JP2020189696A - Tube type container - Google Patents

Abstract

To provide a tube type container capable of being produced from a harder material and easily discharging a content left a little by extruding or squeezing out.SOLUTION: The tube type container includes a laminate comprising a 4-methyl-1-pentene/α-olefin copolymer (A-1) which contains 55 to 85 mol% of a constitutional unit (A-i) derived from 4-methyl-1-pentene and 15 to 45 mol% of a constitutional unit (A-ii) derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene and which may contain 0 to 10 mol% of a constitutional unit (A-iii) optionally derived from a non-conjugated polyene, and a thermoplastic resin (B) other than the 4-methyl-1-pentene/α-olefin copolymer, and a thickness of the layer comprising the thermoplastic resin composition as a main component accounts for 50% or more.SELECTED DRAWING: Figure 2

Description

The present invention relates to a tube type container.

A technique of using a laminate of resin compositions is known as a material for a tube-type container for storing a liquid substance or a paste-like solid substance and discharging it at the time of use.

For example, Patent Document 1 describes a tube-type container for toothpaste, in which the body is composed of a laminate having a plurality of layers made of polyethylene. Further, Patent Document 2 describes a tube-type container for toothpaste, which comprises a body composed of a laminate having a plurality of layers composed of polyethylene, polyethylene terephthalate, urethane, and an ethylene-methacrylic acid copolymer. ..

Further, in Patent Document 3, a basic oxidation in which a body is composed of a laminate in which a layer made of polypropylene-a layer made of modified polyethylene-a gas barrier layer-a layer made of modified polyethylene-a layer made of polyethylene are laminated in this order. A tube-type container for a hair dye containing a dye as a main component is described. According to Patent Document 3, since the innermost layer made of polypropylene does not easily adsorb the basic oxide dye, the dye permeates the inside of the laminate and reaches the innermost layer made of polyethylene, and oxygen in the outside air. It is described that discoloration of the layer made of polyethylene can be suppressed by reacting with. Further, Patent Document 3 describes that since the gas barrier layer is made of a gas barrier resin, it is difficult for a liquid or gas to permeate into the inside of the tube-type container from the outside.

Japanese Unexamined Patent Publication No. 2016-088577 JP-A-2008-162599 JP-A-2006-240666

Highly viscous liquids such as shampoo and paste-like solids such as toothpaste are stored in the tube-type container and discharged during use. It is said that it is difficult for these liquids to have both the ease of extruding and squeezing out from the container when the content in the tube-type container is low and increasing the capacity of the tube-type container. There is a problem.

In Patent Document 1 and Patent Document 2, since a tube-type container is manufactured using a relatively soft material, the container is crushed or rolled to be deformed, and the remaining contents are discharged. Is easy. However, when a tube-type container is manufactured using a relatively soft material, it is difficult to erect the container and it is difficult to increase the capacity of the container. Therefore, the containers described in these documents can be used to store products that are used in small amounts for toothpaste, but can be used in containers for storing shampoos that are used in larger amounts. Is not suitable.

On the other hand, when a tube-type container is manufactured using a resin having a higher hardness at room temperature as in Patent Document 3, although it is possible to increase the capacity of the container, it is difficult to deform the container, and the rest. It is difficult to eject or squeeze out the small contents.

In view of the above problems, the present invention provides a tube-type container that can be manufactured by using a resin having a higher hardness at room temperature and that can be easily discharged by extruding or squeezing out the remaining content. That is the purpose.

The present invention for solving the above problems relates to the following tube-type container.
[1] A laminate formed from a plurality of layers including a layer containing a thermoplastic resin composition as a main component.
The thermoplastic resin composition is
Derived from at least one α-olefin selected from the building blocks (Ai) derived from 4-methyl-1-pentene and α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. Including the structural unit (A-iii) to be obtained
A 4-methyl-1-pentene / α-olefin copolymer that may optionally contain a structural unit (A-iii) derived from a non-conjugated polyene.
When the total of the constituent units (A-i), (A-ii) and (A-iii) is 100 mol%,
The constituent unit (Ai) is 55 to 85 mol%,
Constituent unit (A-ii) 15-45 mol%,
Contains 0-10 mol% of building blocks (A-iii),
4-Methyl-1-pentene / α-olefin copolymer (A-1) and
With the thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer,
Is a composition containing
A tube-type container including a laminate in which the thickness of the layer containing the thermoplastic resin composition as a main component with respect to the thickness of the entire laminate is 50% or more.
[2] The tube-type container according to [1], wherein the laminate further contains a gas barrier layer.
[3] The tube-type container according to [2], wherein the gas barrier layer contains a resin selected from the group consisting of an ethylene-vinyl alcohol copolymer resin, a nylon resin, a polyethylene terephthalate resin, and a polyacrylonitrile resin.
[4] The tube-type container according to any one of [1] to [3], wherein the laminate further contains a layer containing a polyethylene resin or a polypropylene resin as a main component.
[5] The laminate comprises a layer containing a polyethylene resin or a polypropylene resin as a main component, a layer containing the thermoplastic resin composition as a main component, a gas barrier layer, and a polyethylene resin or a polypropylene resin laminated in this order. The tube-type container according to [2] or [3], which contains a layer as a main component.
[6] The tube-type container according to any one of [1] to [5], which comprises at least the laminate in the body.

