TW202248308A - Sheet or film and laminate - Google Patents

Abstract

A sheet or film of the present invention comprises a composition including: a polymer (A) comprising one or more polymers selected from the group consisting of a 4-methyl-1-pentene polymer (A1) and a styrene elastomer (A2); and a silylated polyolefin (B).

Description

sheet or film

The present invention relates to a sheet or film.

Sheets or films formed from polymers are generally prone to blocking (blocking) (a phenomenon in which solid surfaces adhere to each other and the mutual materials become continuous), for example, in rolls of sheets (rolling sheets into rolls or), the sheet cannot be unwound from the coil. In addition, when the sheets are overlapped and cut, etc., the sheets are stuck together due to pressure bonding during cutting, and the sheets are stuck to each other and cannot be peeled off. Therefore, it has been a problem and various countermeasures have been taken. As a method of suppressing such blocking, there is, for example, a method of mixing an antiblocking agent (anti-blocking agent) with an olefin-based copolymer (Patent Document 1, Patent Document 2).

As such a method, Patent Document 1 discloses a polyolefin-based resin composition for sheets in which silica and zeolite are added to an olefin-based copolymer. Patent Document 2 discloses a polyethylene-based resin composition, a sheet using the polyethylene-based resin composition, and a film using the polyethylene-based resin composition. An alkylene disaturated higher fatty acid amide is added to the olefinic interpolymer. [Prior art literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 04-220443 Patent Document 2: Japanese Patent Laid-Open No. 08-269268

[Problem to be Solved by the Invention] As a result of research conducted by the present inventors, it has been found that even the method of adding the anti-blocking agent does not have a sufficient inhibitory effect on the blocking of the sheet or film.

This embodiment is made in view of the above circumstances, and provides the sheet|seat or film in which blocking was suppressed. [Means to solve the problem]

The inventors of the present invention have diligently studied to solve the above-mentioned problems. As a result, they have found that a sheet or film in which blocking is suppressed can be obtained by blending a silylated polyolefin to a predetermined polymer, and completed the present embodiment.

That is, according to this embodiment, the sheet or film shown below is provided.

（於所述通式（1）中，A ¹、A ²及A ³各自獨立地為聚烯烴鏈或碳數1～20的烴基。R為碳數1～20的烴基。各R可相同亦可不同。m為1～10,000的整數。在存在多個A ³的情況下，各A ³可相同亦可不同。其中，A ¹、A ²、A ³中至少一個表示聚烯烴鏈。） [7] 如[1]至[6]中任一項所述的片或膜，其中，聚合體（A）包含4-甲基-1-戊烯系聚合體（A1）、以及苯乙烯系彈性體（A2）。 [8] 如[1]至[7]中任一項所述的片或膜，其中，以相對於所述聚合體（A）100質量份為0.5質量份～10質量份的比例包含所述矽烷基化聚烯烴（B）。 [9] 一種積層體，積層有： 如[1]至[8]中任一項所述的片或膜（L1）；以及 片或膜（L2），包含含有熱塑性彈性體的層。 [10] 如[9]所述的積層體，其中，所述片或膜（L1）包含 來源於4-甲基-1-戊烯的結構單元（a1）與來源於所述4-甲基-1-戊烯以外的碳數2～20的α-烯烴的結構單元（a2）合計為100莫耳%的共聚體， 所述共聚體包含60莫耳%～99莫耳%的結構單元（a1）、及1莫耳%～40莫耳%的結構單元（a2）。 [11] 如[9]或[10]所述的積層體，其中，所述片或膜（L1）與所述片或膜（L2）合計積層有三層以上， 至少一側的外層為片或膜（L1）。 [12] 如[9]至[11]中任一項所述的積層體，其中，所述片或膜（L1）僅含有4-甲基-1-戊烯系聚合體（A1）作為所述聚合體（A）， 所述片或膜（L2）含有苯乙烯系彈性體作為所述熱塑性彈性體。 [13] 如[9]至[12]中任一項所述的積層體，其中，對位於最外層的所述片或膜（L1）的動態黏彈性的溫度依存性進行測定而得的損耗角正切tanδ的最大值於0℃～50℃溫度範圍中為0.6以上。 [發明的效果] [1] A sheet or film comprising a composition comprising: a polymer (A) selected from the group consisting of 4-methyl-1-pentene-based polymer (A1), styrene-based elastomer (A2 ) of one or more polymers from the group consisting of ; and the silylated polyolefin (B). [2] The sheet or film according to [1], wherein the maximum value of the loss tangent tanδ obtained by measuring the temperature dependence of the dynamic viscoelasticity of the sheet or film is within the temperature range of 0°C to 50°C Medium is 0.6 or more. [3] The sheet or film according to [1] or [2], wherein the 4-methyl-1-pentene-based polymer (A1) is derived from 4-methyl-1-pentene The structural unit (a1) of the above-mentioned 4-methyl-1-pentene and the structural unit (a2) derived from an α-olefin with 2 to 20 carbons other than the above-mentioned 4-methyl-1-pentene constitute a total of 100 mole %, and include 60 mole % ˜99 mol% of the structural unit (a1), and 1 mol% to 40 mol% of the structural unit (a2). [4] The sheet or film according to any one of [1] to [3], wherein the styrene-based elastomer (A2) contains a hydrogenated styrene-based elastomer, and in the hydrogenated styrene-based elastomer In 100 mass % of the body, the ratio of the monomer unit derived from styrene is 5 mass % - 80 mass %. [5] The sheet or film according to [1] or [2], wherein the polymer (A) comprises a structural unit (a1) derived from 4-methyl-1-pentene and An interpolymer with a total of 100 mol% of structural units (a2) of α-olefins with 2 to 20 carbon atoms other than 4-methyl-1-pentene, the interpolymer containing 60 mol% to 99 mol% The structural unit (a1) of , and the structural unit (a2) of 1 mol% to 40 mol%. [6] The sheet or film according to any one of [1] to [5], wherein the silylated polyolefin (B) includes a silylated polyolefin represented by the following general formula (1) . [chemical 1]

(In the general formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group with 1 to 20 carbons. R is a hydrocarbon group with 1 to 20 carbons. Each R may be the same or may be different. m is an integer from ¹ to 10,000. ^In the case of multiple ^A3s , each A3 may be the same or different. Among them, at least ^{one of} A1, A2, and A3 represents a polyolefin chain.) [ 7] The sheet or film according to any one of [1] to [6], wherein the polymer (A) includes a 4-methyl-1-pentene polymer (A1), and a styrene-based elastic body (A2). [8] The sheet or film according to any one of [1] to [7], wherein the polymer (A) is contained in a ratio of 0.5 parts by mass to 10 parts by mass relative to 100 parts by mass of the polymer (A). Silylated polyolefin (B). [9] A laminate comprising: the sheet or film (L1) according to any one of [1] to [8]; and the sheet or film (L2) including a layer containing a thermoplastic elastomer. [10] The laminate according to [9], wherein the sheet or film (L1) comprises a structural unit (a1) derived from 4-methyl-1-pentene and - An interpolymer in which the structural units (a2) of α-olefins with 2 to 20 carbon atoms other than 1-pentene account for a total of 100 mol%, and the interpolymer contains 60 mol% to 99 mol% of structural units ( a1), and 1 mol% to 40 mol% of the structural unit (a2). [11] The laminate according to [9] or [10], wherein the sheet or film (L1) and the sheet or film (L2) are laminated in a total of three or more layers, and at least one outer layer is a sheet or Membrane (L1). [12] The laminate according to any one of [9] to [11], wherein the sheet or film (L1) contains only the 4-methyl-1-pentene polymer (A1) as the The polymer (A), the sheet or film (L2) contains a styrene-based elastomer as the thermoplastic elastomer. [13] The laminate according to any one of [9] to [12], wherein the loss obtained by measuring the temperature dependence of the dynamic viscoelasticity of the outermost sheet or film (L1) is The maximum value of the angle tangent tanδ is 0.6 or more in the temperature range of 0°C to 50°C. [Effect of the invention]

According to this embodiment, it is possible to provide a sheet or film in which blocking is suppressed.

Hereinafter, although the sheet|seat or film of this embodiment is demonstrated in detail, it is not limited to the following embodiment at all, It can change suitably within the objective range of this embodiment, and can implement. In the present embodiment, the numerical range represented by "~" refers to a range in which the numerical values described before and after "~" are the lower limit and the upper limit. For example, "1 mass part to 10 mass parts" means " More than 1 part by mass and less than 10 parts by mass". In the numerical ranges described step by step in this embodiment, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps, that is, Any combination of upper limit and lower limit can be used. In addition, the upper limit or lower limit of the numerical range described in this embodiment can also be replaced with the value shown in an Example.

＜sheet or film＞ The sheet or film of this embodiment (hereinafter sometimes simply referred to as a sheet) includes a composition containing: a polymer (A), including a polymer (A) selected from the group consisting of 4-methyl-1-pentene polymers ( One or more polymers in the group consisting of A1), styrene-based elastomer (A2); and silylated polyolefin (B).

