JP7144180B2 - Laminates and release liner - Google Patents

Description

The present invention relates to a laminate having a layer containing a 4-methyl-1-pentene polymer and a base paper layer, and a release paper.

4-Methyl-1-pentene polymer has excellent releasability due to its extremely low surface tension and high heat resistance, so it is used as an industrial release film and synthetic leather members (for example, the surface layer of synthetic leather ) It is used as process paper for manufacturing, etc., and is often used as a laminate of a 4-methyl-1-pentene polymer film and a paper or plastic substrate.

Examples of such laminates include process paper for embossing in the production of synthetic leather members. In order to manufacture a member for synthetic leather, for example, first, a process paper is inserted between a nip roll and an embossing roll to give an embossed pattern or a crimped pattern to the surface of the high-melting resin layer. Next, a polyvinyl chloride (hereinafter referred to as "PVC") sol or a polyurethane solution, which is a raw material for synthetic leather members, is applied to the surface of the high melting point resin layer and cured by heating. After that, the process paper is peeled off to obtain a synthetic leather member made of PVC or polyurethane with the embossed pattern transferred to the surface.

For example, in Patent Document 1, paper, a low melting point 4-methyl-1-pentene resin layer (A), and a high melting point 4-methyl-1-pentene resin layer (B) are laminated in this order. An embossing casting paper is disclosed. More specifically, as a specific example, an embossing process in which paper/4-methyl-1-pentene/1-decene copolymer layer/4-methyl-1-pentene homopolymer layer are laminated in this order. Paper (Example 1 of Patent Document 1), and paper/4-methyl-1-pentene/1-decene copolymer layer/4-methyl-1-pentene/1-decene copolymer layer are laminated in this order. An embossing process paper (Example 2 of Patent Document 1) is disclosed.

On the other hand, as is conventionally known, 4-methyl-1-pentene polymer tends to have low melt viscosity and melt tension at high temperatures such as during lamination molding. tend to exhibit inferior properties in molding when compared to polyethylene or polypropylene. Patent Document 2 discloses blending low-density polyethylene having a high melt viscosity with a 4-methyl-1-pentene/1-decene copolymer or the like in order to improve the properties during molding.

Further, Patent Documents 3 and 4 disclose blending high-pressure low-density polyethylene with 4-methyl-1-pentene copolymer from the viewpoint of crack prevention during embossing.
In Patent Document 5, by using a 4-methyl-1-pentene/1-hexene random copolymer or the like as a 4-methyl-1-pentene polymer, the surface layer is softened and curled. This patent discloses a synthetic leather release paper that is excellent in suppressing cracking and cracking resistance.

In Patent Document 6, the content of structural units (P) derived from 4-methyl-1-pentene and structural units (AQ) derived from other α-olefins having 2 to 20 carbon atoms is specified. The polymer (A) within the range, the copolymer (B ), the layer containing the 4-methyl-1-pentene polymer is less prone to molding defects such as necking and ear sway during molding by extrusion lamination, and the excellent heat resistance that such a laminate conventionally has. and a release paper that exhibits excellent curl suppression and excellent crack resistance after embossing while maintaining release properties.

Japanese Patent No. 2728138 Japanese Patent No. 3320526 JP-A-2002-292716 JP 2003-127284 A JP 2008-143172 A JP 2017-074775 A

Although the release papers described in Patent Documents 2 to 4 have excellent heat resistance, they do not have sufficient extensibility, so fine cracks occur at the embossed edges, and curling occurs due to residual stress during molding. There was a problem of

In addition, the release paper described in Patent Document 5 is excellent in crack resistance and suppression of curling, but has a problem of insufficient release force due to low heat resistance.
The release paper described in Patent Document 6 is less likely to cause molding defects such as necking and ear swaying during molding by extrusion lamination, has an effect of suppressing curling, and has crack resistance. Sex has come to be demanded.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and aims to solve the above problems. That is, the present invention provides a laminate and a release paper having a layer containing a 4-methyl-1-pentene polymer and a base paper layer, wherein the 4-methyl-1-pentene polymer is formed by extrusion lamination. Molding defects such as necking and edge swaying of layers containing coalescence are less likely to occur, excellent curl suppression, excellent crack resistance after embossing, and the ability to maintain the embossed shape even after heating. An object of the present invention is to provide a laminate and a release paper having heat resistance.

Specific means for solving the above problems are as follows.
[1] A laminate having a layer containing a 4-methyl-1-pentene polymer (X) that satisfies the following requirements (Xa), (Xb) and (Xc), and a base paper layer body.
(Xa) The content of structural units derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 - excluding pentene) is 0.3 to 70.0 mol% of structural units derived from at least one olefin.
(Xb) when measured by a cross-fractionated chromatograph (CFC) using an infrared spectrophotometer in the detection part, at least one peak A of the amount of eluted components exists in the range of 100 to 140 ° C., In addition, at least one peak B of the amount of eluted components is present below 100°C.
The mesodiad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 95.0 to 100%.

[2] 10.0 to 95.0 parts by mass of the 4-methyl-1-pentene polymer (X), the 4-methyl-1-pentene polymer (x1) satisfying the following requirements (x1-a); 5.0 to 90.0 parts by mass of a 4-methyl-1-pentene copolymer (x2) that satisfies the following requirements (x2-a) (however, the total of the polymer (x1) and the copolymer (x2) 100 parts by mass).
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene The content of structural units derived from at least one olefin selected from (except for ) is 0 to 20.0 mol%.
(x2-a) The content of structural units derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 - The content of structural units derived from at least one olefin selected from (excluding pentene) is 2.0 to 80.0 mol%, provided that ethylene and 3 carbon atoms in the polymer (x1) is greater than the content of structural units derived from at least one olefin selected from ~20 α-olefins (excluding 4-methyl-1-pentene).

