WO2022270581A1

WO2022270581A1 - Composition and molded body

Info

Publication number: WO2022270581A1
Application number: PCT/JP2022/025106
Authority: WO
Inventors: 賢士野間; 智也又吉; 孝行渡辺; 遼太堀谷
Original assignee: 三井化学株式会社
Priority date: 2021-06-25
Filing date: 2022-06-23
Publication date: 2022-12-29
Also published as: JPWO2022270581A1

Abstract

A composition according to the present invention contains a 4-methyl-1-pentene polymer (a) and a styrene elastomer (b); the 4-methyl-1-pentene polymer (a) comprises a constituent unit derived from 4-methyl-1-pentene and a constituent unit derived from an α-olefin other than 4-methyl-1-pentene, the α-olefin having 2 to 10 carbon atoms; the styrene elastomer (b) is a hydrogenated product of a block copolymer of a polystyrene block and a diene block; the content of the polystyrene block relative to the total mass of the styrene elastomer (b) is more than 0.0% by mass but not more than 70% by mass; and the content of the styrene elastomer (b) relative to 100 parts by mass of the 4-methyl-1-pentene polymer (a) is from 5 parts by mass to 500 parts by mass.

Description

Composition and molded article

The present invention relates to compositions and molded articles. More particularly, the present invention relates to a composition, a molded article, a fabric laminate using the molded article, and a method for producing the same.

4-Methyl-1-pentene-based polymers with 4-methyl-1-pentene as the main constituent monomer are excellent in various performances such as releasability, heat resistance, water resistance, and solvent resistance, and are suitable for various applications. Widely used. Among them, as a technique utilizing the flexibility and followability of a 4-methyl-1-pentene polymer, for example, Patent Document 1 discloses a release film used in the production of a sealing body for a semiconductor module. In order to obtain excellent conformability to the mold, it is provided with a surface layer mainly composed of polymethylpentene resin such as 4-methyl-1-pentene, and an intermediate layer mainly composed of polymethylpentene resin and thermoplastic elastomer. A release film is disclosed. Further, in Patent Document 2, by using a resin composition containing a base resin made of polyethylene resin or polypropylene resin and a low-molecular-weight 4-methyl-1-pentene polymer, excellent releasability and anti-rust properties are achieved. It is disclosed that high flexibility and transparency can be obtained while having blocking properties.

Japanese Patent Application Laid-Open No. 2020-202273 JP 2011-140594 A

The present inventors maintain the characteristics of the conventional 4-methyl-1-pentene-based polymer, such as flexibility against stress, while further imparting new characteristics not disclosed in Patent Documents 1 and 2. Since then, we have conducted an in-depth study. As a result, by combining a 4-methyl-1-pentene polymer and a hydrogenated styrene-based elastomer, it is possible to obtain a high fit and a good feeling of use even at temperatures lower than room temperature. First time I've found what I can get.

The present invention has been made in view of the above circumstances, and provides a composition that has a good feeling of use at low temperatures while obtaining a good fit, and a molded article using the same.

That is, according to the present invention, the composition shown below is provided.

[1] a 4-methyl-1-pentene polymer (a);
a styrene-based elastomer (b);
including
The 4-methyl-1-pentene-based polymer (a) is a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 10 carbon atoms other than 4-methyl-1-pentene and
The styrene-based elastomer (b) is a hydrogenated block copolymer of a polystyrene block and a diene block, and the content of the polystyrene block relative to the total amount of the styrene-based elastomer (b) is greater than 0.0% by mass. 50% by mass or less,
A composition, wherein the content of the styrene elastomer (b) is 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (a).
[2] The 4-methyl-1-pentene polymer (a) is obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4° C./min, a frequency of 1.59 Hz, and a strain of 0.1%. At least one temperature at which the loss tangent (tan δ) exhibits a maximum value is in the range of 10° C. or more and 100° C. or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less [1] The composition according to .
[3] The styrene elastomer (b) includes a hydrogenated styrene/butadiene rubber (HSBR), a hydrogenated styrene/butadiene block copolymer (SEBS), a hydrogenated styrene/isoprene block copolymer (SEPS), and water. 3. The composition according to [1] or 2, which is one or more selected from styrene/isoprene/butadiene block copolymers (SEEPS).
[4] The composition according to any one of [1] to [3], wherein the content of the polystyrene block relative to the total amount of the styrene elastomer (b) is 5% by mass or more and 15% by mass or less.
[5] A saturated hydrocarbon compound (d) having a pour point of -10°C or less is added to 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b). and 0.1 to 20 parts by weight of the composition according to any one of [1] to [5].
[6] the content of the polystyrene block with respect to the total amount of the styrene-based elastomer (b) is more than 25% by mass and not more than 50% by mass;
A saturated hydrocarbon compound (d) having a pour point of -10°C or less is added to 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) to 0. .1 to 20 parts by weight of the composition according to any one of [1] to [5].
[7] The composition has a loss tangent (tan δ) value at 30 ° C. obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4 ° C./min, a frequency of 1.59 Hz, and a strain of 0.1%. The composition according to any one of [1] to [6], which has an absolute value of 0.5 or more.
[8] The composition according to any one of [1] to [7], which satisfies condition i below.
(Condition i)
Using the composition containing 1 part by mass of a chemical foaming agent with respect to 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the die temperature of the extruder was 190. A foam sheet extruded at ℃ is prepared, and the sheets are overlapped so that the total thickness is 7 mm to obtain a test piece a. The Shore A hardness (JIS K6253) of the test piece a is 10-70.
[9] The composition according to any one of [1] to [8], which satisfies the following condition iii.
(Condition iii)
Using the composition containing 1 part by mass of a chemical foaming agent with respect to 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the die temperature of the extruder was 190. A foam sheet extruded at ℃ is prepared, and the sheet is punched into a width of 25 mm and a length of 100 mm to obtain a test piece c. Using a tensile tester (universal tensile tester 3380, manufactured by Instron), the test piece c was subjected to two temperature conditions of 23 ° C. and 40 ° C. with a distance between chucks of 30 mm and a tensile speed of 300 mm / min. Extend c by 50% in the TD direction, and measure the tensile load [N/25 mm] after 60 seconds. When the tensile load obtained at each temperature after 60 seconds is applied to the following formula to determine the degree of softening, the degree of softening is 25% to 80%.
Softness [%] = [Tensile load after 60 seconds at 40°C [N/25mm]]/[Tensile load after 60 seconds at 23°C [N/25mm]
[10] The composition according to any one of [1] to [9], which satisfies condition iv below.
(Condition iv)
Extrusion at a die temperature of 190° C. using the composition containing 1 part by mass of a chemical foaming agent per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) A molded foam sheet is prepared, and the surface impact strength (in accordance with JIS K7211-2) of the sheet measured at a test temperature of 10° C. is 0.6 J or more.
[11] A molded article obtained by molding the composition according to any one of [1] to [10].
[12] The molded article according to [11], wherein the molded article contains cells and has a density of 0.10 to 1.0 g/cm ³ .
[13] The molded article according to [11] or [12] is a sheet,
A fabric laminate in which a fabric is attached to at least one surface of the sheet.
[14] The fabric laminate according to [13], wherein at least a portion of the fabric laminate is curved and has a radius of curvature in the range of 50 mm to 150 mm.
[15] The fabric laminate manufacturing method according to [13] or [14], comprising a step of bonding the sheet and the fabric together at 140 to 190° C. and 1.0 to 1.8 MPa.
[16] Clothing using the fabric laminate according to [13] or [14].
[17] Use of the molded article according to [11] or [12] in a low-temperature environment.

According to the present invention, it is possible to provide a composition and a molded article using the composition that have good fit and feel when used at low temperatures.

Embodiments of the present invention will be described below.

In this specification, the term "substantially" means that it includes a range that takes into account manufacturing tolerances, assembly variations, and the like, unless otherwise explicitly stated.
In this specification, the notation "a to b" in the description of numerical ranges means from a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".

As used herein, the term "low temperature" means a temperature lower than room temperature of 20°C and at which the composition and molded article do not freeze. For example, the temperature may be 15° C. or lower, 10° C. or lower, or 5° C. or lower, or -10° C. or higher, -5° C. or higher, or 0° C. or higher.

