JP7195366B2 - shoe insoles and shoes - Google Patents

Description

The present invention relates to shoe insoles and shoes.

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

Insoles are desired to adhere to the shape of the soles of pedestrians and the like in order to disperse the weight from the entire sole and disperse the impact from the ground to the entire sole. Therefore, an insole made of a material that can be deformed according to the shape of the sole of the foot of a pedestrian or the like has been 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 suitable for use in insoles. According to Patent Document 1, when the mass ratio of low-density polyethylene (A) and ethylene-vinyl acetate copolymer (B) is (A)/(B) = 95/5 to 90/10, compression residual strain Both the modulus and tensile strength are sufficiently large, and when used as an insole, the air bubbles in the resin foam are crushed by the body weight applied from the sole, and the resin composition is plastically deformed along the shape of the sole. It is stated that it is possible.

Further, in Patent Document 2, in a state where a soft film enclosing a photocurable resin composition is pressed against the sole, the photocurable resin composition is cured by irradiation with light, and the shape of the sole is obtained. A method of manufacturing a shaped insole is described.

Japanese Patent Application Laid-Open No. 2007-238790 JP 2016-131718 A

However, according to the findings of the present inventors, the resin foam described in Patent Document 1 is used as an insole because the cushioning properties and impact absorption properties of the resin foam described in Patent Document 1 are reduced when the cells 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. In addition, the method described in Patent Document 2 requires a soft film to be pressed against the sole of the foot and irradiated with light, which is time-consuming to manufacture.

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is 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 Shore A hardness value immediately after the start of contact with the indentor, measured in the state of a pressed sheet with a thickness of 3 mm in accordance with JIS K6253, and 15 seconds after the start of contact with the indenter. A layer mainly composed of a foam of a thermoplastic resin composition having a variation ΔHS between the value of the Shore A hardness and a value of 5 or more and 60 or less, and a foam of an ethylene-vinyl alcohol copolymer resin. A shoe insole comprising a shock absorbing layer as a main component and a non-slip layer.
[2] The shoe insole according to [1], wherein the thermoplastic resin composition foam has a compression set of 50% or less at 23°C measured according to JIS K6262.
[3] The temperature at which 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 reaches a peak value is 0 ° C. or higher and lower than 45 ° C. [ 1] or the shoe insole according to [2].
[4] The foam of the thermoplastic resin composition has a peak value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad/s of 0.4 or more and less than 5.0. ] 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 structural units (ii) derived from at least one selected α-olefin, wherein the structural units (i) and ( 4-methyl-1- containing 60 mol% or more and 90 mol% or less of structural unit (ii) and 10 mol% or more and 40 mol% or less of structural unit (ii) when the total of ii) is 100 mol% A foam of a composition containing a pentene/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 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
[7] A shoe comprising the shoe insole according to any one of [1] to [6].

ADVANTAGE OF THE INVENTION According to this invention, the shoe insole which can deform|transform according to the shape of a sole and can also improve shock absorption, and the shoes which have such a shoe insole are provided.

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

The shoe insole according to one embodiment of the present invention is measured in accordance with JIS K6253 in the state of a pressed sheet with a thickness of 3 mm, the value of Shore A hardness immediately after the start of contact with the indentor, and the value from the start of contact with the indenter. A layer mainly composed of a thermoplastic resin composition having a change amount ΔHS between the value of Shore A hardness after 15 seconds and 5 or more and 60 or less (hereinafter also simply referred to as “concave-conforming layer”). .

The shoe insole may consist only of the unevenness-following layer, or may be a laminate including the unevenness-following layer and other layers. For example, the shoe insole may be provided with an anti-slip layer (hereinafter also simply referred to as an "anti-slip layer") on the side of the irregular-following layer that contacts the sole of a pedestrian or the like.

In addition to the uneven conforming layer, the shoe insole has a layer formed from a foam such as polyethylene, polypropylene, vinyl chloride polymer, ethylene-vinyl acetate resin copolymer, or polyurethane (hereinafter simply referred to as "impact absorption layer ) may be provided.

The shoe insole may include three layers, the uneven conforming layer, the non-slip layer and the shock absorbing layer. At this time, the anti-slip layer may be positioned on the surface such as the side that contacts the soles of pedestrians, etc., and may be laminated in the order of (concave-convex-following layer-shock-absorbing layer-anti-slip layer), or (shock-absorbing It may be laminated in the order of layer-concave-conforming layer-non-slip layer). In addition, although the layers described above are preferably in contact with each other, another layer may be included between these layers as long as the conformability of the shoe insole to irregularities is not significantly reduced.

The thickness of the irregularity conforming 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 even more 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, more preferably 1 mm or more and 10 mm or less.

When the irregularity conforming layer is the thermoplastic resin foam described above, the layers constituting the laminate may correspond to both the irregularity conforming layer and the impact absorbing layer. At this time, when there are two or more layers containing a foam of a thermoplastic resin composition having a ΔHS of 5 or more and 60 or less, one of them may be used as an irregularity conforming layer and the other as an impact absorbing layer. In addition, when there are a layer containing a thermoplastic resin composition foam having a ΔHS of 5 or more and 60 or less and a layer containing a thermoplastic resin composition foam that does not satisfy the above ΔHS conditions, the former is used. As the unevenness conforming layer, the latter may be used as the impact absorbing layer.

A. Concave-convex following layer Concave-convex following layer is measured in accordance with JIS K6253 in the state of a 3 mm thick press sheet, the value of Shore A hardness immediately after the start of contact with the incisor, and the hardness at 15 seconds after the start of contact with the incisor. The main component is a thermoplastic resin composition having a value of Shore A hardness and a variation ΔHS of 5 or more and 60 or less. A thermoplastic resin composition having a ΔHS of 5 or more is easily deformed by application of stress. Further, a thermoplastic resin composition having a ΔHS of 60 or less does not deform excessively even when stress is applied, and can easily conform to the shape of the soles of pedestrians and the like. Therefore, a thermoplastic resin composition having a ΔHS within the above range is excellent in conformability to irregularities when used as a conformable layer. From the above viewpoint, the ΔHS of the thermoplastic resin composition is preferably 10 or more and 60 or less, more preferably 15 or more and 40 or less.