Generally speaking, silica, zeolite, etc. used as an anti-blocking agent have low affinity with olefin-based polymers, so the anti-blocking agent on the surface of the resin composition may dissipate from the resin composition over time. Detached, or buried inside the sheet when surface pressure is applied. Therefore, in addition to easily expressing blocking with the lapse of time, the transparency of the sheet also tends to decrease due to the addition of the polymer (A). In addition, although higher fatty acids ooze out to the surface, they tend to be lost from the surface of the sheet over time, and the anti-blocking effect tends to decrease over time. Therefore, in order to continuously exhibit this effect, it is sometimes required to increase the amount of the anti-blocking agent added. However, when the added amount is increased, there is a problem of deteriorating the characteristics and physical properties of other polymers. In addition, when the amount of higher fatty acid added is large, the sheet tends to become sticky, which may impair the surface quality. On the other hand, the silylated polyolefin (B) used in this embodiment has a high affinity with the polymer (A), and has a large effect of suppressing the expression of sticking, so by adding an appropriate amount, sticking can be suppressed for a long time. even performance.

The present inventors speculate that the surface free energy of the olefin-based resin composition containing the polymer (A) and the silylated polyolefin (B) is high due to the high concentration of silicon on the surface, and thus the performance of adhesion can be suppressed. The highly polar silyl group has low affinity with the polymer (A), so it is arranged on the surface of the sheet or film facing outward, and the olefin moiety of the silylated polyolefin (B) has a high affinity with the polymer (A) , so the olefin moiety interacts with the polymer (A). The inventors of the present invention speculate that, thereby, the silylated polyolefin (B) is less likely to fall off from the surface of the sheet or film, and as a result, the expression of blocking of the sheet or film containing the polymer (A) can be suppressed. In addition, the inventors of the present invention speculate that the silylated polyolefin (B) tends to exist uniformly on the surface of the sheet or film compared to conventional anti-blocking agents, so that blocking can be suppressed on the entire surface of the sheet or film. Performance.

In the sheet or film of the present embodiment, from the viewpoint of further suppressing the expression of blocking, the amount of the silylated polyolefin (B) is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the polymer (A). Preferably, it is 1 mass part or more, More preferably, it is 1.5 mass parts or more. In addition, from the viewpoint of maintaining moldability, compatibility with other polymers, strength, and transparency, it is preferably at most 10 parts by mass, more preferably at most 7 parts by mass, and still more preferably at most 5 parts by mass. That is, in the present embodiment, the silylated polyolefin (B) can be set at preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, relative to 100 parts by mass of the polymer (A). parts by mass, more preferably 1.5 parts by mass to 5 parts by mass. By making the addition amount of the silylated polyolefin into the said range, tensile strength at break, tensile elongation at break, and transparency can be made favorable.

In the sheet or film of this embodiment, regarding the total content of the polymer (A) and silylated polyolefin (B), from the viewpoint of the effect of this embodiment, when the entire sheet is taken as 100% by mass , it is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass. The upper limit is not particularly limited, but is 100% by mass or less.

The thickness of the sheet or film of this embodiment is preferably 0.01 mm to 5 mm, more preferably 0.03 mm to 2 mm, further preferably 0.05 mm to 1.5 mm, particularly preferably 0.1 mm to 1.0 mm, and most preferably 0.1 mm. mm～0.8mm. A sheet|seat or film strength can be made favorable that thickness is more than the said lower limit. Moreover, it becomes easy to maintain the flexibility of a sheet|seat or a film as it is below the said upper limit. That is, by setting the thickness of the sheet or film within the above-mentioned range, the strength and flexibility of the sheet or film are excellent in balance. In the present invention, a film refers to a film with a thickness of 0.01 mm to less than 0.25 mm, and a sheet refers to a film with a thickness of 0.25 mm to 5 mm. Both are solid and can be stacked in a single sheet or rolled by a roll. Distributed separately in the state taken.

Hereinafter, each component constituting the sheet or film of this embodiment will be described.

＜Polymer (A)＞ The polymer (A) of this embodiment is one or more polymers selected from the group consisting of 4-methyl-1-pentene polymer (A1) and styrene elastomer (A2). From the viewpoint of the effects of the present invention, it is more preferable to use the polymer (A1) and the elastomer (A2) in combination.

＜4-methyl-1-pentene polymer (A1)＞ The 4-methyl-1-pentene polymer (A1) of this embodiment contains a structural unit (a1) derived from 4-methyl-1-pentene (hereinafter referred to as "4MP1 unit (a1)") Case.).

In the 4-methyl-1-pentene polymer (A1), if the 4MP1 unit (a1) is 60 mol% or more, the addition of the silylated polyolefin (B) will effectively inhibit the blocking performance sheet or film. In addition, when the 4MP1 unit (a1) of the interpolymer contained in the 4-methyl-1-pentene polymer (A1) is 99 mol% or less, a sheet or film having good mechanical properties such as elongation can be obtained . That is, in the 4-methyl-1-pentene polymer (A1), the 4MP1 unit (a1) can be set to preferably 60 mol % to 99 mol %, more preferably 65 mol % to 98 mol %. mol %, and more preferably 65 mol % to 97 mol %. By including the 4MP1 unit (a1) within the above numerical range, it is possible to obtain a sheet or film that effectively suppresses blocking and has good mechanical properties such as elongation, in other words, a sheet or film with an excellent balance of these effects.

The 4-methyl-1-pentene polymer (A1) further includes a structural unit (a2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene (hereinafter referred to as In the case of "AO unit (a2)".). The 4-methyl-1-pentene polymer (A1) may contain preferably 1 mol % to 40 mol %, more preferably 2 mol % to 35 mol %, and more preferably 3 mol % % to 35 mol% of the structural unit (a2). If the AO unit (a2) of the 4-methyl-1-pentene-based polymer (A1) is within the above range, the addition of silylated polyolefin (B) can effectively suppress the occurrence of blocking .

In this embodiment, in the 4-methyl-1-pentene polymer (A1), preferably the total of 4MP1 units (a1) and AO units (a2) is 100 mole%, and may contain preferably 60 mol% to 99 mol%, more preferably 65 mol% to 98 mol%, further preferably 65 mol% to 97 mol% of 4MP1 unit (a1), may contain preferably 1 mol mol% to 40 mol%, more preferably 2 mol% to 35 mol%, still more preferably 3 mol% to 35 mol% of the AO unit (a2). Thereby, the mechanical physical properties, such as elongation rate, of the sheet|seat or film of this embodiment are more excellent.

The α-olefins with a carbon number of 2 to 20 include, for example, linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functionalized vinyl compounds, etc. . Examples of linear or branched α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other linear α-olefins with carbon numbers of 2 to 20 (preferably 2 to 10); 3-form Base-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-Dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. are preferably C5-20 (more preferably 5-10) Branched α-olefins, etc.

Examples of cyclic olefins include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinyl norbornene, vinylcyclohexane, etc. A compound having 4 to 20 carbon atoms (preferably 5 to 15 carbon atoms).

Examples of aromatic vinyl compounds include: styrene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, p-dimethylbenzene Mono- or poly-alkylstyrenes such as ethylene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc.

Examples of conjugated dienes include: 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methano C4-20 (preferably 4-10) compounds such as 1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene.

Examples of non-conjugated polyenes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, and 1,5-octadiene , 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1, 6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (4,8-dimethyl-1 ,4,8-decatriene, DMDT), dicyclopentadiene, cyclohexadiene, dicycloctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2- Norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3 -Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. 20 (preferably 5-10) compounds.

Examples of functionalized vinyl compounds include: hydroxyl-containing olefins; halogenated olefins; acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7- Unsaturated carboxylic acids such as octenoic acid, 8-nonenoic acid, and 9-decenoic acid; unsaturated amines such as allylamine, 5-hexenylamine, and 6-heptenylamine; (2,7-octanedi Alkenyl) succinic anhydride, pentapropenyl succinic anhydride, unsaturated anhydrides such as anhydrides of the unsaturated carboxylic acids; halides of the unsaturated carboxylic acids; 4-epoxy-1-butene, 5-ring Oxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonan Unsaturated epoxy compounds such as ene, 10-epoxy-1-decene, 11-epoxy-1-undecene, etc.

The hydroxyl-containing olefin is not particularly limited as long as it is an olefin-based compound having a hydroxyl group, but is preferably a terminal hydroxylated olefin compound. Examples of terminal hydroxylated olefin compounds include vinyl alcohol, allyl alcohol, hydroxylated 1-butene, hydroxylated 1-pentene, hydroxylated 1-hexene, and hydroxylated 1-octene. Hydroxylated-1-decene, Hydroxylated-1-Dodecene, Hydroxylated-1-Tetradecene, Hydroxylated-1-Hexadecene, Hydroxylated-1-Octadecene, Hydroxylated-1 - Linear hydroxylated α-olefins with 4 to 20 (preferably 2 to 10) carbon atoms such as eicosene; hydroxylated -3-methyl-1-butene, hydroxylated -4-methyl- 1-pentene, hydroxylated-3-methyl-1-pentene, hydroxylated-3-ethyl-1-pentene, hydroxylated-4,4-dimethyl-1-pentene, hydroxylated- 4-methyl-1-hexene, hydroxylated-4,4-dimethyl-1-hexene, hydroxylated-4-ethyl-1-hexene, hydroxylated-3-ethyl-1-hexene The alkenes and the like are preferably branched hydroxylated α-olefins having 5 to 20 carbon atoms (more preferably 5 to 10 carbon atoms). Examples of halogenated olefins include: halogenated 1-butene, halogenated 1-pentene, halogenated 1-hexene, halogenated 1-octene, halogenated 1-decene, halogenated 1-dodecene , halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1-eicosene and other straight chains with 4 to 20 carbon atoms (preferably 4 to 10) Halogenated α-olefins; halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1 -pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4- Branched halogenated α-olefins having 5 to 20 (preferably 5 to 10) carbon atoms, such as ethyl-1-hexene and halogenated 3-ethyl-1-hexene, and the like.