According to the present invention, there is provided a tube-type container that can be manufactured using a resin having a higher hardness at room temperature and that can be easily discharged by extruding or squeezing out the remaining content.

FIG. 1 is a schematic view showing a tube-type container according to an embodiment of the present invention. 2A, 2B and 2C are partially enlarged cross-sectional views of the region 2 shown in FIG.

As shown in FIG. 1, the tube-type container 100 according to an embodiment of the present invention includes a hollow body portion 110, a bottom portion 120 covering the bottom surface of the body portion 110, and a top portion 130 covering the book surface of the body portion 110. Has. A cap mounting portion 140 into which a cap for keeping the inside of the tube-type container 100 in a substantially sealed state may be fitted may be formed on the top portion 130.

The tube-type container 100 is formed from a laminated body in which resin layers are laminated, as shown in FIG. 2, which is a partially enlarged cross-sectional view of a region 2 surrounded by a dotted line in FIG.

The laminate is composed of a plurality of layers including a layer (hereinafter, also simply referred to as “heated deformation layer”) 210 containing a thermoplastic resin composition satisfying the following (I) and (II) as a main component. Is.
(I) The value of Shore A hardness immediately after the start of needle contact and the value of Shore A hardness 15 seconds after the start of needle contact, measured in the state of a press sheet with a thickness of 3 mm in accordance with JIS K6253. The amount of change ΔHS between and is 5 or more and 50 or less. (II) Storage elastic modulus at 15 ° C. (G'@ 15 ° C.) and 40 ° C. obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s. The ratio (G'@ 15 ° C./G'@ 40 ° C.) to the storage elastic modulus (G'@ 40 ° C.) is 100 or more.

Further, the thickness of the heated deformation layer 210 (“a” in FIG. 2) in the laminated body is 50% or more with respect to the thickness of the entire laminated body (“b” in FIG. 2). By increasing the proportion of the thickness of the heating deformation layer 210 in the laminated body, it becomes difficult for other layers to inhibit the deformation of the tube-type container 100 during heating by the heating deformation layer 210, and the tube-type container 100 Is easy to deform. From the above viewpoint, the thickness (a) of the heating deformation layer 210 in the laminated body is preferably 50% or more, more preferably 45% or more with respect to the thickness (b) of the entire laminated body. , 40% or more is more preferable.

The laminate has sufficient hardness to maintain its shape near room temperature by appropriately selecting the type of resin to be composed (particularly, the type of resin constituting a layer other than the heating deformation layer 210). .. Therefore, the tube-type container 100 including the laminated body can stand on its own even if the capacity is increased. On the other hand, when the laminate is heated (for example, heated to near 40 ° C.), the heating deformation layer 210 softens and becomes deformable. Therefore, the tube-type container 100 containing the laminate is softened when heated by being immersed in hot water such as a bath, and the container is crushed or rolled to be deformed to extrude or squeeze the contents. Is easy.

The deformation after heating means a deformation that reduces the internal volume (volume) of the tube-type container 100 so that the contents can be easily discharged by pushing out or squeezing out. For example, it suffices if the tube-type container 100 can be deformed when it is manually pressed inward of the container.

The tube-type container 100 preferably contains the laminate in at least the body 110. When the body portion 110 includes the laminated body, the body portion 110 is deformed after being heated, and the contents can be more easily discharged by extruding or squeezing out. At this time, it is preferable that the entire body portion 110 is composed of the above-mentioned laminated body, but a part of the body portion (for example, the body portion) as long as the contents can be easily discharged or squeezed out by being deformed after heating. The laminated body may be included only in the region including the central portion of the portion 110).

On the other hand, the tube-type container 100 may include the laminate at the bottom 120 or the top 130. Even if the laminate is contained in these portions, the tube-shaped container 100 can be deformed from the bottom 120 or the top 130 after heating to facilitate the discharge of the contents by extruding or squeezing. From the viewpoint of facilitating the extrusion of the contents due to deformation and the discharge by squeezing out, it is preferable that at least the body 110 and the bottom 120 of the tube-type container 100 include the laminate. Further, from the viewpoint of enabling integral molding and facilitating production, it is preferable that the entire tube-type container 100 except for the cap mounting portion 140 is composed of the laminated body.

1. 1. Heating deformation layer 210
The heated deformation layer 210 has a shore A hardness value immediately after the start of needle contact and a shore 15 seconds after the start of needle contact, which is measured in the state of a press sheet having a thickness of 3 mm in accordance with JIS K6253. Storage elastic modulus at 15 ° C. (G'@ 15 ° C.) obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s and the amount of change ΔHS between the value of A hardness is 5 or more and 50 or less. ) And the storage elastic modulus (G'@ 40 ° C.) at 40 ° C. (G'@ 15 ° C./G'@ 40 ° C.) is 100 or more as the main component of the thermoplastic resin composition.

A thermoplastic resin composition having ΔHS of 5 or more is easily deformed by applying stress. Further, the thermoplastic resin composition having ΔHS of 50 or less does not excessively deform even when stress is applied. Therefore, the thermoplastic resin composition in which ΔHS is in the above range enhances the shape followability of the heating deformation layer 210, and facilitates ejection and squeezing of an appropriate amount of contents when the tube type container 100 is deformed. To. From the above viewpoint, the ΔHS of the thermoplastic resin composition is preferably 5 or more and 45 or less, and more preferably 10 or more and 40 or less.