The Shore A hardness can be obtained by using a press sheet having a thickness of 3 mm as a measurement sample and measuring it with a Shore A hardness tester according to JIS K6253. However, if it is difficult to measure the Shore A hardness of the thermoplastic resin composition, instead the Shore D hardness measured using a Shore D hardness tester is assumed to be the Shore A hardness of the thermoplastic resin composition. good too.

Further, the thermoplastic resin composition preferably has a compression set at 23° C. of 50% or less as measured according to JIS K6262. The thermoplastic resin composition having a compression set of 50% or less has a high impact absorption property, and when it is used as an irregularity conforming layer, it absorbs impact from the ground, so it is easy for pedestrians and the like to wear it comfortably. . In addition, the thermoplastic resin composition having a compression set of 50% or less easily recovers its original shape after a pedestrian takes off their shoes. 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, more preferably 20% or more and 50% or less.

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 becomes a peak value is preferably 0° C. or higher and 45° C. or lower. A thermoplastic resin composition having a temperature of 0° C. or higher and 45° C. or lower is easily deformed by pressure applied by the soles of the feet. Therefore, a thermoplastic resin composition having a temperature at which tan δ reaches a peak value within the above range is easily deformed according to the shape of the sole when used as an irregularity conforming layer. From the above viewpoint, the temperature at which the tan δ of the thermoplastic resin composition reaches a 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.

The thermoplastic resin composition preferably has a tan δ peak value of 0.4 or more and 5.0 or less. A thermoplastic resin composition having a tan δ peak value of 5.0 or less is easily deformed by application of stress. In addition, a thermoplastic resin composition having a tan δ peak value of 0.4 or more does not deform excessively even when stress is applied, and can easily conform to the shape of the sole of a pedestrian or the like. . Therefore, a thermoplastic resin composition having a tan δ peak value within the above range is excellent in conformability to irregularities when formed into a conformable layer. Further, a thermoplastic resin composition having a peak value of tan δ of 0.4 or more has a high stress absorption property, so that the user does not feel a sense of discomfort when it is used as an irregularity conforming layer. 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, more preferably 0.8 or more and 3.5 or less.

tan δ is measured using a 45 mm × 10 mm × 3 mm strip as a measurement sample, using a viscoelasticity measuring device (eg, ANTON Paar MCR301) at a frequency of 10 rad / s Dynamic viscoelasticity from -40 to 150 ° C. can be determined 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 by the above measurement is defined as tan δ. 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 tan δ value at that time is defined as the above tan δ peak value. The above peak is considered to be caused by the glass transition temperature of the thermoplastic resin composition.

Moreover, the thermoplastic resin composition preferably has a tear strength of 10 N/mm or more as measured according to 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 used as an irregularity conforming layer. From the above viewpoint, the tear strength of the thermoplastic resin composition is preferably 20 N/mm or more, more preferably 24 N/mm or more.

Further, the thermoplastic resin composition preferably has a specific gravity of 0.03 or more and 1.0 or less as measured according to JIS K7222. The thermoplastic resin composition having a specific gravity of 0.03 or more is less likely to be damaged during walking or running when used as an irregularity conforming layer. The thermoplastic resin composition having a specific gravity of 1.0 or less has high impact resilience and is lightweight. Easy to wear and comfortable. From the above viewpoint, the specific gravity of the thermoplastic resin composition is more preferably 0.05 or more and 1.0 or less, more preferably 0.05 or more and 0.9 or less, and 0.08 or more and 0.9. 5 or less is particularly preferred.

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

Further, the thermoplastic resin composition preferably 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 more and 160° C. or less or 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 not observed, more preferably not observed.

The melting point (Tm) can be measured using a differential scanning calorimeter (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, the sample is held at 200 ° C. for 5 minutes to completely melt, and then Cool to −50° C. at 10° C./min, allow to stand at −50° C. for 5 minutes, then heat again to 200° C. at 10° C./min. Let the peak value temperature measured by this re-heating (second time) be melting|fusing point (Tm).

In addition, the thermoplastic resin composition has a melt flow rate (MFR) of 0.1 g/10 min or more and 100 g/10 min or less measured at a temperature of 230° C. and a load of 21.18 N in accordance with JIS K6758. is preferred. A thermoplastic resin composition having an MFR within the above range has high fluidity when heated 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, more preferably 4 or more and 40 or less.

The thermoplastic resin composition may be either a foamed body or an unfoamed body, but is preferably a foamed body because it is easy to improve cushioning properties and shock absorption properties.

The thermoplastic resin composition is not limited as long as it satisfies the physical properties described above. ) 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)
Structure of 1-1.4-methyl-1-pentene/α-olefin copolymer (A-1) 4-methyl-1-pentene/α-olefin copolymer (A-1) is composed of 4-methyl- Structural unit (i) derived from 1-pentene and structural unit (ii) derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene 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) has a structural It contains 60 mol % to 90 mol % of unit (i), 10 mol % to 40 mol % of structural unit (ii), and 0 mol % to 10 mol % of structural unit (iii).

The lower limit of the proportion of structural unit (i) is 60 mol %, preferably 67 mol %, more preferably 70 mol %. On the other hand, the upper limit of the proportion of structural unit (ii) is 90 mol %, preferably 86 mol %, 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 Since the temperature at which tan δ of coalescence (A-1) peaks is around room temperature, the temperature at which tan δ of the thermoplastic resin composition peaks 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 equal to or less than the above upper limit, 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 range.

Of course, at this time, the upper limit of the proportion of structural unit (ii) is 40 mol %, preferably 33 mol %, more preferably 30 mol %. On the other hand, the lower limit of the proportion of structural unit (ii) is 10 mol %, preferably 14 mol %, more preferably 20 mol %.

Examples of α-olefins leading to structural unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene linear α-olefins having 2 to 20 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms) including 1-hexadecene, 1-octadecene, 1-eicosene, etc. , as well as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl branched α-olefins having 5 to 20 carbon atoms (preferably 5 to 15 carbon atoms) including 1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene; . Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferred, and ethylene and propylene are particularly preferred. Structural unit (ii) may be derived from one compound among these, or may be derived from two or more compounds.