In this embodiment, the melt flow rate can be measured under the conditions of 230°C and a test load of 2.16 kg according to JIS K7210.

1. Composition The composition of the present embodiment comprises a 4-methyl-1-pentene polymer (a) and a styrene elastomer (b), and the 4-methyl-1-pentene polymer (a) contains a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 10 carbon atoms other than 4-methyl-1-pentene, and the styrene elastomer (b) is a polystyrene block and a diene block, wherein the content of the polystyrene block relative to the total amount of the styrene elastomer (b) is more than 0.0% by mass and 50% by mass or less, and the 4- The content of the styrene-based elastomer (b) with respect to 100 parts by mass of the methyl-1-pentene-based polymer (a) is 5 parts by mass or more and 500 parts by mass or less.

By having such a configuration, the composition of the present embodiment can improve tensile elongation at low temperatures while obtaining stress relaxation properties. As a result, it is possible to obtain a good feeling of use even at a temperature lower than room temperature while obtaining a high fitting property. For example, when applied to clothing, the composition of the present embodiment can appropriately fit human movements and shapes, and retains flexibility even when exposed to cold water and placed at low temperatures during washing. be done. In addition, since good flexibility, tensile properties, etc. are maintained even in cold regions, breakage is suppressed and it can be used satisfactorily. Moreover, according to the composition of the present embodiment, heat resistance and low-temperature impact resistance can be further improved. Although the details of this reason are not clear, it is presumed as follows.
The styrene-based elastomer (b) of the present embodiment is a type of thermoplastic elastomer and includes a block copolymer composed of polystyrene as a hard part and polydiene as a soft part. At a temperature below the glass transition point temperature (Tg) of the polystyrene block, which is the hard part, the polystyrene block forms physical crosslinks to develop rubber elasticity, while the glass transition point temperature (Tg ), it has the characteristic that it is plasticized and can be processed under the temperature above. The present inventors have found that, among others, the hydrogenated product in which the soft portion is hydrogenated tends to increase the tensile strength and is more effective in solving the problem. Therefore, by controlling the ratio of the hard portion of the styrene-based elastomer (b) consisting of the styrene-based monomer and the soft portion of the diene or the like, it is possible to obtain appropriate rubber elasticity at low temperatures while maintaining flexibility. guessed.
In the present embodiment, by combining a specific styrene-based elastomer (b) having such properties with a 4-methyl-1-pentene-based polymer (a), stress relaxation is obtained due to the synergistic effect of both. However, even at low temperatures, it exhibits appropriate rubber elasticity and can improve tensile strength. As a result, it is speculated that a good feeling of use can be obtained even at temperatures lower than room temperature while obtaining high fit. be done.

It should be noted that fit means, for example, that when applied to clothing, it can be moderately matched to human movements and body shapes. Good feeling in use at low temperatures means that the fabric does not easily break or avoid cracking even at temperatures lower than room temperature, and maintains flexibility even when exposed to cold water during washing or the like and placed at low temperatures.

The composition of the present embodiment further has a loss tangent (tan δ) value at 30 ° C. obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4 ° C./min, a frequency of 1.59 Hz, and a strain of 0.1%. is preferably 0.5 or more. As a result, more flexibility can be obtained at a temperature close to that of human skin, and the fit can be improved.

The composition of the present embodiment preferably further satisfies condition i below.
(Condition i)
The extruder die temperature ( Film Forming Temperature) A foam sheet extruded at 190° C. is prepared, and the sheets are superimposed so that the total thickness is 7 mm to obtain a test piece a. The Shore A hardness (JIS K6253) of the test piece a is 10-70.

By satisfying the condition i, the molded article using the composition of the present embodiment has appropriate flexibility and stress relaxation properties, can easily follow human movements and shapes, and has a high fit. Become.

In addition, under condition i, the Shore A hardness (JIS K6253) of test piece a is preferably 20-70, more preferably 30-70, and even more preferably 40-70.

Here, it is preferable that the thickness per expandable sheet under condition i is 0.3 to 0.6 mm, and the specific gravity is preferably 0.73 to 0.81. That is, by using a plurality of expandable sheets, it is possible to obtain a test piece a having a total thickness of 7 mm. The thickness and specific gravity per foamable sheet can be appropriately set by adjusting the extrusion conditions (temperature, extrusion speed, etc.).

The composition of the present embodiment preferably further satisfies the following condition (ii).
(Condition ii)
A sheet is prepared by extruding the above composition, and the sheets are superimposed so that the total thickness is 7 mm to obtain a test piece b. For test piece b, the value ΔHS obtained by subtracting the value of Shore A hardness (JIS K6253) after 15 seconds from the value of Shore A hardness (JIS K6253) immediately after contact with the indentor of the Shore A hardness tester is 10 to 40. is.

By satisfying condition ii, it is possible to obtain good conformability to irregularities and improve fit.

In addition, the ΔHS of the test piece b under condition ii is preferably 15-30. By setting ΔHS to be equal to or higher than the above lower limit, it is possible to enhance conformability to irregularities.

Here, the thickness per sheet of condition ii is preferably 0.3 to 0.6 mm. That is, a test piece b having a total thickness of 7 mm can be obtained by using a plurality of sheets. The thickness per sheet in condition ii can be appropriately set by adjusting extrusion conditions (temperature, extrusion speed, etc.).

The composition of the present embodiment preferably further satisfies condition iii below.
(Condition iii)
Extrusion at a die temperature of 190° C. using the composition containing 1 part by mass of a chemical foaming agent per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) A molded foam sheet is prepared, and the sheet is punched into a width of 25 mm and a length of 100 mm to obtain a test piece c. Using a tensile tester (universal tensile tester 3380, manufactured by Instron), the test piece c was subjected to two temperature conditions of 23 ° C. and 40 ° C. with a distance between chucks of 30 mm and a tensile speed of 300 mm / min. Extend c by 50% in the TD direction, and measure the tensile load [N/25 mm] after 60 seconds. When the tensile load obtained at each temperature after 60 seconds is applied to the following formula to determine the degree of softening, the degree of softening is 25% to 80%.
Softness [%] = [Tensile load after 60 seconds at 40°C [N/25mm]]/[Tensile load after 60 seconds at 23°C [N/25mm]]

By satisfying condition iii, it is possible to obtain good conformability to irregularities in a molded article using the composition of the present embodiment. In particular, good followability is obtained in a temperature range where human skin can warm the composition, making it easier for the composition to adhere to the human body.

Also, in condition iii, the softening degree of the test piece c is preferably 30% to 70%. By setting the softening degree to the above upper limit or less, more flexibility can be obtained, skin familiarity is good, and fit can be improved.

Here, it is preferable that the thickness of each expandable sheet of condition iii is 0.3 to 0.6 mm, and the specific gravity is preferably 0.83 to 0.90. The thickness and specific gravity per foamable sheet in condition iii can be appropriately set by adjusting the extrusion conditions (temperature, extrusion speed, etc.).

The composition of the present embodiment preferably further satisfies condition iv below.
(Condition iv)
Extrusion at a die temperature of 190° C. using the composition containing 1 part by mass of a chemical foaming agent per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) A molded foam sheet is prepared, and the surface impact strength (in accordance with JIS K7211-2) of the sheet measured at a test temperature of 10° C. is 0.6 J or more.

By satisfying condition iv, a molded article using the composition of the present embodiment can have high impact resistance even at low temperatures. As a result, it is possible to reduce breakage due to stress and deformation from the outside, and to improve usability at low temperatures. In addition, when the composition of the present embodiment is applied to clothing, good flexibility and durability can be obtained even when the clothing is washed under cold water or when used in cold climates.

In addition, in condition iv, the surface impact strength of the sheet is preferably 0.7 J or more. On the other hand, the upper limit of the surface impact strength of the sheet is not particularly limited, but is preferably 10 J or less, more preferably 8 J or less, from the viewpoint of maintaining a balance with other performances.