Shore A hardness can be determined by measuring with a Shore A hardness tester in accordance with JIS K6253 using a press sheet with a thickness of 3 mm as a measurement sample. However, if it is difficult to measure the Shore A hardness of the thermoplastic resin composition, the Shore D hardness measured using a Shore D hardness tester instead is estimated as the Shore A hardness of the thermoplastic resin composition. May be good.

Further, the thermoplastic resin having the storage elastic modulus ratio (G'@ 15 ° C./G'@ 40 ° C.) of 100 or more is more easily deformed by pressurization during heating than when stored at a lower temperature. Become. Therefore, the thermoplastic resin composition in which the ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) is in the above range is immersed in hot water such as a bath when the heating deformation layer 210 is formed. When this is done, the tube-type container 100 can be easily deformed. From the above viewpoint, the ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) of the thermoplastic resin composition is preferably 100 or more and 200 or less, and more preferably 100 or more and 150 or less. preferable. The ratio of the storage elastic modulus (G'@ 15 ° C./G'@ 40 ° C.) is not particularly limited, but is preferably 150 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.

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. The thermoplastic resin composition having a temperature of 20 ° C. or higher and 40 ° C. or lower facilitates deformation of the heating deformation layer 210 by pressurization after heating. Therefore, the thermoplastic resin composition in which the temperature at which tan δ reaches the peak value is in the above range can easily deform the tube-shaped container 100 when it is immersed in hot water such as a bath when the heating deformation layer 210 is used. And. 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. The thermoplastic resin composition having a peak value of tan δ of 5.0 or less is easily deformed by applying stress. Further, the thermoplastic resin composition having a peak value of tan δ of 0.5 or more does not excessively deform even when stress is applied. Therefore, the thermoplastic resin composition in which the peak value of tan δ is in the above range enhances the shape followability of the heating deformation layer 210, and by extruding or squeezing an appropriate amount of the contents when the tube type container 100 is deformed. Facilitates discharge. 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 tube-type container 100 due to dropping during use or the like can be suppressed. From the above viewpoint, the peak value of tan δ of the thermoplastic resin composition is preferably 0.5 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 resin composition preferably has a compressive stress relaxation rate of 10% or more at 40 ° C. measured in accordance with JIS K7107. The thermoplastic resin composition having a compressive stress relaxation rate of 10% or more easily recovers its original shape after the pressing is stopped at 40 ° C. Therefore, the thermoplastic resin composition having a compressive stress relaxation rate of 10% or more stands upright after the tube-shaped container 100 is extruded by pressing or discharged by squeezing when the heated deformation layer 210 is used. Makes it easier to return to a well-balanced shape. From the above viewpoint, the compressive stress relaxation rate of the thermoplastic resin composition is preferably 15% or more, more preferably 20% or more.

The compressive stress relaxation rate is 500 N on a test piece at a temperature of 40 ° C. using a compression tester (for example, AG-100kNX manufactured by Shimadzu Corporation) on a press sheet having a thickness of 2 mm formed from the above thermoplastic resin composition. It can be obtained by compressing at 10 mm / min until the amount of compression is applied. At this time, the stress is held for 5 minutes with a compression amount of 500 N applied, and the difference from the stress after holding for 5 minutes (stress after relaxation: W _{5 min} ) is the stress when the compression amount is 500 N (initial stress:). The value (unit:%) obtained by dividing by W ₀ ) is defined as the compressive stress relaxation rate.

Further, the thermoplastic resin composition preferably has a compression set of 50% or less at 40 ° C. measured in accordance with JIS K6262. The thermoplastic resin composition having a compression set of 50% or less easily recovers its original shape after the pressing is stopped. Therefore, the thermoplastic resin composition having a compression set of 50% or more is used to make the tube-shaped container 100 stand upright after the contents are extruded by pressing or discharged by squeezing when the heating deformation layer 210 is used. Make it easier to return to a balanced shape. From the above viewpoint, the compression set of the thermoplastic resin composition is preferably 5% or more and 40% or less, and more preferably 10% or more and 40% or less.

Further, the thermoplastic resin composition preferably has a density measured in accordance with ASTM D 1505 of 830 kg / m ³ or more and 950 kg / m ³ or less. The thermoplastic resin composition having a density of 830 kg / m ³ or more has high strength and shock absorption, and when the heated deformation layer 210 is used, damage to the tube-type container 100 due to dropping during use or the like can be suppressed. The thermoplastic resin composition having a density of 950 kg / m ³ or less is lightweight and facilitates the carrying and handling of the tube-shaped container 100 when the heated deformation layer 210 is used. From the above viewpoint, the density of the thermoplastic resin composition is preferably at most 840 kg / ^{m 3} or more 950 kg / ^{m 3,} more preferably not more than 850 kg / ^{m 3} or more 945 kg / ^{m 3.}

Further, the thermoplastic resin composition preferably has a melting point (Tm) of 50 ° C. or higher and 160 ° C. or lower. The thermoplastic resin composition having a melting point (Tm) of 60 ° C. or higher and 150 ° C. or lower is easy to mold. From the above viewpoint, the melting point (Tm) of the thermoplastic resin composition is preferably 70 ° C. or higher and 145 ° C. or lower, and more preferably 80 ° C. or higher and 140 ° C. or lower.