The 4-methyl-1-pentene polymer (A1) may contain only one kind of AO unit (a2), or may contain two or more kinds thereof.

The α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is preferably selected from the group consisting of: Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hexadecene, and 1-octadecene At least one selected from the group consisting of ethylene, more preferably at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, and 1-octene, and more preferably selected from At least one selected from the group consisting of ethylene, propylene and 1-butene, particularly preferably ethylene and propylene, most preferably propylene.

The content (mole %) of the 4MP1 unit (a1) and the AO unit (a2) contained in the 4-methyl-1-pentene polymer (A1) can be measured by the following method. ~Conditions~ Measuring device: nuclear magnetic resonance apparatus (ECP500, manufactured by JEOL Ltd.) Observation nucleus: ¹³ C (125 MHz) Sequence: monopulse proton decoupling (monopulse proton decoupling) Pulse width: 4.7 microseconds (45° Pulse) Repeat time: 5.5 seconds Cumulative times: more than 10,000 times Solvent: o-dichlorobenzene/deuterated benzene (volume ratio: 80/20) Mixed solvent Sample concentration: 55 mg/0.6 mL Measuring temperature: 120°C Chemistry Benchmark value for displacement: 27.50 ppm

The 4-methyl-1-pentene polymer (A1) is preferably a copolymer in which the total of the 4MP1 units (a1) and the AO units (a2) is 100 mol%. That is, the 4-methyl-1-pentene polymer (A1) preferably does not contain structural units other than the 4MP1 unit (a1) and the AO unit (a2).

The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A1) measured in decahydronaphthalene solvent at 135°C is preferably 0.5 dl/g to 5.0 dl/g, more preferably 0.5 dl /g～4.0 dl/g. When the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A1) is within the above range, there are few low-molecular-weight substances, so the stickiness of the sheet or film is reduced, and extrusion can be performed. Film forming. The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A1) is a value measured by the following method using an Ubbelohde viscometer.

About 20 mg of the 4-methyl-1-pentene polymer (A1) was dissolved in 25 ml of decahydronaphthalene, and the specific viscosity η _sp was measured in an oil bath at 135° C. using an Ubbelohde viscometer. After adding 5 ml of decahydronaphthalene to this decahydronaphthalene solution for dilution, the specific viscosity η _sp was measured in the same manner as above. Furthermore, this dilution operation was repeated twice, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was obtained as the intrinsic viscosity [η] (unit: dl/g) (see formula 1 below). [η]=lim (η _sp /C) (C→0)...Formula 1

From the viewpoint of film formability, the weight average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A1) is preferably 1×10 ⁴ to 2×10 ⁶ , more preferably 1×10 ⁴ to 1×10 ⁶ . In addition, the molecular weight distribution (Mw/Mn) of the 4-methyl-1-pentene polymer (A1) is preferably from 1.0 to 3.5, more preferably from 1.1 to 3.0, in terms of effectively suppressing the expression of blocking. . The weight average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A1), and the molecular weight distribution represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn ) is a value calculated by using the standard polystyrene conversion method of the following gel permeation chromatography (GPC).

~Conditions~ Measuring device: GPC (ALC/GPC 150-C plus type, differential refractometer detector integrated type, manufactured by Waters) String: Connect two GMH6-HTs (manufactured by Tosoh Co., Ltd.) and two GMH6-HTLs (manufactured by Tosoh Co., Ltd.) in series Washing liquid: o-dichlorobenzene Column temperature: 140°C Flow rate: 1.0 mL/min

From the viewpoint of fluidity during molding, the melt flow rate (MFR: Melt Flow Rate) of the 4-methyl-1-pentene polymer (A1) is preferably 0.1 g/10 min to 100 g/ 10 min, more preferably 0.5 g/10 min to 50 g/10 min, more preferably 0.5 g/10 min to 30 g/10 min.

In addition, when the melt flow rate (MFR) of the 4-methyl-1-pentene-based polymer (A1) is within the above-mentioned range, extrusion molding to a relatively uniform film thickness is easy. The melt flow rate (MFR) of the 4-methyl-1-pentene polymer (A1) is based on the American Society for Testing Materials (ASTM) D1238, at 230 ° C at 2.16 kg The value of the load determination.

From the viewpoint of operability, the density of the 4-methyl-1-pentene polymer (A1) measured according to ASTM D 1505 (substitution method in water) is preferably 0.810 g/cm ³ to 0.850 g/cm ³ , more preferably 0.820 g/cm ³ to 0.850 g/cm ³ , further preferably 0.830 g/cm ³ to 0.850 g/cm ³ .

In addition, when the density of the 4-methyl-1-pentene polymer (A1) is 0.810 g/cm ³ or more, the mechanical strength becomes good. If the density of the 4-methyl-1-pentene-based polymer (A1) is 0.850 g/cm ³ or less, the addition of the silylated polyolefin (B) can effectively suppress the occurrence of blocking.

The melting point (Tm) of the 4-methyl-1-pentene-based polymer (A1) is 199° C. or lower, or substantially no melting point (Tm) is observed. When the melting point (Tm) of the 4-methyl-1-pentene-based polymer (A1) is 199° C. or lower, or substantially no melting point (Tm) is observed, a film formable at low temperature can be obtained. The melting point (Tm) of the 4-methyl-1-pentene polymer (A1) is preferably 100° C. to 180° C., or substantially no melting point (Tm) is observed. It should be noted that "substantially no melting point (Tm) is observed" means that no crystal melting peak with a crystal melting heat of 1 J/g or more is observed in the range of -150°C to 200°C. The melting point (Tm) of the 4-methyl-1-pentene polymer (A1) is a value measured by the following method using a differential scanning calorimeter (DSC: Differential Scanning Calorimetry).

About 5 mg of 4-methyl-1-pentene-based polymer (A1) was sealed in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Co., Ltd. The temperature is heated to 200°C at 10°C/min. In order to completely melt the 4-methyl-1-pentene polymer (A1), it was kept at 200°C for 5 minutes, and then cooled to -50°C at 10°C/min. After standing at -50°C for 5 minutes, the second heating was performed at 10°C/min to 200°C, and the peak temperature (°C) during the second heating was taken as the melting point (Tm) of the copolymer. In addition, when a plurality of peaks were detected, the peak detected on the highest temperature side was employed.

The 4-methyl-1-pentene polymer (A1) can be produced by various methods. For example, a magnesium-supported titanium catalyst can be used; International Company No. 01/53369, International Publication No. 01/027124, Japanese Patent Laid-Open Publication No. 3-193796, and Japanese Patent Laid-Open Publication No. 02-41303, etc. The metallocene catalyst described; the known catalyst such as the olefin polymerization catalyst containing the metallocene compound described in International Publication No. 2011/055803.

The content of the 4-methyl-1-pentene copolymer (A1) in the sheet of this embodiment is relative to the 4-methyl-1-pentene copolymer (A1) and the styrene-based elastomer ( The total of 100 parts by mass of A2) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass.

＜Styrenic Elastomer (A2)＞ The styrene-based elastomer (A2) is an elastomer containing styrene as a monomer unit. Based on the overall mass of the styrene-based elastomer, the proportion of monomer units derived from styrene in the styrene-based elastomer is preferably at least 5% by mass, more preferably at least 10% by mass, and the upper limit can be compared with Preferably, it is 80 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less. That is, the proportion of monomer units derived from styrene can be set to preferably 5% by mass to 80% by mass, more preferably 5% by mass to 30% by mass, further preferably 5% by mass to 20% by mass, especially Preferably, it is 10 mass % - 20 mass %. The styrene-based elastomer (A2) may be a part or all of unsaturated bonds derived from alkadienes (generally, excluding unsaturated bonds derived from benzene rings of styrene) of monomers by hydrogenation. And turn into a hydride of a saturated bond. Heat resistance tends to be improved by hydrogenation.

The styrene-based elastomer (A2) may be, for example, a block copolymer composed of a polystyrene block and a polyolefin block containing a monomer unit derived from a diene having 4 to 10 carbon atoms, or a hydrogenated things. From the viewpoint of compatibility with propylene-based polymers and impact resistance, the polyolefin block may contain at least one diene of isoprene or butadiene as a monomer unit. In this specification, elastomers containing styrene and ethylene as monomer units are classified as styrene-based elastomers. The styrene-based elastomer (A2) may be a diblock-type copolymer comprising a polystyrene block and a polyolefin block bonded thereto, or may be a copolymer comprising polystyrene blocks arranged at both ends, And a triblock-type interpolymer of polyolefin blocks disposed therebetween. Triblock type interpolymers can contribute to the improvement of impact resistance.

The proportion of the polyolefin block in the block copolymer that is the styrene-based elastomer (A2) is preferably 95% by mass or less, more preferably 90% by mass or less, based on the mass of the block copolymer. The lower limit is preferably at least 20% by mass, more preferably at least 70% by mass, further preferably at least 80% by mass. That is, the proportion of the polyolefin block can be preferably set at 20% by mass to 95% by mass, more preferably 70% by mass to 95% by mass, still more preferably 80% by mass to 95% by mass, most preferably 80% by mass % to 90% by mass. By the styrene-based elastomer (A2) containing an appropriate proportion of polyolefin blocks, it is easy to obtain a sheet or film having good properties with regard to transparency, impact resistance, and rigidity. Furthermore, when the styrene-based elastomer (A2) contains the polyolefin block in the ratio described above and contains the silylated polyolefin (B), a sheet or film in which blocking is suppressed can be obtained. Preferred specific examples of the styrene-based elastomer (A2) include hydrogenated products of styrene-butadiene-styrene block copolymers, hydrogenated products of styrene-isoprene-styrene block copolymers, And the hydride of styrene-isoprene-butadiene-styrene block copolymer.

