least the body of the thermoplastic resin composition .

According to the present invention, a sheet and a container containing a thermoplastic material composition capable of producing a container capable of controlling a state in which a gaseous substance is diffused from the inside to the outside of the container and a state in which the diffusion of the gaseous substance is suppressed can be controlled. Is provided.

The sheet, film and container according to one embodiment of the present invention are formed containing a thermoplastic resin composition satisfying the following (I) and (II).
(I) The ratio G'@ 15 ° C / G'@ 40 ° C of the storage elastic modulus at 15 ° C and the storage elastic modulus at 40 ° C, which is obtained by dynamic viscoelastic measurement at a frequency of 10 rad / s, is 50 or more. (II) conforming to JIS K7126-1, under the conditions of test temperature 40 ° C. and a test humidity of 0% RH, the oxygen permeability (oxygen permeability, ^{unit: cm 3 · mm / (m} 2 · 24h · atm)) is , 500 or more

When the above thermoplastic resin composition is heated (for example, heated to near 40 ° C.) or deformed (for example, 100% elongation), the gas permeability increases, and the gaseous substance is gradually diffused from the inside of the container to the outside. At lower temperatures (for example, near 15 ° C.) or during shrinkage, gas permeability decreases, and gaseous substances are less likely to diffuse from the inside of the container to the outside. Therefore, the container containing the thermoplastic resin composition diffuses the gaseous substance from the inside to the outside of the container when heated or deformed, and suppresses the diffusion of the gaseous substance when not heated or deformed.

1. 1. Thermoplastic resin composition A thermoplastic resin having a storage elastic modulus ratio (G'@ 15 ° C./G'@ 40 ° C.) of 50 or more has a molecular weight when heated as compared with a state at a lower temperature. Since the fluidity is sufficiently increased to generate a large number of pores through which the gaseous substance can pass, the gaseous substance can be easily permeated. On the other hand, the thermoplastic resin usually has low molecular fluidity and the pores are unlikely to be formed, so that it is difficult for the gaseous substance to permeate. Therefore, the thermoplastic resin composition in which the ratio of the storage elasticity (G'@ 15 ° C./G'@ 40 ° C.) is in the above range diffuses the gaseous substance inside the container when it is heated. At room temperature, the diffusion of gaseous substances inside the container is suppressed. From the above viewpoint, the ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) of the thermoplastic resin composition is preferably 50 or more and 800 or less, and more preferably 80 or more and 600 or less. preferable. The ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) is not particularly limited, but is preferably 800 or less.

The storage elastic modulus is dynamic from 40 to 150 ° C. at a frequency of 10 rad / s using a viscoelasticity measuring device (for example, MCR301 manufactured by ANTONPar) using a strip piece of 45 mm × 10 mm × 3 mm as a measurement sample. It can be obtained by measuring the temperature dependence of viscoelasticity.

The oxygen permeability at 40 ° C. (oxygen permeability, ^{unit: cm 3 · mm / (m} 2 · 24h · atm)) is a thermoplastic resin is 500 or more, a sufficient amount of gaseous substances when heated To be transparent. Therefore, the thermoplastic resin composition having the oxygen gas transmittance at 40 ° C. in the above range tends to sufficiently diffuse the gaseous substance inside the container when it is heated. From the above viewpoint, the oxygen gas transmittance of the thermoplastic resin composition at 40 ° C. is preferably 500 or more and 10000 or less, and more preferably 500 or more and 5000 or less. There is no particular upper limit to the oxygen gas permeability at 40 ° C., but it is preferably 10,000 or less from the viewpoint of enhancing the sustained release property of the container without diffusing a large amount of gaseous substances at one time.

Oxygen gas permeability at ^{40 ℃ (10 -11 cm 3 (} STP) / (cm · s · cmHg), 40 ℃) is in compliance with JIS K7126-1, the gas permeability measuring apparatus (for example MOCON method, It can be obtained by measuring the measurement area of the film at 5 cm ^{2 under} the conditions of a test temperature of 40 ° C. and a test humidity of 0% RH using a differential pressure method gas transmittance measuring device). At this time, for the measurement area of the film, prepare two aluminum masks with adhesive made by Modern Cotrol Co., Ltd. with a hole with a diameter of 25 mm in the center, and sandwich the film to be measured between these two masks. Laminate and adjust. Specifically, the film is arranged so that the holes in the center overlap with each other with two masks. At this time, for example, the thickness of the test piece may be 100 μm or more and 500 μm or less, the environmental temperature of the test room may be 40 ° C., and the pressurization on the high pressure side may be 49 Pa.