The melting point (Tm) can be measured using a differential scanning calorimetry (DSC) (for example, DSC220C manufactured by Seiko Instruments). At this time, about 7 to 12 mg of the thermoplastic resin composition is sealed in an aluminum pan, heated from room temperature to 200 ° C. at 10 ° C./min, and the sample is held at 200 ° C. for 5 minutes for complete melting, and then. Cool to −50 ° C. at 10 ° C./min, allow to stand at −50 ° C. for 5 minutes, and then heat again to 200 ° C. at 10 ° C./min. The peak value temperature measured by this re-heating (second time) is defined as the melting point (Tm).

The thermoplastic resin composition is not limited as long as it satisfies the above-mentioned physical properties, but for example, 4-methyl-1-pentene / α-olefin copolymer (A-1) and the above 4-methyl-1 The composition may contain a thermoplastic resin (B) other than the -pentene / α-olefin copolymer.

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 85 mol% or less, the constituent unit (ii) is 15 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 85 mol%, preferably 84 mol%, and more preferably 80 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 15 mol%, preferably 16 mol%, and more preferably 20 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-shaped 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.

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 in the form of a sheet, which is unlikely to be deteriorated in moldability due to a low molecular weight and low stereoregular polymer. 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.

Requirement (c) ;
Density is preferably at most 870 kg / m ³ or more 830 kg / m ³ as measured according to ASTM D 1505 of 4-methyl-1-pentene · alpha-olefin copolymer (A-1), 865kg / more preferably m ³ or more 830 kg / m ³ or less, and more preferably not more than 855Kg / m ³ or more 830 kg / 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 the tube-type container 100 which 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 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 using the monomer itself that derives the structural unit (i) to the structural unit (iii) 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. Thermoplastic resin (B)
1-2-1. Composition of Thermoplastic Resin (B) The thermoplastic resin (B) may be a thermoplastic resin other than the 4-methyl-1-pentene / α-olefin copolymer (A-1).

The temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s reaches the peak value of the thermoplastic resin (B) is preferably less than 0 ° C., preferably less than −5 ° C. Is more preferable, it is more preferably less than -10 ° C, and particularly preferably less than -30 ° C. The lower limit of the temperature at which tan δ reaches the peak value is not particularly limited, but may be, for example, −60 ° C. From such a thermoplastic resin, it is easy to produce a thermoplastic resin composition in which the temperature at which tan δ has a peak value is 20 ° C. or higher and 40 ° C. or lower.

When the total amount of the 4-methyl-1-pentene / α-olefin copolymer (A-1) and the thermoplastic resin (B) contained in the thermoplastic resin composition is 100 parts by mass, 4-methyl- The upper limit of the content of the 1-pentene / α-olefin copolymer (A-1) is preferably 90 parts by mass, more preferably 75 parts by mass, and further preferably 60 parts by mass. It is preferably 50 parts by mass, and particularly preferably 50 parts by mass. The lower limit of the content of the 4-methyl-1-pentene / α-olefin copolymer (A-1) is preferably 10 parts by mass, more preferably 15 parts by mass, and 25 parts by mass. It is more preferably parts, and particularly preferably 30 parts by mass. With such a composition ratio, the flexibility, stress relaxation property, and unevenness followability of the thermoplastic resin composition can be further enhanced.

In other words, the lower limit of the thermoplastic resin (B) content is preferably 10 parts by mass, more preferably 25 parts by mass, further preferably 40 parts by mass, and 50 parts by mass. Is particularly preferable, and the upper limit value is preferably 90 parts by mass, more preferably 85 parts by mass, further preferably 75 parts by mass, and particularly preferably 70 parts by mass.

The thermoplastic resin (B) may be an olefin resin (B-1), an olefin elastomer (B-2), a styrene elastomer (B-3), or a thermoplastic elastomer composition (B-4). preferable. Further, the thermoplastic resin (B) may be a thermoplastic resin (B-5) other than the above. One type of these thermoplastic resins (B) may be used alone, or a plurality of types may be used in combination.

1-2-1-1. Olefin resin (B-1)
Examples of the olefin resin (B-1) include a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms and a cyclic olefin, and the like. Ethylene-based copolymers using various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid ester as comonome, copolymers of propylene and α-olefin having 4 to 20 carbon atoms, propylene A copolymer of α-olefin having 4 to 20 carbon atoms and a cyclic olefin, and a propylene-based copolymer containing various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid ester as comonomers. Etc. are included. The olefin resin (B-1) is low density polyethylene, medium density polyethylene, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-. Pentene, poly3-methyl-1-butene, cyclic olefin copolymers, chlorinated polyolefins and the like are preferred.