[3] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (x1) measured in decalin at 135°C is in the range of 0.5 to 20 dl/g, and the melting point measured by DSC ( Tm) is in the range of 210 to 260 ° C., and the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (x2) measured in decalin at 135 ° C. is 0.5 to 20 dl / g. range, and the melting point (Tm) measured by DSC is in the range of less than 220°C, or the peak indicating the melting point does not appear in the DSC measurement, the laminate according to the above [2].

[4] The above [1], wherein the 4-methyl-1-pentene polymer (X) has an intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.5 to 10.0 dl/g. The laminate according to any one of [3].

[5] The laminate according to any one of [1] to [4], wherein in the requirement (Xc), the mesodiad fraction (m) is in the range of 98.0 to 100%.
[6] The layer containing the 4-methyl-1-pentene polymer (X) further comprises a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (Aa) to (Ae): ), and the layer containing the 4-methyl-1-pentene polymer (X) comprises the 4-methyl-1-pentene polymer (X) and the 4-methyl-1-pentene polymer (A ), 1 to 99 parts by mass of the 4-methyl-1-pentene polymer (X) and 1 to 99 parts by mass of the 4-methyl-1-pentene polymer (A) in the total amount of 100 parts by mass. The laminate according to any one of [1] to [5].
(Aa) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1- The content of structural units (AQ) derived from at least one olefin selected from (excluding pentene) is 0 to 10 mol %.
(Ab) The intrinsic viscosity [η] measured in decalin at 135°C is
1.0 to 4.0 dl/g.
(Ac) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(Ad) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820-850 kg/m ³ .

[7] Further, it contains a 4-methyl-1-pentene polymer (A) that satisfies the requirements (Aa) to (Ae), and the 4-methyl-1-pentene polymer (X ), wherein the base paper layer, the layer containing the 4-methyl-1-pentene polymer (X), and the second layer are laminated in this order. The laminate according to any one of [1] to [6].

[8] The laminate according to [7], wherein the second layer is located on the outermost layer.
[9] A release liner comprising the laminate according to any one of [1] to [6].
[10] A release paper comprising the laminate according to [7] or [8].
[11] The laminate according to any one of [1] to [8], wherein the base paper layer and the layer containing the 4-methyl-1-pentene polymer (X) are laminated. Production method.
[12] In the above [7] or [8], wherein the base paper layer, the layer containing the 4-methyl-1-pentene polymer (X), and the second layer are laminated in this order. A method for manufacturing the described laminate.

[13] A step of embossing the layer containing the polymer (X) of the release paper according to [9] above, a synthetic leather member on the surface of the embossed layer containing the polymer (X) A synthetic leather member having an embossed pattern, comprising a step of applying a forming material and then curing to form a synthetic leather member having an embossed pattern, and a step of peeling the release paper from the synthetic leather member. manufacturing method.

[14] The step of embossing the second layer of the release paper according to [10], applying a synthetic leather member forming material to the surface of the embossed second layer, and then curing A method for manufacturing a synthetic leather member having an embossed pattern, comprising: forming a synthetic leather member having an embossed pattern; and peeling the release paper from the synthetic leather member.

The laminate of the present invention can be molded while suppressing the occurrence of neck-in and ear swaying of the layer composed of the polymer (X) during molding by extrusion lamination, curling is suppressed, and crack resistance is obtained after embossing. It can be suitably used as a release paper having excellent heat resistance that can maintain the embossed shape even after heating.

Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments at all, and can be carried out with appropriate modifications within the scope of the purpose of the present invention. be able to.

As used herein, the term "polymer" is used to include homopolymers and copolymers. Therefore, for example, the 4-methyl-1-pentene polymer (x1) described later may be a 4-methyl-1-pentene homopolymer or a 4-methyl-1-pentene copolymer. good. Similarly, the term "polymerization" is used to include both homopolymerization and copolymerization.

In addition, "content of structural units derived from at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene)" When there are more than one, it means the total content of two or more structural units derived from the olefin.
The laminate of the present invention has a layer containing a specific 4-methyl-1-pentene polymer (X) (hereinafter also simply referred to as "polymer (X) layer") and a base paper layer. .

[Polymer (X) layer)]
The polymer (X) layer contains 4-methyl-1-pentene polymer (X).

[4-methyl-1-pentene polymer (X)]
The 4-methyl-1-pentene polymer (X) (hereinafter also simply referred to as "polymer (X)") satisfies the requirements (Xa), (Xb) and (Xc) described below. ).

<Requirements (Xa)>
Requirement (Xa): The content of structural units derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl -excluding 1-pentene) is 0.3 to 70.0 mol % of structural units derived from at least one olefin selected from.

The content of structural units derived from 4-methyl-1-pentene is preferably 40.0 to 99.5 mol%, more preferably 50.0 to 99.0 mol%, still more preferably 70.0 to 97.0 mol %, 75.0 to 96.0 mol %, or 80.0 to 95.0 mol %. In addition, the content of structural units derived from at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 0.5 to 60. .0 mol%, more preferably 1.0 to 50.0 mol%, still more preferably 3.0 to 30.0 mol%, 4.0 to 25.0 mol%, or 5.0 to 20.0 mol% in mol %.