Examples of non-conjugated polyenes leading to building block (iii) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene , 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene, etc. Linear non-conjugated dienes, methyltetrahydroindene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl -cyclic non-conjugated dienes, including 5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, and norbornadiene; , and 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7 - including trienes, including nanodienes, and the like; Among these, when the α-olefin leading to the structural unit (ii) is propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferred from the viewpoint of increasing the cross-linking efficiency. ) is preferred. Structural unit (iii) may be derived from one compound among these, or may be derived from two or more compounds.

However, the 4-methyl-1-pentene/α-olefin copolymer (A-1) preferably consists essentially 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 intrinsic viscosity [η] of the 4-methyl-1-pentene/α-olefin copolymer (A-1) measured in decalin at 135°C is 0.1 dL/g or more and 5.0 dL/g or less. , more preferably 0.5 dL/g or more and 4.0 dL/g or less, and even more preferably 0.5 dL/g or more and 3.5 dL/g or less. The 4-methyl-1-pentene/α-olefin copolymer (A-1) having the intrinsic viscosity [η] within the above range is easily molded into a sheet-like thermoplastic resin composition.

The intrinsic viscosity [η] of the 4-methyl-1-pentene/α-olefin copolymer (A-1) is controlled 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 weight average molecular weight (Mw) and the number average molecular weight (Mn) of the 4-methyl-1-pentene/α-olefin copolymer (A-1) measured by gel permeation chromatography (GPC) ( 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 the above Mw/Mn within the above range is less susceptible to deterioration in moldability due to the low molecular weight and low stereoregularity polymer, and can be used in sheet form. Molding into a thermoplastic resin composition is easy.

Further, 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. ,000,000 or more, more preferably 1,000 or more and 5,000,000 or less, and even more preferably 1,000 or more and 2,500,000 or less.

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

For the above Mw and Mw/Mn, for example, a Waters ALC/GPC 150-C plus type (integrated refractometer detector) is used as a liquid chromatograph, and two GMH6-HT columns and GMH6 manufactured by Tosoh Corporation are used as columns. -Connect two HTLs in series, use o-dichlorobenzene as the mobile phase medium, flow rate 1.0 ml / min, chromatogram obtained by measurement at 140 ° C., using a calibration curve using a standard polystyrene sample can be obtained by analyzing

Requirement (c) ;
The density of the 4-methyl-1-pentene/α-olefin copolymer (A-1) measured according to ASTM D 1505 is preferably 870 kg/m ³ or more and 830 kg/m ³ or less. /m ³ or more and 830 kg/m ³ or less, and more preferably 855 kg/m ³ or more and 830 kg/m ³ or less. The 4-methyl-1-pentene/α-olefin copolymer (A-1) having a density within the above range is lightweight, so it is difficult for pedestrians and the like to feel heavy, and it is comfortable for pedestrians and the like to wear. It is easy to manufacture an irregularity conforming layer that does not easily reduce the

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

Intrinsic viscosity [η], Mw/Mn, Mw and density related to the requirements (a) to (c) can be obtained by the same measurement as for the thermoplastic resin composition described above.

1-2. Method for producing 4-methyl-1-pentene/α-olefin copolymer (A-1) 4-methyl-1-pentene/α-olefin copolymer (A-1) comprises the above structural units Monomers leading to structural units (i) to (iii) can be prepared by polymerizing in the presence of a suitable catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst. Polymerization can be carried out by appropriately selecting from a liquid phase polymerization method including solution polymerization and suspension polymerization, a gas phase polymerization method, and the like.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent that constitutes the liquid phase. Examples of such inert hydrocarbons include aliphatic hydrocarbons including propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. aromatic hydrocarbons, including 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, it is also possible to carry out bulk polymerization using the monomer itself leading to the structural units (i) to (iii) as a solvent.

The 4-methyl-1-pentene/α-olefin copolymer (A-1) is formed by carrying out stepwise copolymerization of monomers leading to the structural units (i) to (iii). The composition distribution of structural units (i) to (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, even more preferably 20° C. or higher and 100° C. or lower.

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

During 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 to be added is suitably about 0.001 NL or more and 100 NL or less per 1 kg of the total amount of monomers leading to the structural units (i) to (iii).

2. Styrene-based elastomer (A-2)
2-1. Structure of Styrene Elastomer (A-2) Examples of styrene elastomer (TPS) (A-2) include a polystyrene block as a hard portion (crystal portion) and a conjugated diene monomer such as isoprene or butadiene as a soft portion. 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. The styrene elastomer (A-2) can be used singly 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 conjugated diene-derived component constituting the intermediate block may be hydrogenated. Examples of such a styrene-isoprene-styrene copolymer (SIS) include Hybler 5127 manufactured by Kuraray Co., Ltd. ("Hibler" is a registered trademark of the same company) (styrene content 20 wt%, tan δ peak value = 1.1, peak value temperature = 19°C)” and the like.

When the conjugated diene of the block copolymer (SBC) or styrene-butadiene-styrene copolymer (SBS) is butadiene, the butadiene-derived component may be hydrogenated. Moreover, at this time, the butadiene block that becomes the soft portion may be a copolymer of butadiene and styrene. Examples of such styrene-butadiene-styrene copolymer (SBS) include S.T. O. E. L609 ("S.O.E" is a registered trademark of the same company) (styrene content = 67 wt%, tan δ peak value = 1.3, peak value temperature = 19°C), S.O.E. O. E. L606 (styrene content = 51 wt%, tan δ peak value = 1.7, peak value temperature = 8°C), S.I. O. E. S1605 (styrene content = 67 wt%, tan δ peak value = 1.5, peak value temperature = 17°C) and the like.

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

2-2. Production method of styrene elastomer (A-2) Styrene elastomer (TPS) (A-2) is prepared by using styrene and other conjugated dienes, which lead to structural units constituting the polymer, with an alkyllithium compound as an initiator. It can be produced by anionic polymerization.

