JP2019018497A - Elastic structure and multilayer elastic sheet - Google Patents

Abstract

The present invention provides an elastic structure and an elastic sheet in which an extended structure does not shrink immediately but shrinks over time.
After stretched 150 percent in A tensile rate 200 mm / min, in the range permanent deformation _{(PS 10M)} is 1% to 50% tensile obtained after 10 minutes, obtained after 10 minutes the tensile permanent set _{(PS 10M} ) And the tensile permanent strain (PS _1M ) obtained after 1 minute (PS _1M / PS _10M ) is 1.8 or more, a stretchable structure comprising a resin layer comprising a resin composition. The resin layer may be laminated with paper, a woven fabric or a nonwoven fabric made of natural fibers or synthetic fibers.
[Selection] Figure 1

Description

  The present invention relates to a stretchable structure containing an olefin polymer composition and use thereof.

  There has been a demand for materials having moisture permeability, flexibility and stretchability mainly in medical materials and sanitary materials. In the field of fibers such as films and filaments, a typical material that satisfies these requirements is a polyurethane resin. However, polyurethane-based resins are very expensive and sometimes have a burden on the environment. In addition, due to the high stretchability, there is a problem that the tightening feeling due to the quick return after stretching becomes strong, and the congestion and the like occurs after long time use.

  Various methods for solving such problems are disclosed. For example, Patent Document 1 and Patent Document 2 disclose films made porous by stretching a sheet in which an inorganic filler is blended with a thermoplastic elastomer other than polyurethane. Patent Documents 3 and 4 disclose a stretchable sheet made of a thermoplastic elastomer, a hydrophilic resin, and porous particles.

JP-A-5-50522 JP 2008-88293 A Japanese Patent Laying-Open No. 2015-63633 JP, 2015-86367, A

  In Patent Document 1 and Patent Document 2 described above, a certain degree of moisture permeability is imparted to the thermoplastic elastomer having stretchability and flexibility, but the effect is small, and the moisture permeability, stretchability, and flexibility are respectively reduced. It was not enough to keep it at a high level. Further, in Patent Document 3 and Patent Document 4 described above, although the moisture permeability is improved by the porous particles, there is a problem that it returns quickly due to good stretchability and stress relaxation is low.

  Therefore, there is a need for a stretchable structure made of an olefin resin that solves the above-described problems of the prior art, is rich in stretchability while maintaining a low specific gravity and low water absorption, and has an excellent balance of stress relaxation.

  Therefore, in view of the background of such prior art, the present invention has a feeling of tightening by having elasticity and a restoring force to the original shape and returning slowly after stretching while having high stress relaxation without discomfort even when worn in daily life. Therefore, it is intended to provide a stretchable structure having a small fit and a stretchable structure, and a multilayer stretchable sheet including the stretchable structure.

As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved by the following, and have reached the present invention.
That is, the gist of the present invention is as follows.
[1] Tensile strength obtained after 10 minutes after tensile elongation (PS _10M ) in the range of 1% to 50% after 10% elongation after 150% elongation at 200 mm / min in accordance with JIS K7127 A resin layer (Y) comprising a resin composition, wherein the ratio PS _1M / PS _{10M of the} permanent set (PS _10M ) and the tensile set (PS _1M ) obtained after 1 minute is 1.8 or more, A stretchable structure having a single layer structure or a multilayer structure.
[2] The resin composition includes a resin composition (X) containing 4-methyl-1-pentene / α-olefin copolymer (A) that satisfies the following requirements (a) to (d). The stretchable structure according to [1], which is characterized.
Requirement (a) : The melting point (Tm) of the copolymer (A) measured by a differential scanning calorimeter (DSC) is not observed.
Requirement (b) : The copolymer (A) is derived from a structural unit (i) derived from 4-methyl-1-pentene and an α-olefin (excluding 4-methyl-1-pentene). The total of the structural unit (ii) is 100 mol%, and the structural unit (i) is 50 to 90 mol% and the structural unit (ii) is 10 to 50 mol%.
Requirement (c) : The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.1 to 5.0 dL / g.
Requirement (d) : The density (measured by ASTM D1505) is 830 to 870 kg / m ³ .
[3] The stretchable structure according to [2], wherein the 4-methyl-1-pentene / α-olefin copolymer (A) satisfies the following requirement (e).
Requirement (e ): tan δ peak temperature obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. is 0 ° C. or higher and 40 ° C. or lower. .
[4] The resin composition (X) is a resin composition (X1) comprising a 4-methyl-1-pentene / α-olefin copolymer (A) and a thermoplastic elastomer (B), [2] or The stretchable structure according to [3].
[5] [1] to [4] having a surface layer (Z) made of paper or a woven or non-woven fabric (D) made of natural fiber or synthetic fiber, laminated on the surface of the resin layer (Y). The stretchable structure according to any one of the above.
[6] The stretchable structure according to any one of [1] to [5], which has a multilayer sheet structure.
[7] A multilayer elastic sheet comprising at least one elastic structure according to [6].

  Stretchable structure that has high stress relaxation properties but has wearability and shape retention, and the stretched structure does not shrink immediately, but shrinks over time, and stretch including the stretchable structure Providing sex sheets.

It is drawing which shows the time-dependent change of the tensile set of the sheet | seat obtained in Example 1 and Comparative Example 2 after 150% elongation, after 1 minute, and after 10 minutes.

  Hereinafter, the stretchable structure of the present invention will be described.

  The stretchable structure of the present invention is a single layer structure or a multilayer structure including a resin layer (Y) containing a resin composition having the following characteristics. The stretchable structure having a multilayer structure may be a laminate including a surface layer (Z).

≪Resin layer (Y) ≫
The resin layer (Y) is a layer containing the following resin composition.