Further, in the above thermoplastic resin composition, the temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s reaches a peak value is preferably 20 ° C. or higher and 40 ° C. or lower. In the thermoplastic resin composition having a temperature of 40 ° C. or lower, the fluidity of the molecules is sufficiently increased at the time of heating as compared with the state at a lower temperature, and the gaseous substance is more easily permeated. On the other hand, in the thermoplastic resin composition having a temperature of 20 ° C. or higher, the fluidity of the molecules is usually low, and the pores are less likely to be formed, so that it is difficult for the gaseous substance to permeate. Therefore, the thermoplastic resin composition in which the temperature at which tan δ reaches the peak value is in the above range, diffuses the gaseous substance inside the container when heated, and diffuses the gaseous substance inside the container at room temperature. Suppress. From the above viewpoint, the temperature at which tan δ of the thermoplastic resin composition reaches its peak value is preferably 25 ° C. or higher and 40 ° C. or lower, and more preferably 30 ° C. or higher and 40 ° C. or lower.

Further, in the thermoplastic resin composition, the peak value of tan δ is preferably 0.5 or more and 5.0 or less. When the thermoplastic resin composition has a peak value of tan δ of 5.0 or less, the fluidity of the molecules is sufficiently increased during heating, and the gaseous substance is easily permeated. Further, since the thermoplastic resin composition having a peak value of tan δ of 0.5 or more does not excessively increase the fluidity of the molecules when heated, a large amount of gaseous substances are diffused at one time when used as a container. It is possible to increase the sustained release property of the container without causing it. Further, since the thermoplastic resin composition having a peak value of tan δ of 0.5 or more has high stress absorption, damage to the container due to dropping during use can be suppressed. From the above viewpoint, the peak value of tan δ of the thermoplastic resin composition is preferably 0.6 or more and 3.0 or less, and more preferably 0.8 or more and 3.0 or less.

tan δ can be calculated from the ratio (G "/ G': loss tangent) of the storage elastic modulus (G') and the loss elastic modulus (G") obtained at the time of measuring the storage elastic modulus. At this time, the temperature at which tan δ reaches the peak value (maximum value) in the range of 0 to 30 ° C. is defined as the temperature at which tan δ reaches the peak value, and the value of tan δ at that time is defined as the peak value of tan δ. The peak is considered to be due to the glass transition temperature of the thermoplastic resin composition.

Further, the thermoplastic composition preferably has a tensile elongation at break of 400% or more when stretched at a tensile speed of 200 mm / min in accordance with JIS K7127. The thermoplastic resin composition having a tensile elongation at break of 400% or more is easily deformed, and when deformed (for example, 100% elongation), the fluidity of the molecule is further increased and the pores are more likely to be generated. Therefore, the thermoplastic resin composition having the tensile elongation at break in the above range diffuses the gaseous substance inside the container by stretching when it is made into a container, and suppresses the diffusion of the gaseous substance inside the container when it shrinks. .. From the above viewpoint, the tensile elongation at break of the thermoplastic resin composition is preferably 400% or more and 2000% or less, and more preferably 400% or more and 1500% or less. The ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) is not particularly limited, but is preferably 2000% or less.

The thermoplastic resin composition is not limited as long as it satisfies the above-mentioned physical properties, but is preferably a composition containing a thermoplastic resin (A) and an inorganic filler (B), and 4-methyl-1-. It is more preferable to prepare a composition containing a penten / α-olefin copolymer (A-1) and an inorganic filler (B) (hereinafter, also simply referred to as “4MP1 based composition”). In the composition containing the thermoplastic resin (A) and the inorganic filler (B), the interface between the thermoplastic resin (A) and the inorganic filler (B) is peeled off at the time of stretching, and the pores are sufficiently formed. It becomes possible to reversibly control the gas permeability by closing the pores at the time of contraction. Further, the 4MP1 composition is easy to satisfy the above physical properties and has a releasable property having a material, and pores are likely to be formed by peeling off the interface.