1-2-1-2. Olefin elastomer (B-2)
As an example of the olefin-based elastomer (B-2), an elastomer formed from an olefin-based block copolymer can be used. For example, a block copolymer of a polyolefin block that forms a highly crystalline polymer such as polypropylene that serves as a hard portion and a monomer copolymer that exhibits amorphousness that serves as a soft portion can be mentioned. Includes (crystalline) / ethylene / butylene / olefin block copolymers, polypropylene / polyolefin (amorphous) / polypropylene block copolymers, etc. Examples of commercially available olefin-based elastomers (B-2) include DYNARON manufactured by JSR Corporation (“DYNARON” is a registered trademark of the company), Toughmer manufactured by Mitsui Chemicals Co., Ltd. (“Toughmer” is a registered trademark of the company), and Notio. ("Notio" is a registered trademark of the company), ENGAGE manufactured by Dow Chemical Co., Ltd. ("ENGAGE" is a registered trademark of the company), VERSIFY ("VERSIFY" is a registered trademark of the company), Vistamaxx manufactured by Exxon Mobile Chemical Co., Ltd. "Is a registered trademark of the company).

1-2-1-3. Styrene-based elastomer (B-3)
Examples of the styrene-based elastomer (B-3) include a block copolymer (SBS) of a polystyrene block as a hard portion (crystal portion) and a diene-based monomer block as a soft portion, and hydrogenated styrene / butadiene / styrene. Block copolymer (HSBR), styrene / ethylene / propylene / styrene block copolymer (SEPS), styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / isoprene / styrene block copolymer (SIS) , Styrene-isobutylene-styrene copolymer (SIBS), styrene-isobutylene copolymer (SIB) and the like.

Examples of commercially available hydrogenated styrene-butadiene-styrene block copolymers (HSBR) include Dynaron manufactured by JSR Corporation (“Dynaron” is a registered trademark of JSR Corporation) and the like.

The styrene / ethylene / propylene / styrene block copolymer (SEPS) is obtained by hydrogenating a styrene / isoprene / styrene block copolymer (SIS). Examples of commercial SIS products include JSR SIS (“JSR SIS” is a registered trademark of the company), Kuraray Co., Ltd. (“Hybler” is a registered trademark of the company), and Clayton D, a shell company. ("Clayton" is a registered trademark of the company) and so on.

Examples of commercially available SEPS include Septon manufactured by Kuraray Co., Ltd. (“Septon” is a registered trademark of the company), Clayton manufactured by Shell Co., Ltd., and the like.

Examples of commercially available SEBS products include Asahi Kasei Corporation's Tough Tech (“Tough Tech” is a registered trademark of the company) and Shell Co., Ltd. Clayton.

In addition, examples of commercially available products of SIBS and SIB include Kaneka Corporation's Shibster Co., Ltd. (“Shibster” is a registered trademark of the company.

1-2-1--4. Thermoplastic Elastomer Composition (B-4)
The thermoplastic elastomer composition (B-4) is a composition obtained by dynamically cross-linking a mixture containing an ethylene / α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II].

1-2-1-4-1. Ethylene / α-olefin / non-conjugated polyene copolymer [I]
The ethylene / α-olefin / non-conjugated polyene copolymer [I] has a structural unit (Ia) derived from ethylene and a structural unit (Ib) derived from α-olefin (Ia). ) / (I-b) is preferably 50/50 or more and 95/5 or less, more preferably 60/40 or more and 80/20 or less, and further preferably 65/35 or more and 75/25 or less. preferable.

Further, the content of the structural unit (Ic) derived from the amount of the non-conjugated polyene contained in the ethylene / α-olefin / non-conjugated polyene copolymer [I] is the content of the ethylene / α-olefin / non-conjugated polyene. It is preferably 2% by mass or more and 20% by mass or less with respect to the total mass of the copolymer [I].

The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms. Examples of such α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12- Includes ethyl-1-tetradecene and the like. As the α-olefin, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are preferable, and propylene is more preferable. These α-olefins may be used alone or in combination of two or more.

Examples of the above non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl. Chain non-conjugated diene such as -1,4-hexadiene, 7-methyl-1,6-octadien, 8-methyl-4-ethylidene-1,7-norbornene, and 4-ethylidene-1,7-undecadien, methyl Tetrahydroindene, 5-Etilidene-2-Norbornene (ENB), 5-Methylene-2-Norbornene, 5-Isopropyriden-2-Norbornene, 5-Vinylidene-2-Norbornene, 6-Chloromethyl-5-Isopropenyl-2 Cyclic non-conjugated diene such as -norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, and norbornene, and 2,3-diene. Includes trienes such as isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, and 4-ethylidene-8-methyl-1,7-nanodiene. Is done. The non-conjugated polyene is preferably 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB).

The ethylene / α-olefin / non-conjugated polyene copolymer [I] preferably has an iodine value of 1 or more and 50 or less, which is an index of the content of the structural unit (Ic) derived from the non-conjugated polyene. It is more preferably 5 or more and 40 or less, and further preferably 10 or more and 30 or less.

The ethylene / α-olefin / non-conjugated polyene copolymer [I] preferably has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 1 dl / g or more and 10 dl / g or less, and 1.5 dl / g or more. It is more preferably 8 dl / g or less.

The ethylene / α-olefin / non-conjugated polyene copolymer [I] may be a so-called oil-extended rubber in which a softener, preferably a mineral oil-based softener, is blended in the production thereof. Examples of the above-mentioned mineral oil-based softener include known mineral oil-based softeners such as paraffin-based process oil.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer [I] is preferably 10 or more and 250 or less, and more preferably 30 or more and 150 or less. The ethylene / α-olefin / non-conjugated polyene copolymer [I] may be used alone or in combination of two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymers. The ethylene / α-olefin / non-conjugated polyene copolymer [I] can be produced by a conventionally known method.