The resin composition stretches 150% at a tensile speed of 200 mm / min in accordance with JIS K7127, and after 10 minutes, the tensile permanent strain (PS _10M ) is 1% or more and 50% or less, and 2% or more and 45%. Or less, more preferably 5% or more and 40% or less. In the resin composition, the ratio PS _1M / PS _10M between the tensile permanent strain (PS _10M ) obtained after 10 minutes and the tensile permanent strain (PS _1M ) obtained after 1 minute is 1.8 to 30. Preferably, it is 1.9 or more and 20 or less. The resin composition satisfying such characteristics has the property that the stretched structure does not shrink immediately but shrinks with time, so the stretchable structure of the present invention is applied to, for example, a sheet or a spun yarn. Then, when processed into a wear, tightening due to stretchability is greatly reduced, and thus the problem of poor comfort is also eliminated.

  The resin composition is a resin composition (X) containing 4-methyl-1-pentene / α-olefin copolymer (A), preferably 4-methyl-1-pentene / α-olefin copolymer (A). And a resin composition (X1) composed of a thermoplastic elastomer (B). The resin layer (Y) may be a one-layer structure including these resin compositions (X), or may be a laminated structure including the structure.

  Hereinafter, the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer (B) constituting the resin composition (X) will be described.

<4-Methyl-1-pentene / α-olefin copolymer (A)>
The 4-methyl-1-pentene / α-olefin copolymer (A) (hereinafter also simply referred to as “copolymer (A)”) satisfies all of the following requirements (a) to (d).
Requirement (a) : The melting point (Tm) measured by the differential scanning calorimeter (DSC) of the copolymer (A) is not observed. By satisfying such requirements, it becomes possible to improve the tensile physical properties of the stretchable structure of the present invention and to moderate the temporal change of the tensile set.

Requirement (b) : The copolymer (A) is derived from a structural unit (i) derived from 4-methyl-1-pentene and an α-olefin (excluding 4-methyl-1-pentene). The total of the structural unit (ii) is 100 mol%, and the structural unit (i) is 50 to 90 mol% and the structural unit (ii) is 10 to 50 mol%.

  That is, the lower limit of the proportion of the structural unit (i) is 50 mol%, preferably 60 mol%, more preferably 65 mol%, and further preferably 68 mol%. On the other hand, the upper limit of the proportion of the structural unit (i) is 90 mol%, preferably 87 mol%, more preferably 86 mol%, and particularly preferably 80 mol% or less. . As described above, in the present invention, since the proportion of the structural unit (i) in the copolymer (A) is not less than the lower limit value, the peak value temperature of tan δ is present in the vicinity of room temperature. In addition, the stress relaxation property is excellent, and since the proportion of the structural unit (i) is equal to or less than the upper limit value, moderate flexibility is obtained.

  Moreover, although the upper limit of the ratio of structural unit (ii) is 50 mol%, it is preferable that it is 40 mol%, it is more preferable that it is 35 mol%, and it is further more preferable that it is 32 mol%. On the other hand, the lower limit of the proportion of the structural unit (ii) is 13 mol%, more preferably 14 mol%, and particularly preferably 20 mol%.

  Examples of the α-olefin that leads to the structural unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- A linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. 3 -Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene And branched α-olefins having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms, such as 4-ethyl-1-hexene and 3-ethyl-1-hexene. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and ethylene and propylene are particularly preferable.

  Here, in one embodiment of the present invention, the copolymer (A) usually comprises only the structural unit (i) and the structural unit (ii). However, the copolymer (A) may be a structural unit (i) in addition to the structural unit (i) and the structural unit (ii) as long as it is a small amount (for example, 10 mol% or less) that does not impair the object of the present invention. As iii), a structural unit derived from 4-methyl-1-pentene and another monomer that is not any α-olefin leading to the structural unit (ii) may further be included. Preferable specific examples of such other monomers include 5-vinyl-2-norbornene and 5-ethylidene when the copolymer (A) is a 4-methyl-1-pentene / propylene copolymer. -2-norbornene and the like.

Requirement (c) ;
The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.1 to 5.0 dL / g, preferably 0.5 to 4.0 dL / g, more preferably 0.5 to 3.5 dL / g. It is.

  As described later, when hydrogen is used together during polymerization, the molecular weight can be controlled, and the intrinsic viscosity [η] can be adjusted by freely obtaining from a low molecular weight body to a high molecular weight body. If the intrinsic viscosity [η] is less than 0.1 dL / g or more than 5.0 dL / g, moldability when processing the polymer composition into a sheet or the like may be impaired. is there.

Requirement (d) ;
Density (measured by ASTM D1505) is, 830~870kg / ^{m 3,} preferably not 830~865kg / ^{m 3,} more preferably a 830~855kg / ^{m 3.} The details of the measurement conditions and the like are as described in the column of Examples described later.

  The density can be appropriately changed depending on the comonomer composition ratio of the copolymer (A), and the copolymer (A) having the density within the above range is advantageous in producing a lightweight sheet.

  A particularly preferred form of the 4-methyl-1-pentene / α-olefin copolymer (A) is the following requirement (e) in addition to the requirements (a), (b), (c) and (d): In an especially preferred embodiment, in addition to the requirements (a) to (e), one or more, preferably two or more selected from the requirements (f), (g), (h) and (i) More preferably 3 or more, particularly preferably all of them are satisfied.

Requirement (e) ;
The ratio (molecular weight distribution; Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.0 to 3.5, preferably 1. It is 2-3.0, More preferably, it is the range of 1.5-2.8. The details of the measurement conditions and the like are as described in the column of Examples described later. If the Mw / Mn is more than 3.5, the influence of the low molecular weight, low stereoregular polymer derived from the composition distribution is concerned, and the moldability is deteriorated.

  Here, in the present invention, if a catalyst described later is used, a copolymer (A) satisfying the requirement (c) can be obtained within the range of the intrinsic viscosity [η] indicated by the requirement (b). it can. In addition, the value of said Mw / Mn and the following Mw is a value at the time of measuring by the method employ | adopted in the Example mentioned later.

  Further, the weight average molecular weight (Mw) of the copolymer (A) measured by gel permeation chromatography (GPC) is preferably 500 to 10,000,000, more preferably 1,000 in terms of polystyrene. To 5,000,000, more preferably 1,000 to 2,500,000.