The 4MP1 system composition contains 50% by mass or more and 99% by mass or less of the 4-methyl-1-pentene / α-olefin copolymer (A-1) and 1% by mass or more and 50% by mass of the inorganic filler (B). It contains the following. When the ratio of the 4-methyl-1-pentene / α-olefin copolymer (A-1) to the inorganic filler (B) is within the above range, a sufficient amount of pores are formed during heating to form a gaseous substance. And because the amount of the pores is not too large, it is possible to enhance the sustained release property of the container without allowing a large amount of gaseous substance to permeate at one time. From the above viewpoint, the content of the 4-methyl-1-pentene / α-olefin copolymer (A-1) is preferably 50% by mass or more and 98% by mass or less, and 60% by mass or more and 90% by mass or less. Is more preferable. The content of the inorganic filler (B) is preferably 2% by mass or more and 50% by mass, and more preferably 10% by mass or more and 40% by mass or less.

1-1.4-Methyl-1-pentene / α-olefin copolymer (A-1)
Composition of 1-1-1.4-Methyl-1-pentene / α-olefin copolymer (A-1) 4-Methyl-1-pentene / α-olefin copolymer (A-1) is 4- A structural unit derived from methyl-1-pentene (i) and a structural unit derived from at least one α-olefin selected from an α-olefin having 2 to 20 carbon atoms excluding 4-methyl-1-pentene (a structural unit derived from at least one α-olefin) ii) is included. The 4-methyl-1-pentene / α-olefin copolymer (A-1) may optionally contain a structural unit (iii) derived from a non-conjugated polyene. The 4-methyl-1-pentene / α-olefin copolymer (A-1) can be used alone or in combination of two or more.

The 4-methyl-1-pentene / α-olefin copolymer (A-1) is composed when the total of the structural unit (i), the structural unit (ii) and the structural unit (iii) is 100 mol%. The unit (i) is 55 mol% or more and 90 mol% or less, the constituent unit (ii) is 10 mol% or more and 45 mol% or less, and the constituent unit (iii) is 0 mol% or more and 10 mol% or less.

The lower limit of the ratio of the constituent unit (i) is 55 mol%, preferably 60 mol%, and more preferably 68 mol%. On the other hand, the upper limit of the ratio of the constituent unit (ii) is 90 mol%, preferably 86 mol%, and more preferably 84 mol%. When the ratio of the structural unit (ii) contained in the 4-methyl-1-pentene / α-olefin copolymer (A-1) is equal to or higher than the above lower limit, the 4-methyl-1-pentene / α-olefin copolymer weight Since the temperature at which tan δ of the coalescence (A-1) reaches its peak value is around room temperature, the temperature at which tan δ of the thermoplastic resin composition reaches its peak value can be easily adjusted within the above range. Further, when the ratio of the structural unit (i) contained in the 4-methyl-1-pentene / α-olefin copolymer (A-1) is not more than the above upper limit value, 4-methyl-1-pentene / α-olefin Since the copolymer (A-1) has appropriate flexibility, it is easy to adjust the ΔHS of the thermoplastic resin composition within the above-mentioned range.

As a matter of course, at this time, the upper limit of the ratio of the constituent unit (ii) is 45 mol%, preferably 40 mol%, and more preferably 32 mol%. On the other hand, the lower limit of the ratio of the constituent unit (ii) is 10 mol%, preferably 14 mol%, and more preferably 16 mol%.

Examples of α-olefins that lead to the building block (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene. , 1-Hexadecene, 1-octadecene, 1-eicocene and the like, linear α-olefins having 2 to 20 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms). , And 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl. Examples thereof include branched α-olefins having 5 to 20 carbon atoms (preferably 5 to 15 carbon atoms) containing -1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like. .. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and ethylene and propylene are particularly preferable. The structural unit (ii) may be derived from one of these compounds, or may be derived from two or more compounds.

Examples of non-conjugated polyenes leading to the building block (iii) include 1,4-hexadien, 3-methyl-1,4-hexadien, 4-methyl-1,4-hexadien, 5-methyl-1,4-hexadien. , 4,5-Dimethyl-1,4-hexadiene, 7-methyl-1,6-octadien, 8-methyl-4-ethylidene-1,7-norbornene, and 4-ethylidene-1,7-undecadien and the like. Chain non-conjugated diene, methyltetrahydroinden, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-isopropyriden-2-norbornene, 5-binylidene-2-norbornene, 6-chloromethyl Cyclic non-conjugated diene, including -5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornene, etc. , And 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, and 4-ethylidene-8-methyl-1,7. -Includes triene, etc., including norbornene. Of these, especially when the α-olefin that leads to the structural unit (ii) is propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are used from the viewpoint of increasing the cross-linking efficiency. ) Is preferable. The structural unit (iii) may be derived from one of these compounds, or may be derived from two or more compounds.