Examples of the olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. is mentioned. The olefin can be appropriately selected depending on the application and required physical properties of the polymer (X). For example, the olefin is preferably an α-olefin having 8 to 18 carbon atoms from the viewpoint of imparting appropriate elastic modulus, flexibility, and flexibility to the polymer (X) layer, 1-octene, At least one selected from 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferred.

The polymer (X) contains structural units other than structural units derived from 4-methyl-1-pentene and structural units derived from the olefin (hereinafter also referred to as "other structural units"), as long as the effects of the present invention are not impaired. ). The content of other structural units is, for example, 0 to 10.0 mol %.

Examples of monomers leading to other structural units include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins and halogenated olefins include, for example, paragraphs [0035] to [0041] of JP-A-2013-169685. compounds can be used.
When the polymer (X) has other structural units, the other structural units may be contained singly or in combination of two or more.

<Requirements (Xb)>
Requirement (Xb): When measured with a cross-fractionation chromatograph (CFC) using an infrared spectrophotometer as a detection part, there is at least one peak A in the amount of eluted components in the range of 100 to 140 ° C. In addition, at least one peak B of the eluted component amount exists in the range of less than 100°C, preferably from 0°C to less than 100°C. Peak A may be unimodal or multimodal. Also, the peak B may be a single peak or multiple peaks.

By using a polymer having peaks A and B of the amount of eluted components within the above range, it is excellent in that a molded article with low rigidity (high flexibility) can be obtained while maintaining high heat resistance.

For example, in the method for producing the polymer (X) described later, peak A is derived from the polymer (x1) produced in step (1), and peak B is derived from the copolymer (x2) produced in step (2). derived from

<Requirements (Xc)>
Requirement (Xc): The mesodiad fraction (m) measured by ¹³ C-NMR is in the range of 95.0 to 100%. The mesodiad fraction (m) is preferably in the range of 96.0 to 100%, more preferably 97.0 to 100%, even more preferably 98.0 to 100%, particularly preferably 98.5 to 100%. . The upper limit is preferably 100%, but can also be 99.9%. Within this range, fish eyes and poor appearance due to eye mucus during molding of the polymer (X) and its resin composition are less likely to occur. It is presumed that this is because the uniformity of the composition distribution is improved by narrowing the melting point distribution.

<Other requirements>
The polymer (X) has an intrinsic viscosity [η] measured in decalin at 135°C of preferably 0.5 to 10.0 dl/g, more preferably 0.5 to 5.0 dl/g, further preferably It is in the range of 1.0 to 5.0 dl/g.

The intrinsic viscosity [η] of the polymer (X) can be adjusted, for example, by adjusting the [η] values and content ratios of the polymer (x1) and the copolymer (x2), which will be described later.
Details of the measurement conditions for the above requirements are described in Examples.

<Polymer component contained in 4-methyl-1-pentene polymer (X)>
The 4-methyl-1-pentene polymer (X) comprises 10.0 to 95.0 parts by mass of a 4-methyl-1-pentene polymer (x1) that satisfies the following requirement (x1-a), and the following requirement (x2 It is preferable to contain 5.0 to 90.0 parts by mass of a 4-methyl-1-pentene copolymer (x2) that satisfies -a). However, the total amount of polymer (x1) and copolymer (x2) is 100 parts by mass. Polymer (X) is usually preferably a resin obtained by melting particles (x) containing polymer (x1) and copolymer (x2) in the same particle.

The amount of polymer (x1) is preferably 20.0 to 90.0 parts by mass, more preferably 30.0 to 85.0 parts by mass. The amount of copolymer (x2) is preferably 10.0 to 80.0 parts by mass, more preferably 15.0 to 70.0 parts by mass. However, the total amount of polymer (x1) and copolymer (x2) is 100 parts by mass.

<<4-methyl-1-pentene polymer (x1)>>
The 4-methyl-1-pentene polymer (x1) (hereinafter also simply referred to as "polymer (x1)") satisfies the following requirement (x1-a).
Requirement (x1-a): The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, preferably 85.0 to 100 mol%, more preferably 90.0 to 100 mol%, more preferably 95.0 to 100 mol%, at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter (Also referred to as "comonomer 1".) is 0 to 20.0 mol%, preferably 0 to 15.0 mol%, more preferably 0 to 10.0 mol%, still more preferably is 0 to 5.0 mol %.

As for the content of the structural units, the total amount of repeating structural units is 100 mol %.
Examples of comonomers 1 include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene. is mentioned. Comonomer 1 can be appropriately selected according to the application and required physical properties of the polymer (X). For example, the comonomer 1 is preferably an α-olefin having 8 to 18 carbon atoms from the viewpoint of imparting appropriate elastic modulus, flexibility, and flexibility to the polymer (X) layer, 1-octene, At least one selected from 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferred.

When the polymer (x1) has a structural unit derived from comonomer 1, only one type of the structural unit may be contained, or two or more types may be contained.
The polymer (x1) is a structural unit derived from another monomer 1 other than 4-methyl-1-pentene and comonomer 1 (hereinafter also referred to as "other structural unit 1"), as long as the effects of the present invention are not impaired. .). The content of other structural unit 1 is, for example, 0 to 10.0 mol %.

Other monomers 1 include, for example, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins and halogenated olefins include, for example, paragraphs [0035] to [0041] of JP-A-2013-169685. compounds can be used.

When the polymer (x1) has the other structural unit 1, only one type of the other structural unit 1 may be contained, or two or more types may be contained.
The polymer (x1) preferably satisfies at least one physical property requirement selected from the following physical properties ([η], melting point).

