JP2021118859A - Shoe insole and shoe - Google Patents

Abstract

To provide a shoe insole that can be changed in shape in accordance with the shape of the sole and that can also increase impact absorbability, and to provide the shoe therewith.SOLUTION: The shoe insole of the present invention includes a layer with a thermoplastic resin composition as the main component. The thermoplastic resin composition has an amount of change Δ HS not less than 5 and not more than 60 in the value of Shore hardness A immediately after the start of indenter-point contact and 15 seconds after the start thereof. The Shore hardness A is measured in the state of 3 mm thick press sheet in conformity with JIS K6253. The shoe of the present invention contains the foregoing shoe insole.SELECTED DRAWING: None

Description

The present invention relates to shoe insoles and shoes.

The shoes support and disperse the weight of pedestrians, runners, and other people who use the shoes (hereinafter, also simply referred to as "pedestrians, etc."), and absorb and disperse the impact from the ground to the pedestrians. Therefore, an insole is provided. The insole is formed of an elastic synthetic resin or the like, including a foam of an ethylene-vinyl acetate copolymer or the like.

Since the insole distributes the weight from the entire sole and the impact from the ground to the entire sole, it is desired that the insole adheres to the shape of the sole of a pedestrian or the like. Therefore, an insole formed of a material that can be deformed according to the shape of the sole of a pedestrian or the like is being studied.

For example, in Patent Document 1, a resin foam obtained by foaming and cross-linking a resin composition containing low-density polyethylene and ethylene-vinyl acetate copolymer (EVA) can easily retain a shape deformed by an external force. Therefore, it is described that it is preferably used for insoles. According to Patent Document 1, when the mass ratio of the low-density polyethylene (A) and the ethylene-vinyl acetate copolymer (B) is (A) / (B) = 95/5 to 90/10, the compressive residual strain Both the rate and the tensile strength are sufficiently large, and when used as an insole, the air bubbles in the resin foam are crushed by the weight applied from the sole of the foot, and the resin composition is plastically deformed along the shape of the back of the foot. It is stated that it can be done.

Further, in Patent Document 2, in a state where a soft film containing a photocurable resin composition is pressed against the sole of the foot, the photocurable resin composition is cured by irradiation with light to form the shape of the sole. Describes how to make a shaped insole.

JP-A-2007-238790 Japanese Unexamined Patent Publication No. 2016-131718

However, according to the findings of the present inventor, the resin foam described in Patent Document 1 is used as an insole because the cushioning property is lowered and the shock absorption is lowered when the bubbles are crushed and plastically deformed. Sometimes it is difficult to absorb the impact from the ground, and it is difficult to maintain good comfort for pedestrians and the like. Further, in the method described in Patent Document 2, a soft film must be pressed against the sole of the foot to irradiate light, which is troublesome to manufacture.

In view of the above problems, it is an object of the present invention to provide a shoe insole that can be deformed according to the shape of the sole of the foot and that can also enhance shock absorption, and a shoe having such a shoe insole. And.

The present invention for solving the above problems relates to the following shoe insoles and shoes.
[1] The value of Shore A hardness immediately after the start of needle contact and 15 seconds from the start of needle contact, measured in the state of a press sheet with a thickness of 3 mm, which is laminated in this order and in accordance with JIS K6253. A layer containing a foam of a thermoplastic resin composition having a change amount ΔHS of 5 or more and 60 or less between the value of Shore A hardness and the value of Shore A hardness as a main component and a foam of an ethylene-vinyl alcohol copolymer resin are formed. A shoe insole that includes a shock absorbing layer and a non-slip layer that are the main components.
[2] The shoe insole according to [1], wherein the compression set of the foam of the thermoplastic resin composition at 23 ° C. measured in accordance with JIS K6262 is 50% or less.
[3] The temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the foam of the thermoplastic resin composition reaches a peak value is 0 ° C. or higher and lower than 45 ° C. [3]. The shoe insole according to 1] or [2].
[4] The peak value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement of the foam of the thermoplastic resin composition at a frequency of 10 rad / s is 0.4 or more and less than 5.0, [1] ] To the shoe insole according to any one of [3].
[5] The foam of the thermoplastic resin composition is composed of a structural unit (i) derived from 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. A 4-methyl-1-pentene / α-olefin copolymer (A-1) containing a structural unit (ii) derived from at least one selected α-olefin, wherein the structural unit (i) and ( When the total of ii) is 100 mol%, 4-methyl-1-containing the constituent unit (i) of 60 mol% or more and 90 mol% or less and the constituent unit (ii) of 10 mol% or more and 40 mol% or less. A foam of a composition containing a penten / α-olefin copolymer (A-1) and a thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer. , The shoe insole according to any one of [1] to [4].
[6] The foam of the thermoplastic resin composition is a composition containing a styrene-based elastomer (A-2) and a thermoplastic resin other than a 4-methyl-1-pentene / α-olefin copolymer. The shoe insole according to any one of [1] to [4], which is a foam of the above.
[7] A shoe including the shoe insole according to any one of [1] to [6].

According to the present invention, there is provided a shoe insole that can be deformed according to the shape of the sole of the foot and that can also enhance shock absorption, and a shoe having such a shoe insole.

Hereinafter, the shoe insole of the present invention will be described in more detail.

The shoe insole according to an embodiment of the present invention has a shore A hardness value immediately after the start of needle contact and a value of Shore A hardness immediately 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. A layer containing a thermoplastic resin composition as a main component (hereinafter, also simply referred to as “concavo-convex follow-up layer”) having a change amount ΔHS between the value of Shore A hardness after 15 seconds and the amount of change ΔHS of 5 or more and 60 or less is included. ..