However, it is preferable that the 4-methyl-1-pentene / α-olefin copolymer (A-1) is substantially composed of the structural unit (i) and the structural unit (ii).

The 4-methyl-1-pentene / α-olefin copolymer (A-1) preferably satisfies one or more requirements selected from the following requirements (a), (b) and (c).
Requirement (a) ;
The ultimate viscosity [η] of 4-methyl-1-pentene / α-olefin copolymer (A-1) measured at 135 ° C. in decalin shall be 0.1 dL / g or more and 5.0 dL / g or less. Is more preferable, 0.5 dL / g or more and 4.0 dL / g or less is more preferable, and 0.5 dL / g or more and 3.5 dL / g or less is further preferable. The 4-methyl-1-pentene / α-olefin copolymer (A-1) having the above-mentioned ultimate viscosity [η] in the above-mentioned range can be easily molded into a sheet or film-like thermoplastic resin composition.

The extreme viscosity [η] of the 4-methyl-1-pentene / α-olefin copolymer (A-1) is within the above range by adding hydrogen during production by polymerization to control the molecular weight and polymerization activity. Can be adjusted.

The ultimate viscosity [η] is the reduced viscosity η _rad by determining the viscosity increase rate η _sp per unit concentration c of each polymer when different amounts of thermoplastic resin compositions are dissolved in decalin at 135 ° C. Then, η _rad can be extrapolated so that the unit concentration c of the polymer becomes zero.

Requirement (b) ;
Ratio of 4-methyl-1-pentene / α-olefin copolymer (A-1) to weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mn) The molecular weight distribution (Mw / Mn) is preferably 1.0 or more and 3.5, more preferably 1.2 or more and 3.0 or less, and further preferably 1.5 or more and 2.8 or less. preferable. The 4-methyl-1-pentene / α-olefin copolymer (A-1) having Mw / Mn in the above range is less likely to be deteriorated in moldability due to a low molecular weight and low stereoregular polymer, and is a sheet or film. It is easy to mold into a thermoplastic resin composition.

The weight average molecular weight (Mw) of the 4-methyl-1-pentene / α-olefin copolymer (A-1) measured by gel permeation chromatography (GPC) is 500 or more and 10 in terms of polystyrene. It is preferably 000,000 or more, more preferably 1,000 or more and 5,000,000 or less, and further preferably 1,000 or more and 2,500,000 or less.

The Mw / Mn and Mw of the 4-methyl-1-pentene / α-olefin copolymer (A-1) can be adjusted to the above range by using, for example, a metallocene catalyst.

For the above Mw and Mw / Mn, for example, a Waters ALC / GPC 150-C plus type (integrated with a differential refractometer detector) is used as a liquid chromatograph, and two GMH6-HT x 2 and GMH6 manufactured by Toso Co., Ltd. are used as columns. -HTL x 2 are connected in series, o-dichlorobenzene is used as the mobile phase medium, and the chromatogram obtained by measuring at a flow rate of 1.0 ml / min and 140 ° C. is obtained using a calibration curve using a standard polystyrene sample. Can be analyzed and obtained.

Requirement (c) ;
Density is preferably at most 830 kg / m ³ or more 870 kg / m ³ as measured according to ASTM D 1505 of 4-methyl-1-pentene · alpha-olefin copolymer (A-1), 830kg / more preferably m ³ or more 865Kg / m ³ or less, and more preferably not more than 830 kg / m ³ or more 855Kg / m ^3. Since the 4-methyl-1-pentene / α-olefin copolymer (A-1) having the above density in the above range is lightweight, it is easy to manufacture a container that is easy to carry and handle.

The density of the 4-methyl-1-pentene / α-olefin copolymer (A-1) can be appropriately adjusted depending on the composition ratio of the structural unit (i) to the structural unit (iii).

The ultimate viscosities [η], Mw / Mn, Mw and densities according to the above requirements (a) to (c) can be obtained by the same measurement as the above-mentioned thermoplastic resin composition.