1-2-1-4-2. Polyolefin resin [II]
Is the polyolefin resin [II] a copolymer of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene? Or, it is a copolymer of two or more kinds of the above-mentioned α-olefins, and the content of the main α-olefin is 90 mol% or more. The polyolefin resin [II] preferably has a melting point (Tm) of 70 ° C. or higher and 200 ° C. or lower, and preferably 80 ° C. or higher and 170 ° C. or lower.

It is preferable that the polyolefin resin [II] has substantially no unsaturated bond in the main chain.

The polyolefin resin [II] may be used alone or in combination of two or more olefin-based polymers.

Among these polyolefin resins [II], a propylene-based polymer (II-1) and an ethylene-based polymer (II-2) are preferable.

1-2-1-4-2-1. Propylene polymer (II-1)
The propylene-based polymer (II-1) is a homopolymer of propylene, a random copolymer of propylene and an α-olefin having 2 to 10 carbon atoms of 10 mol% or less, or a homopolymer of propylene and amorphous. It is a block copolymer with a propylene / ethylene random copolymer of sex or low crystallinity. Examples of the α-olefin having 2 to 10 carbon atoms include ethylene, 1-butene, 1-pentene, and 4-methyl-1-pentene. The melting point (Tm) of the propylene-based polymer (II-1) is preferably 120 ° C. or higher and 170 ° C. or lower, and more preferably 145 ° C. or higher and 165 ° C. or lower.

The propylene-based polymer (II-1) can be commercially available as a polypropylene resin.

The propylene-based polymer (II-1) preferably has an isotactic structure as a three-dimensional structure, but has a syndiotactic structure, a mixture of these structures, or a partially atactic structure. There may be.

The propylene-based polymer (II-1) preferably has a melt flow rate (MFR) of 0.05 g / 10 minutes or more and 100 g / 10 minutes or less as measured at a temperature of 230 ° C. and a load of 21.18 N, preferably 0.1 g. It is more preferably / 10 minutes or more and 50 g / 10 minutes or less.

The propylene-based polymer (II-1) is polymerized by various known polymerization methods.

1-2-1-4-2-2. Ethylene polymer (II-2)
The ethylene-based polymer (II-2) is a homopolymer of ethylene or a random copolymer of ethylene and an α-olefin having 2 to 10 carbon atoms having 10 mol% or less. Examples of the α-olefin having 2 to 10 carbon atoms include propylene, ethylene, 1-butene, 1-pentene, and 4-methyl-1-pentene. The ethylene polymer (II-2) preferably has a melting point (Tm) of 80 ° C. or higher and 150 ° C. or lower, and more preferably 90 ° C. or higher and 130 ° C. or lower.

The ethylene polymer (II-2) can be commercially available as high pressure method low density polyethylene, linear low density polyethylene, or high density polyethylene.

The ethylene polymer (II-2) preferably has a melt flow rate (MFR) of 0.05 g / 10 minutes or more and 100 g / 10 minutes or less as measured at a temperature of 230 ° C. and a load of 21.18 N, preferably 0.1 g. More preferably, it is 10 minutes or more and 50 g / 10 minutes or less.

The ethylene-based polymer (II-2) is polymerized by various known polymerization methods.

1-2-1-5. Other thermoplastic resins (B-5)
The thermoplastic resin (B) may be a thermoplastic resin (B-5) other than the above. Examples of such thermoplastic resins (B-%) include polyamide resins including aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 612), polyethylene terephthalates, and polybutylene. Polyamide-based elastomers such as terephthalate, vinyl aromatic resins, polyester resins including polystyrene, ABS resin, and AS resin, thermoplastic polyurethanes, vinyl chloride resins, vinylidene chloride resins, acrylic resins, ethylene / vinyl acetate copolymers, Includes ethylene / methacrylate acrylate copolymers, known ionomers, ethylene / vinyl alcohol copolymers, polyvinyl alcohols, fluororesin polycarbonates, polyacetals, polyphenylene oxides, polyphenylene sulfide polyimides, polyarylates, polysulfones, and polyether sulfone. Is done.

1-2-2. Method for Producing Thermoplastic Resin (B) The above-mentioned olefin-based resin (B-1), olefin-based elastomer (B-2), styrene-based elastomer (B-3), and other thermoplastic resins (B-5) are , It is obtained by polymerizing a monomer that leads to a constituent unit constituting these by a known polymerization method.

The thermoplastic elastomer composition (B-4) is a mixture containing the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer [I] and polyolefin resin [II], preferably ethylene / α-olefin / non-conjugated. The polyene copolymer [I] and the polyolefin resin [II] have a [I] / [II] (mass ratio) of 90/10 or more and 5/95 or less, more preferably 70/30 or more and 10/90 or less. It is obtained by dynamically cross-linking a mixture containing the mixture, or a mixture (precursor) containing a predetermined amount of a known softener or the like, if necessary. When performing dynamic cross-linking, it is preferable to dynamically heat-treat in the presence of a known cross-linking agent or in the presence of the above-mentioned cross-linking agent and a known cross-linking aid. Here, "dynamically heat-treating" means kneading in a molten state.