The shoe insole may be composed of only the unevenness-following layer, but may be a laminated body including the unevenness-following layer and another layer. For example, the shoe insole may be provided with a layer for preventing slippage (hereinafter, also simply referred to as “non-slip layer”) on the side of the uneven follow-up layer that comes into contact with the sole of a pedestrian or the like.

Further, the shoe insole is a layer formed of a foam such as polyethylene, polypropylene, vinyl chloride polymer, ethylene-vinyl acetate resin copolymer or polyurethane in addition to the above-mentioned uneven follow-up layer (hereinafter, simply "shock absorbing layer"). ”) May be provided.

The shoe insole may include the three layers of the uneven follow-up layer, the non-slip layer, and the shock absorbing layer. At this time, the non-slip layer may be located on the surface of a pedestrian or the like on the side in contact with the sole of the foot, and may be laminated in the order of (concavo-convex follow-up layer-shock absorption layer-non-slip layer) or (shock absorption). Layer-concavo-convex follow-up layer-non-slip layer) may be laminated in this order. Further, although the above-mentioned layers are preferably in contact with each other, another layer may be contained between these layers as long as the unevenness followability of the shoe insole is not significantly reduced.

The thickness of the unevenness following layer is preferably 0.1 mm or more and 200 mm or less, more preferably 0.5 mm or more and 50 mm or less, and further preferably 1 mm or more and 10 mm or less.

The thickness of the shock absorbing layer is preferably 0.5 mm or more and 20 mm or less, and more preferably 1 mm or more and 10 mm or less.

When the unevenness-following layer is a foam of the above-mentioned thermoplastic resin, the layer constituting the laminated body may correspond to both the unevenness-following layer and the shock absorbing layer. At this time, when there are two or more layers containing the foam of the thermoplastic resin composition having ΔHS of 5 or more and 60 or less, one of them may be used as the unevenness following layer and the other may be used as the shock absorbing layer. When there is a layer containing a foam of a thermoplastic resin composition having a ΔHS of 5 or more and 60 or less and a layer containing a foam of a thermoplastic resin composition that does not satisfy the above-mentioned condition of ΔHS, the former is used. As the unevenness following layer, the latter may be the shock absorbing layer.

A. Concavo-convex follow-up layer The concavo-convex follow-up layer is measured in the state of a press sheet with a thickness of 3 mm in accordance with JIS K6253. The main component is a thermoplastic resin composition in which the amount of change ΔHS between the value of Shore A hardness and the value of Shore A hardness is 5 or more and 60 or less. A thermoplastic resin composition having ΔHS of 5 or more is easily deformed by applying stress. Further, the thermoplastic resin composition having a ΔHS of 60 or less does not excessively deform even when stress is applied, and can easily fit the shape of the sole of a pedestrian or the like. Therefore, the thermoplastic resin composition in which ΔHS is in the above range is excellent in the unevenness-following property when it is used as the unevenness-following layer. From the above viewpoint, the ΔHS of the thermoplastic resin composition is preferably 10 or more and 60 or less, and more preferably 15 or more and 40 or less.

The Shore A hardness can be determined by measuring with a Shore A hardness tester in accordance with JIS K6253 using a press sheet having 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 meter is estimated as the Shore A hardness of the thermoplastic resin composition instead. May be good.

Further, the thermoplastic resin composition preferably has a compression set of 50% or less at 23 ° C. measured in accordance with JIS K6262. The thermoplastic resin composition having a compression set of 50% or less has high impact absorption and absorbs impact from the ground when it is used as a concave-convex follow-up layer, so that it tends to be comfortable for pedestrians and the like. .. Further, since the thermoplastic resin composition having a compression set of 50% or less easily recovers its original shape after the pedestrian or the like takes off the shoes, even when the shape of the sole of the pedestrian or the like changes. It can easily adapt to new shapes. From the above viewpoint, the compression set of the thermoplastic resin composition is preferably 10% or more and 50% or less, and more preferably 20% or more and 50% or less.

Further, in the 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 0 ° C. or higher and 45 ° C. or lower. The thermoplastic resin composition having the above temperature of 0 ° C. or higher and 45 ° C. or lower is easily deformed by the pressure applied by the sole of the foot. Therefore, the thermoplastic resin composition in which the temperature at which tan δ reaches the peak value is in the above range is easily deformed according to the shape of the sole of the foot when it is used as the unevenness-following layer. 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 45 ° C. or lower, and more preferably 28 ° C. or higher and 40 ° C. or lower.

Further, in the thermoplastic resin composition, the peak value of tan δ is preferably 0.4 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 0.4 or more does not excessively deform even when stress is applied, and can be easily adapted to the shape of the sole of a pedestrian or the like. .. Therefore, the thermoplastic resin composition in which the peak value of tan δ is in the above range is excellent in the unevenness-following property when it is used as the unevenness-following layer. Further, since the thermoplastic resin composition having a peak value of tan δ of 0.4 or more has high stress absorption, it is difficult for the user to feel a sense of discomfort when the concave-convex follow-up layer is used. From the above viewpoint, the peak value of tan δ of the thermoplastic resin composition is preferably 0.6 or more and 4.0 or less, and more preferably 0.8 or more and 3.5 or less.