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

Examples of the polymerization method include (1) a method of sequentially polymerizing styrene and then a conjugated diene using an alkyllithium compound as an initiator and then sequential polymerization of styrene; is coupled with a coupling agent, and the like. Examples of such coupling agents include dichloromethane, dibromomethane, dibromobenzene, and the like.

Solvents are preferably used during the polymerization for proper control of the reaction. Examples of the above solvents include organic solvents inert to polymerization initiators, such as hexane, heptane, cyclohexane, methylcyclohexane, and aliphatic high hydrogen atoms having 6 to 12 carbon atoms such as benzene; Hydrogen, as well as aromatic hydrocarbons and the like are included.

The polymerization temperature is preferably −70° C. or more and 80° C. or less, and the polymerization time is preferably 0.5 hours or more and 50 hours or less.

The tan δ peak value, peak value temperature, and ΔHS of the block copolymer are obtained by adjusting the number of 3,4 bonds or 1,2 bonds of isoprene and butadiene and the molecular weights of the styrene block, isoprene, and butadiene blocks. It can be adjusted and can be adjusted relatively easily by using a Lewis base as a co-catalyst. Lewis bases 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), N-methylmorpholine and the like. and the like. These Lewis bases are preferably used in an amount of 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 hydrogen addition and the hydrogen conversion rate.

3. Thermoplastic resin (B)
3-1. The thermoplastic resin (B) constituting the thermoplastic resin (B) is a thermoplastic resin other than the 4-methyl-1-pentene/α-olefin copolymer (A-1) or the styrene elastomer (A-2). If it is

In the thermoplastic resin (B), the temperature at which the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad/s becomes a peak value is less than 0°C. is preferably less than -5°C, more preferably less than -10°C, and particularly preferably less than -30°C. Although the lower limit of the temperature at which tan δ reaches a peak value is not particularly limited, it can be -60°C, for example. From such a thermoplastic resin, it is easy to produce a thermoplastic resin composition having a temperature at which tan δ reaches a peak value of 0° C. or higher and 45° C. or lower.

The total amount of 4-methyl-1-pentene/α-olefin copolymer (A-1) or styrene elastomer (A-2) and thermoplastic resin (B) contained in the thermoplastic resin composition is 100 mass When expressed as parts, the upper limit of the content of the 4-methyl-1-pentene/α-olefin copolymer (A-1) or the styrene elastomer (A-2) is preferably 90 parts by mass. It is more preferably 75 parts by mass, still more preferably 60 parts by mass, and particularly preferably 50 parts by mass. In addition, 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, more preferably 15 parts by mass. 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 conformability to irregularities 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, even more preferably 40 parts by mass, and 50 parts by mass. is particularly preferred, and the upper limit is preferably 90 parts by mass, more preferably 85 parts by mass, even more preferably 75 parts by mass, and particularly preferably 70 parts by mass.

The thermoplastic resin (B) is an olefin resin (B-1), an olefin elastomer (B-2), a styrene elastomer (B-3), or a thermoplastic elastomer composition (B-4). preferable. The thermoplastic resin (B) may also 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 copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, copolymers of ethylene, α-olefins having 3 to 20 carbon atoms and cyclic olefins, Ethylene-based copolymers containing various vinyl compounds such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters as comonomers, copolymers of propylene and α-olefins having 4 to 20 carbon atoms, propylene and a copolymer of an 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. and so on. Olefin resin (B-1) includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, poly-4-methyl-1- Pentene, poly-3-methyl-1-butene, cyclic olefin copolymers, chlorinated polyolefins and the like are preferred.

3-1-2. Olefin-based elastomer (B-2)
An example of the olefinic elastomer (B-2) is an elastomer formed from an olefinic block copolymer. Examples include block copolymers 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. Specifically, olefin ( crystalline)/ethylene/butylene/olefin block copolymers, and polypropylene/polyolefin (amorphous)/polypropylene block copolymers. Examples of commercially available olefin elastomers (B-2) include DYNARON manufactured by JSR Corporation ("DYNARON" is a registered trademark of the same company), Toughmer manufactured by Mitsui Chemicals, Inc. ("Toughmer" is a registered trademark of the same company), Notio ("Notio" is a registered trademark of the same company), ENGAGE manufactured by Dow Chemical Co., Ltd. ("ENGAGE" is a registered trademark of the same company), VERSIFY ("VERSIFY" is a registered trademark of the same company), Vistamaxx manufactured by ExxonMobil Chemical Co., Ltd. ("Vistamaxx ” are registered trademarks of the company).

3-1-3. Styrene-based elastomer (B-3)
Examples of the styrene elastomer (B-3) include a block copolymer (SBS) of a polystyrene block as a hard part (crystal part) and a diene monomer block as a soft part (SBS), 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), and styrene-isobutylene copolymer (SIB).

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

Styrene-ethylene-propylene-styrene block copolymer (SEPS) is obtained by hydrogenating styrene-isoprene-styrene block copolymer (SIS). Commercially available examples of SIS include JSR SIS manufactured by JSR Corporation ("JSR SIS" is a registered trademark of the same company), Hybler manufactured by Kuraray Co., Ltd. ("Hibler" is a registered trademark of the same company), and Kraton D manufactured by Shell Co., Ltd. ("Clayton" is a registered trademark of the company).

Commercially available examples of SEPS include Septon manufactured by Kuraray Co., Ltd. (“Septon” is a registered trademark of the same company), and Kraton manufactured by Shell Corporation.

Commercially available examples of SEBS include Tuftec manufactured by Asahi Kasei Corporation (“Tuftec” is a registered trademark of Asahi Kasei Corporation), and Kraton manufactured by Shell Corporation.

Examples of commercial products of SIBS and SIB include Kaneka Co., Ltd.'s Sibster ("Sibster" is a registered trademark of the same company).

3-1-4. Thermoplastic elastomer composition (B-4)
The thermoplastic elastomer composition (B-4) is a composition obtained by dynamically crosslinking a mixture containing the ethylene/α-olefin/non-conjugated polyene copolymer [I] and the polyolefin resin [II].