Method for Producing 1-1-2.4-Methyl-1-pentene / α-olefin Copolymer (A-1) The 4-methyl-1-pentene / α-olefin copolymer (A-1) is described above. The monomer leading from the structural unit (i) to the structural unit (iii) can be polymerized in the presence of a suitable catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst to produce the product. The polymerization can be appropriately selected from a liquid phase polymerization method including dissolution polymerization, suspension polymerization and the like, a gas phase polymerization method and the like.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as the solvent constituting the liquid phase. Examples of the above-mentioned inert hydrocarbons include aliphatic hydrocarbons including propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Aliphatic hydrocarbons, including aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons, including ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof. included.

Further, in the liquid phase polymerization method, bulk polymerization may be carried out in which the monomer itself that derives the structural unit (i) to the structural unit (iii) is used as a solvent.

The 4-methyl-1-pentene / α-olefin copolymer (A-1) is formed by stepwise copolymerizing the monomers leading from the structural units (i) to the structural units (iii). The composition distribution of the structural unit (i) to the structural unit (iii) can also be appropriately controlled.

The polymerization temperature is preferably −50 ° C. or higher and 200 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and further preferably 20 ° C. or higher and 100 ° C. or lower.

The polymerization pressure is preferably normal pressure or higher and 10 MPa gauge pressure, and more preferably normal pressure or higher and 5 MPa gauge pressure.

At the time of polymerization, hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the polymer to be produced. The amount of hydrogen added is appropriately about 0.001 NL or more and 100 NL or less with respect to 1 kg of the total amount of the monomers leading from the structural unit (i) to the structural unit (iii).

1-2. Inorganic filler (B)
The inorganic filler (B) may be any inorganic compound added to the thermoplastic resin composition. Examples of the inorganic filler (B) include carbon black or carbon black surface-treated with graphite or a silane coupling agent, fine powder silicic acid, silica (focal silica, precipitated silica, diatomaceous earth, quartz, etc.). ), Alumina, iron oxide, magnesium oxide, titanium oxide, antimony trioxide, zirconium oxide, barium oxide and calcium oxide, oxide-based fillers, aluminum hydroxide and magnesium hydroxide, hydroxide-based fillers, silicic acid Silicate fillers containing aluminum (clay), magnesium silicate (talc), mica, calcium silicate, glass fibers, glass flakes, glass beads, etc., sedimentary rock fillers containing diatomaceous earth and limestone, montmorillonite (montmorillonite), Magnesian montmorillonite, Tetsumonmorillonite, Tetsumagnesian montmorillonite, Bidelite, Aluminian Bidelite, Nontron stone, Aluminian nontronite, Support stone (supportite), Aluminian support stone, Hectrite, Saconite, Steven site , And clay mineral fillers including bentonite, magnetic fillers including ferrite, iron and cobalt, conductive fillers containing silver, gold, copper and alloys thereof, calcium carbonate, basic magnesium carbonate, aluminum sulfate, etc. Includes barium sulfate, barium titanate, potassium titanate, calcium sulfate, calcium sulfite, silicon carbite, boron nitride and the like.

Of these, silica, calcium carbonate and barium sulfate are preferable, and silica is more preferable. The silica may be surface-treated with a reactive silane containing hexamethyldisilazane, chlorosilane, alkoxysilane, or the like, or a low molecular weight siloxane.

1-3. Other Ingredients The thermoplastic resin composition may further contain known additives, if necessary.

For example, the thermoplastic resin composition is a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a pigment, a dye, etc. Additives such as plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, fungicides, antibacterial agents, flame retardants, organic fillers, and softeners may be included.

Examples of the softeners include process oils, lubricating oils, paraffins, liquid paraffins, polyethylene waxes, polypropylene waxes, petroleum-based substances including petroleum asphalt and vaseline, coulters including coultar and coultar pitch, and sunflower. Fat oil including oil, flaxseed oil, rapeseed oil, soybean oil and coconut oil, waxes including tall oil, beeswax, carnauba wax and lanolin, ricinolic acid, palmitic acid, stearic acid, 12-stearic hydroxide, Ester-based plastics containing fatty acids or metal salts thereof including montanic acid, oleic acid and erucic acid, synthetic polymers including petroleum resin, kumaron inden resin and tactic polypropylene, dioctyl phthalate, dioctyl adipate and dioctyl sebacate, etc. Included are known softeners, including agents, microcrystallin wax, liquid polypropylene or modified or hydrogenated products thereof, as well as liquid thiocol and the like.