For tan δ, a strip piece of 45 mm × 10 mm × 3 mm is used as a measurement sample, and a viscoelasticity measuring device (for example, MCR301 manufactured by ANTONPar) is used to perform dynamic viscoelasticity from 40 to 150 ° C. at a frequency of 10 rad / s. Can be obtained by measuring the temperature dependence of. Specifically, the ratio (G "/ G': loss tangent) between the storage elastic modulus (G') and the loss elastic modulus (G") obtained in the above measurement is defined as tan δ. The temperature at which tan δ reaches its peak value (maximum value) in the range of 0 to 30 ° C. is defined as the temperature at which tan δ reaches its 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 tear strength of 10 N / mm or more as measured in accordance with ASTM D 412. The thermoplastic resin composition having a tear strength of 10 N / mm or more is less likely to be damaged during walking or running when it is used as an uneven follow-up layer. From the above viewpoint, the tear strength of the thermoplastic resin composition is preferably 20 N / mm or more, and more preferably 24 N / mm or more.

Further, the thermoplastic resin composition preferably has a specific gravity measured in accordance with JIS K7222 of 0.03 or more and 1.0 or less. The thermoplastic resin composition having a specific gravity of 0.03 or more is less likely to be damaged during walking or running when it is used as an unevenness-following layer. Since the thermoplastic resin composition having a specific gravity of 1.0 or less has high rebound resilience and is lightweight, it is difficult for pedestrians and the like to feel a sense of weight when it is used as an unevenness-following layer, and pedestrians and the like do not feel heavy. Easy to increase comfort. From the above viewpoint, the specific gravity of the thermoplastic resin composition is more preferably 0.05 or more and 1.0 or less, further preferably 0.05 or more and 0.9 or less, and 0.08 or more and 0. It is particularly preferably 5 or less.

The specific gravity is measured using a sample cut from the inside by 20 mm or more from the end (side surface) of the thermoplastic resin composition molded on the insole and from the inside by 2.5 mm or more from the upper and lower surfaces. At this time, from the viewpoint of further enhancing the uniformity of the thermoplastic resin composition, the difference between the maximum value and the minimum value among the specific gravities obtained by measuring the samples cut from five different points is 0.08 or less. It is preferably present, and more preferably 0.05 or less.

Further, it is preferable that the thermoplastic resin composition has a melting point (Tm) of 50 ° C. or higher and 160 ° C. or lower, or is not observed. A thermoplastic resin composition having a melting point (Tm) of 50 ° C. or higher and 160 ° C. or lower, or which is not observed, is easy to mold. From the above viewpoint, the melting point (Tm) of the thermoplastic resin composition is preferably 80 ° C. or higher and 160 ° C. or lower, or is preferably not observed, and more preferably not observed.

The melting point (Tm) can be measured using a differential scanning calorimetry (DSC) (for example, DSC220C manufactured by Seiko Instruments Inc.). 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).

Further, the thermoplastic resin composition has a melt flow rate (MFR) of 0.1 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 in accordance with JIS K6758. Is preferable. The thermoplastic resin composition having the above MFR in the above range has high fluidity at the time of heating and is easy to mold. From the above viewpoint, the MFR of the thermoplastic resin composition is preferably 1 or more and 50 or less, and more preferably 4 or more and 40 or less.

Further, the thermoplastic resin composition may be a foamed material or a non-foamed material, but is preferably a foamed material because it easily enhances cushioning property and shock absorption.

The thermoplastic resin composition is not limited as long as it satisfies the above-mentioned physical properties, and is, for example, a 4-methyl-1-pentene / α-olefin copolymer (A-1) or a styrene-based elastomer (A-2). ) And a thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer.

1.4-Methyl-1-pentene / α-olefin copolymer (A-1)
Composition of 1-1.4-Methyl-1-pentene / α-olefin copolymer (A-1) 4-Methyl-1-pentene / α-olefin copolymer (A-1) is 4-methyl- A structural unit derived from 1-pentene (i) and a structural unit derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene (ii). including. 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 60 mol% or more and 90 mol% or less, the constituent unit (ii) is 10 mol% or more and 40 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 60 mol%, preferably 67 mol%, and more preferably 70 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 80 mol%. When the proportion 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 is equal to or higher than the above lower limit. 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-mentioned 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 is formed. 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 40 mol%, but it is preferably 33 mol%, more preferably 30 mol%. On the other hand, the lower limit of the ratio of the constituent unit (ii) is 10 mol%, preferably 14 mol%, 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-hexadien, 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 the 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 limit viscosity [η] in the above 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) ;
The ratio of the 4-methyl-1-pentene / α-olefin copolymer (A-1) to the weight average molecular weight (Mw) and the 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 or more 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, Waters ALC / GPC 150-C plus type (integrated with a differential refractometer detector) is used as a liquid chromatograph, and Toso Co., Ltd. GMH6-HT × 2 and GMH6 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 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 difficult for pedestrians and the like to feel a heavy feeling, and it is comfortable for pedestrians and the like to wear. It is easy to manufacture an uneven follow-up layer that does not easily reduce the amount of unevenness.

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 1-2.4-Methyl-1-pentene / α-olefin Copolymer (A-1) The 4-methyl-1-pentene / α-olefin copolymer (A-1) is the above-mentioned structural unit. (I) The monomer leading to the structural unit (iii) can be produced by polymerizing in the presence of a suitable catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst. 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).

2. Styrene-based elastomer (A-2)
2-1. Composition of Styrene-based Elastomer (A-2) Examples of styrene-based elastomer (TPS) (A-2) include a polystyrene block as a hard part (crystal part) and a conjugated diene-based monomer such as isoprene or butadiene as a soft part. Block copolymer with block (SBC), styrene / ethylene / propylene / styrene block copolymer (SEPS), styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / isoprene / styrene block copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), styrene / isobutylene / styrene copolymer (SIBS), styrene / isobutylene copolymer (SIB) and the like are included. The styrene-based elastomer (A-2) can be used alone or in combination of two or more.