The styrene-based elastomer (A2) can be produced by common methods such as anionic polymerization and cationic polymerization. Examples of commercially available styrene-based elastomers (A2) include the trade name "Kraton" manufactured by Kraton Polymer Co., Ltd., and the trade name "Taftec" manufactured by Asahi Kasei Corporation. (Tuftec), "S.O.E.", "Septon" and "Hybrar" manufactured by Kuraray, and "Dynaron" manufactured by JSR ".

The content of the styrene-based elastomer (A2) in the sheet or film of this embodiment is based on 100 parts by mass of the total of the 4-methyl-1-pentene copolymer (A1) and the styrene-based elastomer (A2) On the other hand, it is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass.

Among the above, from the viewpoint of further suppressing the performance of blocking while maintaining the mechanical properties such as elongation, flexibility, and toughness of the sheet or film of the present embodiment, among the polymer (A), the above-mentioned The total of the structural unit (a1) derived from 4-methyl-1-pentene and the structural unit (a2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 100 mol%, and contains 60 mol% to 99 mol%, preferably 70 mol% to 90 mol%, more preferably 72 mol% to 85 mol% of the structural unit (a1), and Contains 1 mol% to 40 mol%, preferably 10 mol% to 30 mol%, more preferably 15 mol% to 28 mol% of the structural unit (a2).

＜Silylated polyolefin (B)＞ The silylated polyolefin (B) of this embodiment may have any structure as long as it has a silicone chain and a polyolefin chain. For example, silicone-grafted polyolefin having a structure grafted with silicone, a block copolymer of polyolefin and silicone, a structure in which polyolefin is grafted on silicone, and The silicone part of the block copolymer is grafted with a polyolefin structure and the like. One type of silylated polyolefin (B) may be used, or two or more types may be used in combination.

Examples of block copolymers include: (polyolefin chain)-(silicone chain) bonded block copolymers, (polyolefin chain)-(silicone chain)-(polyolefin chain) Sequentially bonded block copolymers, etc. The polyolefin chain can be, for example, a polymer chain including a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms. Among them, it is preferable to have a structure represented by the following general formula (1).

[Chem 2]

In the formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. When a plurality of A ³ exists, each A ³ may be the same or different. Wherein, at least one of A ¹ , A ² and A ³ represents a polyolefin chain.

The polyolefin chains in A ¹ , A ² and A ³ are polymer chains including structural units derived from olefins with 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms.

Specific examples of the olefin having 2 to 50 carbon atoms include ethylene, α-olefins having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,4-methyl-1-pentene, 4-methyl-1-hexene, 3-ethane Dimethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-di Methyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinyl cyclohexane, etc.). Among these, ethylene and an α-olefin having 3 to 12 carbon atoms are preferred, ethylene and an α-olefin having 3 to 8 carbon atoms are more preferred, and ethylene is particularly preferred. The polyolefin chain may be a homopolymer chain or a copolymer chain.

Among them, polymer chains consisting only of olefins with 2 to 50 carbons selected from ethylene and α-olefins with 3 to 50 carbons are preferable, and further, ethylene homopolymer chains and propylene homopolymer chains are preferable. , or an ethylene-copolymer chain of an α-olefin with 3 to 20 carbon atoms. In the copolymer chain of ethylene-α-olefin with 3 to 20 carbons, when all the structural units are taken as 100 mol%, the structural unit derived from the α-olefin with 3 to 20 carbons can be set as more than 0 mol% to 20 mol% or less, or more than 0 mol% to 10 mol% or less.

In addition, the polyolefin chain may contain structural units derived from other olefins as needed. Examples of other olefins include olefins containing internal double bonds such as cis-2-butene; vinylidene compounds such as isobutylene; arylvinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene. Compounds; functional group-substituted vinylene compounds such as methyl methacrylate; 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene and other fats containing internal double bonds cyclic olefins; indene and other cyclic olefins containing aromatic rings; chain or cyclic polyenes such as butadiene, isoprene, ethylidene norbornene, vinyl norbornene, etc.

When all the structural units constituting the polyolefin chain are taken as 100 mol %, the content of structural units derived from other olefins is preferably 0 mol % to 10 mol %, more preferably 0 mol % to 5 mol % Ear%.

The number average molecular weight of the polyolefin chain determined by the following GPC method is preferably 100-500,000, more preferably 200-100,000, more preferably 500-50,000, particularly preferably 700-10,000. In addition, the polyolefin chain preferably has a molecular weight distribution (Mw/Mn) determined by the following GPC method in the range of 1.1 to 3.0.

GPC assay: GPC measurement is performed at a temperature of 140°C using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn), and Mw/Mn) can be obtained as polyethylene conversion values.

Measurement can be performed under the following conditions. In addition, the molecular weight can be obtained by using commercially available monodisperse standard polystyrene to prepare a calibration curve and obtain it based on the following conversion method. Device: Gel Permeation Chromatograph Alliance GPC2000 (manufactured by Waters) Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh) × 4 Flow rate: 1.0 ml/min Sample: 0.15 mg/mL o-dichlorobenzene solution temperature: 140°C Molecular weight conversion: polystyrene (PS) conversion/universal calibration method In addition, in the calculation of general calibration, the following can be used The coefficients of the Mark-Houwink viscosity formula shown. Polystyrene (PS) coefficient: KPS=1.38×10 ^-4 , aPS=0.70 Polyethylene (PE) coefficient: KPE=5.06×10 ^-4 , aPE=0.70

Among the above-mentioned A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms include alkyl, arylalkyl, alkenyl and aryl.

Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, decyl, octadecyl linear or branched alkyl groups such as alkyl groups; cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, and norbornyl groups; and the like. As the arylalkyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, etc. are mentioned. As an alkenyl group, a vinyl group, a propenyl group, a cyclohexenyl group, etc. are mentioned. Examples of the aryl group include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, naphthyl and the like.

In said formula (1), m is an integer of 1-10,000. m is preferably at least 5, more preferably at least 10. In addition, m is preferably at most 1,000, more preferably at most 300, even more preferably at most 50. That is, m is preferably an integer of 5-1,000, more preferably an integer of 10-300, and still more preferably an integer of 10-50.

The A ¹ , A ² , single or multiple A ³ may all be polyolefin chains, or may be a part of the groups are polyolefin chains and other groups are hydrocarbon groups with 1-20 carbons.

In the formula (1), when m is ² or more, and at least one ^of A3 is different from the other A3, there are many kinds of the following units, but there is no particular restriction on their arrangement order, and it can be embedded Segments can also be random.

[Chem 3]

The formula (1) is preferably a structure represented by the following (1A), (1B) or (1C), among which (1A) is more preferable.

(1A) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a structure of a hydrocarbon group having 1 to 20 carbon atoms. (1B) In the formula (1), one of A ¹ and A ² is a polyolefin chain, the other is a hydrocarbon group with 1 to 20 carbons, and A ³ is a hydrocarbon group with 1 to 20 carbons body. (1C) In the formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 20 carbon atoms, and at least one of A ³ is a polyolefin chain.

In the silylated polyolefin (B) of this embodiment, the silicone chain/polyolefin chain (mass ratio) is not particularly limited, for example, it is preferably 5/95-99/1, more preferably 10/90- 95/5.

The method for producing the silylated polyolefin (B) of the present embodiment is not particularly limited, for example, it can be prepared by the methods described in paragraphs 0089 to 0145 or 0196 to 0207 of International Publication No. 2012/098865. manufacture.

The content of the silylated polyolefin (B) in the sheet or film of this embodiment is not particularly limited, and when the entire sheet or film containing both the polymer (A) and the silylated polyolefin (B) is set When it is 100% by mass, it is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass from the viewpoint of further suppressing the expression of blocking. From the viewpoint of compatibility, strength, and transparency of the polymer, it is preferably at most 10% by mass, more preferably at most 7% by mass, still more preferably at most 5% by mass, particularly preferably at most 3% by mass. That is, when the entire sheet or film is taken as 100% by mass, the content of the silylated polyolefin (B) is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 7% by mass. , More preferably, it is 1% by mass to 5% by mass, and particularly preferably, it is 1% by mass to 3% by mass. It is preferable from the point of tensile breaking strength, tensile breaking elongation, and transparency that the addition amount of a silylated polyolefin is below the said upper limit. That is, by using the silylated polyolefin (B) within the above numerical range, the above effects are excellent, in other words, the balance of these effects is excellent.

＜Other polymers＞ The sheet or film of this embodiment can be obtained from a composition containing the polymer (A), the silylated polyolefin (B), and other polymers. Examples of other polymers include polyolefins other than polymer (A) and silylated polyolefin (B), polystyrene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, ethylene - Polyesters such as (meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, polyethylene terephthalate, polycarbonate, polyamide, acrylonitrile-butadiene-styrene ( acrylonitrile-butadiene-styrene, ABS) resin, polyacetal resin, polyimide, polyurethane, polylactic acid, phenolic resin, epoxy resin, silicone resin, (meth)acrylic resin, fluorine-based resin etc.