3-1-4-1. Ethylene/α-olefin/non-conjugated polyene copolymer [I]
The ethylene/α-olefin/non-conjugated polyene copolymer [I] comprises a structural unit (Ia) derived from ethylene and a structural unit (Ib) derived from an α-olefin, and (Ia )/(Ib) 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 non-conjugated polyene contained in the ethylene/α-olefin/non-conjugated polyene copolymer [I] is 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-heptene, 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- and ethyl-1-tetradecene. 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 such non-conjugated polyenes include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl Acyclic non-conjugated dienes such as 1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene, methyl Tetrahydroindene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2 - cyclic non-conjugated dienes such as norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, and norbornadiene, and 2,3-di trienes such as isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nanodiene; be 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 indicator of the content of the structural unit (Ic) derived from the non-conjugated polyene. , 5 or more and 40 or less, and more preferably 10 or more and 30 or less.

The ethylene/α-olefin/non-conjugated polyene copolymer [I] preferably has an intrinsic viscosity [η] of 1 dl/g or more and 10 dl/g or less, measured at 135°C in decalin, preferably 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 softening agent, preferably a mineral oil-based softening agent is blended during its production. Examples of the mineral oil softeners include known mineral oil softeners such as paraffinic process oils.

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, 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 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 homopolymer of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene? Alternatively, it is a copolymer of two or more of the above α-olefins in which 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, preferably 80° C. or higher and 170° C. or lower.

The polyolefin resin [II] preferably has substantially no unsaturated bonds in its main chain.

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

Among these polyolefin resins [II], the propylene polymer (II-1) and the ethylene polymer (II-2) are preferred.

3-1-4-2-1. Propylene-based polymer (II-1)
The propylene-based polymer (II-1) is a propylene homopolymer, a random copolymer of propylene and 10 mol% or less of an α-olefin having 2 to 10 carbon atoms, or a propylene homopolymer and amorphous It is a block copolymer with a propylene-ethylene random copolymer with low crystallinity or low crystallinity. Examples of the C2-C10 α-olefins include ethylene, 1-butene, 1-pentene, and 4-methyl-1-pentene. The propylene-based polymer (II-1) preferably has a melting point (Tm) of 120° C. or higher and 170° C. or lower, more preferably 145° C. or higher and 165° C. or lower.

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

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

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

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 an ethylene homopolymer or a random copolymer of ethylene and 10 mol % or less of an α-olefin having 2 to 10 carbon atoms. Examples of the C2-C10 α-olefins 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, more preferably 90° C. or higher and 130° C. or lower.

Ethylene-based polymer (II-2) can be commercially available as high pressure 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 min or more and 100 g/10 min or less measured at a temperature of 230° C. and a load of 21.18 N. /10 minutes or more and 50 g/10 minutes or less is more preferable.

The ethylene 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 terephthalate and polybutylene. Polyester elastomers such as terephthalate, polyester resins including vinyl aromatic resins, polystyrene, ABS resins, and AS resins, thermoplastic polyurethanes, vinyl chloride resins, vinylidene chloride resins, acrylic resins, ethylene/vinyl acetate copolymers, Ethylene-methacrylic acid acrylate copolymer, known ionomer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, fluorine-based resin polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide polyimide, polyarylate, polysulfone, polyethersulfone, etc. be

3-2. Method for producing thermoplastic resin (B) , can be obtained by polymerizing monomers leading to the structural units constituting these by a known polymerization method.

The thermoplastic elastomer composition (B-4) is a mixture containing the ethylene/α-olefin/non-conjugated polyene copolymer [I] and the 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. or, if necessary, a mixture (precursor) containing a predetermined amount of a known softening agent, etc., is dynamically crosslinked. When performing dynamic cross-linking, it is preferable to perform dynamic heat treatment in the presence of a known cross-linking agent, or in the presence of the cross-linking agent and a known cross-linking aid. Here, "dynamically heat-treating" means kneading in a molten state.

Dynamic heat treatment is preferably carried out in closed equipment. Moreover, the dynamic heat treatment is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide gas. The temperature of the heat treatment is in the range of the melting point of the polyolefin resin [II] to 300°C, preferably 150°C to 270°C, more preferably 170°C to 250°C. The kneading time is preferably 1 minute or more and 20 minutes or less, more preferably 1 minute or more and 10 minutes or less. At this time, it is preferable to apply a shearing force with a shear rate of 10 sec ^-1 or more and 50,000 sec ^-1 or less, preferably 100 sec ^-1 or more and 10,000 sec ^-1 or less.

As a kneading device, a mixing roll, an intensive mixer (eg, Banbury mixer, kneader), a single-screw or twin-screw extruder, etc. can be used, but a non-open type device is preferred.

4. Other Components The thermoplastic resin composition may further contain additives other than those mentioned above, if necessary.

For example, the thermoplastic resin composition may include weather stabilizers, heat stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, Additives such as plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, antifungal agents, antibacterial agents, flame retardants, fillers (inorganic fillers, organic fillers), and softeners It's okay.

Examples of such softening agents include process oils, lubricating oils, paraffins, liquid paraffins, polyethylene waxes, polypropylene waxes, petroleum-based materials such as petroleum asphalt and petroleum jelly, coal tars including coal tar and coal tar pitch, castor oil, and the like. oil, fatty oils including linseed oil, rapeseed oil, soybean oil and coconut oil, waxes including tall oil, beeswax, carnauba wax and lanolin, ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, Fatty acids including montanic acid, oleic acid and erucic acid or metal salts thereof, synthetic polymers including petroleum resins, coumarone-indene resins and atactic polypropylene, ester plasticizers including dioctyl phthalate, dioctyl adipate and dioctyl sebacate agents, microcrystalline wax, liquid polybutadiene or its modified or hydrogenated products, and liquid thiocol.

Examples of the filler include powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, and aluminum; fibrous fillers including glass fibers and metal fibers; hydrophilic layered clay minerals; , and known specific forms (excluding layered) hydrophilic inorganic compounds.

Examples of the hydrophilic layered clay mineral include phyllosilicate minerals in which a plurality of two-dimensionally extending layers are laminated, such as smectite. Smectites are montmorillonite group minerals. Examples of smectites include montmorillonite (montmorillonite), magnesian montmorillonite, tetsumontmorillonite, tetsumagnesian montmorillonite, beidellite, aluminianbeidellite, nontronite, aluminiannontronite, saponite (saponite). ), aluminian sapphoite, hectorite, sauconite, stevensite, and bentonite.