The composition of the present embodiment preferably further satisfies condition v below.
(Condition v)
Extrusion at a die temperature of 190° C. using the composition containing 1 part by mass of a chemical foaming agent per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) A molded foam sheet is prepared, and the sheet is punched into a width of 25 mm and a length of 100 mm to obtain a test piece d. Using a tensile tester (universal tensile tester 3380, manufactured by Instron), the test piece d was subjected to two temperature conditions of 23 ° C. and 40 ° C. with a distance between chucks of 30 mm and a tensile speed of 300 mm / min. d is stretched by 50% in the TD direction, and the tensile load [N/25 mm] immediately after stretching and the tensile load [N/25 mm] after 60 seconds under each temperature condition are measured. {(Tensile load after 60 seconds [N / 25 mm]) ÷ (Tensile load immediately after elongation [N / 25 mm])} × 100 [%] as the initial load residual rate [%], the initial load at 23 ° C. The load retention rate is 15-60%, and the initial load retention rate at 40° C. is 50-80%.

The composition of the present embodiment has an initial load residual rate of 15 to 60% at 23 ° C. under condition v, so that even after deformation at room temperature, it returns to its original shape and exhibits a moderate tightening feeling. With an initial load residual rate of 50 to 80%, it has a moderate initial load residual rate after being warmed by human skin, so even if tension is applied, it is difficult to create a feeling of tightening. It is preferable in terms of excellent fit.

These conditions i to v are indicators newly devised by the present inventor from the viewpoint of obtaining a composition that more stably provides a good feel in use at low temperatures while obtaining a better fit. That is, the effects of fit and feeling in use at low temperatures are new effects not found in conventional compositions, and indices based on existing measurement methods do not provide sufficient fit and feel in use at low temperatures. there was a case. On the other hand, in the composition of the present embodiment, by satisfying the conditions iv, it is possible to obtain a better fit and a more stable feeling of use at low temperatures.

The composition of the present embodiment that satisfies the properties and conditions described above can be realized, for example, by combining the materials of the composition by a known method. Specifically, focusing on the difference in melt flow rate (g/10 min) between the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the styrene elastomer (b) and adjusting the ratio of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b). However, the composition of this embodiment is not limited to such materials and production methods.

Each component contained in the composition of the present embodiment will be described in detail below.

[4-methyl-1-pentene polymer (a)]
The 4-methyl-1-pentene-based polymer (a) according to the present embodiment is a polymer having structural units derived from 4-methyl-1-pentene.

The 4-methyl-1-pentene-based polymer (a) according to the present embodiment includes, for example, a structural unit (c1) derived from 4-methyl-1-pentene and carbon atoms other than 4-methyl-1-pentene and a 4-methyl-1-pentene/α-olefin copolymer (c) containing a structural unit (c2) derived from an α-olefin of number 2 to 20.
Here, in the present embodiment, "α-olefin having 2 to 20 carbon atoms" means not containing 4-methyl-1-pentene unless otherwise specified.

From the viewpoint of further improving the flexibility and moldability of the composition, the 4-methyl-1-pentene/α-olefin copolymer (c) according to the present embodiment has the structural unit (c1) and the structural unit (c2). ) is 100 mol%, the content of the structural unit (c1) is 10 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 90 mol% or less. Preferably.
In addition, the 4-methyl-1-pentene/α-olefin copolymer (c) according to the present embodiment contains the structural unit (c1) and When the total with the structural unit (c2) is 100 mol%, the following order is more preferable.
The content of the structural unit (c1) is 30 mol% or more and 95 mol% or less, and the content of the structural unit (c2) is 5 mol% or more and 70 mol% or less;
The content of the structural unit (c1) is 30 mol% or more and 93 mol% or less, and the content of the structural unit (c2) is 7 mol% or more and 70 mol% or less;
The content of the structural unit (c1) is 30 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 70 mol% or less;
The content of the structural unit (c1) is 50 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 50 mol% or less;
The content of the structural unit (c1) is 60 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 40 mol% or less;
The content of the structural unit (c1) is 65 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 35 mol% or less;
The content of the structural unit (c1) is 65 mol% or more and 85 mol% or less, the content of the structural unit (c2) is 15 mol% or more and 35 mol% or less, and the content of the structural unit (c1) is 65 mol % or more and 80 mol % or less, and the content of the structural unit (c2) is 20 mol % or more and 35 mol % or less.

In the present embodiment, the α-olefin having 2 to 20 carbon atoms used in the 4-methyl-1-pentene/α-olefin copolymer (c) includes, for example, a linear or branched α-olefin , cyclic olefins, aromatic vinyl compounds, conjugated dienes, functionalized vinyl compounds, etc., and linear α-olefins are preferred.

The linear α-olefin preferably has 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms. Linear α-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, etc., and ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1- One or more selected from decene is preferred, and at least one selected from ethylene and propylene is more preferred.
The number of carbon atoms in the branched α-olefin is preferably 5-20, more preferably 5-15. Branched α-olefins include, for example, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene and the like.
The number of carbon atoms in the cyclic olefin is preferably 5-15. Cyclic olefins include, for example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane, and the like.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Examples include mono- or polyalkylstyrenes such as ethylstyrene.
The number of carbon atoms in the conjugated diene is preferably 4-20, more preferably 4-10. Conjugated dienes include, for example, 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3- - Octadiene and the like.

Examples of functionalized vinyl compounds include hydroxyl group-containing olefins, halogenated olefins, (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, and 7-octene. Acids, unsaturated carboxylic acids such as 8-nonenoic acid, 9-decenoic acid and 10-undecenoic acid and their acid anhydrides and acid halides, unsaturated amines such as allylamine, 5-hexeneamine and 6-heptenamine, (2, 7-octadienyl)succinic anhydride, pentapropenyl succinic anhydride, unsaturated epoxy compounds, ethylenically unsaturated silane compounds, and the like.
Examples of the hydroxyl group-containing olefins include linear or branched α-olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and hydroxyl-terminated α-olefins.
Examples of the halogenated olefin include linear or branched halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms.

These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more. Among the above, ethylene and propylene are preferable, and propylene is particularly preferable because it can improve flexibility and the like.

The 4-methyl-1-pentene/α-olefin copolymer (c) contains structural units other than the structural unit (c1) and the structural unit (c2) within a range that does not impair the object of the present invention. good too. Other configurations include structural units derived from non-conjugated polyenes.
Non-conjugated polyenes include linear, branched or cyclic dienes having preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, various norbornenes, norbornadiene, and the like. Among these, 5-vinylidene-2-norbornene and 5-ethylidene-2-norbornene are preferred.

In the present embodiment, the 4-methyl-1-pentene polymer (a) is determined by dynamic viscoelasticity measurement under the conditions of a temperature increase rate of 4° C./min, a frequency of 1.59 Hz, and a strain amount of 0.1%. At least one temperature showing the maximum value of loss tangent (tan δ) is in the range of 10 ° C. or more and 100 ° C. or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less. preferable.

In the dynamic viscoelasticity measurement, for example, a 4-methyl-1-pentene polymer (a) is used to prepare a test piece of 30 mm long x 10 mm wide, and the frequency is 1.59 Hz and the temperature rise rate is 4 ° C./ Minutes, measurement temperature range of 0° C. to 110° C., amount of strain of 0.1%, distance between chucks of 20 mm, and torsion mode, using a rheometer.

The present inventors prepared a 4-methyl-1-pentene-based polymer (a) having a specific maximum value of loss tangent (tan δ) and a specific temperature range showing the maximum value, and a styrene-based elastomer (b ), the temperature at which the tangent loss is maximized can be shifted to the low temperature side, and the elongation at low temperatures can be improved more stably.

Although the details of this reason are not clear, it is considered as follows.
First, in the 4-methyl-1-pentene-based polymer (a), by setting the maximum value of the loss tangent in the range of 10 ° C. or more and 100 ° C. or less, in this temperature range, the dynamics given when deforming Most of the energy can be converted into thermal energy, and much of the energy can be absorbed, so it is thought that the restoration speed after deformation becomes slow. As a result, it is considered that the 4-methyl-1-pentene polymer (a) can well follow deformation while maintaining the flexibility of the 4-methyl-1-pentene polymer (a).
Also, by controlling the loss tangent (tan δ) in a relatively low frequency region of 1.59 Hz, it is intended to obtain followability to a force that takes time (also referred to as a slow force).
Therefore, the present inventors combined a 4-methyl-1-pentene-based polymer (a) having such a specific property with a new specific styrene-based elastomer (b) to obtain a 4-methyl-1-pentene-based polymer. The temperature (Tg) at which the loss tangent (tan δ) of coalescence (a) exhibits a maximum value can be effectively shifted to the low temperature side, and the resulting composition can exhibit stress relaxation properties while maintaining tensile strength at low temperatures. It has been found that elongation can be improved, and low-temperature impact resistance and heat resistance can also be obtained.