＜Additives＞ The sheet or film of this embodiment can be obtained from a composition containing various known additives used in the production of polyolefin products as needed within a range that does not impair the purpose of this embodiment. Examples of such additives include softeners, antiaging agents, processing aids, activators, reaction inhibitors, colorants, dispersants, flame retardants, plasticizers, antioxidants, ultraviolet absorbers, antistatic Agents, lubricants, antibacterial agents, antifungal agents, surfactants, etc.

The composition of this embodiment can be obtained by mixing the above-mentioned components by a conventionally known method, and the sheet or film of this embodiment can be produced by extrusion molding.

＜Physical properties of sheet or film＞ The tan δ obtained by dynamic viscoelasticity measurement will be described. For the polymer (A) contained in the sheet or film of this embodiment, the dynamic viscoelasticity was measured while continuously changing the ambient temperature, and the storage elastic modulus E' (Pa) and the loss elastic modulus E'' ( Pa), and find the loss tangent tanδ given by E''/E'. When looking at the relationship between temperature and loss tangent tan δ, the loss tangent tan δ generally has a peak at a specific temperature. The temperature at which the peak appears is generally called a glass transition temperature (hereinafter also referred to as Tg). The temperature at which the peak of the loss tangent tan δ appears can be obtained based on the dynamic viscoelasticity measurement described later. Here, in this embodiment, normally, the peak value of the loss tangent tan δ is the maximum value of the loss tangent tan δ in this embodiment. In addition, when two or more peaks of the loss tangent tanδ are observed, the peak value of the largest peak is the maximum value of the loss tangent tanδ in this embodiment.

The maximum value of the loss tangent tanδ in the temperature range of 0°C to 50°C of the sheet or film of this embodiment is 0.6 or more, more preferably the maximum value of the loss tangent tanδ in the temperature range of 0°C to 50°C is 0.8 The above, and more preferably, the maximum value of the loss tangent tanδ in the temperature range of 0°C to 50°C is 1.0 or more. By setting the maximum value of the loss tangent tanδ in the above-mentioned range, the effect of suppressing the blocking expression by the addition of the silylated polyolefin (B) can be further enhanced. Here, the upper limit of the maximum value of the loss tangent tanδ in the temperature range of 0°C to 50°C is not particularly limited, but is preferably 5.0 or less. The loss tangent tanδ can be measured by the method described later. Furthermore, the loss tangent tanδ can be changed by changing the unit structural elements of the polymer (A) and their molar ratio, weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio of these, that is, the molecular weight distribution (Mw /Mn) etc. to adjust.

The glass transition temperature (Tg) of the sheet or film of this embodiment is preferably -60°C to 60°C, more preferably -50°C to 50°C, further preferably -50°C to 40°C, particularly preferably -40°C. ℃～40℃. By setting the glass transition temperature (Tg) in the above-mentioned range, the expression of blocking can be further suppressed by adding the silylated polyolefin (B). The glass transition temperature (Tg) can be changed by changing the unit structural elements of the polymer (A) and its molar ratio, weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio of these, namely the molecular weight distribution (Mw/Mn ) and so on to adjust.

The content of the polymer (A) in this embodiment is not particularly limited, but it is preferable when the entire sheet or film containing both the polymer (A) and the silylated polyolefin (B) is 100% by mass. It is 90 mass % or more, more preferably 95 mass % or more, still more preferably 97 mass % or more, especially preferably 99 mass % or more, and preferably 99.5 mass % or less, more preferably 99 mass % or less. That is, when the entire sheet or film is 100% by mass, the content of the polymer (A) is preferably from 90% by mass to 99.5% by mass, more preferably from 95% by mass to 99.5% by mass, still more preferably 97% by mass. % by mass to 99.5% by mass, particularly preferably 99% by mass to 99.5% by mass. By setting it as the said range, the expression of the blocking of an olefin-based resin composition can be further suppressed, and the sheet|seat which is more excellent in balance, such as light weight, mechanical characteristic, handleability, appearance, transparency, moldability, etc. can be obtained.

＜Laminates＞ The laminate of the present embodiment is formed by laminating the sheet or film (L1) of the present embodiment and the sheet or film (L2) including a layer containing a thermoplastic elastomer. Furthermore, the multilayer body may also be described as a multilayer sheet or a multilayer film. In addition, the number of laminated layers of (L1) and (L2) is not particularly limited, as long as at least one layer is laminated each. The lamination order is also not particularly limited, and (L1) or (L2) may be laminated.

As will be described later, in the case of a laminate comprising a plurality of sheets or films, at least one sheet or film constituting the laminate contains both the polymer (A) and the silylated polyolefin (B) ( Let the sheet or film including both (A) and (B) be the sheet or film (L1)). Although not particularly limited, it is preferable to contain the silylated polyolefin (B) only in the sheet or film (L1). The polymer (A) and silylated polyolefin (B) contained in the sheet may be one type, or may be multiple types with different molecular skeletons or physical properties.

The sheet or film (L1) constituting the laminate of this embodiment contains the polymer (A) and the silylated polyolefin (B), and the loss tangent tanδ obtained by measuring the temperature dependence of dynamic viscoelasticity When the maximum value is 0.6 or more in the temperature range of 0°C to 50°C, further Improves durability while further suppressing the appearance of sticking. Among them, the polymer (A) preferably contains the 4-methyl-1-pentene copolymer (A1) from the viewpoint of improving the transparency of the sheet.

The inventors of the present invention found that in a sheet comprising a blend of a 4-methyl-1-pentene copolymer and a thermoplastic elastomer, the 4-methyl-1-pentene copolymer and the thermoplastic elastomer described later It is difficult to be completely compatible with each other at the molecular level, and due to the difference in refractive index between the two, white turbidity easily occurs in the film. From this point of view, if the 4-methyl-1-pentene copolymer and the thermoplastic elastomer are not blended, but are multilayered in a phase-separated form from each other, the cloudiness of the sheet can be suppressed, and each can be provided. A laminate in which the transparency of the phase is maintained.

That is, the laminate of this embodiment preferably contains only one type of 4-methyl-1-pentene polymer (A1) as the polymer (A) and a silyl group in the sheet or film (L1). Polyolefin (B), and a styrene-based elastomer is contained in the sheet or film (L2) as the thermoplastic elastomer. By setting it as this structure, the laminated body more excellent in transparency can be obtained.

The sheet or film (L2) contains a thermoplastic elastomer to be described later. At the same time, by adopting the above structure, the permanent deformation of the sheet can be suppressed, the bending resistance of the sheet in a low temperature environment (for example, less than 20° C.) can be improved, and the durability of the sheet can be further improved. Furthermore, from the viewpoint of suppressing the blocking expression, it is more preferable to make the outer layer of the laminate into (L1) containing the silylated polyolefin (B).

The thickness of one layer of the sheet or film (L1) is preferably 0.01 mm to 2 mm, more preferably 0.02 mm to 1 mm, further preferably 0.03 mm to 0.5 mm, particularly preferably 0.03 mm to 0.3 mm, most preferably 0.04 mm to 0.1 mm. The flexibility of a sheet|seat can be made favorable that it is below the said upper limit. That is, when the thickness of one layer of the sheet or film (L1) is within the above-mentioned range, the flexibility of the sheet is excellent. The thickness of one layer of the sheet or film (L2) is preferably 0.01 mm to 2 mm, more preferably 0.02 mm to 1 mm, further preferably 0.02 mm to 0.5 mm, particularly preferably 0.03 mm to 0.5 mm, most preferably 0.05 mm to 0.2 mm. Sheet strength, heat resistance, and cold resistance can be made favorable that thickness is more than the said lower limit. Moreover, the flexibility of a sheet|seat can be made favorable as it is below the said upper limit. That is, when the thickness of one layer of the sheet or film (L2) is within the above-mentioned range, the flexibility of the sheet is excellent, in other words, the balance of these characteristics is excellent.

Such a laminate can be produced by, for example, a co-extrusion molding method, and specific examples include the following structures. (1) A layer containing a polymer (A) containing a 4-methyl-1-pentene copolymer and a silylated polyolefin (B)/a layer containing a thermoplastic elastomer/containing a 4-methyl-1- - Layers of polymer (A) of pentene-based interpolymer and silylated polyolefin (B) = 0.075 mm/0.15 mm/0.075 mm, total thickness 0.3 mm (2) Layer containing polymer (A) containing 4-methyl-1-pentene copolymer and silylated polyolefin (B)/layer 1 containing thermoplastic elastomer/layer 2 containing thermoplastic elastomer /layer 3 containing thermoplastic elastomer/layer containing polymer (A) containing 4-methyl-1-pentene copolymer and silylated polyolefin (B)=0.075 mm/0.03 mm/0.09 mm/ 0.03 mm/0.075 mm, total thickness 0.3 mm In this way, when a total of three or more layers of the sheet or film (L1) and the sheet or film (L2) are laminated, it is preferable to use the sheet or film (L1) as the outer layer of at least one side of the laminate. ).

The blocking resistance and transparency were evaluated using the laminates of (1) and (2) above using a styrene-based elastomer as the thermoplastic elastomer, and the results were favorable.