Requirement (f);
The tan δ peak value obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. is preferably 1.0 or more and 5.0 or less. 1.5 or more and 5.0 or less is more preferable, and 2.0 or more and 4.0 or less is more preferable.

Requirement (g) ;
From the viewpoint of further enhancing the room temperature stress absorbability of the stretchable structure of the present invention, dynamic viscoelasticity measurement is performed at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. The tan δ peak temperature of the obtained copolymer (A) is preferably 0 ° C. or higher and 40 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and 20 ° C. or higher and 40 ° C. or lower. More preferably, it is 25 degreeC or more and 40 degrees C or less.

  By setting the tan δ peak temperature of the copolymer (A) to the above temperature range, the value of tan δ at room temperature can be further increased. Further, by having a tan δ peak value at room temperature, it is possible to change the vibration absorbability, the hardness of the material, and the followability according to the speed of tension or deformation.

Requirement (h) ;
From the viewpoint of further improving the flexibility of the stretchable structure according to the present invention, a copolymer (measured in the state of a press sheet having a thickness of 3 mm in accordance with JIS K6253, after 15 seconds from the start of pressing needle contact ( The Shore A hardness of A) is preferably 5 or more and 95 or less, more preferably 10 or more and 95 or less, further preferably 25 or more and 90 or less, and particularly preferably 50 or more and 90 or less. .

  From the viewpoint of further improving the stress relaxation property and shape following property of the stretchable structure of the present invention, the copolymer (A) is measured in the state of a press sheet having a thickness of 3 mm in accordance with JIS K6253. The amount of change ΔHS between the Shore A hardness value immediately after the start of pressing needle contact and the Shore A hardness value 15 seconds after the start of pressing needle contact is preferably 10 or more and 60 or less. More preferably, it is 15 or more and 45 or less.

Note that ΔHS is a value obtained according to the following equation.
ΔHS = (Shore A hardness value immediately after start of pressing needle contact−Shore A hardness value 15 seconds after start of pressing needle contact)

Requirement (i);
From the viewpoint of reducing the width of the composition distribution to reduce the amount of low molecular weight components and making it difficult to cause molding defects due to stickiness caused by the low molecular weight components, the extraction amount of the copolymer (A) with methyl acetate is 0. The mass is preferably from 1.5% by mass to 1.5% by mass, more preferably from 0% by mass to 1.0% by mass, and still more preferably from 0% by mass to 0.8% by mass. More preferably, it is at least 0.7% by mass.

  The amount extracted into methyl acetate is measured, for example, as the amount of change in the mass of copolymer (A) before and after extraction when the components contained in copolymer (A) are extracted into methyl acetate by the Soxhlet extraction method. Can do.

<Method for producing 4-methyl-1-pentene / α-olefin copolymer (A)>
Although the manufacturing method of the copolymer (A) is not particularly limited, the copolymer (A) is, for example, 4-methyl-1-pentene and the above-mentioned “α-olefin leading to the structural unit (ii)”. Can be obtained by polymerizing in the presence of a suitable polymerization catalyst.

  Here, as a polymerization catalyst that can be used in the present invention, a conventionally known catalyst, for example, a magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. 01/27124, Japanese Patent Application Laid-Open No. 3-193796, or In JP-A-02-41303, metallocene catalysts described in International Publication No. 2011/055803, International Publication No. 2014/050817, and the like are preferably used.

<Thermoplastic elastomer (B)>
The resin composition (X) constituting the resin layer (Y) has a copolymer (A) as long as the excellent properties of the 4-methyl-1-pentene / α-olefin copolymer (A) are not impaired. Other thermoplastic elastomers (B) may be added. In the present invention, the case where the resin composition (X) is composed of the copolymer (A) and the thermoplastic elastomer (B) may be particularly referred to as a resin composition (X1).

  When the total amount of the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer (B) is 100 parts by mass, from the viewpoint of flexibility and stress relaxation, The upper limit of the content of the copolymer (A) is usually 100 parts by mass, preferably 90 parts by mass, more preferably 75 parts by mass, particularly preferably 60 parts by mass, and the lower limit is usually 10 parts by mass, Preferably it is 15 mass parts, More preferably, it is 25 mass parts, Most preferably, it is 30 mass parts.

  In other words, the lower limit of the content of the thermoplastic elastomer (B) is usually 0 parts by mass, preferably 10 parts by mass, more preferably 25 parts by mass, particularly preferably 40 parts by mass, and the upper limit is usually 90 parts by mass. Parts, preferably 85 parts by weight, more preferably 75 parts by weight, particularly preferably 70 parts by weight.

  The thermoplastic elastomer (B) referred to in the present invention is a polymer that exhibits a thermoplastic property when heated to a melting point or higher, while exhibiting a rubber elasticity property at room temperature. Specifically, such thermoplastic elastomer (B) is polyolefin elastomer (B-1), polystyrene elastomer (B-2), polyester elastomer (B-3), polyamide elastomer (B-4). Is mentioned.

≪Olefin elastomer (B-1) ≫
As a first aspect of the olefin elastomer (B-1), one selected from the group consisting of polyethylene and polypropylene, and polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, polyisobutylene, and α-olefin are used. And a copolymer with one selected from the group consisting of: The form of copolymerization may be either block copolymerization or graft copolymerization, but only in the case of one selected from the group consisting of polyethylene and polypropylene and a copolymer consisting of α-olefin, the form of copolymerization is random copolymerization. It may be polymerization. The α-olefin is an olefin having a double bond at one end of a molecular chain, and 1-butene, 1-octene, or the like is preferably used.

  For example, a block copolymer of a polyolefin block that forms a polymer with high crystallinity such as polypropylene that becomes a hard part and a monomer copolymer that shows amorphousness that becomes a soft part can be mentioned. Specifically, an olefin ( Crystalline) / ethylene / butylene / olefin block copolymer, polypropylene / polyolefin (amorphous) / polypropylene block copolymer, and the like. As specific examples, trade names: DYNARON (registered trademark) from JSR Corporation, trade names: Toughmer (registered trademark), Notio (registered trademark) from Mitsui Chemicals, Inc., trade names: ENGAGE from Dow Chemical Co., Ltd. (Registered trademark), VERSIFY (registered trademark), and those commercially available from ExxonMobil Chemical Co., Ltd. under the trade name: Vistamaxx (registered trademark).