In the block copolymer (SBC) or styrene / isoprene / styrene copolymer (SIS), when the conjugated diene is isoprene, the intermediate block is preferably vinyl-polyisoprene. At this time, the components derived from the conjugated diene constituting the intermediate block may be hydrogenated. Examples of such a styrene / isoprene / styrene copolymer (SIS) include Kuraray Co., Ltd. Hybler 5127 (“Hybuler” is a registered trademark of the company) (styrene content 20 wt%, tan δ peak value = 1.1, Peak value temperature = 19 ° C.) ”etc. are included.

Further, in the block copolymer (SBC) or the styrene-butadiene-styrene copolymer (SBS), when the conjugated diene is butadiene, the component derived from butadiene may be hydrogenated. Further, at this time, the butadiene block to be the soft portion may be a copolymer of butadiene and styrene. An example of such a styrene-butadiene-styrene copolymer (SBS) is S.A., manufactured by Asahi Kasei Chemicals Co., Ltd. O. E. L609 (“SOE” is a registered trademark of the company) (styrene content = 67 wt%, tan δ peak value = 1.3, peak value temperature = 19 ° C.), S.A. O. E. L606 (styrene content = 51 wt%, tan δ peak value = 1.7, peak value temperature = 8 ° C.), S.A. O. E. S1605 (styrene content = 67 wt%, tan δ peak value = 1.5, peak value temperature = 17 ° C.) and the like are included.

The styrene-based elastomer (A-2) also preferably satisfies one or more requirements selected from the above-mentioned requirements (a), (b) and (c).

2-2. Method for Producing Styrene-based Elastomer (A-2) The styrene-based elastomer (TPS) (A-2) uses an alkyllithium compound as an initiator for styrene and other conjugated dienes that lead to constituent units constituting the polymer. It can be produced by anionic polymerization.

Examples of the alkyllithium compound include alkyllithium having an alkyl group having 1 or more and 10 or less carbon atoms such as methyllithium, ethyllithium, pentyllithium, and butyllithium, naphthalenedilithium, and dithiohexylbenzyllithium. ..

Examples of the polymerization method include (1) a method of sequentially polymerizing a conjugated diene following styrene using an alkyllithium compound as an initiator, and then sequentially polymerizing styrene, and (2) polymerizing a conjugated diene following styrene. Is included, such as a method of coupling with a coupling agent. Examples of the coupling agent include dichloromethane, dibromomethane, dibromobenzene and the like.

During the polymerization, it is preferable to use a solvent in order to appropriately control the reaction. Examples of the above solvent include organic solvents inactive to the polymerization initiator, such as hexane, heptane, cyclohexane, methylcyclohexane, and benzene, which are aliphatic high hydrogens having 6 to 12 carbon atoms and alicyclic hydrocarbons. Includes hydrogen, as well as aromatic hydrocarbons.

The polymerization temperature is preferably −70 ° C. or higher and 80 ° C. or lower, and the polymerization time is preferably 0.5 hours or longer and 50 hours or lower.

The peak value and peak value temperature of tan δ of the block copolymer, ΔHS can be determined by adjusting the number of 3,4 or 1,2 bonds of isoprene and butadiene and the molecular weights of styrene block and isoprene and butadiene block. It can be adjusted and can be adjusted relatively easily by using a Lewis base as a cocatalyst. Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, triethylamine, N, N, N'N-tetramethylethylenediamine (TMEDA) and N-methylmorpholine. Examples of the amine compound of. These Lewis bases are preferably used 0.1 to 1000 times the number of moles of lithium in the polymerization initiator. The peak temperature and peak value can also be adjusted by adjusting the presence or absence of hydrogenation and the hydrogen conversion rate.

3. 3. Thermoplastic resin (B)
3-1. Composition of Thermoplastic Resin (B) The thermoplastic resin (B) is a thermoplastic resin other than the above-mentioned 4-methyl-1-pentene / α-olefin copolymer (A-1) or styrene-based elastomer (A-2). Anything is fine.

The thermoplastic resin (B) has a temperature at which the peak value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s is less than 0 ° C. Is more preferable, it is more preferably less than −5 ° C., further 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 0 ° C. or higher and 45 ° C. or lower.

The total amount of the 4-methyl-1-pentene / α-olefin copolymer (A-1) or styrene elastomer (A-2) contained in the thermoplastic resin composition and the thermoplastic resin (B) is 100 mass by mass. When the portion is taken as a portion, the upper limit of the content of the 4-methyl-1-pentene / α-olefin copolymer (A-1) or the styrene-based elastomer (A-2) is preferably 90 parts by mass. It is more preferably 75 parts by mass, further preferably 60 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) or the styrene elastomer (A-2) is preferably 10 parts by mass, preferably 15 parts by mass. It is more preferably 25 parts by mass, 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.

3-1-1. 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 copolymer using various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester as comonomer, copolymer of propylene and α-olefin having 4 to 20 carbon atoms, propylene A copolymer of α-olefin and cyclic olefin having 4 to 20 carbon atoms, 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.

3-1-2. 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, and specific examples thereof include olefins. Includes (crystalline), ethylene, butylene, olefin block copolymers, polypropylene, polyolefin (amorphous), polypropylene block copolymers, and the like. Examples of commercially available olefin 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. ("Vistamaxx") "Is a registered trademark of the company).

3-1-3. 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).

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.'s 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.

3-1-4. 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].

3-1-4-1. Ethylene / α-olefin / non-conjugated polyene copolymer [I]
The ethylene / α-olefin / non-conjugated polyene copolymer [I] contains 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 polymer [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. The α-olefin is preferably propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene, more preferably propylene. 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. More preferably, it is 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.