The polymer (x1) preferably has a limiting viscosity [η] measured in decalin at 135° C. of 0.5 to 20 dl/g, more preferably 0.5 to 5.0 dl/g.
The polymer (x1) preferably has a melting point (Tm) of 210 to 260°C, more preferably 220 to 260°C, still more preferably 225 to 260°C, as measured by a differential scanning calorimeter (DSC). When the melting point of the polymer (x1) is within the above range, the obtained polymer (X) has excellent heat resistance.
The details of the method for measuring the above configuration, physical properties, etc. are described in Examples.

<<4-methyl-1-pentene copolymer (x2)>>
The 4-methyl-1-pentene copolymer (x2) (hereinafter also simply referred to as "copolymer (x2)") satisfies the following requirement (x2-a).
Requirement (x2-a): The content of structural units derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, preferably 25.0 to 95.0 mol%, more preferably 30.0 to 95.0 mol%, more preferably 30.0 to 92.0 mol%, selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) The content of structural units derived from at least one olefin (hereinafter also referred to as "comonomer 2") is 2.0 to 80.0 mol%, preferably 5.0 to 75.0 mol%, more preferably is 5.0 to 70.0 mol%, more preferably 8.0 to 70.0 mol%. However, the content (mol%) of the structural unit derived from the comonomer 2 in the copolymer (x2) is higher than the content (mol%) of the structural unit derived from the comonomer 1 in the polymer (x1).

As for the content of the structural units, the total amount of repeating structural units is 100 mol %.
Comonomer 2 includes, for example, the olefins exemplified as comonomer 1 in requirement (x1-a). The comonomer 2 can be appropriately selected depending on the application and required physical properties of the polymer (X).

In the copolymer (x2), only one kind of structural unit derived from the comonomer 2 may be contained, or two or more kinds thereof may be contained. When polymer (x1) has a structural unit derived from comonomer 1, comonomer 1 of polymer (x1) and comonomer 2 of copolymer (x2) may be the same or different.

The copolymer (x2) is a structural unit derived from a monomer 2 other than 4-methyl-1-pentene and comonomer 2 (hereinafter also referred to as "other structural unit 2"), as long as the effects of the present invention are not impaired. ). The content of other structural units 2 is, for example, 0 to 10.0 mol %.

Other monomers 2 include, for example, the compounds exemplified as other monomers 1 in the polymer (x1). When the copolymer (x2) has the other structural unit 2, only one type of the other structural unit 2 may be contained, or two or more types may be contained.

The copolymer (x2) preferably satisfies at least one physical property requirement selected from the following physical properties ([η], melting point).
Copolymer (x2) preferably has a limiting viscosity [η] measured in decalin at 135° C. of 0.5 to 20 dl/g, more preferably 1.0 to 7.0 dl/g.

The copolymer (x2) preferably has a melting point (Tm) of less than 220° C. as measured by a differential scanning calorimeter (DSC), or does not exhibit a melting point peak in the DSC measurement. More preferably, the melting point (Tm) is in the range of less than 210°C, or no peak indicating the melting point appears in DSC measurement. More preferably, the melting point (Tm) is in the range of 120 to 200°C, or no peak indicating the melting point appears in DSC measurement. Particularly preferably, the melting point (Tm) is in the range of 130 to 180°C, or no peak indicating the melting point appears in DSC measurement. Such a mode is preferable in that a 4-methyl-1-pentene polymer having a high content of structural units derived from the comonomer can be obtained.

The details of the method for measuring the above configuration, physical properties, etc. are described in Examples. The content of the constituent units of the copolymer (x2), [η] and Tm are the measurement results of the polymer (x1) and the polymer (X), and the ratio of the polymer (x1) and the copolymer (x2). It can be calculated from the mass ratio.

<Method for producing 4-methyl-1-pentene polymer (X)>
The 4-methyl-1-pentene polymer (X) can be prepared, for example, by the step (1) of producing the 4-methyl-1-pentene polymer (x1) by slurry polymerization, and the polymer obtained in the step (1). In the presence of the coalescence (x1), the 4-methyl-1-pentene copolymer (x2) is added to the above when the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass. The copolymer (x2) can be produced by a production method comprising the step (2) of producing by slurry polymerization in a range of 5.0 to 90.0 parts by mass.

That is, the production method has steps (1) and (2) with different polymerization conditions, but a two-stage polymerization of steps (1) and (2) may be used, and in addition to steps (1) and (2) It may be a three-stage or higher polymerization that further includes other steps.

<<Step (1)>>
In step (1), a 4-methyl-1-pentene polymer (x1) is produced by slurry polymerization.
In step (1), when comonomer 1 is used, the supply amount ratio of 4-methyl-1-pentene and comonomer 1 is set so that the content of structural units derived from each is within the above range, and comonomer 1 is Although it varies depending on the reactivity, for example, the supply amount ratio 4-methyl-1-pentene/comonomer 1 (molar ratio) is 100/0 to 80/20, preferably 100/0 to 90/10, more preferably 100/ It ranges from 0 to 95/5, more preferably from 100/0 to 97/3, particularly preferably from 100/0 to 98/2, and is within a range where slurry polymerization is possible.

In step (1), a slurry containing polymer (x1) is obtained. The slurry concentration, that is, the polymer (x1) particle concentration is usually 0.015 to 45% by mass, preferably 0.03 to 35% by mass. The slurry concentration can be calculated by filtering, for example, by the method described in the Examples section.