The loss tangent of the 4-methyl-1-pentene-based polymer (a) according to the present embodiment is, for example, the type and blending ratio of the 4-methyl-1-pentene-based polymer (a), the presence or absence of crosslinking, the composition It is possible to control within the above range by appropriately adjusting the molding method of the object.
Specifically, for example, by increasing the blending ratio of the 4-methyl-1-pentene polymer (a) in the composition, and by subjecting the 4-methyl-1-pentene polymer (a) to cross-linking treatment. and the like.

In the present embodiment, the 4-methyl-1-pentene polymer (a) is preferably uncrosslinked from the viewpoint of obtaining flexibility, conformability, and stress relaxation. That is, the 4-methyl-1-pentene polymer (a) according to the present embodiment is, for example, uncrosslinked without undergoing crosslinking treatment such as ionizing radiation crosslinking using electron beams or γ rays. preferable. As a result, the maximum value of the loss tangent in the range of 10 ° C. or higher and 100 ° C. or lower can be improved, and the 4-methyl-1-pentene polymer (a) which is more excellent in the balance of stress relaxation and low-temperature tensile elongation is obtained. Obtainable.

In the present embodiment, the 4-methyl-1-pentene polymer (a) has at least one temperature in the range of at least 10° C. or higher and 40° C. or lower at which the dynamic viscoelasticity loss tangent (tan δ) exhibits the maximum value. and the maximum value of the loss tangent is preferably 0.8 or more and 3.0 or less.
This makes it easier to improve low-temperature properties such as tensile elongation at low temperatures and low-temperature impact resistance.

Further, in the present embodiment, the maximum value of the loss tangent of the 4-methyl-1-pentene polymer (a) is preferably 0.8 or more, more preferably 1.0 or more, and 1 .2 or more is more preferable. In this embodiment, the maximum value of the loss tangent is preferably 3.0 or less, more preferably 2.8 or less.
Thereby, the stress relaxation property of the composition of the present embodiment and the performance balance of elongation at low temperature can be improved.
Here, the larger the maximum value of the loss tangent, the stronger the viscous properties of the composition. Compositions with strong viscous properties can convert more of the mechanical energy given during deformation into thermal energy, and can absorb more energy, so it is thought that the recovery speed after deformation becomes much slower. . As a result, it is thought that the shape after deformation can be better maintained and that the composition can follow the deformation better while maintaining the flexibility of the composition.

The melt flow rate of the 4-methyl-1-pentene polymer (a) according to the present embodiment is preferably 0.1 to 100 (g/10 minutes), more preferably 1 to 70 (g/10 minutes). , more preferably 2 to 20 (g/10 min), and even more preferably 3 to 15 (g/10 min).

The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (a) according to the present embodiment in decalin at 135° C. is, from the viewpoint of improving the flexibility and mechanical strength of the composition, It is preferably 0.01 to 5.0 dL/g, more preferably 0.1 to 4.0 dL/g, even more preferably 0.5 to 3.0 dL/g, and 1.0 ~2.8 dL/g is particularly preferred.

The density of the 4-methyl-1-pentene polymer (a) according to the present embodiment measured according to ASTM D 1505 (water substitution method) is preferably 0.810 to 0.850 g/cm ³ , more preferably 0.820 to 0.850 g/cm ³ , more preferably 0.830 to 0.850 g/cm ³ .

The 4-methyl-1-pentene polymer (a) according to this embodiment can be produced by various methods. For example, magnesium-supported titanium catalysts; metallocene catalysts described in WO 01/53369, WO 01/027124, JP-A-3-193796, and JP-A-02-41303; It can be produced using a known catalyst such as an olefin polymerization catalyst containing a metallocene compound described in 2011/055803.

The content of the 4-methyl-1-pentene polymer (a) in the composition according to the present embodiment is not particularly limited, but when the total composition is 100% by mass, preferably 20% by mass or more, More preferably 30% by mass or more, still more preferably 40% by mass or more, on the other hand, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
As a result, it is possible to enhance fit and improve the feeling of use at low temperatures. In addition, it becomes easy to improve the balance of flexibility, shape followability, lightness, mechanical properties, and moldability.

[Styrene-based elastomer (b)]
The styrene-based elastomer (b) of the present embodiment is a hydrogenated block copolymer of a polystyrene block and a diene block. A block copolymer can be hydrogenated by a known method in an inert solvent in the presence of a hydrogenation catalyst.

The hydrogenation of the block copolymer may be partially or wholly, but the hydrogenation reduces the unsaturated bonds and makes it easier to obtain flexibility, heat resistance, mechanical properties, etc. Therefore, the degree of hydrogenation is such that 50% or more of the olefinic double bonds in the copolymer block are hydrogenated, preferably 80% or more.

The content of the polystyrene block (styrene content) relative to the total amount of the styrene elastomer (b) is greater than 0.0% by mass and 50% by mass or less, preferably 5% by mass or more and 50% by mass or less, It is more preferably 30% by mass or less, and even more preferably 15% by mass or less.
On the other hand, when the below-described saturated hydrocarbon compound (d) having a pour point of -10°C or less is included, the content of the polystyrene block with respect to the total amount of the styrene elastomer (b) is more than 25% by mass and 50% by mass or less. and 0.1 to 20 parts by weight of the saturated hydrocarbon compound (d) with respect to 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) It is preferable to include Furthermore, when the saturated hydrocarbon compound (d) is included, the content of the polystyrene block with respect to the total amount of the styrene elastomer (b) is 30% by mass or more and 40% by mass or less, and the saturated hydrocarbon compound (d) is more preferably contained in an amount of 1 to 15 parts by weight per 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b).

The styrene elastomer (b) includes hydrogenated styrene/butadiene rubber, hydrogenated styrene/butadiene block copolymer (SEBS), hydrogenated styrene/isoprene block copolymer (SEPS) and hydrogenated styrene/isoprene/butadiene block copolymer. It is preferably one or more selected from polymers (SEEPS), and among them, from the viewpoint of obtaining heat resistance and low-temperature tensile elongation, hydrogenated styrene-butadiene block copolymer (SEBS) It is more preferable to have Also, it may have a structure mainly composed of vinyl bonds (30 to 50% of 1,2-vinyl bonds), and may be so-called vinyl SEBS, vinyl SEPS, or vinyl SEEPS.

The Shore A hardness (JIS K6253) of the styrene elastomer (b) is preferably 10-100, more preferably 20-90, even more preferably 30-80.

The weight average molecular weight of the styrene-based elastomer (b) is preferably 10,000 to 450,000, more preferably 30,000 to 350,000, even more preferably 40,000 to 300,000.
The weight average molecular weight is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography.

The melt flow rate of the styrene-based elastomer (b) of the present embodiment is preferably 0.1 to 20 (g/10 min), more preferably 0.5 to 15 (g/10 min), still more preferably 1 to 10 (g/10 minutes).

Examples of the styrene-based elastomer (b) of the present embodiment include "Clayton (registered trademark) G" manufactured by Kraton Polymer Co., Ltd., "Hibler (registered trademark)" and "Septon (registered trademark)" manufactured by Kuraray Co., Ltd., and "Tuftec" manufactured by Asahi Kasei Corporation. (registered trademark)”, “SOE (registered trademark)”, and “DYNARON (registered trademark)” manufactured by JRS may be used.

Further, in the composition of the present embodiment, the absolute value of the difference in melt flow rate (g/10 min) between the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) is 10 or less. One is preferred, nine is more preferred, and eight is even more preferred.

In the present embodiment, the content of the styrene elastomer (b) with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (a) is 5 parts by mass or more and 500 parts by mass or less, preferably 10 to 400 parts by mass. , more preferably 20 to 300 parts by mass, still more preferably 40 to 200 parts by mass.
By setting the content of the styrene-based elastomer (b) to the above lower limit or more, it is possible to improve the tensile elongation at low temperatures while maintaining the stress relaxation properties. On the other hand, by setting the content of the styrene-based elastomer (b) to the above upper limit or less, good stress relaxation properties and flexibility can be achieved while maintaining tensile elongation at low temperatures.