3-1-4-2. 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.

The polyolefin resin [II] preferably 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.

3-1-4-2-1. Propylene polymer (II-1)
The propylene-based polymer (II-1) is a homopolymer of propylene, a random copolymer of propylene and 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 sex or low crystallinity propylene / ethylene random copolymer. 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. More preferably, it is 10 minutes or more and 50 g / 10 minutes or less.

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

3-1-4-2-2. 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-based 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.

3-1-5. 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. Polyester elastomers such as terephthalate, vinyl aromatic resins, polystyrenes, ABS resins, polyester resins including AS resins, 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.

3-2. 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. Polyolefin copolymer [I] and polyolefin resin [II] in the range of [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.

4. 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. Contains additives such as plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, fungicides, antibacterial agents, flame retardants, fillers (inorganic fillers, organic fillers), and softeners. It may be.

Examples of the softener include process oils, lubricating oils, paraffins, liquid paraffins, polyethylene waxes, polypropylene waxes, petroleum-based substances including petroleum asphalt and vaseline, coultars 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 polybutadiene or modified or hydrogenated products thereof, as well as 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 and metal fibers, hydrophilic layered clay minerals. , And known specific shapes (excluding layered) hydrophilic inorganic compounds and the like are included.

Examples of the 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 group mineral. Examples of smectite 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 Kogyo Co., Ltd., Bengel series (bentonite) manufactured by Hojun Co., Ltd., and Somashift ME series (swelling mica) manufactured by Corp Chemical Co., Ltd. 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 synthetic product has a smaller maximum length than the natural product, so that small oil droplets can be obtained. Therefore, the hydrophilic layered clay mineral is preferably a synthetic product.

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 tetrabromodipentaerythritol. Includes flame retardants, as well as mixtures thereof.

The total amount of these additives used is 4-methyl-1-pentene / α-olefin copolymer (A-1) or styrene-based elastomer (A-2) and 4-methyl-1-pentene. The total amount of the thermoplastic resin (B) other than the α-olefin copolymer is preferably 0.001 to 50 parts by mass, with 100 parts by mass.

5. Method for Producing Thermoplastic Resin Composition The above-mentioned thermoplastic resin composition can be produced by a known method. For example, other than the above-mentioned 4-methyl-1-pentene / α-olefin copolymer (A-1) or styrene-based elastomer (A-2) and the above-mentioned 4-methyl-1-pentene / α-olefin copolymer. The thermoplastic resin (B) of No. 1 and the above-mentioned other components optionally contained can be mixed to obtain a thermoplastic resin composition. At this time, the resins may be mixed by heating them above the melting temperature of each of the above resins.

B. Shock absorption layer
1. 1. Structure of shock absorbing layer The shock absorbing layer is a resin composition having a shore A hardness value of less than 40 immediately 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. Is preferable as the main component. The resin composition having a Shore A hardness value of less than 40 has high cushioning properties and shock absorption. Therefore, in the laminated body including the layer containing the resin composition as a main component, the cushioning property and the shock absorbing property are further enhanced by the shock absorbing layer in addition to the high unevenness following property by the unevenness following layer.

The foam forming the shock absorbing layer can be a known thermoplastic resin or ionomer foam. Examples of the above-mentioned thermoplastic technique include olefin resin, styrene resin, vinyl resin, rubber, polyurethane, acrylic copolymer and the like. Of these, olefin resins, styrene resins, vinyl resins, rubber, polyurethane and the like are preferable.

Examples of the olefin-based resin 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, styrene, and vinyl acetate. , Ethylene copolymer using various vinyl compounds such as (meth) acrylic acid and (meth) acrylic acid ester as commonomonates, copolymer of propylene and α-olefin having 4 to 20 carbon atoms, propylene and carbon number of 4 Copolymers of ~ 20 α-olefins and cyclic olefins, and propylene-based copolymers containing various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid ester as comonomers, etc. included. Of these, 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, poly 3-methyl. -1-butene, cyclic olefin copolymers, and chlorinated polyolefins are preferred.

Examples of the styrene-based resin include polystyrene, ABS resin, AS resin, hydrogenated styrene / butadiene / styrene block copolymer (HSBR), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene / ethylene. -Includes butene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene copolymer (SIBS), styrene-isobutylene copolymer (SIB), etc. Is done.

The acrylic copolymer is a copolymer containing a structural unit derived from an acrylic monomer. Examples of the above-mentioned acrylic copolymer include a copolymer composed of an acrylic acid ester monomer and another monomer. Examples of the above acrylic acid ester monomer include acrylic acid and carbon such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl ester acrylate. Includes number 1-10 alkyl or hydroxyalkyl ester compounds. Examples of the above other monomers include acrylic acid, methacrylate, acrylamide, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, ethylene, styrene, achlorine, 2-chloroethyl. Includes acrylate, butadiene, N-vinylpyrrolidone and the like. The above-mentioned other monomers can be selected from the viewpoint of improving the flexibility, weather resistance, etc. of the obtained copolymer. The copolymerization ratio of the acrylic acid ester monomer and the other monomer can be appropriately selected, but the molar ratio of the acrylic acid ester monomer: the other monomer is preferably about 1: 90 to 90: 1.