The dynamic heat treatment is preferably performed in a non-open device. Further, the dynamic heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature of the heat treatment is in the range of the melting point of the polyolefin resin [II] or more and 300 ° C. or less, preferably 150 ° C. or more and 270 ° C. or less, and more preferably 170 ° C. or more and 250 ° C. or less. The kneading time is preferably 1 minute or more and 20 minutes or less, and more preferably 1 minute or more and 10 minutes or less. At this time, 10 sec ^-1 or more 50,000Sec ^-1 or less at a shear rate, preferably 100 sec ^-1 or more 10,000Sec ^-1 less shear force is preferably applied.

As the kneading device, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder, or the like can be used, but a non-open type device is preferable.

1-3. Other Ingredients The thermoplastic resin composition may further contain additives other than those described above, 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, as long as the object of the present invention is not impaired. Includes additives such as plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, anti-mold agents, antibacterial agents, flame retardants, fillers (inorganic fillers, organic fillers), and softeners. It may be.

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

Examples of the fillers include powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, and aluminum; fibrous fillers containing glass fibers, metal fibers, etc., hydrophilic layered clay minerals. , And known specific shapes (excluding layered) hydrophilic inorganic compounds and the like are included.

Examples of the above-mentioned hydrophilic layered clay minerals include phyllosilicate minerals in which a plurality of layers spreading in two dimensions are laminated, for example, smectite. Smectite is a montmorillonite mineral. Examples of smectites are montmorillonite (montmorillonite), magnesian montmorillonite, tetsumonmorironite, tetsumagnesian montmorillonite, bidelite, aluminian bidelite, nontronite, aluminian nontronite, support stone (saponite). ), Aluminian support stones, Hectorite, Saponite, Stephensite, and Bentonite.

Examples of the hydrophilic layered clay minerals include vermiculite, halloysite, swelling mica, graphite and the like. Examples of commercially available products of such hydrophilic layered clay minerals are Kunipia series (montmorillonite) manufactured by Kunimine Industries, Bengel series (bentonite) manufactured by Hojun, and Somasif ME series (swelling mica) manufactured by Corp Chemical. Natural products including the above, as well as synthetic products such as smectone (saponite) manufactured by Kunimine Industries, Lucentite SWN series (hectorite) manufactured by Corp Chemical Co., Ltd., and laponite (hectorite) manufactured by Rockwood Holdings Co., Ltd. are included. In general, the hydrophilic layered clay mineral is preferably a synthetic product because the maximum length of the synthetic product is smaller than that of the natural product and small oil droplets can be obtained.

Examples of the flame retardants include antimony flame retardants, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine flame retardants, zirconium flame retardants and other inorganic compounds, ammonium polyphosphate, ethylene bistris (2-cyanoethyl). Phosphonium chloride, tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate, phosphate esters such as tris (3-hydroxypropyl) phosphine oxide and other phosphorus compounds, chlorinated paraffin, chlorinated polyolefin, per Brominated flame retardants such as chlorocyclopentadecane, hexabromobenzene, ethylenebisdibromonorbornandicarboxyimide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivative, tetrabromobisphenol S, and bromine-based difficulties such as tetrabromodipentaerythritol. Includes flame retardants, as well as mixtures thereof.

The total amount of additives other than the tackifier, such as softeners, fillers, and flame retardants, is 4-methyl-1-pentene / α-olefin copolymer (A-1) and the above 4 The total amount of the thermoplastic resin (B) other than the -methyl-1-pentene / α-olefin copolymer is preferably 0.001 to 50 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 above-mentioned 4-methyl-1-pentene / α-olefin copolymer (A-1) and the thermoplastic resin (B) other than the above-mentioned 4-methyl-1-pentene / α-olefin copolymer are used. The above-mentioned other components optionally contained can be mixed to obtain a thermoplastic resin composition. At this time, the resin may be heated or mixed above the melting temperature of each of the above resins.

2. 2. The other layer laminates, as layers other than the heating deformation layer 210, protect the contents by maintaining the shape of the gas barrier layer 220 (FIG. 2A) for reducing the permeability of liquid or gas, and the shape of the container. A protective layer 230 (FIG. 2B) for the purpose may be provided. Further, the laminate may further have a print layer (not shown) or the like.

The gas barrier layer 220 suppresses the permeation of liquid from the inside to the outside of the tube-type container 100 to suppress an unintentional decrease in the content and deterioration of the tube-type container 100, and also suppresses the deterioration of the tube-type container 100 from the outside to the inside. Any layer may be formed from a material capable of suppressing the permeation of liquid into the container and suppressing unintended deterioration of the contents. The gas barrier layer 220 can be selected from ethylene-vinyl alcohol copolymers, nylon, polyethylene terephthalate, polyacrylonitrile, etc., which are usually used for tube-type containers.

The protective layer 230 may be a layer formed of a material that is easy to mold, has strength that can maintain the shape of the tube-type container 100, and has low reactivity with the contents of the tube-type container 100. The protective layer 230 can be a layer made of polyethylene or polypropylene commonly used in tube-type containers.