Examples of the flame retardants include ammonium polyphosphate, ethylenebistris (2-cyanoethyl) phosphonium chloride, tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate, tris (3-hydroxypropyl) phosphine oxide. Phosphate and other phosphorus compounds such as, chlorinated paraffin, chlorinated polyolefin, chlorine-based flame retardants such as perchlorocyclopentadecane, hexabromobenzene, ethylenebisdibromonorbornandicarboxyimide, ethylenebistetrabromophthalimide, tetrabromo Includes brominated flame retardants such as bisphenol A derivatives, tetrabromobisphenol S, and tetrabromodipentaerythritol, and mixtures thereof.

The total content of the other additives is 0.001 part by mass or more and 50 parts by mass with 100 parts by mass of the thermoplastic resin (for example, 4-methyl-1-pentene / α-olefin copolymer (A-1)). It is preferably less than or equal to parts by mass.

1-4. Method for Producing Thermoplastic Resin Composition The above-mentioned thermoplastic resin composition can be produced by a known method. For example, the 4MP1 system composition can be produced by substantially uniformly dispersing the inorganic filler (B) in the 4-methyl-1-pentene / α-olefin copolymer (A-1). For example, 4-methyl-1-pentene / α-olefin copolymer (A-1), inorganic filler (B) and other additives may be melt-kneaded by a roll mill, a Banbury mixer or an extruder. From the viewpoint of facilitating the production of the container, the thermoplastic resin composition may be molded into a sheet or a film.

2. Container The container may be formed from the above-mentioned thermoplastic resin at least partially. When the entire container is formed from the above-mentioned thermoplastic resin composition, the container can be integrally molded, so that the container can be easily manufactured. When a part of the container is made of another material, each part may be molded separately and joined by an adhesive, heat fusion, ultrasonic fusion, or the like to manufacture the container.

The shape of the container is not particularly limited, and can be a known shape such as a three-way seal flat bag, a standing pouch, a gusset packaging bag, a pillow packaging bag, or a bottle shape, an ampoule shape, a bag shape, a box shape, or the like. The container may be self-supporting, or may be held by a string or the like. Containers having these shapes can be molded from the above thermoplastic resin composition by a known method. At this time, the container may be formed from the sheet or film-shaped thermoplastic resin composition, or the thermoplastic resin may be molded into a container shape, and the sheet or film-like thermoplastic resin may be formed on a part of the container. A resin composition may be included.

The container holds substances such as air fresheners and insecticides and insect repellents inside, and can be released slowly when heated or when deformed by stretching or the like. The above-mentioned air fresheners and substances such as insecticides and insect repellents may be in a gaseous state, or may be in a solid state or a liquid state as long as they can be vaporized or sublimated. The fragrance and substances such as pesticides and insect repellents may be encapsulated directly inside the container as long as they do not significantly change the physical properties of the thermoplastic resin composition or other components that form the container. , These may be put in another bag having gas permeability and sealed in the container together with the above bag.

The container is gaseous from the inside to the outside by heating with a heater or a range, heating with human skin or breath, heating by immersing in hot water such as a bath, and by pulling the container by hand. The substance can be released slowly. In addition, if the temperature of the container is lowered by stopping heating, the diffusion of gaseous substances from the inside of the container to the outside can be suppressed, and the stretched container also returns to its original shape and becomes gaseous. Diffusion of substances can also be suppressed. With either method, it is possible to easily control the state in which the gaseous substance is diffused from the inside to the outside of the container and the state in which the diffusion of the gaseous substance is suppressed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

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 (α-olefin having 3 carbon atoms) in the copolymer was measured by ¹³ C-NMR. The measurement conditions are as follows.

Measuring device: Nuclear magnetic resonance device (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 Accumulation number: 10,000 times or more Solvent: Ortodichlorobenzene / 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

[Ultimate viscosity [η]]
The ultimate viscosity [η] of the copolymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscous meter as a measuring device.

Specifically, about 20 mg of a 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 adding 5 ml of decalin to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner as above. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) (see Equation 1 below).
[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 was calculated by a standard polystyrene conversion method using Permeation Chromatography). The measurement conditions are as follows.

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

[Melting Flow Rate (MFR)]
The melt flow rate (MFR: Melt Flow Rate) of the copolymer was measured at 230 ° C. under 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 (density gradient tube method).

[Melting point (T _m )]
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 measuring aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The copolymer was held at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min to completely melt the copolymer. After standing at −50 ° C. for 5 minutes, the second heating was performed at 10 ° C./min to 200 ° C. The peak temperature (° C.) at the second heating was defined as the melting point ( _Tm ) of the copolymer.