Here, examples of the thermoplastic elastomer include olefin-based elastomers, styrene-based elastomers, urethane-based elastomers, ester-based elastomers, and amide-based elastomers. These thermoplastic elastomers may be used alone or in combination of two or more. Among these thermoplastic elastomers, especially the styrene-based elastomer has moderate compatibility with the copolymer (A), and when a co-extruded multilayer sheet including both is formed, it is easy to ensure interlayer adhesion. The advantages. In addition, among styrene-based elastomers, hydrogenated styrene-based elastomers having a low styrene content have good compatibility with the copolymer (A), and thus can be preferably used. Specific examples of such hydrogenated styrene-based elastomer products include: the trademark "Kraton" G1657MS manufactured by Kraton Polymer Japan; (Tuftec)” H1221, trademark “Tuftec” H1062, trademark “Tuftec” H1521, trademark “Tuftec” 1052, trademark S.O.E.1606, trademark S.O.E.1605; Trademark "Septon" 2004F and trademark "Hybrar" 7311F manufactured by Kuraray Corporation.

The laminate of this embodiment may contain other layers or members between the layers (between L1 and L2, between L1 and L1, and between L2 and L2). As another layer, an adhesive layer etc. are mentioned, and as a member, reinforcing materials, such as stretchable fiber, etc. are mentioned.

A composite can be produced by laminating other members on the sheet or laminated volume of the present embodiment, and if necessary, heat-compression bonding or welding with a press or the like. In addition, a composite can also be produced by providing an adhesive between the sheet or laminate and other members, and then joining the sheet or laminate and other members via the adhesive. In the case of layering other members in a laminated volume, it is preferable that the layer (outer layer) of the laminated body on the opposite side to the layer facing the other members be made to contain silylated polymers from the viewpoint of suppressing the expression of adhesion. Alkenes (B) (L1). As the adhesive, it is preferable to use a styrene-butadiene rubber (styrene-butadiene rubber, SBR)-based solvent adhesive, or an adhesive containing ethylene vinyl acetate (ethyl vinyl acetate, EVA), petroleum resin, or EVA and Hot-melt adhesives such as mixtures of petroleum resins. Other members are not particularly limited, and examples include: woven fabrics, nonwoven fabrics, synthetic fibers, artificial leather, synthetic leather, natural leather, fur, metal, carbon materials, rubber, thermoplastic elastomers, thermoplastic resins, thermosetting resins, high Molecular foam, mesh structure (warp knitted fiber, double Russel mesh, three-dimensional spring structure, etc.), fiber-reinforced plastic, paper, wood, glass, stone, ceramics, etc. . These members may be used alone or in combination of two or more.

＜Physical properties of laminates＞ The tan δ obtained by the dynamic viscoelasticity measurement of the sheet or film (L1) located in the outermost layer of the laminate according to this embodiment will be described. For the polymer (A) contained in the sheet or film (L1) of this embodiment, the dynamic viscoelasticity was measured while changing the ambient temperature continuously, and the storage elastic modulus E' (Pa) and the loss elastic modulus E were measured. ''(Pa), and find the loss tangent tanδ given by E''/E'. When looking at the relationship between temperature and loss tangent tan δ, the loss tangent tan δ generally has a peak at a specific temperature. The temperature at which the peak appears is generally called a glass transition temperature (hereinafter also referred to as Tg). The temperature at which the peak of the loss tangent tan δ appears can be obtained based on the dynamic viscoelasticity measurement described later. Here, in this embodiment, normally, the peak value of the loss tangent tan δ is the maximum value of the loss tangent tan δ in this embodiment. In addition, when two or more peaks of the loss tangent tanδ are observed, the peak value of the largest peak is the maximum value of the loss tangent tanδ in this embodiment.

The maximum value of the loss tangent tanδ of the sheet or film (L1) located in the outermost layer of the laminate in the temperature range of 0°C to 50°C is 0.6 or more, more preferably the loss tangent in the temperature range of 0°C to 50°C The maximum value of tanδ is 0.8 or more, and it is more preferable that the maximum value of the loss tangent tanδ in the temperature range of 0° C. to 50° C. is 1.0 or more.

By setting the maximum value of the loss tangent tanδ of the outermost sheet or film (L1) within the above range, the adhesion to the laminate due to the addition of the silylated polyolefin (B) can be further improved Inhibition of performance. Here, the upper limit of the maximum value of the loss tangent tanδ in the temperature range of 0°C to 50°C is not particularly limited, but is preferably 5.0 or less. Furthermore, when the sheet or film (L1) exists in both outermost layers of the laminate of this embodiment, it is preferable that the maximum values of the loss tangent tanδ of both sheets or films (L1) are within the above-mentioned range. On the other hand, the maximum value of the loss tangent tanδ of the sheet or film (L1) located between layers of the laminate is not particularly limited.

The loss tangent tanδ can be measured by the method described later. Furthermore, the loss tangent tanδ can be adjusted by changing the unit structural elements of the polymer (A) and its molar ratio.

The glass transition temperature (Tg) of the sheet or film (L1) of the present embodiment is preferably -60°C to 60°C, more preferably -50°C to 50°C, further preferably -50°C to 40°C, particularly preferably -40°C to 40°C. By setting the glass transition temperature (Tg) in the above-mentioned range, the expression of blocking can be further suppressed by adding the silylated polyolefin (B). The glass transition temperature (Tg) can be adjusted by changing the unit structural element of the polymer (A), its molar ratio, and the like.

As mentioned above, although embodiment was described, these are examples, and various structures other than the above can also be employ|adopted. [Example]

Hereinafter, although this embodiment is demonstrated concretely based on an Example, this embodiment is not limited to these Examples.

1. Measurement and evaluation method (1) The content rate (mole %) of 4-methyl-1-pentene and α-olefin constituting the 4-methyl-1-pentene polymer (A1) by carbon Spectrum nuclear magnetic resonance ( ¹³ C-nuclear magnetic resonance, ¹³ C-NMR) to determine. The measurement conditions are as follows. ~Measurement conditions~ Measuring device: NMR apparatus (ECP500, manufactured by JEOL Ltd.) Observation nucleus: ¹³ C (125 MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 microseconds (45° pulse) Repeat Time: 5.5 seconds Cumulative times: more than 10,000 times Solvent: o-dichlorobenzene/deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg/0.6 mL Measurement temperature: 120°C Reference value of chemical shift : 27.50ppm

(2) Intrinsic Viscosity The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A1) was measured at 135° C. in a decahydronaphthalene solvent using an Ubbelohde viscometer as a measuring device. Specifically, about 20 mg of the powdery polymer (A) was dissolved in 25 ml of decahydronaphthalene, and the specific viscosity η _sp was measured in an oil bath at 135° C. using an Ubbelohde viscometer. After adding 5 ml of decahydronaphthalene to this decahydronaphthalene solution for dilution, the specific viscosity _ηsp was measured in the same manner as above. This dilution operation was repeated twice, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was obtained as the intrinsic viscosity [η] (unit: dl/g) (see Formula 1). [η]=lim (η _sp /C) (C→0)...Formula 1

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) In the GPC measurement, the temperature is 140°C, o-dichlorobenzene is used as a solvent, and a polystyrene calibration curve is used to measure, and the analytical value can be obtained as a polyethylene conversion value (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw/Mn). The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the 4-methyl-1-pentene polymer (A1) and the silylated polyolefin (B) were measured under the following conditions, respectively.

(3.1) Determination conditions for 4-methyl-1-pentene polymer (A1): Calculated by standard polystyrene conversion method. ・Apparatus: GPC (ALC/GPC 150-C plus type, differential refractometer and detector integrated type, manufactured by Waters Corporation, trade name) ・Solvent: o-dichlorobenzene ・Hub string: A structure in which two GMH6-HT (trade name) manufactured by Tosoh Co., Ltd. and two GMH-HTL (trade name) manufactured by Tosoh Co., Ltd. are connected in series ・Flow rate: 1.0 mL/min ・Column temperature: 140°C ・Molecular weight conversion: standard polystyrene conversion method

(3.2) Measurement conditions for silylated polyolefin (B): A calibration curve was prepared using a commercially available monodisperse standard polystyrene, and obtained based on the following conversion method.・Apparatus: Gel Permeation Chromatograph Alliance GPC2000 (manufactured by Waters) ・Solvent: o-dichlorobenzene ・Column: Four Tosoh Co., Ltd.・Flow rate: 1.0 ml/min ・Temperature: 140°C ・Sample: 0.15 mg/mL o-dichlorobenzene solution ・Molecular weight conversion: PS conversion/universal calibration method In the calculation of , the coefficient of the Mark-Houwink viscosity formula shown below is used. Polystyrene (PS) coefficient: KPS=1.38×10 ^-4 , aPS=0.70 Polyethylene (PE) coefficient: KPE=5.06×10 ^-4 , aPE=0.70

(4) Melt flow rate (MFR) The melt flow rate (MFR: Melt Flow Rate) of the 4-methyl-1-pentene polymer (A1) was measured at 230° C. under a load of 2.16 kg in accordance with ASTM D1238. The unit is g/10min.

(5) Density The density of the 4-methyl-1-pentene polymer (A1) was measured in accordance with ASTM D1505 (displacement method in water).

(6) Melting point (Tm) The melting point (Tm) of the 4-methyl-1-pentene polymer (A1) was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Co., Ltd.) as a measuring device.

(7) Dynamic viscoelasticity measurement The produced resin sheet was cut into strips with a length of 20 mm×a width of 10 mm. Using a viscoelasticity measurement device RSA-III (trade name) manufactured by TA Instruments Japan Inc., the temperature dependence data of dynamic viscoelasticity were measured under the following measurement conditions in the tension mode. The ratio (E''/E': loss tangent) of the storage elastic modulus (E') and the loss elastic modulus (E'') obtained by this measurement was made into tanδ. In addition, when tan δ is plotted against temperature, if an upwardly convex curve, that is, a peak is obtained within a specific temperature range, the temperature at the maximum value at the apex of the peak is taken as the glass transition temperature (Tg). (measurement conditions) Frequency: 1.59Hz Temperature: -70℃～80℃ Ramp Rate: 4.0°C/min Strain: 0.1% Here, when the resin sheet is a laminate, a single-layer sheet (thickness 0.075 mm) having the same composition as L1, which is the outermost layer of the resin sheet, was separately produced, and the dynamic viscoelasticity was measured by the same method as above, Calculate tan δ and its peak temperature (glass transition temperature: Tg).