  As the second aspect of the polyolefin-based elastomer referred to in the present invention, one selected from the group consisting of polyethylene and polypropylene, an ethylene / propylene copolymer, an ethylene / propylene / diene copolymer, an ethylene / butene copolymer, Examples thereof include a blend with one selected from the group consisting of hydrogenated styrene butadiene. At this time, the ethylene / propylene copolymer, the ethylene / propylene / diene copolymer, and the ethylene / butene copolymer may be partially or completely crosslinked.

  Specific examples include Mitsui Chemicals, Inc., trade name: Miralastomer (registered trademark), Sumitomo Chemical Co., Ltd., trade name: Espolex (registered trademark), and Mitsubishi Chemical Corporation, trade names: Thermoran (registered trademark), Zelas ( Registered trademark) and those sold by ExxonMobil Chemical Company under the trade name: Santoprene (registered trademark).

  The olefin elastomer according to the present invention is at least one selected from the group consisting of an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group. The functional group may be modified.

≪Styrene elastomer (B-2) ≫
As the styrene elastomer (B-2), a block copolymer (SBS) of a polystyrene block that becomes a hard part (crystal part) and a diene monomer block that becomes a soft part, hydrogenated styrene / butadiene / styrene block Polymer (HSBR), Styrene / Ethylene / Propylene / Styrene Block Copolymer (SEPS), Styrene / Ethylene / Butene / Styrene Block Copolymer (SEBS), Styrene / Isoprene / Styrene Block Copolymer (SIS), Styrene -An isobutylene styrene copolymer (SIBS), a styrene isobutylene copolymer (SIB), etc. can be illustrated. Styrenic elastomers are used singly or in combination of two or more.

  Specific examples of the hydrogenated styrene / butadiene / styrene block copolymer include those commercially available from JSR Corporation under the trade name: Dynalon (registered trademark). The styrene / ethylene / propylene / styrene block copolymer is obtained by hydrogenating a styrene / isoprene / styrene block copolymer (SIS). Specific examples of SIS include: JSR Corporation as trade name: JSR SIS (registered trademark), Kuraray Co., Ltd. as trade name: Hibler (registered trademark), or Shell Corporation as trade name: Clayton D (registered trademark) The thing marketed etc. are mentioned.

  Specific examples of SEPS include those commercially available from Kuraray Co., Ltd. under the trade name: Septon (registered trademark), or from Shell Co., Ltd. under the trade name: Clayton (registered trademark).

  Specific examples of SEBS include those commercially available from Asahi Kasei Corporation under the trade name: Tuftec (registered trademark), or from Shell Corporation under the trade name: Clayton (registered trademark).

  Moreover, as a specific example of SIB and SIBS, what is marketed by Kaneka Co., Ltd. as a brand name: Shibustar (trademark), etc. are mentioned.

≪Polyester elastomer (B-3) ≫
Examples of the polyester elastomer (B-3) include a block copolymer of an aromatic polyester and an aliphatic polyester, and a block copolymer of an aromatic polyester and an aliphatic polyether. A block copolymer with an aliphatic polyether is preferred.

  The aromatic polyester in the polyester elastomer is preferably a polybutylene terephthalate resin and / or a polyethylene terephthalate resin. Here, the polybutylene terephthalate resin refers to a polyester using terephthalic acid as a dicarboxylic acid component, or a combination of terephthalic acid and isophthalic acid, and 1,4-butanediol as a diol component. Replacing part of this dicarboxylic acid component (less than 50 mol%) with another dicarboxylic acid component or oxycarboxylic acid component, or replacing part of the diol component (less than 50 mol%) with a low molecular diol component other than the butanediol component It may be replaced with polyester. The polyethylene terephthalate resin refers to a polyester using terephthalic acid as a dicarboxylic acid component or a dicarboxylic acid component in which terephthalic acid and isophthalic acid are combined and ethylene glycol as a diol component. Part of the component (less than 50 mol%) was replaced with another dicarboxylic acid component or oxycarboxylic acid component, or part of the diol component (less than 50 mol%) was replaced with a low molecular diol component other than the ethylene glycol component Polyester may be used.

  The aliphatic polyether in the polyester elastomer is preferably a polyalkylene glycol resin, and more preferably a polytetramethylene glycol resin and / or a polyethylene glycol resin. Here, the polyalkylene glycol-based resin refers to an aliphatic polyether having polyalkylene glycol as a main component, but a part of the polyether portion (less than 50% by mass) is dioxygen other than the alkylene glycol component. It may be an aliphatic polyether replaced with a component. The polytetramethylene glycol resin refers to a polyalkylene glycol having polytetramethylene glycol as a main component, and a part (less than 50% by mass) of an aliphatic polyether moiety is converted into a tetramethylene glycol component. Aliphatic polyethers replaced with other dioxy components may be used. Furthermore, the polyethylene glycol-based resin refers to a polyalkylene glycol having polyethylene glycol as a main component, and a part (less than 50% by mass) of the aliphatic polyether portion is formed with a dioxy component other than the ethylene glycol component. It may be a substituted aliphatic polyether. Here, the “main” means a case where 50% by mass or more is occupied when the entire aliphatic polyether portion is 100% by mass.

  Specific examples of polyester elastomers include: Toray DuPont, trade name: Hytrel (registered trademark), Toyobo Co., Ltd., trade name: Perprene (registered trademark), Mitsubishi Chemical Corporation: Trade name: Primalloy (registered trademark) Are commercially available.

≪Polyamide elastomer (B-4) ≫
As polyamide-based elastomer (B-4), in addition to polyamide resins such as aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612), block co-polymerization of polyamide and aliphatic polyester Examples thereof include block copolymers and block copolymers of polyamide and aliphatic polyether.

  Commercially available polyamide-based elastomers are trade names: UBESTA (registered trademark) from Ube Industries, Ltd., trade names: Daiamide (registered trademark), Vestamide E (registered trademark), from Arkema, Inc. Product name: those marketed as Pebax (registered trademark).