[Dynamic viscoelasticity]
In the measurement of dynamic viscoelasticity, a press sheet having a thickness of 3 mm was used as a measurement sample, and a strip piece of 45 mm × 10 mm × 3 mm necessary for dynamic viscoelasticity measurement was cut out. Using MCR301 manufactured by ANTONPar, the temperature dependence of dynamic viscoelasticity from -40 to 150 ° C. was measured at a frequency of 10 rad / s, and the loss tangent (tanδ) due to the glass transition temperature was measured in the range of 0 to 40 ° C. ) At the peak value (maximum value) (hereinafter, also referred to as “peak value temperature”), and the value of the loss tangent (tan δ) at that time were measured.

[Mechanical properties (tensile breaking elongation, tensile breaking strength, Young's modulus]
A sheet having a thickness of 200 μm cut into a dumbbell shape having a width of 25 mm and a length of 100 mm was used as a test piece.
In accordance with JIS K7127 (1999), a tensile tester (universal tensile tester 3380, manufactured by Instron) is used to pull the test piece under the conditions of a chuck distance of 50 mm, a tensile speed of 200 mm / min, and a temperature of 23 ° C. The elastic modulus (YM) (unit: MPa), tensile elongation at break (EL) (unit:%), and tensile strength at break (TS) (unit: MPa) were measured.

[Gas permeability (oxygen permeability coefficient)]
A film having a thickness of 100 μm cut into a shape having a width of 30 mm and a length of 30 mm was used as a test piece. The measurement area of the film was set to 5 cm ^{2 under} the conditions of a test temperature of 23 ° C. and a test humidity of 0% RH using a differential pressure method gas transmittance measuring device (manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7126-1. .. For the measurement area of the film, prepare two aluminum masks with adhesive made by Modern Cotrol Co., Ltd. with a hole with a diameter of 25 mm in the center, and stack them so that the film to be measured is sandwiched between these two masks. ,It was adjusted. Specifically, the film is arranged so that the holes in the center overlap with each other with two masks.

[Synthesis Example 1] Synthesis of copolymer A-1 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. ), And 450 ml of 4-methyl-1-pentene was charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, 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 0.19 MPa.

Subsequently, 1 mmol of methylaluminoxane in terms of Al and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance. 0.34 ml of a toluene solution containing butyl-fluorenyl) zirconium dichloride was press-fitted into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

60 minutes after the start of polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

Then, the polymerization reaction product containing the obtained solvent was dried under reduced pressure at 100 ° C. 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%. The density of the copolymer A-1 was 838 kg / m ³ . The limit viscosity [η] of the copolymer A-1 is 1.5 dl / g, the weight average molecular weight (Mw) is 340,000, the molecular weight distribution (Mw / Mn) is 2.1, and the melt flow. The rate (MFR) was 11 g / 10 min. The melting point ( _Tm ) of the copolymer A-1 was 132 ° C.

[Synthesis Example 2] Synthesis of copolymer A-2 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. ), And 450 ml of 4-methyl-1-pentene was charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, 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 in terms of Al and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance. 0.34 ml of a toluene solution containing butyl-fluorenyl) zirconium dichloride was press-fitted into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

60 minutes after the start of polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

Next, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 100 ° C. 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%. The density of the copolymer A-2 was 839 kg / m ³ . The limit viscosity [η] of the copolymer A-2 is 1.5 dl / g, the weight average molecular weight (Mw) is 337,000, the molecular weight distribution (Mw / Mn) is 2.1, and the melt flow. The rate (MFR) was 11 g / 10 min. The melting point ( _Tm ) of the copolymer A-2 was not observed.

[Synthesis Example 3] Synthesis of Copolymer A-3 In Comparative Example 7 of International Publication No. 2006/054613, the copolymer A was obtained by changing the ratio of 4-methyl-1-pentene to 1-decene. I got -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 98.0 mol%, and the content of 1-decene was 2.0 mol%. The density of the copolymer A-3 was 833 kg / m ³ . The intrinsic viscosity [η] of the copolymer A-3 was 2.4 dl / g, and the melt flow rate (MFR) was 4 g / 10 min. The melting point ( _Tm ) of the copolymer A-3 was 238 ° C.