Examples of the hydrophilic layered clay minerals include vermiculite, halloysite, swelling mica, and graphite. Commercially available examples of such hydrophilic layered clay minerals include the Knipia series (montmorillonite) manufactured by Kunimine Industries, the Bengel series (bentonite) manufactured by Hojun, and the Somasif ME series (swellable mica) manufactured by Co-op Chemical. and synthetic products such as Sumecton (saponite) manufactured by Kunimine Industries, Lucentite SWN series (hectorite) manufactured by Co-op Chemicals, and Laponite (hectorite) manufactured by Rockwood Holdings. Synthetic products are generally preferable for the hydrophilic layered clay mineral, because synthetic products generally have a smaller maximum length than natural products, and thus smaller oil droplets can be obtained.

Examples of the flame retardant include inorganic compounds such as antimony-based flame retardants, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine-based flame retardants, and zirconium-based flame retardants, ammonium polyphosphate, and ethylenebistris(2-cyanoethyl). Phosphonic esters such as phosphonium chloride, tris(tribromophenyl)phosphate, tris(tribromophenyl)phosphate, tris(3-hydroxypropyl)phosphine oxide and other phosphorus compounds, chlorinated paraffins, chlorinated polyolefins, per Chlorinated flame retardants such as chlorocyclopentadecane; Includes fuels, as well as mixtures thereof.

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

5. Method for producing thermoplastic resin composition The thermoplastic resin composition can be produced by a known method. For example, the above 4-methyl-1-pentene/α-olefin copolymer (A-1) or styrene elastomer (A-2) and the above 4-methyl-1-pentene/α-olefin copolymer A thermoplastic resin composition can be prepared by mixing the thermoplastic resin (B) of (1) with the above-described other optionally contained components. At this time, the resins may be mixed while being heated to a temperature higher than the melting temperature of each resin.

B. shock absorbing layer
1. Structure of Impact Absorbing Layer The impact absorbing layer is a resin composition having a Shore A hardness value of less than 40 immediately after the start of contact with an indenter, measured in the state of a pressed sheet with a thickness of 3 mm in accordance with JIS K6253. is preferably the main component. The resin composition having a Shore A hardness value of less than 40 has high cushioning properties and shock absorption properties. Therefore, in a laminate containing a layer containing such a resin composition as a main component, in addition to the high irregularity conformability due to the irregularity conforming layer, the impact absorbing layer further enhances cushioning properties and impact absorption.

The foam forming the impact absorbing layer may be a known thermoplastic resin or ionomer foam. Examples of such thermoplastics include olefinic resins, styrenic resins, vinyl resins, rubbers, polyurethanes, and acrylic copolymers. Among these, olefin resins, styrene resins, vinyl resins, rubbers, polyurethanes, and the like are preferred.

Examples of the above olefin resins include copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, copolymers of ethylene, α-olefins having 3 to 20 carbon atoms and cyclic olefins, styrene, and vinyl acetate. , (meth)acrylic acid, (meth)acrylic acid esters and other vinyl compounds as comonomers, ethylene copolymers, copolymers of propylene and α-olefins having 4 to 20 carbon atoms, propylene and 4 carbon atoms Copolymers of α-olefins of up to 20 and cyclic olefins, and propylene-based copolymers with various vinyl compounds such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters as comonomers, etc. included. Among these, low density polyethylene, medium density polyethylene, high density polyethylene, high pressure 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 resin include polystyrene, ABS resin, AS resin, 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), and styrene-isobutylene copolymer (SIB) be

The acrylic copolymer is a copolymer containing structural units derived from acrylic monomers. Examples of the above acrylic copolymers include copolymers composed of acrylic acid ester monomers and other monomers. Examples of the acrylic acid ester monomers include acrylic acid and carbon, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Included are alkyl or hydroxyalkyl ester compounds of numbers 1-10. Examples of such other monomers include acrylic acid, methacrylic acid, acrylamide, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, ethylene, styrene, acrolein, 2-chloroethyl. Acrylates, 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 other monomers can be appropriately selected, but the molar ratio of acrylic acid ester monomer: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 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 rubber-like properties at room temperature and exhibits thermoplasticity at high temperatures is particularly preferred because it facilitates molding operations, control of cell structure, and the like. Examples of such thermoplastic elastomers include olefinic elastomers, styrene-isoprene-styrene copolymers, including ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and ethylene-vinyl acetate copolymers. , and styrene-based elastomers including styrene-isoprene-butadiene-styrene copolymers, polyester-based elastomers, and polyurethane-based elastomers. These polymers may be used alone or in combination of two or more.

Examples of the olefinic elastomer include elastomers made of olefinic block copolymers. Examples of the olefin-based elastomer include a block copolymer of a polyolefin block forming a highly crystalline polymer, such as polypropylene, which serves as the hard portion, and a monomer copolymer exhibiting amorphous property, which serves as the 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, Inc., ENGAGE and VERSIFY manufactured by Dow Chemical Co., Ltd., and Vistamaxx manufactured by ExxonMobil Chemical Co., Ltd. included.

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

The foam preferably has an apparent density of 0.01 kg/m ³ or more and 0.8 kg/m ³ or less. A foam having an apparent density of 0.01 kg/m ³ or more has higher strength and shock absorbability, and therefore, when used as an irregularity conforming layer, it is easy for pedestrians and the like to wear it comfortably. Since the foam having an apparent density of 0.8 kg/m ³ or less is lightweight, it is difficult for pedestrians, etc., to feel a heavy feeling, and it is easy to manufacture an irregularity-following layer that does not impede wear comfort for pedestrians, etc. From the above viewpoint, it is more preferable that the foam has an apparent density of 0.1 kg/m ³ or more and 0.5 or less kg/m ³ .

1-2. Method for producing impact-absorbing layer The foam can be produced by adding a predetermined amount of an inorganic or organic chemical foaming agent to the above thermoplastic resin or ionomer and molding.