<Other polymers>
The resin composition (X) is a conventionally known low density, medium density, high density polyethylene, high pressure, other than the copolymer (A) and the thermoplastic elastomer (B), as long as the effects of the present invention are not impaired. Low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1-butene, cyclic olefin copolymer, chlorinated polyolefin, thermoplastic It may contain a resin typified by polyurethane or the like and an additive described later.

<Additives>
The resin composition (X) may have been subjected to various modifications by adding secondary additives. Specific examples of secondary additives include plasticizers, ultraviolet absorbers, infrared absorbers, fluorescent brighteners, mold release agents, antibacterial agents, nucleating agents, thermal stabilizers, antioxidants, slip agents, antistatic agents Examples include, but are not limited to, agents, anti-coloring agents, regulators, matting agents, antifoaming agents, preservatives, gelling agents, latexes, fillers, inks, coloring agents, dyes, pigments and fragrances. These secondary additives may be used alone or in combination.

  Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

  Antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.) Phosphorus-based (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate etc.), amine-based (N, N-diisopropyl-p-phenylenediamine etc.) antioxidants Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above surfactants, fatty acid esters, and polymer antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. Although the addition amount of these pigments and dyes is not particularly limited, the total amount is usually 5 parts by mass or less, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the copolymer (A).

  Examples of slip agents include waxes (carnauba wax etc.), higher fatty acids (eg stearic acid), training fatty acid salts (eg calcium stearate), higher alcohols (stearyl alcohol etc.), higher fatty acid amides (stearic amide, erucic acid amide etc.) Etc.

  The addition amount of the above-mentioned various additives is not particularly limited depending on the use within the range not impairing the object of the present invention, but with respect to the 4-methyl-1-pentene / α-olefin copolymer (A). And it is preferable that it is 0.01-30 mass parts, respectively.

  The thickness of the resin layer (Y) in the stretchable structure of the present invention is preferably 20 μm to 2000 μm, more preferably 20 μm to 1500 μm, and more preferably 50 μm to 1000 μm in terms of easy handling. More preferably it is.

  The resin layer (Y) constituting the stretchable structure of the present invention may be a single layer or multiple layers. In the case of a multilayer structure, for example, a structure comprising a plurality of resin compositions (X), a structure comprising a layer comprising a resin composition (X) and a layer comprising a thermoplastic elastomer (B), etc. Is mentioned.

  The stretchable structure according to the present invention has a structure in which the resin layer (Y) and a surface layer (Z) made of paper, a woven or non-woven fabric made of natural fiber or synthetic fiber, a film or a sheet are laminated. . A preferred embodiment of such a multilayer structure is a multilayer sheet.

≪Surface layer (Z) ≫
The surface layer (Z) in the stretchable structure having a multilayer structure of the present invention comprises a woven fabric or a non-woven fabric (D) made of paper, natural fibers or synthetic fibers. The woven or non-woven fabric (D) made of paper, natural fiber or synthetic fiber is not particularly limited, and conventionally known ones can be used. Examples of the fiber material include natural fibers such as cotton, hemp, silk, and wool, regenerated fibers such as rayon and cupra, polyester, nylon, acrylic, polyurethane, polypropylene, polyethylene, poly-4-methyl-1-pentene, and polychlorinated. Mention may be made of synthetic fibers such as vinyl. Examples of the woven fabric include woven fabrics and knitted fabrics made from the fibrous material. Examples of the non-woven fabric include webs obtained by intertwining the fibrous material with a chemical method, a mechanical method, or a combination thereof.

  The thickness of the woven or non-woven fabric (D) made of paper, natural fiber or synthetic fiber is preferably 20 μm to 2000 μm, and more preferably 20 μm to 1500 μm in terms of easy handling. More preferably, it is 50 micrometers-1000 micrometers.

  Moreover, it is preferable that the surface layer (Z) in this invention is a layer in which at least one part is contacting the resin layer (Y). Here, “at least a part is in contact with the base material layer” means that the surface layer is in contact with a part of the base material layer, or the surface layer is in contact with the whole base material layer. The contact ratio between the base material layer and the surface layer is preferably 30% to 100% and more preferably 50% to 100% with respect to the total area of the base material layer.

  Moreover, the surface layer (Z) in this invention may be laminated | stacked only on the single side | surface side of a sheet-like resin layer (Y), or may be laminated | stacked on the both surfaces side of a sheet-like resin layer (Y). Good.

  The ratio of the thickness of the base material layer to the surface layer [the thickness of the base material layer / the thickness of the surface layer] in the elastic structure having a multilayer structure of the present invention is not particularly limited, but is 1 to 100/100. / 1-100 are preferable, and 1-50 / 100 / 1-50 are more preferable.

<Method for producing stretchable structure>
There is no limitation in particular in the manufacturing method (molding method) of the resin layer (Y) which comprises the elastic structure of this invention, For example, a conventionally well-known manufacturing method can be used.

  It is possible to produce a composition by uniformly mixing a solution in which each component is dissolved in a solvent, and then removing the solvent. However, practical steps such as dissolving the raw material in the solvent and removing the solvent are unnecessary. It is preferable to employ a melt-kneading method, which is a method for producing a composition by melt-kneading each component. The melt-kneading method is not particularly limited, and a known kneader such as a kneader, a roll mill, a Banbury mixer, a single-screw or twin-screw extruder, and the like are used, for example, at 180 to 250 ° C. After smelting, a method of granulating or pulverizing can be employed. Among them, the use of a twin screw extruder is preferable from the viewpoint of mixing property and productivity. By this method, high-quality resin composition pellets in which each component and additive are uniformly dispersed and mixed can be obtained.

  The stretchable structure according to the present invention can be obtained, for example, by molding with a general T-die extrusion molding machine and a mold printing molding machine. For example, the sheet is formed by molding at a cylinder-cylinder temperature of 170 to 250 ° C. and a cast roll temperature of 0 to 70 ° C. in a single screw extruder.