The rubber is not particularly limited as long as it is a polymer exhibiting rubber elasticity. Examples of the above rubber include natural rubber and various synthetic rubbers such as isoprene rubber, butadiene rubber, nitrile rubber, acrylic rubber, and urethane rubber. In particular, a thermoplastic elastomer that exhibits properties as a rubber at room temperature and is thermoplastic at high temperatures is particularly preferable because it is easy to perform molding operations and control the bubble structure. Examples of such thermoplastic elastomers include olefin-based elastomers including ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and ethylene-vinyl acetate copolymers, and styrene-isoprene-styrene copolymers. , And styrene-based elastomers including styrene-isoprene-butadiene-styrene copolymers and the like, polyester-based elastomers, and polyurethane-based elastomers. These polymers may be used alone or in admixture of two or more.

Examples of the olefin-based elastomer include an elastomer composed of an olefin-based block copolymer. Examples of the olefin-based elastomer include 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. .. Examples of such block copolymers include olefin (crystalline) / ethylene / butylene / olefin block copolymers and polypropylene / polyolefin (amorphous) / polypropylene block copolymers. Examples of commercially available block copolymers include DYNARON manufactured by JSR Corporation, Toughmer and Notio manufactured by Mitsui Chemicals Co., Ltd., ENGAGE and VERSIFY manufactured by Dow Chemicals Co., Ltd., and Vistamaxx manufactured by ExxonMobil Chemicals Co., Ltd. included.

Of these, vinyl chloride resin, polyethylene resin, polyethylene resin, ethylene-vinyl alcohol copolymer resin and urethane resin are preferable, and ethylene-vinyl alcohol copolymer resin and polyurethane resin are more preferable.

The foam has an apparent density is preferably at most 0.01 kg / m ³ or more 0.8 kg / m ^3. Since the foam having an apparent density of 0.01 kg / m ³ or more has higher strength and shock absorption, it is easy to improve the comfort of pedestrians and the like when it is used as an uneven follow-up layer. Since the foam having an apparent density of 0.8 kg / m ³ or less is lightweight, it is difficult for pedestrians and the like to feel a sense of weight, and it is easy to manufacture an uneven follow-up layer that does not easily reduce the comfort of pedestrians and the like. From the above viewpoint, the apparent density of the foam is more preferably ^{0.1 kg / m 3} or more and 0.5 or less kg / m ^3.

1-2. Method for Producing Shock Absorption Layer The foam can be produced by adding a predetermined amount of an inorganic or organic chemical foaming agent to the thermoplastic resin or ionomer and molding the foam.

Examples of the above-mentioned inorganic foaming agent include sodium bicarbonate (baking soda), ammonium bicarbonate, ammonium carbonate and the like.

Examples of the above organic foaming agents include N, N'-dinitroso pentamethylene tetramine (DPT), azodicarbonamide (ADCA), azobis isobutyronitrile, benzene sulfonyl hydrazide, 4,4'-. Includes oxybis (benzenesulfonyl hydrazide), toluene sulfonyl hydrazide, p-toluene sulfonyl semicarbazide, barium azodicarboxylate and the like.

Further, the foam may be produced by water foaming using water (steam) and a foaming agent.

Examples of the foaming agent include water of crystallization-containing inorganic substances, hygroscopic resins such as potassium ionomer, and the like.

At the time of foaming, it is desirable to use a foaming aid such as fatty acid metal salt, metal oxide, and urea in combination from the viewpoint of adjusting the decomposition temperature and deodorizing.

C. Non-slip layer The non- slip layer may be formed from natural fibers such as fabric, paper, rayon and cotton, olefin polymers such as polyethylene and polypropylene, polyesters such as polyester terephthalate (PET), and ethylene-acetate. It is formed from synthetic fibers containing vinyl alcohol-based resins such as vinyl copolymer (EVA), natural leather, artificial leather and the like. The non-slip layer may retain a deodorant for enhancing deodorant properties and an antibacterial agent for enhancing antibacterial properties. The non-slip layer may be a mesh material to enhance breathability.

D. Method for Manufacturing Shoe Insoles Shoe insoles can be manufactured by adhering the above-mentioned layers. These bonding methods are not particularly limited, and can be appropriately selected depending on the materials of the uneven follow-up layer, the non-slip layer, and the shock absorbing layer. Examples of bonding methods include adhesive bonding, heat fusion, ultrasonic fusion, suturing, and the like.

E. Shoe Shoe insole, can be molded to fit the shape of the inner bottom surface of the shoe, it is arranged on the inner bottom surface of the shoe. The shoe insole may be formed integrally with the shoe or may be detachably formed from the shoe. Shoes including shoe insoles are excellent in comfort for pedestrians and the like because the shoe insoles can be easily deformed according to the shape of the sole of the foot and have high shock absorption.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" means parts by mass unless otherwise specified.

[Measurement conditions, etc.]
The measurement conditions and the like of the physical properties in the examples are as follows.

〔composition〕
The 4-methyl-1-pentene content and α-olefin content in the polymer were ^{measured by 13} C-NMR with the following equipment and conditions. Using ECP500 type nuclear magnetic resonance equipment manufactured by JEOL Ltd., orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration frequency is 10,000 times or more, 27.50 ppm is the standard for chemical shift. Measured as a value.

[Density / specific gravity]
The density of the polymer and the specific gravity of the composition were calculated from the weight of each sample measured in water and air using an ALFA MIRAGE electronic hydrometer MD-300S according to ASTM D 1505 (underwater substitution method).

[Melting point (Tm)]
The melting point (Tm) of the polymer was measured by a differential scanning calorimeter (DSC) with a DSC220C device manufactured by Seiko Instruments Inc. Samples 7-12 mg were sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes for complete melting and then cooled to −50 ° C. at 10 ° C./min. After standing at −50 ° C. for 5 minutes, the sample was reheated to 200 ° C. at 10 ° C./min. The peak value temperature in this second (second) heating was adopted as the melting point (Tm).