Examples of the inorganic foaming agents include sodium bicarbonate (baking soda), ammonium bicarbonate, ammonium carbonate, and the like.

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

The foam may also be produced by water foaming using water (steam) and a foaming agent.

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

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

C. Antiskid Layer The antiskid 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-acetic acid. It is formed from synthetic fibers containing vinyl alcohol resin such as vinyl copolymer (EVA), natural leather, artificial leather, and the like. The non-slip layer may contain a deodorant to enhance deodorant properties or an antibacterial agent to enhance antibacterial properties. The non-slip layer may be made of a mesh material to improve breathability.

D. Manufacturing Method of Shoe Insole A shoe insole can be manufactured by adhering the layers described above. These bonding methods are not particularly limited, and can be appropriately selected depending on the materials of the irregularity conforming layer, anti-slip layer and impact absorbing layer. Examples of bonding methods include adhesive bonding, heat fusion, ultrasonic fusion, suturing, and the like.

E. The shoe insole can be molded to the shape of the inner bottom surface of the shoe and placed on the inner bottom surface of the shoe. The shoe insole may be formed integrally with the shoe, or may be formed detachably from the shoe. A shoe including a shoe insole is easily deformable according to the shape of the sole of the foot and has a high impact absorption property, so that it is comfortable to wear for pedestrians and the like.

EXAMPLES The present invention will be described below 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 physical property measurement conditions and the like 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 using the following equipment and conditions. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of ortho-dichlorobenzene/heavy benzene (80/20% by volume) as a solvent, a sample concentration of 55 mg/0.6 mL, a measurement temperature of 120° C., and ¹³ observation nuclei. C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45° pulse), repetition time is 5.5 seconds, integration count is 10,000 or more, chemical shift standard is 27.50 ppm 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 electronic hydrometer MD-300S from ALFA MIRAGE in accordance with ASTM D 1505 (water replacement method).

[Melting point (Tm)]
The melting point (Tm) of the polymer was measured by a differential scanning calorimeter (DSC) on a Seiko Instruments DSC220C device. A 7-12 mg sample was 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 5 minutes at -50°C, 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).

[Limiting viscosity]
The intrinsic viscosity [η] of the polymer was measured at 135°C using decalin solvent.

[Molecular weight (Mw, Mn), molecular weight distribution (Mw/Mn)]
The molecular weight of the polymer (A) was measured using a liquid chromatograph: ALC/GPC 150-C plus type manufactured by Waters (integrated with a refractometer detector), and GMH6-HT × 2 and GMH6-HT manufactured by Tosoh Corporation as columns. 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 using a calibration curve using a standard polystyrene sample by a known method. The measurement time per sample was 60 minutes.

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

[Method for making press sheets for various measurements]
Press sheets (sheet layers) used for physical property measurement in Examples and Comparative Examples were formed into sheets at a pressure of 10 MPa using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190°C. In the case of a 1 to 3 mm thick sheet (spacer shape; 80 x 80 x 0.5 to 3 mm on a 240 x 240 x 2 mm thick plate, 4 pieces), preheat for about 5 to 7 minutes and heat 1 to 2 at 10 MPa. After pressing for 1 minute, using another hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 20° C., it was compressed at 10 MPa and cooled for about 5 minutes to prepare a sample for measurement. A brass plate with a thickness of 5 mm was used as a hot plate. The samples prepared by the above method were used for evaluating various physical properties.

[Compression set]
In the measurement of compression set (according to JIS K6262), a pressed sheet with a thickness of 12 mm and a diameter of 20 mmφ was left for 22 hours while being compressed to 25% at room temperature. Calculated.

[Shore hardness measurement]
In the measurement of Shore hardness (according to JIS K6253), a press sheet with a thickness of 3 mm was used as a measurement sample, and the scale of the Shore A hardness meter was read immediately after the start of contact with the indentor and 15 seconds after the start of contact with the indenter.

Furthermore, the change ΔHS in the Shore hardness value defined by the following formula was obtained.
ΔHS = (Shore hardness value immediately after start of contact with indentor - Shore hardness value 15 seconds after start of contact with indentor)
In principle, the Shore hardness was measured using a Shore A hardness tester, but for measurement samples for which it was difficult to measure the Shore A hardness, a Shore D hardness tester was used instead. Here, when the same kind of hardness tester is used, it can be said that the larger ΔHS is, the higher the irregularity followability is.

[Dynamic viscoelasticity]
In the measurement of dynamic viscoelasticity, a press sheet with a thickness of 3 mm was used as a measurement sample, and a strip of 45 mm×10 mm×3 mm required for the dynamic viscoelasticity measurement was cut out. Using ANTONPaar MCR301, the temperature dependence of dynamic viscoelasticity is measured from -40 to 150 ° C. at a frequency of 10 rad / s, and the loss tangent (tan δ ) reaches a peak value (maximum value) (hereinafter also referred to as “peak value temperature”), and the value of loss tangent (tan δ) at that time was measured.

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

[Manufacturing method of insole]
The laminates used for measuring physical properties in Examples and Comparative Examples were obtained by using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 220 ° C. in the same manner as [Method for making press sheets for various measurements]. A sheet-like sample of 120×3 mm thickness was produced. If necessary, the above sample was made of EVA foam (a foam with a thickness of 2 mmt was produced using EVAFLEX manufactured by Mitsui DuPont Polychemical Co., Ltd.) and polyurethane foam (PORON manufactured by Inoac Corporation, product number L-24, thickness 2 mmt). foam and adhesive.

[Acquisition at the time of heating (evaluation)]
The produced insole was placed in an oven set at 50° C. for 30 minutes to soften the entire sheet. After that, the insole was taken out of the oven, and a total of 5 men and women in their 20s to 50s were asked to sit on the sheet, and the sheet was deformed by its own weight to produce an insole that matched the shape of each person's foot.
After that, the insole was allowed to stand at 23° C. for 2 hours, and the comfortability was evaluated visually and by the feel of wearing the insole again.
〇: The shape of the foot was maintained ×: The shape 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. Each subject was asked to enter an environmental test room conditioned at 23°C and 50% RH, rest for a while, and then put the insoles prepared in Examples or Comparative Examples into shoes and wear them. , was evaluated in the following five stages.
5: Comfortable to wear.
4: Comfortable to wear is slightly excellent.
3: Normal.
2: Slightly inferior comfort.
1: Poor wearing comfort.