(8) Total light transmittance According to the test standard Japanese Industrial Standards (JIS) K7361, the total light transmittance of the resin sheet was measured at room temperature (23° C.). (9) Anti-adhesion property Cut out two rectangular test pieces (10 cm×5 cm) from the resin sheet (single-layer sheet or laminate), after overlapping each of the test pieces, use the support body and hammer to The overlapped parts of the two resin sheets were clamped up and down so that a constant surface pressure of 0.4 N/cm ² was applied to the square-shaped (5 cm×5 cm) part from the vertical direction. Then, for the single-layer sheet, after standing in an oven at a temperature of 60° C. for 12 hours, the overlapping sheet of two resin sheets was taken out from the oven, and cooled at room temperature (23° C.) for 20 minutes. Then, about the overlapping of two resin sheets, the peeling easiness when the film was peeled off by hand was regarded as blocking resistance, and it was judged by the following criteria. <Evaluation criteria for single-layer sheet or film> ○: Adhesive force is present, but peeling occurs without elongation. ×: When peeled, peeled with elongation. On the other hand, the laminated body was left still in an oven at 80°C for 12 hours, and then the stacked sheet of two resin sheets was taken out from the oven, and cooled at room temperature (23°C) for 20 minutes. Then, about the overlapping of two resin sheets, the peeling easiness when the film was peeled off by hand was regarded as blocking resistance, and it was judged by the following criteria. <Evaluation criteria for laminates> ◯: There is almost no adhesiveness, and it is easy to peel off without resistance. ×: Adhesiveness is present.

2. Raw material The raw materials used in Examples and Comparative Examples are shown below.

(1) Polymer (A) <Synthesis of Copolymer A-1> 300 ml of n-hexane ( dry nitrogen environment, dried on activated alumina), and 450 ml of 4-methyl-1-pentene. 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutyl aluminum (TIBAL) was charged into the autoclave, and the stirrer was turned. Next, the autoclave was heated to an internal temperature of 60° C., and pressurized with propylene so that the total pressure became 0.40 MPa (gage pressure). Next, using nitrogen, 1 mmol of methyl aluminoxane (methyl aluminoxane) prepared in advance and 0.01 mmol of diphenylmethylene (1-ethyl-3-tert-butyl - Cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) toluene solution 0.34 ml of zirconium dichloride was pressed into the autoclave to start polymerization. During the polymerization reaction, temperature adjustment was performed so that the inner temperature of the autoclave became 60°C. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressurized into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution while stirring. The polymer containing the thus obtained solvent was dried at 100° C. under reduced pressure for 12 hours to obtain an olefin-based copolymer (A-1). The content of the structural unit derived from 4-methyl-1-pentene in this olefin-based interpolymer (A-1) was 72 mol%, and the content of the structural unit derived from propylene was 28 mol%. In addition, the intrinsic viscosity [η] of the olefin-based interpolymer (A-1) was 1.5, the weight average molecular weight (Mw) was 337,000, the molecular weight distribution (Mw/Mn) was 2.1, and the MFR measured in accordance with ASTM D1238 was 10 g/ After 10 minutes, the density measured according to ASTM D1505 (water displacement method) was 0.84 g/cm ³ . No melting point (Tm) observed. The maximum value of the loss tangent tanδ in the two temperature ranges of -20°C to 80°C and 0°C to 60°C measured by the method is 2.5. The temperature at which tan δ shows the maximum value, that is, the glass transition temperature (Tg) was 28° C.

＜Synthesis of Copolymer A-2＞ In a stainless steel autoclave with a capacity of 1.5 liters that has been fully replaced with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) was charged at 23°C, and 4 - Methyl-1-pentene 450 ml. 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was charged into the autoclave, and the stirrer was turned. Next, the autoclave was heated to an internal temperature of 60° C., and pressurized with propylene so that the total pressure became 0.19 MPa (gauge pressure). Next, using nitrogen, 1 mmol of methylaluminoxane prepared in advance and 0.01 mmol of diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadiene 0.34 ml of a toluene solution of alkenyl)(2,7-di-tert-butyl-fluorenyl)zirconium dichloride was pressed into the autoclave to start polymerization. During the polymerization reaction, temperature adjustment was performed so that the inner temperature of the autoclave became 60°C. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressurized into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution while stirring.

The polymer containing the thus obtained solvent was dried at 100° C. under reduced pressure for 12 hours to obtain an olefin-based copolymer (A-2). The content of the structural unit derived from 4-methyl-1-pentene in this olefin-based interpolymer (A-2) was 85 mol%, and the content of the structural unit derived from propylene was 15 mol%. The olefin-based interpolymer (A-2) had an intrinsic viscosity [η] of 1.4, a weight average molecular weight (Mw) of 340,000, a molecular weight distribution (Mw/Mn) of 2.1, and an MFR of 10 g/Mn measured in accordance with ASTM D1238. After 10 minutes, the density measured according to ASTM D1505 (water displacement method) was 0.84 g/cm ³ . The melting point (Tm) is 130°C. The maximum value of the loss tangent tanδ in the two temperature ranges of -20°C to 80°C and 0°C to 60°C measured by the method is 1.7. The temperature at which tan δ shows the maximum value, that is, the glass transition temperature (Tg) is 40° C.

(2) Silylated polyolefin (B) [Synthesis Example 1] (Synthesis of polyethylene having a vinyl group at one end) According to the method described in Synthesis Example 2 of International Publication No. 2012/098865, a single end containing Vinyl vinyl polymer (P-1). It was confirmed by ¹ H-NMR measurement that the obtained polymer was a homopolyethylene, and only one end contained a double bond. The physical properties of the single-terminal double bond-containing vinyl polymer (P-1) (monomer) are as follows. Melting point (Tm) 127°C Mw=4770, Mw/Mn=2.25 (GPC) terminal unsaturation rate 97%

[Synthesis Example 2] (Preparation of Platinum Catalyst Composition (C-1)) In a 50 ml sample tube equipped with a magnet stirrer chip, 0.50 g of platinum(II) chloride was suspended in the following HS (hydrosilane) (A), manufactured by Gelest, Inc. (Gelest, Inc., DMS-H11) (10 ml), was stirred under a nitrogen stream at room temperature. After stirring for 190 hours, take about 0.4 ml of the reaction solution with a syringe, filter it with a 0.45 μm polytetrafluoroethylene (PTFE) filter, and take the filtrate in a 10 ml sample tube to obtain a platinum concentration of 3.8% by mass. Catalyst composition (C-1). Hydrosilane A (HS(A)): HSi(CH ₃ ) ₂ O-(-Si(CH ₃ ) ₂ -O-) _n -Si(CH ₃ ) ₂ H (n=12～13)

[Synthesis Example 3] (Introduction of polyethylene having a terminal vinyl group into hydrosilane) The single-terminal vinyl group-containing vinyl polymer ( P-1) 25.1 g (11.8 mmol), under nitrogen atmosphere, further charged with hydrosilane A (HS (A)) 6.7 g (5.9 mmol; equivalent to 11.8 mmol in terms of Si-H group), and [synthesized The platinum catalyst composition (C-1) prepared in Example 2] was diluted 200 times with hydrosilane A (HS (A)) (C-1a) 150 μl (1.4×10 ^-6 in terms of Pt mmol). The above-mentioned two-necked flask was placed in an oil bath whose internal temperature was previously raised to 130° C., and stirred. After about 3 minutes the polymer melted. Then, after cooling for 6 hours, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker, followed by stirring for 2 hours. Then, the solid was collected by filtration, washed with methanol, and dried at 60° C. under a reduced pressure of 2 hPa or lower to obtain 33.1 g of a white solid silylated polyolefin (B-1). As a result of NMR analysis, the yield of the obtained silylated polyolefin (B-1) was 98%, the olefin conversion rate was 100%, and the isomerization rate was 2%. The MFR is above the measurement upper limit (MFR>100 g/10 min), and the polyorganosiloxane content in (B-1) calculated by the molecular formula is 23% by mass.

Here, details of the resin sheets (single-layer sheets) shown in Table 1 are as follows. PMP-A1 contains 4-methyl-1-pentene/propylene copolymer (A-1): 30 parts by mass, 4-methyl-1-pentene/propylene copolymer (A-2): 10 parts by mass , Hydrogenated styrene-based elastomer ("Hybrar" manufactured by Kuraray, trademark 7311F, content of monomer units derived from styrene: 12% by mass): 60 parts by mass, and silane Alkylated polyolefin (B-1): A sheet having a thickness of 0.1 mm obtained by extruding 1 part by mass of the blend through a T-die. PMP-A2 and PMP-A3 are sheets with a thickness of 0.1 mm obtained in the same manner as PMP-A1 except that the blending amount of the silylated polyolefin (B-1) was changed to the value described in Table 1. PMP-A4 is a sheet with a thickness of 0.1 mm obtained in the same manner as PMP-A1 except that silylated polyolefin (B-1) was not used. PMP-A5 is the same as PMP except that the silylated polyolefin (B-1) is changed to erucamide (Alflow P-10 (trade name), manufactured by NOF Corporation): 0.3 parts by mass -A1 A sheet with a thickness of 0.1 mm obtained in the same manner.