  Although the thickness of the sheet depends on the intended use, it is usually 5 to 1000 μm, preferably 30 to 200 μm, which is excellent in sheet productivity and does not cause pinholes when forming the sheet and has sufficient strength. Is also preferable.

  Further, the sheet surface may be embossed, or may be stretched during or after the sheet molding. Further, the sheet obtained by molding may be annealed at a temperature lower than the melting point of the resin.

  The sheet-like stretchable structure may be produced by an inflation molding method. Specifically, an inflation film can be obtained by extruding from an inflation die in an upward direction opposite to the direction of gravity with a single cylinder extruder at a predetermined cylinder temperature.

  The take-up speed of the inflation film is usually 2 to 40 m / min, preferably 4 to 30 m / min. Although the thickness of a film is not specifically limited, Usually, 10-300 micrometers, Preferably it is 20-250 micrometers, More preferably, it is 30-60 micrometers.

  The sheet-like stretchable structure may be produced by a mold printing method. Specifically, it refers to a molding method in which a thermoplastic water-absorbing resin melt-extruded and filled in the indented part of the cylinder surface is pressure-transferred and fused to the substrate surface, and the melt-extruded thermoplastic resin is A step of filling the indented portion of the cylinder surface, and a step of pressing and transferring the resin filled in the indented portion of the cylinder onto the surface of the base material and fusing it. The indented portion on the cylinder surface can have various patterns, and the resin is fused in a convex shape on the substrate in the various patterns. Introducing an extrusion molding machine when filling the indented portion of the cylinder surface with the melt-extruded thermoplastic water-absorbing resin is preferable because it can improve the mass production speed.

  The film thickness at the time of mold printing is not particularly limited, and is desirably 30 to 1000 μm, preferably 30 to 800 μm. When a film thickness is less than 30 micrometers, there exists a possibility that the water absorption performance and moisture absorption / release performance of the mold printing molding sheet obtained may fall. Moreover, when a film thickness exceeds 800 micrometers, there exists a possibility that the softness | flexibility of the mold printing molding sheet obtained may deteriorate.

The stretchable structure having a multilayer structure according to the present invention can be obtained by laminating the resin layer (Y) and the surface layer (Z). The method of lamination is not particularly limited, but for example,
(1) Resin layer (Z) A method for producing a laminate comprising a base material layer and a surface layer by coextruding the resin composition (X) for molding, and laminating the surface layer (Z) material at that time (hereinafter, Also called "coextrusion method"),
(2) A method in which the resin layer (Y) and the surface layer (Z) are separately formed in advance, and the formed base material layer (Y) and the surface layer (Z) are thermally fused (hereinafter referred to as “thermal fusion”). Also called “the wearing method”),
(3) A method in which a resin layer (Y) layer is molded in advance and the other layer is laminated on the surface of the molded one layer by extrusion coating (hereinafter also referred to as “extrusion coating method”),
(4) A method in which the resin layer (Y) is formed in advance and the surface layer (Z) is bonded with an adhesive or an adhesive material, and a method in which layers are bonded and stitched with a stitch bond is used. It is done.

<Applications of stretchable structures>
The stretchable structure of the present invention has features such as a high stress relaxation property and stretchability possessed by the resin composition (X), a slow relaxation feature, and a speed dependency in which the elongation at break and strength of the material change depending on the tensile speed. Furthermore, by laminating a woven or non-woven fabric (D) made of paper, natural fiber or synthetic fiber on the surface layer, it is possible to achieve both flexibility and wear, which was difficult with conventional resin compositions alone, Strength and design can be imparted, and it can be developed for various uses.

  The elastic structure of the present invention is a conventionally known application, such as clothing materials, medical materials, sanitary materials, food packaging materials, fishery materials, agricultural and forestry materials, civil engineering and building materials, shoe materials, It can be used for applications such as sports materials, leisure materials, and industrial materials. For example, clothing materials include underwear, socks, shirts, briefs, trunks, shorts, camisole, spats, bras, tights, belly band, innerwear, T-shirts, sweaters, coats, jackets, jumpers, pants, skirts, hats , Outerwear such as gloves, training wear, ski wear, swimwear, leotards, supporters and other sportswear, and medical materials include surgical sheets, medical wear, blood absorbers, chemical absorbers, medical tapes, adhesive bandages, Sanitary materials such as poultice materials, diapers, incontinence pads, sanitary products, maternity pads, breast milk pads, mask straps, eyepatch straps, wound dressings, etc. Agricultural and forestry materials such as insect nets, aquaculture nets, insect nets, wind nets, shading nets, weeds Stopping nets, bird nets, curly nets, flower nets, etc., as civil engineering and construction materials, water retention sheets, anti-condensation sheets, greening sheets, seedling sheets, vegetation nets, sandbag nets, etc. Sports materials such as skins, shoelaces, sports, leisure, golf, baseball, tennis, table tennis, volleyball, badminton, soccer, handball, basketball, hockey, ice hockey, water polo, etc. Industrial materials such as nets include hats, towels, car wash goods, toys and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

  Various physical properties in Examples and Comparative Examples were measured by the following methods.

〔composition〕
The content (mol%) of each structural unit (4-methyl-1-pentene and α-olefin) in the 4-methyl-1-pentene / α-olefin copolymer (A) was measured by ¹³ C-NMR. did.
Measurement device: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
-Observation nucleus: ¹³ C (125 MHz)
・ Sequence: Single pulse proton decoupling ・ Pulse width: 4.7 μsec (45 ° pulse)
・ Repetition time: 5.5 seconds ・ Number of integration: 10,000 times or more ・ Solvent: orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent ・ Sample concentration: 55 mg / 0.6 mL
・ Measurement temperature: 120 ℃
-Standard value of chemical shift: 27.50ppm

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the copolymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device.