[Other ingredients]
The composition according to this embodiment may contain components other than the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b).

[Saturated hydrocarbon compound (d)]
The composition of the present embodiment may further contain a saturated hydrocarbon compound (d) having a pour point of -10°C or lower. This makes it easier to further improve the tensile elongation at low temperatures.
Also, the pour point is preferably -11°C or lower, more preferably -12°C or lower. By setting the pour point to the upper limit or less, it becomes easier to obtain conformability and flexibility at low temperatures, and good tensile elongation can be obtained.
The pour point is measured according to JIS K2269.

The saturated hydrocarbon compound (d) preferably has 20 or more carbon atoms, and more preferably liquid paraffin or the like.

The content of the saturated hydrocarbon compound (d) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b). Yes, preferably 1 to 15 parts by mass, more preferably 2 to 12 parts by mass.

[Modified resin (a2)]
From the viewpoint of improving the appearance and touch, the composition according to the present embodiment is a modified resin (a2) (however, the 4-methyl-1-pentene polymer (a) according to the present embodiment, and styrene-based elastomer (except for (b)) may be contained. The modified resin (a2) according to the present embodiment includes, for example, one or more selected from thermoplastic resins, thermoplastic elastomers and rubbers.

Examples of the above thermoplastic resins (excluding the 4-methyl-1-pentene polymer (a1) according to the present embodiment) include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density Polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α - thermoplastic polyolefin resins such as olefin copolymers, cyclic olefin copolymers, chlorinated polyolefins; aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612), polyether block amide co Thermoplastic polyamide resins such as polymers; Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Thermoplastic vinyl aromatic resins such as polystyrene, ABS resin, and AS resin; Vinyl chloride resin; Vinylidene chloride resin; Resin; ethylene/vinyl acetate copolymer; ethylene/methacrylic acid acrylate copolymer; ionomer; ethylene/vinyl alcohol copolymer; polyvinyl alcohol; fluorine such as polyvinyl fluoride resin, polytetrafluoroethylene, polyvinylidene fluoride, and ETFE polyacetal; polyphenylene oxide; polyphenylene sulfide; polyimide; polyarylate; polysulfone;
Examples of the rubber include ethylene/α-olefin/diene copolymer rubber and propylene/α-olefin/diene copolymer rubber.
Furthermore, thermoplastic elastomers include, for example, olefin-based elastomers, styrene-based elastomers (excluding the above styrene-based elastomer (b)), acid-modified styrene-based elastomers, vinyl chloride-based elastomers, urethane-based elastomers, ester-based elastomers, amide-based elastomers, Elastomers and the like can be mentioned.
Also, these modified resins (a2) may be acid-modified with acrylic acid, methacrylic acid, maleic acid, or the like.
These modified resins (a2) may be used singly or in combination of two or more.

Among these modified resins (a2), low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl- One or two or more selected from 1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, and 1-butene/α-olefin copolymer are preferred, and polyethylene, polypropylene, and poly(1) -butene, poly 4-methyl-1-pentene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, ethylene/vinyl acetate copolymer, poly One or two or more selected from ether block amides, ionomers, fluorine resins, acid-modified fluorine resins, rosin resins, terpene resins, and petroleum resins, and those that improve the melt tension by addition are more preferable.

The composition according to the present embodiment can be used singly or in combination of two or more of these modified resins (a2).

The content of the modified resin (a2) in the composition according to the present embodiment is not particularly limited. above, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, still more preferably 30% by mass % or less, particularly preferably 25 mass % or less.
When the content of the modified resin (a2) is at least the above lower limit, the composition according to the present embodiment can have better appearance, touch, and the like. When the content of the modified resin (a2) is equal to or less than the above upper limit value, it is possible to improve the performance balance of the composition according to the present embodiment, such as flexibility.

[Other ingredients]
The composition according to the present embodiment optionally contains a foaming agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizer, a plasticizer, Additives such as nucleating agents, weather stabilizers, light stabilizers, antioxidants, fatty acid metal salts, softeners, dispersants, colorants, lubricants, natural oils, synthetic oils and waxes may be added. Among these, plasticizers, softeners, natural oils and synthetic oils are used to adjust the temperature at which the solid viscoelasticity loss tangent (tan δ) of the composition according to the present embodiment reaches its maximum value and the loss tangent maximum value. In addition, the type and amount added may be controlled.

Examples of the foaming agent include chemical foaming agents and physical foaming agents.
Chemical foaming agents include sodium bicarbonate, ammonium bicarbonate, various carboxylates, sodium borohydride, azodicarbamide, N,N-dinitrosopentamethylenetetramine, P,P-oxybis(benzenesulfonylhydrazide). , azobisisobutyronitrile, p-toluenesulfonyl hydrazide, sodium bicarbonate sodium citrate, and the like.
Physical blowing agents include carbon dioxide, nitrogen, a mixture of carbon dioxide and nitrogen, and the like, all of which can be supplied in a gaseous, liquid, or supercritical state.

[form]
The composition of this embodiment may be in a foamed state containing air bubbles. In this case, the density of the composition is preferably 0.10 to 1.0 g/cm ³ , more preferably 0.5 to 0.9 g/cm ³ , and more preferably 0.7 to 0.8 g/cm 3 . cm ³ is more preferred.
Although the shape of the composition according to this embodiment is not particularly limited, it may be in the form of a sheet. In the case of a sheet, the thickness is preferably 0.1 mm or more and 30 mm or less, more preferably 0.2 mm or more and 20 mm or less, and still more preferably 0.3 mm or more and 10 mm or less. By setting the thickness to the above lower limit or more, a good balance of low-temperature tensile elongation, flexibility, mechanical properties, moldability, low-temperature impact resistance, and the like can be obtained. On the other hand, by setting the thickness to be equal to or less than the above upper limit value, lightness, appearance, and handleability can be improved.
Moreover, the composition of the present embodiment may be a foam processed into a sheet.

<Method for producing composition>
The composition of the present embodiment is prepared by dry blending the 4-methyl-1-pentene polymer (a), the organic compound (b), and other optional components as raw materials, using a tumbler mixer, a Banbury mixer, and a single screw extruder. , a twin-screw extruder, a high-speed twin-screw extruder, a hot roll, or the like.

Moreover, when the composition according to the present embodiment is in a foamed state, for example, the chemical foaming agent can be blended with the composition and uniformly mixed before being fed into the extruder. Further, when carbon dioxide is used as a physical blowing agent, the composition is kneaded in an extruder, and after being plasticized, it can be obtained by injecting carbon dioxide directly into the extruder.
The expansion ratio is not particularly limited, and can be appropriately determined in consideration of the use of the composition.

2. Molded Article The molded article of the present embodiment is obtained by molding the composition described above by a known method. The shape of the molded body is not particularly limited, and it may be processed into any shape depending on the application.

The molded article of the present embodiment preferably satisfies the following condition a.
(Condition A)
When the molded bodies are superimposed as necessary to prepare a test piece A so that the molded body has a thickness of 7 mm, the Shore A hardness (JIS K6253) of the test piece is 10 to 70.

By satisfying the condition a, the molded article of the present embodiment can have moderate flexibility and stress relaxation properties, can easily follow human movements and shapes, and can have a high fit.

Also, in condition a, the Shore A hardness (JIS K6253) of the test piece a is preferably 20-70, more preferably 30-70.

The molded article of the present embodiment preferably satisfies the following condition a.
(Condition A)
A 25 mm wide×100 mm long test piece is punched out of the compact. Using a tensile tester (universal tensile tester 3380, manufactured by Instron), the test piece (a) was subjected to two temperature conditions of 23 ° C. and 40 ° C. with a distance between chucks of 30 mm and a tensile speed of 300 mm / min. A is stretched by 50% in the TD direction, and the tensile load [N/25 mm] after 60 seconds is measured. When the tensile load obtained at each temperature after 60 seconds is applied to the following formula to determine the degree of softening, the degree of softening is 25% to 80%.
Softness [%] = [Tensile load after 60 seconds at 40°C [N/25mm]]/[Tensile load after 60 seconds at 23°C [N/25mm]]

By satisfying the condition (a), it is possible to obtain good irregularity followability in the molded article of the present embodiment. In particular, good followability is obtained in a temperature range where human skin can warm the body, making it easier for the molded body to adhere to the human body.