<<Step (2)>>
In step (2), a 4-methyl-1-pentene copolymer (x2) is produced by slurry polymerization in the presence of the polymer (x1) obtained in step (1).
In step (2), the supply ratio of 4-methyl-1-pentene and comonomer 2 is set so that the content of structural units derived from each is within the above range, and varies depending on the reactivity of comonomer 2. , for example, a supply ratio of 4-methyl-1-pentene/comonomer 2 (molar ratio) of 20/80 to 98/2, preferably 30/70 to 95/5, more preferably 30/70 to 92/8, More preferably, it is in the range of 30/70 to 90/10.

In the step (2), when the total amount of the polymer (x1) obtained in the step (1) and the copolymer (x2) obtained in the step (2) is 100 parts by mass, the copolymer (x2) The amount of 5.0 to 90.0 parts by mass, preferably 10.0 to 80.0 parts by mass, more preferably 15.0 to 70.0 parts by mass, the copolymer (x2) is produced do. When these polymers are produced in such a ratio, a 4-methyl-1-pentene polymer having a high content of constitutional units derived from comonomers (collectively referred to as comonomer 1 and comonomer 2) is produced. It is preferable in that it can be obtained.

In addition, after producing the polymer (x1) in the step (1), by producing the copolymer (x2) in the step (2), if the order is reversed, solution polymerization tends to occur. Slurry polymerization is possible in each of the above steps compared to the above.

In step (2), the amounts of 4-methyl-1-pentene and comonomer 2 supplied are selected so that the amount ratio of polymer (x1) to copolymer (x2) is within the above range.
In step (2), in one embodiment, 4-methyl-1-pentene and comonomer 2 can be added to the slurry containing polymer (x1) and slurry polymerization of these monomers can be carried out.

In step (2), a slurry containing particles (x) containing polymer (x1) and copolymer (x2) is obtained. The slurry concentration, that is, the particle (x) concentration is usually 3 to 50% by mass, preferably 5 to 40% by mass. The slurry concentration can be calculated by filtering, for example, by the method described in the Examples section.

<<Polymerization conditions>>
Polymerization conditions in steps (1) and (2) are described below.
Examples of the polymerization solvent include hydrocarbon media, and specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures of two or more selected from these. Olefins such as 4-methyl-1-pentene and other α-olefins can also be used as polymerization solvents. Thus, in the present invention, olefin polymerization can be carried out in a hydrocarbon medium and/or using the olefin itself used for polymerization as a medium.

Slurry polymerization is employed in the above production method, and the term “slurry polymerization” means that the polymer produced by the polymerization does not substantially dissolve in the medium used during polymerization, for example, in the form of fine particles dispersed in the medium. A polymerization characterized by the presence of

In steps (1) and (2), the olefin polymerization temperature is usually 0 to 100° C., preferably 20 to 70° C.; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. These conditions for steps (1) and (2) may be the same or different.

In particular, hydrogen can be said to be a preferable additive because it can have the effect of improving the polymerization activity of the catalyst that can be used in olefin polymerization and the effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added to the system, the appropriate amount is about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system can be adjusted by a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, a method of It can also be adjusted by discharging the gas out of the system.

The molecular weight of the resulting polymer can be adjusted in each of step (1) and step (2) by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by adjusting the carrier (D) described later that can constitute the metallocene catalyst or by adjusting the concentration of 4-methyl-1-pentene in the polymerization solvent.

《Metallocene catalyst》
In steps (1) and (2), polymer (x1) and copolymer (x2) are each preferably produced using a metallocene catalyst. Compared to the case of using a Ziegler catalyst, the use of a metallocene catalyst reduces the amount of the solvent-soluble portion of the resulting polymer and improves the slurry properties. Good properties. Therefore, the desired solvent-insoluble particles can be efficiently separated and recovered from the slurry.

The metallocene catalyst contains a metallocene compound (C).
The metallocene catalyst can further contain a support (D).
The metallocene catalyst is preferably a particulate catalyst with a volume statistic D50 in the range of 1 to 500 μm, more preferably in the range of 2 to 200 μm, more preferably in the range of 5 to 50 μm. D50 in terms of volume statistics can be determined by laser diffraction/scattering method using, for example, MT3300EX II manufactured by Microtrac. The D50 of the metallocene catalyst is usually equivalent to the D50 of the carrier (D) described later, that is, usually in the range of 0.90 to 1.10 times the D50 of the carrier (D), preferably 0.95 to 1.05. It is in the range of 1.0-fold, more preferably in the range of 1.0-1.03-fold.

<Metallocene compound (C)>
Examples of the metallocene compound (C) include compounds disclosed in WO 2005/121192, WO 2014/050817, WO 2014/123212, WO 2017/150265, etc. . Bridged metallocene compounds disclosed in International Publication No. 2014/050817, International Publication No. 2017/150265, etc. are preferably mentioned, but the scope of the present invention is not limited thereto.
The metallocene compound (C) is preferably a compound represented by general formula [C1].

In formula [C1], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, R ² to R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group and may be the same or different, and the respective substituents may be combined with each other to form a ring. M is a transition metal of Group 4 of the periodic table, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand and a neutral capable of being coordinated with a lone electron pair are selected from the same or different combinations of ligands, j is an integer from 1 to 4;

As a particularly preferred metallocene compound (C), there is little decrease in polymerization activity throughout the steps (1) and (2), high stereoregular polymerization is possible, excellent comonomer copolymerization performance, and high molecular weight copolymerization is possible. A complex compound capable of obtaining coalescence is preferably used. By enabling highly stereoregular polymerization, elution of polymer components during slurry polymerization is suppressed, and the melting point of polymer (x1) can be adjusted to a high range, resulting polymer (X). It is possible to adjust the heat resistance of In addition, excellent comonomer copolymerization performance makes it possible to freely change the copolymerization composition of the polymer (x1) and the copolymer (x2), and the flexibility according to the application of the polymer (X) can be appropriately adjusted. can be set to In addition, the fact that a copolymer with a high molecular weight can be obtained makes it possible to adjust the molecular weight of the copolymer (x2) to a high level, and to increase the strength and toughness of the resulting polymer (X). preferred because it can

From such a viewpoint, among the compounds represented by the general formula [C1], compounds represented by the general formula [C2] described in International Publication No. 2014-050817 and the like are particularly preferable.