[Table 1] resin sheet Evaluation Resin prescription [parts by mass] Thickness [mm] Temperature range 0℃～50℃ Adhesion Total light transmittance[%] tanδ peak temperature (Tg) [°C] tan delta peak [-] Example 1 PMP-A1 Copolymer (A-1)/Copolymer (A-2)/Hydrogenated Styrenic Elastomer/Silylated Polyolefin (B-1)=30/10/60/1 0.1 29 1.8 〇 88 Example 2 PMP-A2 Copolymer (A-1)/Copolymer (A-2)/Hydrogenated Styrenic Elastomer/Silylated Polyolefin (B-1)=30/10/60/3 0.1 29 1.8 〇 86 Example 3 PMP-A3 Copolymer (A-1)/Copolymer (A-2)/Hydrogenated Styrenic Elastomer/Silylated Polyolefin (B-1)=30/10/60/5 0.1 29 1.7 〇 86 Comparative example 1 PMP-A4 Copolymer (A-1)/Copolymer (A-2)/Hydrogenated Styrenic Elastomer/Silylated Polyolefin (B-1)=30/10/60/0 0.1 29 1.8 x - Comparative example 2 PMP-A5 Copolymer (A-1)/copolymer (A-2)/hydrogenated styrene elastomer/erucamide=30/10/60/0.3 0.1 29 1.8 x -

Here, the details of the resin sheets (laminates) shown in Table 2 are as follows. PMP-B1 is when blending 4-methyl-1-pentene/propylene copolymer (A-1) and 4-methyl-1-pentene/propylene copolymer at a blending ratio of 60/40/0.5 parts by mass (A-2), and the layer composed of silylated polyolefin (B-1) is referred to as (L1), which will only be manufactured by Kraton Polymer Japan Co., Ltd., which is a hydrogenated styrene-based elastomer. When the layer composed of Kraton G1657VS is set as (L2), the cross-sectional structure becomes (L1)/(L2)/(L1)=0.075 mm/0.15 mm/0.075 mm, and is co-extruded by T-die A sheet with a total thickness of 0.3 mm obtained by sheet forming. PMP-B2 and PMP-B3 are sheets with a total thickness of 0.3 mm obtained in the same manner as PMP-B1 except that the compounded amount of the silylated polyolefin (B-1) was changed to the value shown in Table 2. PMP-B4 is a sheet with a thickness of 0.3 mm obtained in the same manner as PMP-B1 except that silylated polyolefin (B-1) was not used. PMP-B5 is the same as PMP except that silylated polyolefin (B-1) is changed to erucamide (Alflow P-10 (trade name), manufactured by NOF Corporation): 0.3 parts by mass - B1 A sheet with a total thickness of 0.3 mm obtained in the same manner.

[Table 2] resin sheet Evaluation Resin prescription [parts by mass] Thickness [mm] Total thickness [mm] Temperature range 0℃～50℃ Adhesion Total light transmittance[%] L1 tanδ peak temperature (Tg) [°C] L1 peak tan delta [-] Example 4 PMP-B1 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/0.5 0.075 0.3 32 2.2 〇 92 L2: hydrogenated styrene-based elastomer = 100 0.15 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/0.5 0.075 Example 5 PMP-B2 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/1 0.075 0.3 32 2.2 〇 92 L2: hydrogenated styrene-based elastomer = 100 0.15 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/1 0.075 Example 6 PMP-B3 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/3 0.075 0.3 32 2.1 〇 92 L2: hydrogenated styrene-based elastomer = 100 0.15 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/3 0.075 Comparative example 3 PMP-B4 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/0 0.075 0.3 32 2.2 x - L2: hydrogenated styrene-based elastomer = 100 0.15 L1: Copolymer (A-1)/copolymer (A-2)/silylated polyolefin (B-1)=60/40/0 0.075 Comparative example 4 PMP-B5 L1: Copolymer (A-1) / Copolymer (A-2) / Erucamide = 60/40/0.3 0.075 0.3 32 2.2 x - L2: hydrogenated styrene-based elastomer = 100 0.15 L1: Copolymer (A-1) / Copolymer (A-2) / Erucamide = 60/40/0.3 0.075

As is clear from Table 1, the anti-blocking properties of the resin sheets of Example 1, Example 2, and Example 3 containing the composition containing the polymer (A) and the silylated polyolefin (B) can be seen excellent. On the other hand, the resin sheets of Comparative Example 1 and Comparative Example 2 that did not contain the silylated polyolefin (B) were inferior in blocking resistance. As is clear from Table 2, it can be seen that the following resin sheet is included, that is, a laminate of a resin sheet including a composition containing a polymer (A) and a silylated polyolefin (B) (Example 4, Example 5 , and Example 6) Even if they are overlapped, they have almost no adhesiveness and are easy to peel off without resistance, so the anti-adhesion property is very excellent. On the other hand, comparative example 3 and comparative example 4 using the multilayer body containing the resin sheet which does not contain a silylated polyolefin (B) showed adhesiveness at the time of lamination, and there was room for improvement in blocking resistance. Thus, since the resin sheet or laminated body of the Example of this embodiment is excellent in blocking resistance, even when it winds up into a roll shape and makes a roll material, it thinks that it can be easily unwound. Furthermore, since the resin sheets or the laminates are suppressed from sticking due to pressure bonding or the like at the time of overlapping cutting, etc., it is considered that the workability is excellent, and the production stability of products using the resin sheets or laminates of this embodiment is considered to be excellent. excellent. Furthermore, as is clear from Table 1 and Table 2, it was shown that the total light transmittance related to transparency is more excellent by making it into a multilayer body.

This application claims priority based on Japanese application Japanese Patent Application No. 2021-047656 for which it applied on March 22, 2021, and the entire disclosure is incorporated herein.

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Claims (13)

A sheet or film comprising a composition comprising: The polymer (A) contains at least one polymer selected from the group consisting of 4-methyl-1-pentene polymer (A1) and styrene elastomer (A2); and Silylated polyolefin (B). The sheet or film according to claim 1, wherein the maximum value of the loss tangent tanδ obtained by measuring the temperature dependence of the dynamic viscoelasticity of the sheet or film is 0.6 in the temperature range of 0°C to 50°C above. The sheet or film according to claim 1 or claim 2, wherein, in the 4-methyl-1-pentene polymer (A1), a structural unit derived from 4-methyl-1-pentene (a1) and the structural unit (a2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 100 mol% in total, and Contains 60 mol% to 99 mol% of the structural unit (a1), and 1 mol% to 40 mol% of the structural unit (a2). The sheet or film according to claim 1 or claim 2, wherein the styrene-based elastomer (A2) comprises a hydrogenated styrene-based elastomer, The proportion of monomer units derived from styrene in 100% by mass of the hydrogenated styrene-based elastomer is 5% by mass to 80% by mass. The sheet or film according to Claim 1 or Claim 2, wherein the polymer (A) comprises a structural unit (a1) derived from 4-methyl-1-pentene and Interpolymers in which the structural units (a2) of α-olefins with 2 to 20 carbon atoms other than 1-pentene account for a total of 100 mol%, The interpolymer comprises 60 mol% to 99 mol% of the structural unit (a1), and 1 mol% to 40 mol% of the structural unit (a2). The sheet or film according to claim 1 or claim 2, wherein the silylated polyolefin (B) comprises a silylated polyolefin represented by the following general formula (1),

(In the general formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group with 1 to 20 carbons; R is a hydrocarbon group with 1 to 20 carbons; each R can be the same or may be different; m is an integer from 1 to 10,000; in the case of multiple A ^3s , each A ³ may be the same or different; wherein, at least one of A ¹ , A ² , and A ³ represents a polyolefin chain). The sheet or film according to Claim 1 or Claim 2, wherein the polymer (A) includes a 4-methyl-1-pentene polymer (A1) and a styrene elastomer (A2). The sheet or film according to Claim 1 or Claim 2, wherein the silylated polyolefin (B ). A laminated body, the laminate has: The sheet or film (L1) according to any one of claim 1 to claim 8; and A sheet or film (L2) comprising a layer comprising a thermoplastic elastomer. The laminate according to Claim 9, wherein the sheet or film (L1) comprises: The total of the structural unit (a1) derived from 4-methyl-1-pentene and the structural unit (a2) derived from an α-olefin having 2 to 20 carbon atoms other than the above-mentioned 4-methyl-1-pentene is 100 mol% copolymer, The interpolymer comprises 60 mol% to 99 mol% of the structural unit (a1), and 1 mol% to 40 mol% of the structural unit (a2). The laminated body according to Claim 9 or Claim 10, wherein the sheet or film (L1) and the sheet or film (L2) are laminated with a total of three or more layers, At least one outer layer is a sheet or film (L1). The laminate according to Claim 9 or Claim 10, wherein the sheet or film (L1) contains only a 4-methyl-1-pentene polymer (A1) as the polymer (A), The sheet or film (L2) contains a styrene-based elastomer as the thermoplastic elastomer. The laminate according to Claim 9 or Claim 10, wherein the maximum value of the loss tangent tanδ obtained by measuring the temperature dependence of the dynamic viscoelasticity of the sheet or film (L1) located on the outermost layer is less than or equal to 0.6 or more in the temperature range of 0°C to 50°C.