In addition, the softening degree of the test piece a is preferably 30% to 70% under condition b. By setting the softening degree to the above upper limit or less, more flexibility can be obtained, skin familiarity is good, and fit can be improved.

The molded article of the present embodiment preferably satisfies the following condition c.
(Condition c)
The surface impact strength (in accordance with JIS K7211-2) of the molded product measured at a test temperature of 10° C. is 0.6 J or more.

By satisfying condition (c), the molded article of this embodiment can have high impact resistance even at low temperatures. As a result, it is possible to reduce breakage due to stress and deformation from the outside, and to improve usability at low temperatures. In addition, when the molded article of the present embodiment is applied to clothing, good flexibility and durability can be obtained even when the article is washed under cold water or used in cold climates.

In addition, in condition c, the surface impact strength of the sheet is preferably 0.7 J or more. On the other hand, the upper limit of the surface impact strength of the sheet is not particularly limited, but is preferably 10 J or less, more preferably 8 J or less, from the viewpoint of maintaining a balance with other performances.

The molded article of the present embodiment that satisfies the above conditions a to c can be realized by selecting the material of the composition constituting the molded article, controlling the manufacturing conditions of the molded article, and the like. For example, focusing on the difference in melt flow rate (g/10 min) between the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the styrene elastomer (b) can be selected. , adjusting the ratio of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b). However, the molded article of this embodiment is not limited to such materials and manufacturing methods.

In addition, it is preferable that the molded body of the present embodiment contain air bubbles. The air bubbles are not limited to individual air bubbles, but may be a plurality of continuous air bubbles, or a mixture of air bubbles.

In addition, the density of the molded article of the present embodiment is preferably 0.10 g/cm ³ or more, more preferably 0.20 g/cm ³ or more, still more preferably 0.30 g/cm ³ or more, More preferably, it is 0.40 g/cm ³ or more. On the other hand, the density of the molded article of the present embodiment is preferably 1.0 g/cm ³ or less, more preferably 0.90 g/cm ³ or less, still more preferably 0.85 g/cm ³ or less, More preferably, it is 0.80 g/cm ³ or less.

The molded article of the present embodiment is preferably a sheet, and the thickness of the sheet is preferably 0.1 mm or more and 10 mm or less, more preferably 0.2 mm or more and 8 mm or less, and still more preferably 0.3 mm or more and 5 mm. or less, and more preferably 0.4 mm or more and 3 mm or less.

[Fabric laminate]
Moreover, when the molded article of the present embodiment is a sheet, it may be a fabric laminate in which a fabric is bonded to at least one surface of the sheet. As a result, it is possible to realize a new fabric laminate that can obtain new functions such as stress relaxation and low-temperature tensile elongation properties of the molded article of the present embodiment, while taking advantage of the flexibility and texture of the fabric.

The fabrics are made by thinly processing fibers such as natural fibers, synthetic fibers, and chemical fibers, and include woven fabrics such as fabrics and non-woven fabrics. Specific examples include knitted fabrics having a weft knitting structure such as jersey, milled, smooth and double knit; knitted fabrics having a warp knitting structure such as tricot and raschel; and woven fabrics having a structure such as plain weave, twill weave and satin.

The thickness of the fabric is preferably 0.2 to 1.0 mm, more preferably 0.2 to 0.8 mm, even more preferably 0.2 to 0.6 mm.

The basis weight of the fabric is preferably 50 to 250 g/m ² , more preferably 70 to 180 g/m ² and even more preferably 100 to 150 g/m ² .

Natural fibers such as cotton, linen, wool, and silk; regenerated fibers such as rayon and cupra; semi-synthetic fibers such as acetate and triacetate; synthetic fibers such as nylon, polyester, polyurethane, and acrylic; Mentioned are chemical fiber products consisting of mixed fibers of fibers.

In addition, at least a portion of the fabric laminate of this embodiment may be curved, and the radius of curvature may be in the range of 50 mm to 150 mm. This makes it easier for the fabric laminate of the present embodiment to follow the curved surface. Curved surfaces include rounded portions of the human body, such as the head, chest, elbows, knees, and the like. Clothing worn on curved surfaces includes, for example, hats, hoods, brassieres, undergarments, and supporters.

In addition, the thickness of the fabric laminate of this embodiment is appropriately adjusted in consideration of flexibility, workability, ease of sewing, and the like.

The manufacturing method of the fabric laminate is not particularly limited, but when it is attached to the fabric, it is suitable to attach it at 140 to 190°C and 1.0 to 1.8 MPa. The production efficiency is good when the bonding time is 30 seconds to 10 minutes. As a result, a fabric laminate can be obtained while maintaining the properties of the sheet composition of the present embodiment.

In addition, the molded article according to the present embodiment may have ventilation holes to improve breathability depending on the application. For example, a large number of communicating vent holes can be provided on the front and back sides by processing techniques such as mechanical punching, needle processing, laser perforation, and water jetting.

<Application>
The composition and molded article according to the present embodiment are widely used in any field, for example, mobility goods such as automobile parts, railway parts, aircraft parts, ship parts, bicycle parts; electronic equipment; Audio equipment; camera equipment; precision equipment; game equipment; VR equipment; , Leisure goods such as backpacks; Agricultural goods such as gardening; eyeglasses, etc.), shoe supplies (various insoles, shoe lining materials, various equipment, shoes, shoelaces, etc.), decorative products such as accessories and small portable miscellaneous goods; medical supplies such as medical supplies and healthcare supplies; Educational/toy goods such as books and toys; Packaging-related goods such as packaging goods; Cosmetics-related goods such as face washing and makeup goods; It can be used for safety goods such as child seats; music goods; pet goods; fishing goods and the like.

Among them, clothing and clothing parts are preferable. That is, it is more preferably used for clothes in general, undergarments, undergarments, hats, shoes, and the like, which use fabrics. Also, the garment component is intended to be part of such a garment. For example, the core material of underwear, the insole of shoes, etc. are mentioned. As a result, for example, even when such clothing and clothing members are used in cold regions or when the clothing and clothing members are washed with cold water, good stress relaxation properties and flexibility are obtained, and good Since tensile elongation can be obtained, damage to clothing can be reduced. In addition, when worn by a person, it appropriately follows the movements and body shape of the person, provides a smooth and soft feel, feels good on the skin, and provides a good fit and feeling of use.

In addition, the molded article according to the present embodiment is suitable for use in a low-temperature environment. Examples include use in cold regions and use under cold water such as swimming pools and sea bathing. It is also suitable for use as a member that is attached to rounded parts of the human body. Examples thereof include members that constitute hats, hoods, brassieres, undergarments, supporters, and the like.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted. Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. It should be noted that the present embodiment is not limited to the description of these examples.

<Analysis and measurement of 4-methyl-1-pentene polymer (a)>
(1) Solid Viscoelasticity A 4-methyl-1-pentene polymer (a) was cut into strips of 30 mm long and 10 mm wide to prepare test pieces. Next, the obtained test piece was subjected to a chuck distance of 20 mm, a frequency of 1.59 Hz, a strain amount of 0.1%, a heating rate of 4 ° C./min, and a tensile mode using RSA-III manufactured by TA Instruments. The temperature dependence of dynamic viscoelasticity was measured in a temperature range of -60°C to 110°C. From the obtained graph, the temperature (T _a ) showing the maximum value of loss tangent (tan δ) and the maximum value of tan δ were obtained.

(2) Intrinsic viscosity [η] of 4-methyl-1-pentene polymer (a)
The intrinsic viscosity [η] was measured at 135°C using decalin solvent.

(3) Composition of 4-methyl-1-pentene polymer (a) The content of 4-methyl-1-pentene and α-olefin in the 4-methyl-1-pentene polymer (a) is ¹³ C - quantified by NMR.