[Ultimate viscosity]
The ultimate viscosity [η] of the polymer was measured at 135 ° C. using a decalin solvent.

[Molecular weight (Mw, Mn), molecular weight distribution (Mw / Mn)]
For the molecular weight of the polymer (A), a liquid chromatograph: ALC / GPC 150-C plus type manufactured by Waters (integrated type with a differential refractometer detector) was used, and as columns, GMH6-HT × 2 manufactured by Toso Co., Ltd. and GMH6- Two HTLs were connected in series, o-dichlorobenzene was used as a mobile phase medium, and the measurement was performed at a flow rate of 1.0 ml / min and 140 ° C.

The Mw / Mn value was calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.

[Melt flow rate (MFR)]
The MFR of the polymer was measured at 230 ° C. under a 2.16 kg load according to JIS K-6721.

[Manufacturing method of various measurement press sheets]
The press sheet (sheet layer) used for measuring the physical properties of Examples and Comparative Examples was sheet-molded at a pressure of 10 MPa using a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. set at 190 ° C. In the case of a sheet with a thickness of 1 to 3 mm (spacer shape; 80 x 80 x 0.5 to 3 mm on a plate with a thickness of 240 x 240 x 2 mm, 4 pieces), the residual heat is about 5 to 7 minutes, and 1 to 2 at 10 MPa. After pressurizing for 1 minute, another hydraulic hot press machine manufactured by Shinto Metal Industry Co., Ltd., which was set at 20 ° C., was used to compress at 10 MPa and cool for about 5 minutes to prepare a sample for measurement. A brass plate having a thickness of 5 mm was used as the hot plate. The samples prepared by the above method were used as various physical property evaluation samples.

[Compressive permanent distortion]
In the measurement of compression set (according to JIS K6262), a press sheet with a thickness of 12 mm and a diameter of 20 mmφ is used, and the sheet is allowed to stand for 22 hours in a state of being compressed to 25% at room temperature, and from the thickness of the sheet 30 minutes after release. Calculated.

[Shore hardness measurement]
In the measurement of shore hardness (according to JIS K6253), a press sheet having a thickness of 3 mm was used as a measurement sample, and the scales immediately after the start of needle contact and 15 seconds after the start of needle contact of the Shore A hardness tester were read.

Furthermore, the change ΔHS of the value of the shore hardness defined by the following equation was obtained.
ΔHS = (Shore hardness value immediately after the start of needle contact − Shore hardness value 15 seconds after the start of needle contact)
Here, in principle, the shore hardness was measured using a shore A hardness tester, but for a measurement sample in which it is difficult to measure the shore A hardness, a shore D hardness tester was used instead. Here, when the same type of hardness tester is used, it can be said that the larger ΔHS, the higher the unevenness followability.

[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 ANTONPaar, the temperature dependence of dynamic viscoelasticity from -40 to 150 ° C. was measured at a frequency of 10 rad / s, and the loss tangent (tan δ) due to the glass transition temperature was measured in the range of 0 to 30 ° 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.

In the measurement of the dynamic viscoelasticity of each of the polymer (A) and the polymer (B), a press sheet having a thickness of 3 mm made of each polymer was prepared by the same method as described above, and this press sheet was measured. It was used as a sample. In the case of the polymer (A), the temperature dependence of the dynamic viscoelasticity from -40 to 150 ° C. was measured, and the peak value temperature and the value of tan δ were measured in the range of 0 to 45 ° C. In the case of the polymer (B), the temperature dependence of the dynamic viscoelasticity from −70 to 150 ° C. was measured, and the peak value temperature and the value of tan δ were measured in the range of −60 to 0 ° C.

[How to make insoles]
The laminate used for measuring the physical properties of Examples and Comparative Examples was a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. set at 220 ° C., and 120 × by the same method as [Method for producing various measurement press sheets]. A sheet-shaped sample having a thickness of 120 × 3 mm was prepared. If necessary, the above sample is used as an EVA foam (a foam having a thickness of 2 mmt is produced using EVAflex manufactured by Mitsui DuPont Polychemical Co., Ltd.) and a polyurethane foam (PORON manufactured by Inoac Corporation, product number L-24, thickness 2 mmt). It was adhered to the foam of the above with an adhesive.

[Evaluation]
The prepared insoles were placed in an oven set at 50 ° C. for 30 minutes to soften the entire sheet. After that, they were taken out of the oven, and a total of five men and women between the ages of 20 and 50 were asked to ride on the seat and deformed by their own weight to prepare an insole that matched the shape of each person's foot.
Then, the insole was allowed to stand at 23 ° C. for 2 hours, and the insole was evaluated for its shapeability by visual inspection and the feeling of wearing it again.
〇: The shape of the foot was maintained ×: The shape has returned to its original shape

[Tactile sensation (sensory evaluation)]
A total of 5 men and women between the ages of 20 and 50 were collected as subjects. Have each subject enter an environmental test room with humidity control at 23 ° C and 50% RH, rest for a while, and then put on the insoles prepared in the example or comparative example in shoes. , The evaluation was made on the following 5 grades.
5: Excellent comfort.
4: Comfortable to wear.
3: Normal.
2: Slightly inferior in comfort.
1: Inferior comfort.

[Synthesis Example 1]
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently nitrogen-substituted. 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 became 0.13 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride. 0.34 ml of a toluene solution containing 0.01 mmol of the mixture was press-fitted into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the temperature inside the autoclave was 60 ° C. 60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.
The powdery polymer containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer weighed 36.9 g, and the 4-methyl-1-pentene content in the polymer was 72.5 mol% and the propylene content was 27.5 mol%. Table 1 shows the results of physical property measurement.