式［Ｃ２］中、Ｒ^1bは炭化水素基、ケイ素含有基またはハロゲン含有炭化水素基であり、Ｒ^2b～Ｒ^12bは水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、それぞれの置換基は互いに結合して環を形成してもよい。Ｍは周期表第４族遷移金属であり、ｎは１～３の整数であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、ｊは１～４の整数である。

In formula [C2], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, R ^2b to R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group and may be the same or different, and the respective substituents may be combined with each other to form a ring. M is a Group 4 transition metal of the periodic table, n is an integer of 1 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anion ligand and lone pair-coordinable neutral ligands are selected in the same or different combinations, and j is an integer of 1-4.

(R ¹ to R ¹⁰ , R ^1b to R ^12b )
Examples of hydrocarbon groups for R ¹ to R ¹⁰ and R ^1b to R ^12b include linear hydrocarbon groups, branched hydrocarbon groups, saturated cyclic hydrocarbon groups, unsaturated cyclic hydrocarbon groups, and saturated hydrocarbon groups. A group obtained by substituting one or more hydrogen atoms of with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1-20, preferably 1-15, more preferably 1-10.

Linear hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl straight-chain alkyl groups such as groups, n-decanyl groups; and straight-chain alkenyl groups such as allyl groups.

Branched hydrocarbon groups include, for example, isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group and other branched alkyl groups.

Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and methylcyclohexyl group; polycyclic groups such as norbornyl group, adamantyl group and methyladamantyl group. be done.

Examples of cyclic unsaturated hydrocarbon groups include phenyl, tolyl, naphthyl, biphenyl, phenanthryl, anthracenyl and other aryl groups; cyclohexenyl and other cycloalkenyl groups; 5-bicyclo[2.2. 1] polycyclic unsaturated alicyclic groups such as hept-2-enyl group.

Examples of the group obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, a triphenylmethyl group, and the like. A group obtained by substituting one or more hydrogen atoms of the alkyl group of with an aryl group.

Examples of the silicon-containing group for R ¹ to R ¹⁰ and R ^1b to R ^12b include the formula -SiR ₃ (wherein , and each of a plurality of R is independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.).

Halogen-containing hydrocarbon groups for R ¹ to R ¹⁰ and R ^1b to R ^12b are obtained by substituting one or more hydrogen atoms of the above hydrocarbon groups with halogen atoms, such as a trifluoromethyl group. groups.

Halogen atoms in R ² to R ¹⁰ and R ^2b to R ^12b include, for example, fluorine, chlorine, bromine and iodine atoms.
Of the substituents R ² to R ¹⁰ and R ^2b to R ^12b , two substituents (e.g., R ^2b and R ^3b , R ^3b and R ^4b , R ^5b and R ^6b , R ^6b and R ^7b , R ^8b and R ^9b ; ^{R 9b} and R ^10b ; R ^10b and R ^{11b ;} may

In the present invention, the ring (spiro ring, additional ring) formed by bonding two substituents to each other includes, for example, an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring and a cyclopentene ring, preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Moreover, such a ring structure may further have a substituent such as an alkyl group on the ring.

From the viewpoint of stereoregularity, R ^1b is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, further preferably not an aryl group, and a linear hydrocarbon group. A group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferred, and a substituent in which the carbon having a free valence (the carbon attached to the cyclopentadienyl ring) is a tertiary carbon is particularly preferred. preferable.

Specific examples of R ^1b include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group and a 1-adamantyl group, which are more preferred. is a tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group, and the like. It is an adamantyl group.

In general formula [C2], the fluorene ring portion is not particularly limited as long as it has a structure obtained from a known fluorene derivative, but R ^4b and R ^5b are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.

R ^2b , R ^3b , R ^6b and R ^7b are preferably hydrogen atoms or hydrocarbon groups, more preferably hydrocarbon groups, still more preferably hydrocarbon groups having 1 to 20 carbon atoms. In addition, R ^2b and R ^3b may combine with each other to form a ring, and R ^6b and R ^7b may combine with each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2 ,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta [b,h]fluorenyl group, particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- 1H-dibenzo[b,h]fluorenyl group.

R ^8b is preferably a hydrogen atom.
R ^9b is more preferably a hydrocarbon group, R ^9b is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, Particularly preferably, R ^9b is an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R ^10b and R ^11b are also preferably hydrogen atoms.

Alternatively, when n=1, it is more preferable that R ^9b and R ^10b combine with each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring. In this case, R ^11b is preferably a hydrogen atom.
R ^12b is preferably a hydrocarbon group, particularly preferably an alkyl group.

(for M, Q, n and j)
M is a Group 4 transition metal of the periodic table, for example Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.
Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair.
Halogen atoms for Q include, for example, fluorine, chlorine, bromine, and iodine.