After dissolving about 20 mg of the specific 4MP1 copolymer in 25 ml of decalin, the specific viscosity η _sp is measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin is added to the decalin solution for dilution, the specific viscosity η _sp is measured in the same manner as described above. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) of the copolymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC: Gel). It calculated by the standard polystyrene conversion method using Permeation Chromatography).
-Condition-
Measuring device: GPC (ALC / GPC 150-C plus type, suggested refractometer detector integrated type, manufactured by Waters)
Column: 2 GMH6-HT (manufactured by Tosoh Corp.) and 2 GMH6-HTL (manufactured by Tosoh Corp.) connected in series Eluent: o-dichlorobenzene Column temperature: 140 ° C
Flow rate: 1.0 mL / min

[Melt flow rate (MFR)]
The melt flow rate (MFR) of copolymer (A-1) and PP was measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238. The unit is g / 10 min.

〔density〕
The density of the copolymer was measured according to JIS K7112 (density gradient tube method). This density (kg / m ³ ) was used as an indicator of lightness.

[Melting point (Tm)]
The melting point (Tm) of the copolymer was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device. About 5 mg of polymer is sealed in a measuring aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. In order to completely melt the polymer, it is held at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating is performed to 200 ° C. at 10 ° C./min, and the peak temperature (° C.) at the second heating is defined as the melting point (Tm) of the polymer. When a plurality of peaks are detected, the peak detected on the highest temperature side is adopted.

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

[Mechanical properties (elongation at break, tensile strength at break, Young's modulus)
A sheet having a thickness of 400 μm cut into a dumbbell shape having a width of 25 mm and a length of 100 mm was used as a test piece.
In accordance with JIS K7127 (1999), using a tensile tester (universal tensile tester 3380, manufactured by Instron), the tension of the test piece was measured under the conditions of a distance between chucks of 50 mm, a tensile speed of 200 mm / min, and a temperature of 23 ° C. Elastic modulus (YM) (unit: MPa), tensile breaking elongation (EL) (unit:%), and tensile breaking strength (TS) (unit: MPa) were measured.

[Tensile stress relaxation rate (%)]
Using a constant speed extension type tensile tester (Autograph AG-500C manufactured by Shimadzu Corporation), a sheet or filament cut to 10 mm width was stretched 100 and 300% at a gripping interval of 100 mm and a speed of 100 mm / min. . The stress at that time (initial stress) was measured, the filament was held as it was for 120 seconds, and the change in stress during that time was also measured. Then, the stress relaxation rate was calculated from the difference between the initial stress and the stress 60 seconds after elongation.
SR = (F ₀ −F) / F ₀ × 100
SR: Tensile stress relaxation rate (%)
F ₀ : initial stress at 100% and 300% elongation (MPa)
F: Stress (MPa) after 120 seconds after 100% and 300% elongation

[Tensile set / stretch ratio]
A sheet having a thickness of 400 μm cut into a JIS K7127 No. 5 dumbbell was used as a test piece.
In accordance with JIS K7127 (1999), using a tensile tester (universal tensile tester 3380, manufactured by Instron), the sheet is stretched 150% under conditions of a distance between chucks of 80 mm, a tensile speed of 200 mm / min, and a temperature of 23 ° C. Held for 10 minutes. The held chuck was released, the sheet was removed from the testing machine, the distance between the chucks 1 minute and 10 minutes after the release was measured, and the tensile permanent strain was calculated from the following formula.
PS = (I−I ₀ ) / I ₀ × 100
PS: Tensile set (%)
I: Distance between chucks after 1 minute or 10 minutes (mm)
I ₀ : Distance between chucks before test (mm)

Further, the ratio (PS _1M / PS _10M ) of the tensile permanent strain (PS _10M ) 10 minutes after opening obtained above and the tensile permanent strain (PS _1M ) after 1 minute was determined as the expansion / contraction ratio.

(Measurement of pressure stress relaxation of stretch laminate)
The produced stretchable sheet was rolled into a cylindrical shape and the ends were fixed with an adhesive tape to produce a cylindrical laminate (effective length 13 cm). The laminate was attached to the arm portion (25 cm around the arm) of the humanoid mannequin, and a pressure sensor (air pack method) was installed on the attachment portion. Then, using a pressure tester (AM TECHNO Co., Ltd., model number AMI3037-10), the stress (initial stress) applied after a certain amount of air was put into the pressure sensor was measured and held for 30 seconds. The change in stress was also measured. Then, the difference between the initial stress and the stress 300 seconds after elongation was calculated as the relaxation rate.
SR = (F ₀ −F) / F ₀ × 100
SR: Tensile stress relaxation rate (%)
F ₀ : Initial stress (MPa)
F: Stress after 300 seconds (MPa)

<Synthesis Example 1>
<Synthesis of 4-methyl-1-pentene / α-olefin copolymer (A-1)>
Into a SUS autoclave with a stirring blade with a capacity of 1.5 L that has been sufficiently purged with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were added. Charged at 23 ° C. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa.

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

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

  Subsequently, the polymerization reaction product containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours to obtain 36.9 g of a powdery copolymer A-1. Table 1 shows the measurement results of various physical properties of the obtained copolymer A-1.

The content of 4-methyl-1-pentene in the copolymer A-1 was 72.5 mol%, and the content of propylene was 27.5 mol%. Moreover, the density of the copolymer A-1 was 839 kg / m ³ . Copolymer A-1 has an intrinsic viscosity [η] of 1.5 dl / g, a weight average molecular weight (Mw) of 337,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow. The rate (MFR) was 11 g / 10 min. The melting point (Tm) of copolymer A-1 was not observed.

<Synthesis of 4-methyl-1-pentene / α-olefin copolymer (A-2)>
Into a SUS autoclave with a stirring blade with a capacity of 1.5 L that has been sufficiently purged with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were added. After charging at 23 ° C., 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged and the stirrer was turned.

  Next, the autoclave was heated until the internal temperature reached 60 ° C., and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa.

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

  Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent. Subsequently, the polymerization reaction product containing the obtained solvent was dried at 130 ° C. under reduced pressure for 12 hours to obtain 44.0 g of a powdery 4-methyl-1-pentene copolymer (A-2). .

The content of 4-methyl-1-pentene in the copolymer A-2 was 84.1 mol%, and the content of propylene was 25.9 mol%. Further, the density of the copolymer A-2 was 838 kg / m ³ . Copolymer A-2 has an intrinsic viscosity [η] of 1.5 dl / g, a weight average molecular weight (Mw) of 340,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow. The rate (MFR) was 11 g / 10 min. The melting point (Tm) of the copolymer A-2 was 132 ° C.