(4) Density of 4-methyl-1-pentene polymer (a) According to ASTM D 1505 (water replacement method), using an electronic hydrometer MD-300S from ALFA MIRAGE, each sample measured in water and air. calculated from the weight of

(5) Melt flow rate (MFR) of 4-methyl-1-pentene polymer (a)
It was measured under conditions of 230° C. and a test load of 2.16 kg according to JIS K7210.

<Raw materials for composition and molding>
Raw materials used in Examples, Comparative Examples and Reference Examples are shown below.
[4-methyl-1-pentene polymer (a)]
4-methyl-1-pentene-based polymer (a-1): copolymer of 4-methyl-1-pentene and propylene (content of structural units derived from 4-methyl-1-pentene: 72 mol% , content of structural units derived from propylene: 28 mol%)
Temperature Ta showing maximum value of loss tangent (tan δ): 28°C
Maximum value of loss tangent: 2.6
Glass transition temperature: 28°C
Intrinsic viscosity [η] in decalin at 135°C: 1.5 dL/g
Density: 0.84g/ ^cm3
MFR: 10g/10min

[Styrene-based elastomer (b)]
・ Styrene-based elastomer (b-1): Hydrogenated styrene/isoprene/butadiene block copolymer (vinyl SEEPS) “Hybler 7311F” (manufactured by Kuraray Co., Ltd.) polystyrene block content 12% by mass, MFR 0.5 g/10 min
・ Styrene-based elastomer (b-2): Hydrogenated styrene-butadiene rubber (HSBR) "Dynaron 1320P" (manufactured by JSR) polystyrene block content 10% by mass, MFR 3.5g/10min
・ Styrene-based elastomer (b-3): Hydrogenated styrene/butadiene block copolymer (SEBS) “Kraton G1657” (manufactured by Kraton Polymer Co., Ltd.) polystyrene block content 13% by mass, MFR 9 g/10 min
・Styrene elastomer (b-4) Hydrogenated styrene/butadiene block copolymer (SEBS) “Kraton G1651” (manufactured by Kraton Polymer Co., Ltd.) Polystyrene block content 33% by mass, MFR less than 1 g/10 min ・Styrene elastomer (b- 5): Hydrogenated styrene/butadiene block copolymer (SEBS) “Tuftec H1221” (manufactured by Asahi Kasei Corporation) polystyrene block content 12% by mass, MFR 4.5 g/10 min
Styrene-based elastomer (b-6): Hydrogenated styrene/butadiene block copolymer (SEBS) "SOE1605" (manufactured by Asahi Kasei Corporation) polystyrene block content 67% by mass, MFR 5g/10min
Styrene-based elastomer (b-7): Hydrogenated styrene-butadiene block (SEBS) "SOE1606" (manufactured by Asahi Kasei Corporation) polystyrene block content 51% by mass, MFR 4g/10min

[Saturated hydrocarbon compound (d)]
・ Saturated hydrocarbon compound (d-1): liquid paraffin “No.530-SP” (manufactured by Sanko Chemical Industry Co., Ltd.) (density: 0.86 g/cm ³ , viscosity: 87 (mPa s), pour point: − 15°C)

[Blowing agent]
・Baking soda-based chemical foaming agent masterbatch “Polythrene EE275F” (manufactured by Eiwa Kasei Kogyo Co., Ltd.)

<Preparation of composition and molding>
(1) Production of foam As a molding machine, a single screw extruder (cylinder inner diameter D: 50 mm, full flight screw, L / D when the effective screw length is L: 32 mm), T die (die width: 320 mm , lip opening: 0.2 to 0.3 mm), cooling roll (outer diameter 50 mm, steel with mirror finish hard chrome plating surface treatment, water cooling type), cooling roll, and take-up machine. board.
First, the above raw materials and 1 part by weight of a chemical foaming agent (polystyrene EE275F) are put into an extruder at the ratios shown in Tables 1 and 2. Melting and kneading (raw materials for each component) under the conditions of 10 to 13 rpm, the resin temperature of the cylinder head part is 190 to 204 ° C., and the extrusion rate is 3.5 to 4.4 kg / hour T die (die temperature 190 °C) into sheets.
The extruded sheet is cooled with a cooling roll (water flow temperature inside the roll: 30° C.), taken up using a take-up machine (take-up speed: 0.8 to 0.9 m/min), and a sheet with a width of about 240 to 270 mm. A composition processed into a shape (foam: molded article) was obtained.

(2) Production of non-foamed body As a molding machine, a single screw extruder (cylinder inner diameter D: 50 mm, full flight screw, L / D when the effective screw length is L: 32 mm), T die (die width: 320 mm, lip opening: 0.5 to 1.8 mm), cooling roll (outer diameter 50 mm, steel with mirror finish hard chrome plating surface treatment, water cooling), cooling roll, and take-up machine. Using.
First, the above raw materials are put into an extruder in the proportions shown in Tables 3 and 4, melted and kneaded under the conditions of a temperature of 100 to 230 ° C. and a screw rotation speed of 20 to 36 rpm in each part of the cylinder, and the resin of the cylinder head part At a temperature of 130 to 195° C., a sheet was extruded through a T-die (die temperature: 190° C.) at an extrusion rate of 5 to 8.5 kg/hour.
The extruded sheet is cooled with a cooling roll (water flow temperature inside the roll: 30°C), taken up using a take-up machine (take-up speed: 0.4 to 2.3 m/min), and formed into a sheet with a width of about 300 mm. A processed composition (unfoamed; molded body) was obtained respectively.

The following measurements and evaluations were performed using each of the obtained sheet-like compositions (molded bodies). The results are shown in Tables 1-4.

<Measurement and Evaluation of Composition and Molded Body>
(1) Solid viscoelasticity The resulting sheet-like composition was cut into strips (length 30 mm x width 10 mm) to obtain test pieces. Next, the obtained test piece was subjected to a chuck distance of 20 mm, a frequency of 1.59 Hz, a strain amount of 0.1%, a heating rate of 4 ° C./min, and a tensile mode using RSA-III manufactured by TA Instruments. The temperature dependence of dynamic viscoelasticity was measured in a temperature range of -60°C to 110°C. A value of loss tangent (tan δ) at 30° C. was obtained.

(2) Tensile test Using the obtained sheet composition, a test piece was prepared under the following conditions, and a tensile test was performed to measure the breaking load and breaking elongation.
・ Specimen shape: Strip shape, width 25 mm (common)
・Specimen direction: MD direction (common)
・Distance between chucks: 30 mm (common)
・ Tensile speed: 300 mm / min (common)
・Measurement temperature: 10°C and 23°C each
・ Number of measurement points: Number of measurement points n = 1 at each temperature

(3) Measurement of Shore A hardness Using the obtained sheet-like composition, a test piece was prepared under the following conditions, and a tensile test was performed to measure the Shore A hardness.
・Test standard: JIS K6253
・Test temperature: 23°C
・Thickness of test piece: 7 mm
Apparatus: Shore A hardness tester A plurality of sheets were superimposed and used as a test piece so that the total thickness was 7 mm. Using the test piece, the value (HS0) immediately after the start of contact with the indenter (condition i) of the Shore A hardness tester and the value (HS1) 15 seconds after the start of contact with the indenter were read. Furthermore, the change ΔHS (condition ii) in the Shore A hardness value defined by the following formula was obtained.
ΔHS = (HS0) - (HS1)
Here, it is shown that the larger ΔHS is, the higher the irregularity followability is.

(4) Stress Relaxation Test Using the obtained sheet-like composition, a test piece of 25 mm width×100 mm length was punched to prepare a test piece, and a tensile test was performed to measure the tensile load.
・Test piece: Strip shape, width 25 mm (common)
・Specimen direction: TD direction (common)
・Distance between chucks: 30 mm (common)
・ Tensile speed: 300 mm / min (common)
・Measurement temperature: 23°C and 40°C
・ Number of measurement points: Number of measurement points n = 1 at each temperature
- The tension was stopped when the constant strain amount reached 50%, and the tensile load [N/25 mm] immediately after elongation and the tensile load [N/25 mm] after 60 seconds were measured.