As the hydrocarbon group for Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include 1,3-trimethylbutyl group and neopentyl group; examples of cycloalkyl groups having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group and 1-methyl-1-cyclohexyl group. More preferably, the number of carbon atoms in the hydrocarbon group is 5 or less.

Neutral conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4- diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η Examples include 4-1,4 ^{-ditolyl-1,3-butadiene, s-cis- or s-trans-η 4 -1,4} -bis(trimethylsilyl)-1,3-butadiene.

Examples of anionic ligands include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate.

Neutral ligands capable of coordinating with a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Ethers such as ethane are exemplified.

A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
n is an integer of 1 to 3, preferably 1 or 2, more preferably 1; When n is the above value, it is preferable from the viewpoint of efficiently obtaining the produced polymer.

j is an integer of 1 to 4, preferably 2;
Preferred embodiments of the structures of the compounds represented by formula [C1] or [C2], ie, R ¹ to R ¹⁰ , R ^1b to R ^12b , M, n, Q and j, have been described above. In the present invention, any combination of each preferred aspect is also a preferred aspect. Such a bridged metallocene compound can be suitably used to obtain the polymer (X) having the physical properties described above.

The compound represented by the general formula [C2] includes (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6, 7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride or (8-(2,3,6,7-tetramethylfluorene)-12'-yl-(2-(adamantan-1-yl )-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))-zirconium dichloride is particularly preferred. Here, the octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b ,h]fluorene.

<Carrier (D)>
The carrier (D) is preferably particulate, and the metallocene catalyst is formed by immobilizing the metallocene compound (C) on its surface and inside. Such forms of catalysts are generally referred to as supported metallocene catalysts.

The carrier (D) is mainly composed of an organoaluminum compound (D-1), an organoboron compound (D-2), an inorganic compound (D-3), or a composite of two or more selected from them.

Examples of the organoaluminum compound (D-1) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-normaloctylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, tricycloalkylaluminum, and aluminoxanes. Representative organoaluminum oxy compounds can be mentioned. Further, the organoaluminum compound (D-1) includes, for example, an organoaluminumoxy compound containing a boron atom, and a halogen-containing compound as exemplified in WO 2005/066191 and WO 2007/131010. Mention may also be made of aluminoxanes, ionic aluminoxanes such as those exemplified in WO 2003/082879.

Examples of the organic boron compound (D-2) include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis (o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2, 4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium Tetrakis(3,5-ditrifluoromethylphenyl)borate, Tri(n-butyl)ammonium tetrakis(o-tolyl)borate, Dioctadecylmethylammonium tetraphenylborate, Dioctadecylmethylammoniumtetrakis(p-tolyl)borate, Dioctadecyl methylammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, dioctadecylmethylammonium, N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylaniliniumtetraphenylborate, N,N- diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-2,4,6-pentame Thilanilinium tetraphenylborate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

Examples of inorganic compounds (D-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchangeable layered compounds.
Examples of porous oxides include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or composites containing these or mixtures. For example, natural or synthetic zeolites, _SiO2 -MgO, _SiO2 - _Al2O3 , _SiO2 - _TiO2 , _{SiO2 - V2O5} , _{SiO2 - Cr2O3} , _{SiO2 - TiO2} -MgO, etc. can be exemplified.

Inorganic halides include, for example, _MgCl2 , _MgBr2 , _MnCl2 , _MnBr2 . The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.

Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used. Clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, or ionic crystalline compounds having layered crystal structures such as hexagonal close-packed type, antimony type, _CdCl2 type, _CdI2 type, etc. can be exemplified.

It is also preferable to chemically treat clay and clay minerals. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, or the like. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment, and the like.

As the carrier (D), a carrier containing an aluminum atom is preferable from the viewpoint of high activity and further suppression of the amount of the solvent-soluble portion. The content of aluminum atoms in the carrier (D) is preferably 20% by mass or more, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 35 to 47% by mass.

In addition, D50 of the carrier (D) as a volume statistical value is preferably 1 to 500 μm, more preferably 2 to 200 μm, and still more preferably 5 to 50 μm. D50 in terms of volume statistics can be determined by laser diffraction/scattering method using, for example, MT3300EX II manufactured by Microtrac.

As such a carrier (D), a solid aluminoxane is suitably used. Solid aluminoxanes are particularly preferably used.

By "solid" is meant that the aluminoxane remains substantially solid under the reaction environment in which the solid aluminoxane is used. More specifically, for example, when each component constituting an olefin polymerization catalyst is brought into contact with each other to prepare an olefin polymerization solid catalyst component, in an inert hydrocarbon medium such as hexane or toluene used for the reaction, a specific temperature and pressure It indicates that the aluminoxane is in a solid state under the environment.

Solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2), more preferably formula (1 ), more preferably polymethylaluminoxane consisting of only the structural unit represented by formula (1).

式（１）中、Ｍｅはメチル基である。

In formula (1), Me is a methyl group.

In formula (2), R ¹ is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, more preferably a hydrocarbon group having 2 to 10 carbon atoms. Hydrocarbon groups include, for example, ethyl, propyl, n-butyl, pentyl, hexyl, octyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3 -alkyl groups such as methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl and 2-ethylhexyl; cycloalkyl groups such as cyclohexyl and cyclooctyl; and aryl groups such as phenyl and tolyl.

The structure of the solid aluminoxane is not necessarily clarified, and it is usually assumed to have a structure in which the structural units represented by formula (1) and/or formula (2) are repeated about 2 to 50 times. However, it is not limited to this configuration. In addition, the bonding mode of the structural units is various, for example, linear, cyclic, or clustered, and the aluminoxane is usually composed of one of these, or is presumed to be a mixture thereof. . Further, the aluminoxane may consist only of structural units represented by formula (1) or formula (2).