<Example 1>
A 20 mmφ single screw extruder (single screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) using a 4-methyl-1-pentene / α-olefin copolymer A-1 and a T-die having a lip width of 240 mm. Was put into the hopper. Then, the sheet of Example 1 was obtained by setting the cylinder temperature to 230 ° C. and the die temperature to 230 ° C., extruding the melt-kneaded material from the T die with a thickness of 400 μm, and molding the cast sheet. Table 2 shows the physical property evaluation results of the obtained sheet.

<Example 2>
80 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and olefin-based thermoplastic elastomer (B-1) (trade name: TAFMER (registered trademark) PN manufactured by Mitsui Chemicals, Inc. A sheet of Example 2 was obtained in the same manner as in Example 1 except that 20 parts by mass of -2060) was used. Table 2 shows the physical property evaluation results of the obtained sheet. In addition, a laminated structure in which the sheet of Example 1 is used as the resin layer (Y), the polyester woven fabric as the surface layer (Z), and heat-sealed at 0.2 MPa and 150 ° C. for 30 seconds using a hot press apparatus is used. Then, stress relaxation measurement was performed by a pressure test. The results are shown in Table 2.

<Example 3>
60 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and olefin-based thermoplastic elastomer (B-1) (trade name: TAFMER (registered trademark) PN manufactured by Mitsui Chemicals, Inc. A sheet of Example 3 was obtained in the same manner as in Example 1 except that 40 parts by mass of -2060) was used. Table 2 shows the physical property evaluation results of the obtained sheet.

<Example 4>
40 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and olefinic thermoplastic elastomer (B-1) (trade name: TAFMER (registered trademark) PN manufactured by Mitsui Chemicals, Inc.) A sheet of Example 4 was obtained in the same manner as in Example 1 except that 60 parts by mass of −2060) was used. Table 2 shows the physical property evaluation results of the obtained sheet.

<Example 5>
70 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and styrenic thermoplastic elastomer (B-2) (trade name: Tuftec (registered trademark) H manufactured by Asahi Kasei Chemicals Corporation) A sheet of Example 5 was obtained in the same manner as in Example 1 except that 30 parts by mass of -1221) was used. Table 2 shows the physical property evaluation results of the obtained sheet.

<Example 6>
70 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1) and olefin-based thermoplastic elastomer (B-3) (trade name: Miralastomer (registered trademark) 5030NS, manufactured by Mitsui Chemicals, Inc. ) Was used in the same manner as in Example 1 except that 30 parts by mass of) was used. Table 2 shows the physical property evaluation results of the obtained sheet.

<Comparative Example 1>
A sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that 100 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-2) was used. Table 2 shows the physical property evaluation results of the obtained sheet.

<Comparative example 2>
A sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that styrene thermoplastic elastomer (B-2) (Asahi Kasei Chemicals Corporation, trade name: Tuftec (registered trademark) H1221) was used. Table 2 shows the physical property evaluation results of the obtained sheet. Also, using a laminated structure in which the sheet of Comparative Example 2 was used as the resin layer (Y), the polyester woven fabric as the surface layer (Z), and heat-sealed at 0.2 MPa at 150 ° C. for 30 seconds. Then, stress relaxation measurement was performed by a pressure test. The results are shown in Table 2.

FIG. 1 shows a plot of the change over time of the tensile permanent strain at the time of pressing in Example 1 and Comparative Example 2. It can be seen that Example 1 shows a low stress after 300 seconds. On the other hand, it can be read that Comparative Example 2 has not changed significantly. A stretch structure including a stretch structure having a PS _1M / PS _10M value of 1.8 or more returns slowly after stretching. For example, when applied to an application such as wear, the feeling of tightening is reduced and the comfort is reduced. Is expected to improve.

Claims (7)

Tensile permanent strain (PS _10M ) obtained after 10 minutes after stretching 150% at a tensile speed of 200 mm / min according to JIS K7127 is in the range of 1% to 50%.
A resin composition characterized in that a ratio PS _1M / PS _{10M of a} tensile permanent strain (PS _10M ) obtained after 10 minutes and a tensile permanent strain (PS _1M ) obtained after 1 minute is 1.8 or more is included. Resin layer (Y),
A stretchable structure having a single layer structure or a multilayer structure. The resin composition includes a resin composition (X) containing 4-methyl-1-pentene / α-olefin copolymer (A) that satisfies the following requirements (a) to (d): The stretchable structure according to claim 1.
Requirement (a) : The melting point (Tm) of the copolymer (A) measured by a differential scanning calorimeter (DSC) is not observed.
Requirement (b) : The copolymer (A) is derived from a structural unit (i) derived from 4-methyl-1-pentene and an α-olefin (excluding 4-methyl-1-pentene). The total of the structural unit (ii) is 100 mol%, and the structural unit (i) is 50 to 90 mol% and the structural unit (ii) is 10 to 50 mol%.
Requirement (c) : The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.1 to 5.0 dL / g.
Requirement (d) : The density (measured by ASTM D1505) is 830 to 870 kg / m ³ . The stretchable structure according to claim 2, wherein the 4-methyl-1-pentene / α-olefin copolymer (A) satisfies the following requirement (e).
Requirement (e ): tan δ peak temperature obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. is 0 ° C. or higher and 40 ° C. or lower. .   The resin composition (X) is a resin composition (X1) composed of a 4-methyl-1-pentene / α-olefin copolymer (A) and a thermoplastic elastomer (B). Elastic structure. Laminated on the surface of the resin layer (Y), has a surface layer (Z) made of paper, or a woven or non-woven fabric (D) made of natural fiber or synthetic fiber,
The stretchable structure according to any one of claims 1 to 4.   It has a multilayer sheet structure, The elastic structure of any one of Claims 1-5 characterized by the above-mentioned.   A multilayer stretchable sheet comprising at least one layer of the stretchable structure according to claim 6.

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