A plurality of the heating deformation layer 210, the gas barrier layer 220, and the protective layer 230 may be provided. Further, an adhesive layer made of a heat-sealing resin such as modified polyethylene may be provided between these layers. In addition, polyethylene and polypropylene have high adhesiveness to the gas barrier layer formed from the above materials. When the layers have sufficient adhesiveness to each other in this way, the adhesive layer may not be provided.

In particular, it is preferable that a plurality of protective layers 230 are provided so as to sandwich the heating deformation layer 210 (and the optional gas barrier layer 220). That is, as shown in FIG. 2B, it is preferable that the protective layer 230, the heating deformation layer 210, the gas barrier layer 220, and the protective layer 230 are laminated in this order. In FIG. 2B, the heating deformation layer 210 is arranged inside the tube type container 100 with respect to the gas barrier layer 220, but the arrangement order of these layers is not particularly limited, and the heating deformation layer 210 is the gas barrier layer 220. It may be arranged outside the tube type container 100.

The thickness of the gas barrier layer 220 and the protective layer 230 is such that the functions of the above layers are exhibited, and the thickness (a) of the heating deformation layer 210 in the laminated body is 50% of the thickness (b) of the entire laminated body. It can be arbitrarily determined within the above range.

3. 3. Method for Manufacturing Laminated Body The laminated body includes a heating deformation layer 210 formed by molding the above-mentioned thermoplastic resin composition into a sheet shape, and another layer formed by molding the above-mentioned material into a sheet shape. Can be laminated and manufactured. The laminating method includes molding of a multi-layer sheet using a multi-layer sheet molding machine and direct molding of a tubular laminated body using an extruder having a multi-layer die, but is not particularly limited, and each is molded. The sheets may be laminated by using the above-mentioned adhesive layer, or may be laminated by heat fusion or ultrasonic fusion depending on the type of material.

4. In addition, the above-mentioned laminate can be formed into a container shape by a known method to manufacture a tube-type container 100.

At this time, when the body portion 110, the bottom portion 120, and the top portion 130 are all formed from the above-mentioned laminate, the tube-type container 100 can be integrally molded, so that the tube-type container 100 can be easily manufactured. When any of these is made of a different material, each part is separately molded and joined by an adhesive, heat fusion, ultrasonic fusion, or the like to manufacture a tube-type container 100. May be good.

When the tube-type container 100 has a cap mounting portion, a pump mounting portion, or the like, these mounting portions are separately molded and joined by an adhesive, heat fusion, ultrasonic fusion, or the like to form a tube-type container. 100 may be manufactured.

In the above description, the tube-type container 100 having the body 110, the bottom 120, and the top 130 has been described as an example, but the shape of the tube-type container 100 is not particularly limited, and a three-way seal body, a standing pouch, or the like is used. It may have any shape. The tube-shaped container 100 having these shapes can also be produced from the above-mentioned laminate by a known method.

Further, the cap mounting portion 140 into which the cap can be fitted may have a shape that functions as a pump mounting portion or the like into which the pump can be fitted.

The tube-type container 100 can store and discharge wire rods such as liquid detergent for kitchen and liquid detergent for laundry, liquid softener, shampoo, conditioner, cleaning liquid such as body soap, food and drink, and the like. Of these, it is preferable that it is used for storing and discharging shampoo, conditioner, body soap and other cleaning liquids used in bathrooms where it is easy to heat to around 40 ° C, and foods and drinks used by heating in a microwave oven.

100 Tube type container 110 Body 120 Bottom 130 Top 140 Cap mounting 210 Heating deformation layer 220 Gas barrier layer 230 Protective layer

Claims (6)

A laminate formed from a plurality of layers including a layer containing a thermoplastic resin composition as a main component.
The thermoplastic resin composition is
Derived from at least one α-olefin selected from the building blocks (Ai) derived from 4-methyl-1-pentene and α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. Including the structural unit (A-iii) to be obtained
A 4-methyl-1-pentene / α-olefin copolymer that may optionally contain a structural unit (A-iii) derived from a non-conjugated polyene.
When the total of the structural units (A-i), (A-ii) and (A-iii) is 100 mol%,
The constituent unit (Ai) is 55 to 85 mol%,
The constituent unit (A-ii) is 15 to 45 mol%,
Contains 0-10 mol% of building blocks (A-iii),
4-Methyl-1-pentene / α-olefin copolymer (A-1) and
With the thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer,
Is a composition containing
A tube-type container including a laminate in which the thickness of the layer containing the thermoplastic resin composition as a main component with respect to the thickness of the entire laminate is 50% or more. The tube-type container according to claim 1, wherein the laminate further includes a gas barrier layer. The tube-type container according to claim 2, wherein the gas barrier layer contains a resin selected from the group consisting of an ethylene-vinyl alcohol copolymer resin, a nylon resin, a polyethylene terephthalate resin, and a polyacrylonitrile resin. The tube-type container according to any one of claims 1 to 3, wherein the laminate further contains a layer containing polyethylene resin or polypropylene resin as a main component. The laminate contains a layer mainly composed of polyethylene resin or polypropylene resin, a layer containing the thermoplastic resin composition as a main component, the gas barrier layer, and a polyethylene resin or polypropylene resin as main components, which are laminated in this order. The tube-type container according to claim 2 or 3, which comprises a layer comprising. The tube-type container according to any one of claims 1 to 5, wherein at least the body thereof contains the laminate.