(5) Surface Impact Test Using the obtained sheet-like composition, a high-speed surface impact test was performed to measure maximum impact (J) and puncture (J).
・Test standard: JIS K7211-2
・Test temperature: 10°C
・Number of test points: n=1

(6) Evaluation Using the obtained sheet-like composition, a skilled technician performed the following evaluations.
·Fitness Each sheet was cut into a width of 1.5 cm and a length of 30 cm, wrapped around the wrist so as to fit, and then evaluated according to the following criteria.
(standard)
⊚ (excellent): Absolutely no feeling of tightness was felt even after 1 minute from winding. After that, even if I moved my wrist, I didn't feel a tightening feeling.
◯ (Good): I did not feel any tightness even after 1 minute from wrapping, but after that, I felt that my wrist was caught.
(triangle|delta) (acceptable): After about 1 minute from wrapping, the feeling of close contact increased, and after about 30 minutes, the feeling of tightness was felt. After that, when the wrist is moved, there is a feeling that it is caught. × (impossible): A feeling of tightness was felt considerably immediately after wrapping.

Feeling in Use at Low Temperature Immediately after each sheet was cooled in a refrigerator (3 to 4° C.), both ends of the sheet were held with both hands and evaluated according to the following criteria.
(standard)
⊚ (excellent): The film did not avoid or crack even when pulled with a strong force.
◯ (Good): The film did not avoid or crack even when pulled with a slightly strong force.
(triangle|delta) (acceptable): When it pulls by a rather strong force, it avoided or cracked in some cases.
x (impossible): Avoided or cracked when pulled with a weak force.

<Production of fabric laminate>
Using the following materials, a fabric was placed on one side of the sheet-shaped composition, and the two were bonded together at 190° C. and 1.3 MPa for 5 minutes to obtain a fabric laminate sample. At this time, the sheets were superimposed so that the MD direction of the sheet composition and the vertical direction of the fabric were parallel to each other.
(material)
- Sheet composition: Foam sheet produced in Example 1 - Fabric: Fast Retailing Co., Ltd. "AIRism" (registered trademark), crew neck T (short sleeve), thickness 0.2 mm, basis weight 100 g / m ² , material: polyester 88%, 12% polyurethane

<Measurement and evaluation of fabric laminate>
- Stress relaxation test Using the obtained sample, a tensile test was performed under the following conditions in the same manner as in the above "(4) Stress relaxation test". The tension was stopped when the constant strain amount reached 50% at each measurement temperature, and the tensile load [N/25 mm] immediately after elongation and the tensile load [N/25 mm] after 60 seconds were measured.
The initial load residual rate [%] and the degree of softening [%] at each measurement temperature were calculated using the following formulas. Table 5 shows the results.
Initial load residual rate = {(tensile load after 60 seconds [N/25mm]) ÷ (tensile load immediately after elongation [N/25mm])} × 100 [%]
Softness [%] = [Tensile load after 60 seconds at 40°C [N/25mm]]/[Tensile load after 60 seconds at 23°C [N/25mm]
(conditions)
Test piece size: Width 25 mm (strip shape)
Distance between chucks: 30mm
Tensile strain rate: 1,000%/min Measurement temperature: 23°C, 40°C
Number of measurement points: n = 1

・Evaluation Using the obtained fabric laminate, single layer of fabric, and two layers of fabric, "fitness" and "feeling of use at low temperature" are evaluated in the same manner as in "(6) Evaluation" above. did. Table 5 shows the results.
It should be noted that the two fabrics were piled up so that the directions of the fabrics were in the same direction without adhesion or the like.

Compared to Reference Examples 1 and 2 with only the fabric, the fabric laminate of Example 13 has the same initial load residual rate at 23 ° C. as in Example 2 in which the fabric is not laminated, and the softening degree is It was in the range of 25-80%, and a good fit was also obtained.

This application claims priority based on Japanese Patent Application No. 2021-105799 filed on June 25, 2021, and the entire disclosure thereof is incorporated herein.

Claims

4-methyl-1-pentene polymer (a);
a styrene-based elastomer (b);
including
The 4-methyl-1-pentene-based polymer (a) is a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 10 carbon atoms other than 4-methyl-1-pentene and
The styrene-based elastomer (b) is a hydrogenated block copolymer of a polystyrene block and a diene block, and the content of the polystyrene block relative to the total amount of the styrene-based elastomer (b) is greater than 0.0% by mass. 50% by mass or less,
A composition, wherein the content of the styrene elastomer (b) is 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (a).
The 4-methyl-1-pentene polymer (a) has a loss tangent ( tan δ) has at least one temperature in the range of 10° C. or higher and 100° C. or lower, and the maximum value of the loss tangent is 0.5 or higher and 3.5 or lower. Composition.
The styrene elastomer (b) includes hydrogenated styrene/butadiene rubber (HSBR), hydrogenated styrene/butadiene block copolymer (SEBS), hydrogenated styrene/isoprene block copolymer (SEPS), and hydrogenated styrene/ 3. The composition according to claim 1, which is one or more selected from isoprene-butadiene block copolymers (SEEPS).
The composition according to any one of claims 1 to 3, wherein the content of said polystyrene block relative to the total amount of said styrene-based elastomer (b) is 5% by mass or more and 15% by mass or less.
A saturated hydrocarbon compound (d) having a pour point of -10°C or less is added to 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) to 0. .1 to 20 parts by weight of the composition according to any one of the preceding claims.
The content of the polystyrene block with respect to the total amount of the styrene elastomer (b) is more than 25% by mass and 50% by mass or less,
A saturated hydrocarbon compound (d) having a pour point of -10°C or less is added to 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) to 0. .1 to 20 parts by weight of the composition according to any one of the preceding claims.
The composition has an absolute value of loss tangent (tan δ) at 30° C. obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4° C./min, a frequency of 1.59 Hz, and a strain of 0.1%. 7. A composition according to any one of claims 1 to 6, which is greater than or equal to 0.5.
8. A composition according to any one of claims 1 to 7, which satisfies condition i below.
(Condition i)
Using the composition containing 1 part by mass of a chemical foaming agent with respect to 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the die temperature of the extruder was 190. A foam sheet extruded at ℃ is prepared, and the sheets are overlapped so that the total thickness is 7 mm to obtain a test piece a. The Shore A hardness (JIS K6253) of the test piece a is 10-70.
9. A composition according to any one of claims 1 to 8, which satisfies condition iii below.
(Condition iii)
Using the composition containing 1 part by mass of a chemical foaming agent with respect to 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b), the die temperature of the extruder was 190. A foam sheet extruded at ℃ is prepared, and the sheet is punched into a width of 25 mm and a length of 100 mm to obtain a test piece c. Using a tensile tester (universal tensile tester 3380, manufactured by Instron), the test piece c was subjected to two temperature conditions of 23 ° C. and 40 ° C. with a distance between chucks of 30 mm and a tensile speed of 300 mm / min. Extend c by 50% in the TD direction, and measure the tensile load [N/25 mm] after 60 seconds. When the tensile load obtained at each temperature after 60 seconds is applied to the following formula to determine the degree of softening, the degree of softening is 25% to 80%.
Softness [%] = [Tensile load after 60 seconds at 40°C [N/25mm]]/[Tensile load after 60 seconds at 23°C [N/25mm]
10. A composition according to any one of claims 1 to 9, which satisfies condition iv below.
(Condition iv)
Extrusion at a die temperature of 190° C. using the composition containing 1 part by mass of a chemical foaming agent per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer (a) and the styrene elastomer (b) A molded foam sheet is prepared, and the surface impact strength (in accordance with JIS K7211-2) of the sheet measured at a test temperature of 10° C. is 0.6 J or more.
A molded article obtained by molding the composition according to any one of claims 1 to 10.
The molded article according to claim 11, wherein the molded article contains cells and has a density of 0.10 to 1.0 g/cm 3 .
The molded article according to claim 11 or 12 is a sheet,
A fabric laminate in which a fabric is attached to at least one surface of the sheet.
The fabric laminate according to claim 13, wherein at least a portion of the fabric laminate is curved and has a radius of curvature in the range of 50 mm to 150 mm.
The fabric laminate manufacturing method according to claim 13 or 14, comprising a step of bonding the sheet and the fabric together at 140 to 190°C and 1.0 to 1.8 MPa.
A garment using the fabric laminate according to claim 13 or 14.
Use of the molded article according to claim 11 or 12 in a low temperature environment.