[Synthesis Example 1]
750 ml of 4-methyl-1-pentene was charged at 23° C. into a 1.5-liter SUS autoclave equipped with a stirring blade that was sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL), and a stirrer was turned.
Next, the autoclave was heated to an internal temperature of 60° C. and pressurized with propylene so that the total pressure was 0.13 MPa (gauge pressure). Subsequently, 1 mmol of previously prepared methylaluminoxane in terms of Al, diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was injected into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. After 60 minutes from the start of the polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution while stirring.
The powdery polymer containing the obtained solvent was dried at 100° C. under reduced pressure for 12 hours. The resulting polymer weighed 36.9 g, and had a 4-methyl-1-pentene content of 72.5 mol % and a propylene content of 27.5 mol %. Table 1 shows the physical property measurement results.

[Example 1]
25 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1 and 75 parts by mass of Milastomer 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 properties of the sheet layer were measured.
In addition, a laminate was formed by adhering a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) by the method described above, and the physical properties of the laminate were measured. Various physical properties are shown in Table 2.

[Example 2]
30 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1, Milastomer 5030NS manufactured by Mitsui Chemicals Co., Ltd.: 45 parts, and Tuftec H1221 manufactured by Asahi Kasei Chemicals Corporation: 25 parts were mixed to form a polymer composition. got This composition was press molded to form a sheet layer, and the physical properties of the sheet layer were measured.
In addition, a laminate was formed by adhering a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) by the method described above, and the physical properties of the laminate were measured. Various physical properties are shown in Table 2.

[Example 3]
30 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1, 70 parts by mass of Tuftec H1221 manufactured by Asahi Kasei Chemicals Co., Ltd. and Cellmic C-2 as a blowing agent (trade name: Sankyo Kasei Co., Ltd. Azodicarbonamide (abbreviation) ADCA) was mixed to obtain a polymer composition, which was press molded to form a sheet layer, and the physical properties of the sheet layer were measured.
In addition, a laminate was formed by adhering a 3 mm-thick press sheet of the polymer composition and a polyurethane foam (2 mm-thick sheet) by the method described above, and the physical properties of the laminate were measured. Various physical properties are shown in Table 2.

[Example 4]
30 parts by mass of the 4-methyl-1-pentene copolymer of Synthesis Example 1, 70 parts by mass of Tuftec H1221 manufactured by Asahi Kasei Chemicals Corporation, Cellmic C-2 as a blowing agent (trade name: Sankyo Kasei Co., Ltd. Azodicarbonamide (abbreviation) ADCA) was mixed to obtain a polymer composition, which 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 Milastomer 5030NS manufactured by Mitsui Chemicals, Inc., and Cellmic C-2 as a foaming agent (trade name: Sankyo Kasei Co., Ltd. Azodicarbonamide ( (abbreviation: ADCA) was mixed with 2 parts by mass to obtain a polymer composition, which was press-molded to form a sheet layer, and the physical properties of the sheet layer were measured.

[Comparative Example 1]
A sheet layer was formed by press-molding 100 parts by mass of Milastomer 5030NS manufactured by Mitsui Chemicals, Inc., and physical properties of the sheet layer were measured.
In addition, a laminate was formed by adhering a 3 mm-thick press sheet of the polymer composition and an EVA foam (2 mm-thick sheet) by the method described above, and the physical properties of the laminate were measured. Various physical properties are shown in Table 2.

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

Note that Milastomer 5030NHS manufactured by Mitsui Chemicals, Inc. has a tan δ peak temperature of −40° C. and a peak value of 0.5, Milastomer 5030NS has a tan δ peak temperature of −41° C. and a peak value of 0.55, and Milastomer 8030NHS has a tan δ peak. The value temperature is -40 ° C., the peak value is 0.25, and a blend of 45 parts of Milastomer 5030NS manufactured by Mitsui Chemicals Co., Ltd. and 25 parts of Tuftec H1221 manufactured by Asahi Kasei Chemicals Co., Ltd. has a tan δ peak temperature of -28 ° C. and a peak value of 0. .7.

In accordance with JIS K6253, the value of the Shore A hardness immediately after the start of contact with the incisor, measured in the state of a 3 mm thick pressed sheet, and the value of the Shore A hardness 15 seconds after the start of contact with the indenter. Examples 1 to 5, which are sheet layers mainly composed of a thermoplastic resin composition having a change amount ΔHS between 5 or more and 60 or less, exhibited good shapeability and comfort in a heated state. rice field.

Claims (7)

Laminated in this order,
In accordance with JIS K6253, the value of the Shore A hardness immediately after the start of contact with the incisor, measured in the state of a 3 mm thick pressed sheet, and the value of the Shore A hardness 15 seconds after the start of contact with the indenter. a layer mainly composed of a foam of a thermoplastic resin composition having a variation ΔHS between the layers of 5 or more and 60 or less;
A shock absorbing layer mainly composed of a foam of ethylene-vinyl alcohol copolymer resin;
an anti-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 measured according to JIS K6262. 1 or 2. The shoe insole according to 2. Claims 1 to 3, wherein the foam of the thermoplastic resin composition has a peak value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s of 0.4 or more and less than 5.0. The shoe insole according to any one of Claims 1 to 3. The foam of the thermoplastic resin composition is
A structural unit (i) derived from 4-methyl-1-pentene and a structure 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 structural units (i) and (ii) is 100 mol%,
60 mol% or more and 90 mol% or less of the structural unit (i),
Containing 10 mol% or more and 40 mol% or less of the structural unit (ii),
4-methyl-1-pentene/α-olefin copolymer (A-1);
a 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 a composition containing The foam of the thermoplastic resin composition is
a styrene-based elastomer (A-2);
a thermoplastic resin other than a 4-methyl-1-pentene/α-olefin copolymer;
The shoe insole according to any one of claims 1 to 4, which is a foam of a composition containing A shoe comprising a shoe insole according to any one of claims 1-6.