In Table 1, "4MP1 unit" means the structural unit (i) derived from 4-methyl-1-pentene, and "AO unit" has 2 to 20 carbon atoms excluding 4-methyl-1-pentene. It means a structural unit (ii) derived from at least one α-olefin selected from the α-olefins of the above.

<Example 1>
100 parts by mass of the copolymer A-1 was put into a hopper of a 20 mmφ single-screw extruder (single-screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T-die having a lip width of 240 mm. Then, the cylinder temperature was set to 230 ° C. and the die temperature was set to 230 ° C., and the melt-kneaded product was extruded from the T-die to a thickness of 200 μm and cast-molded to obtain the film of Example 1.

<Example 2>
The film of Example 2 (thickness:) by the same method as in Example 1 except that 40 parts by mass of the copolymer A-1 and 60 parts by mass of the copolymer A-2 were mixed (dry blended). 200 μm) was obtained.

<Example 3>
Obtained by mixing 40 parts by mass of copolymer A-1, 60 parts by mass of copolymer A-2, and 30 parts by mass of calcium carbonate B-1 with a twin-screw extruder (manufactured by Thermoplastics Co., Ltd.). The pellet of the composition was molded by the same method as in Example 1 to obtain a film (thickness: 200 μm) of Example 3.

<Comparative example 1>
A film (thickness: 200 μm) of Comparative Example 1 was obtained by molding by the same method as in Example 1 except that 100 parts by mass of the copolymer A-3 was used.

As can be seen from Table 2, a sheet obtained from the composition of the 4-methyl-1-pentene polymer and the 4-methyl-1-pentene polymer of Examples satisfying the above-mentioned (i) and (ii) and an inorganic filler. Then, G'@ 15 ° C./G'@ 40 ° C., which indicates the temperature dependence of the storage elastic modulus, can be set high. This allows control of flexibility and gas permeability. On the other hand, in Comparative Example 1, since the temperature dependence of the storage elastic modulus and the tensile elongation at break are low, it is difficult to control the gas permeability by the temperature and elongation.

Claims (7)

Look containing a thermoplastic resin composition which satisfies the following (I) and (II),
(I) The ratio G'@ 15 ° C./G'@ 40 ° C. of the storage elastic modulus at 15 ° C. and the storage elastic modulus at 40 ° C., which is obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s, is 50 or more. (II) conforming to JIS K7126-1, under the conditions of test temperature 40 ° C. and a test humidity of 0% RH, the oxygen permeability (oxygen permeability, ^{unit: cm 3 · mm / (m} 2 · 24h · atm)) is , 500 or more
The thermoplastic resin composition is
Constituent unit (i) derived from 4-methyl-1-pentene and
Containing a structural unit (ii) derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene.
It may optionally contain a building block (iii) derived from a non-conjugated polyene.
4-Methyl-1-pentene / α-olefin copolymer
When the total of the constituent units (i), (ii) and (iii) is 100 mol%,
The constituent unit (i) is 55 to 90 mol%,
The constituent unit (ii) is 10 to 45 mol%,
Containing 0-10 mol% of building blocks (iii),
A composition containing a 4-methyl-1-pentene / α-olefin copolymer (A-1).
A container capable of changing its state between a state in which an internal gaseous substance is diffused to the outside and a state in which the diffusion of the gaseous substance is suppressed by a temperature change or expansion and deformation to the original shape. The container according to claim 1, wherein the temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the thermoplastic resin composition reaches a peak value is 20 ° C. or higher and 40 ° C. or lower. .. The peak value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the thermoplastic resin composition is 0.5 or more and 5.0 or less, according to claim 1 or 2. Container . The container according to any one of claims 1 to 3, wherein the thermoplastic composition has a tensile elongation at break of 400% or more when stretched at a tensile speed of 200 mm / min in accordance with JIS K7127. The thermoplastic resin composition is
Claims 1 to 4, which are compositions containing the thermoplastic resin (A) containing the 4-methyl-1-pentene / α-olefin copolymer (A-1 ) and the inorganic filler (B). The container according to any one of the above. The thermoplastic resin composition is
The 4-methyl-1-pentene / α-olefin copolymer (A-1) is contained in an amount of 50% by mass or more and 99% by mass or less.
An inorganic filler (B) a composition containing less than 50 wt% 1 mass% or more, containers according to any one of claims 1 to 5. The container according to any one of claims 1 to 6 , wherein at least the body thereof contains the thermoplastic resin composition .