[Example 1]
25 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1 and 75 parts by mass of Mirastomer 5030NS manufactured by Mitsui Chemicals, Inc. were mixed to obtain a polymer composition. This composition was press-molded to form a sheet layer, and the physical characteristics of the sheet layer were measured.
Further, a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) were adhered to each other by the above-mentioned preparation method to form a laminate, and the physical properties of the laminate were measured. Table 2 shows various physical characteristics.

[Example 2]
30 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1, 45 parts of Mirastomer 5030NS manufactured by Mitsui Chemicals, Inc. and 25 parts of Tough Tech H1221: 25 parts manufactured by Asahi Kasei Chemicals Co., Ltd. are mixed to form a polymer composition. Got This composition was press-molded to form a sheet layer, and the physical characteristics of the sheet layer were measured.
Further, a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) were adhered to each other by the above-mentioned preparation method to form a laminate, and the physical properties of the laminate were measured. Table 2 shows various physical characteristics.

[Example 3]
30 parts by mass of 4-methyl-1-pentene copolymer of Synthesis Example 1, 70 parts by mass of Tough Tech H1221 manufactured by Asahi Kasei Chemicals Co., Ltd. and SELMIC C-2 as a foaming agent (trade name: Sankyo Kasei Co., Ltd. azodicarbonamide (abbreviation) 2 parts by mass of ADCA) was mixed to obtain a polymer composition. This composition was press-molded to form a sheet layer, and the physical properties of the sheet layer were measured.
Further, a 3 mm-thick press sheet of the polymer composition and a polyurethane foam (2 mm-thick sheet) were adhered to each other by the above-mentioned preparation method to form a laminate, and the physical properties of the laminate were measured. Table 2 shows various physical characteristics.

[Example 4]
30 parts by mass of 4-methyl-1-pentene copolymer of Synthesis Example 1, 70 parts by mass of Tough Tech H1221 manufactured by Asahi Kasei Chemicals Co., Ltd. 2 parts by mass of ADCA) was mixed to obtain a polymer composition. This composition was press-molded to form a sheet layer, and the physical properties of the sheet layer were measured.

[Example 5]
50 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1, 50 parts by mass of Mirastomer 5030NS manufactured by Mitsui Chemicals, Inc., and SELMIC C-2 as a foaming agent (trade name: Azodicarbonamide of Sankyo Kasei Co., Ltd.) Abbreviation ADCA) 2 parts by mass was mixed to obtain a polymer composition. This composition was press-molded to form a sheet layer, and the physical properties of the sheet layer were measured.

[Comparative Example 1]
100 parts by mass of Mirastomer 5030NS manufactured by Mitsui Chemicals, Inc. was press-molded to form a sheet layer, and the physical properties of the sheet layer were measured.
Further, a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) were adhered to each other by the above-mentioned preparation method to form a laminate, and the physical properties of the laminate were measured. Table 2 shows various physical characteristics.

[Comparative Example 2]
Table 2 shows the physical characteristics of only the EVA foam (12 mm thick sheet).

The Mirastomer 5030NHS manufactured by Mitsui Chemicals, Inc. has a tanδ peak temperature of -40 ° C and a peak value of 0.5, the Mirastomer 5030NS has a tanδ peak temperature of −41 ° C. and a peak value of 0.55, and the Mirastomer 8030NHS has a tanδ peak. The value temperature is -40 ° C and the peak value is 0.25. The blend of Mitsui Chemicals Co., Ltd. Mirastomer 5030NS: 45 parts and Asahi Kasei Chemicals Co., Ltd. Tough Tech H1221: 25 parts is tan δ peak value temperature -28 ° C, peak value 0. It is 0.7.

According to JIS K6253, 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. Examples 1 to 5, which are sheet layers mainly composed of a thermoplastic resin composition in which the amount of change ΔHS between them is 5 or more and 60 or less, are good in shape and comfort in a heated state. rice field.

Claims (7)

Stacked in this order,
According to JIS K6253, 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. A layer containing a foam of a thermoplastic resin composition having a change amount ΔHS of 5 or more and 60 or less as a main component,
A shock absorbing layer containing a foam of an ethylene-vinyl alcohol copolymer resin as a main component,
With a non-slip layer,
Including shoe insoles. The shoe insole according to claim 1, wherein the foam of the thermoplastic resin composition has a compression set of 50% or less at 23 ° C. as measured according to JIS K6262. The temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the foam of the thermoplastic resin composition reaches a peak value is 0 ° C. or higher and lower than 45 ° C., claim 1 or The shoe insole described in 2. The peak value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of the foam of the thermoplastic resin composition is 0.4 or more and less than 5.0, claims 1 to 3. The shoe insole according to any one of the items. The foam of the thermoplastic resin composition is
Constituent unit derived from 4-methyl-1-pentene (i) and composition derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. A 4-methyl-1-pentene / α-olefin copolymer (A-1) containing the unit (ii).
When the total of the constituent units (i) and (ii) is 100 mol%,
The structural unit (i) is 60 mol% or more and 90 mol% or less,
Containing the constituent unit (ii) of 10 mol% or more and 40 mol% or less,
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,
The shoe insole according to any one of claims 1 to 4, which is a foam of the composition containing the above. The foam of the thermoplastic resin composition is
Styrene-based elastomer (A-2) and
With thermoplastic resins other than 4-methyl-1-pentene / α-olefin copolymer,
The shoe insole according to any one of claims 1 to 4, which is a foam of the composition containing the above. A shoe including the shoe insole according to any one of claims 1 to 6.