As the solid aluminoxane, solid polymethylaluminoxane is preferable, and solid polymethylaluminoxane consisting only of structural units represented by formula (1) is more preferable.
The solid aluminoxane is usually particulate and preferably has a D50 of 1 to 500 μm, more preferably 2 to 200 μm, more preferably 5 to 50 μm in terms of volume statistics. D50 in terms of volume statistics can be determined by laser diffraction/scattering method using, for example, MT3300EX II manufactured by Microtrac.

The solid aluminoxane preferably has a specific surface area of 100-1000 m ² /g, more preferably 300-800 m ² /g. The specific surface area can be obtained by using the BET adsorption isotherm and utilizing gas adsorption and desorption phenomena on a solid surface.

A solid aluminoxane functions as a catalyst support. Therefore, in addition to solid aluminoxane, solid inorganic carriers such as silica, alumina, silica-alumina, and magnesium chloride, or solid organic carriers such as polystyrene beads, may not be used as catalyst carriers.
Solid aluminoxanes can be prepared, for example, by the methods described in WO2010/055652 and WO2014/123212.

<Organic compound component (E)>
The metallocene catalyst can also contain an organic compound component (E), if desired. The organic compound component (E) is used for the purpose of improving the polymerization performance and physical properties of the produced polymer, if necessary. As the organic compound component (E), the aforementioned organoaluminum compound (D-1) can be used. Other examples include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.

<Usage and order of addition of each component>
In the olefin polymerization, the method of using each component and the order of addition can be arbitrarily selected, but the following methods are exemplified. Hereinafter, the metallocene compound (C), the carrier (D) and the organic compound component (E) are also referred to as "components (C) to (E)" respectively.
(i) A method of adding components (C) and (D) to a polymerization vessel in any order.
(ii) A method of adding a catalyst component in which component (C) is supported on component (D) to a polymerization reactor.

In each of the above methods (i) to (ii), component (E) may be added at any stage. Also, at least two of each catalyst component may be pre-contacted.
Further, in the solid catalyst component in which component (C) is supported on component (D), olefins such as 4-methyl-1-pentene and 3-methyl-1-pentene may be prepolymerized. A further catalyst component may be supported on the solid catalyst component thus formed.

In the present invention, it is preferred to prepare a metallocene catalyst from the metallocene compound (C), the support (D) and optionally other components, and polymerize olefins containing 4-methyl-1-pentene in the presence of this catalyst. , that is, steps (1) and (2) are preferably performed. "Polymerizing an olefin containing 4-methyl-1-pentene in the presence of a metallocene catalyst" means adding each component constituting the metallocene catalyst to a polymerization vessel by any method, such as the above methods, to produce an olefin. A polymerizing embodiment is included.

In the steps (1) and (2), the amount of each component that can constitute the metallocene catalyst to be used in the olefin polymerization using the metallocene catalyst is as follows. Moreover, in the metallocene catalyst, the content of each component can be adjusted as follows.

Component (C) is generally used in an amount of 10 ^-10 to 10 ^-2 mol, preferably 10 ^-8 to 10 ^-3 mol, per liter of reaction volume. In component (D-1), the molar ratio [Al/M] of aluminum atoms in component (D-1) to all transition metal atoms (M) in component (C) is usually 10 to 10,000, preferably It can be used in an amount of 30-2000, particularly preferably 150-500. In component (D-2), the molar ratio [(D-2)/M] of component (D-2) to all transition metal atoms (M) in component (C) is usually 10 to 10,000, preferably It can be used in an amount of 30-2000, more preferably 150-500. In component (D-3), the molar ratio [(D-3)/M] of component (D-3) to all transition metal atoms (M) in component (C) is usually 10 to 10,000, preferably It can be used in an amount of 30-2000, more preferably 150-500.

When component (E) is used, when component (D) is component (D-1), the molar ratio of aluminum atoms in component (D-1) to component (E) [Al/(E)] is usually 0.002 to 500, preferably 0.01 to 60, and when component (D) is component (D-2), component (D-2) and component (E) When component (D) is component (D-3) in an amount such that the molar ratio [(D-2) / (E)] of is usually 0.002 to 500, preferably 0.01 to 60 is used in such an amount that the molar ratio [(D-3)/(E)] of component (D-3) to component (E) is usually 0.002 to 500, preferably 0.01 to 60. be able to.

《Solid-liquid separation process》
The slurry containing 4-methyl-1-pentene polymer particles (x) containing polymer (x1) and copolymer (x2) obtained in step (2) is subjected to solid-liquid separation, for example, filtration. Thus, particles (x) can be separated and collected. Particles (x) can be efficiently recovered by this solid-liquid separation step.

《Post-treatment process》
For the particles (x) obtained by the above production method, after production by the above method, if necessary, a known post-treatment process such as a catalyst deactivation treatment process, a catalyst residue removal process, a drying process, etc. is performed. good.
The 4-methyl-1-pentene polymer (X) is preferably a resin obtained by melting (preferably melt-kneading) the particles (x). The melting temperature is usually in the range of 180-350°C, preferably 200-320°C, more preferably 250-320°C.

Although the shape of the polymer (X) is not limited, it is usually preferably in the form of pellets for ease of handling. At this time, if necessary, various additives described later may be blended.
Pelletization methods include, for example, the following methods (1) and (2).
(1) A method of melt-kneading the particles (x) and other optional ingredients using an extruder, kneader, etc., and cutting them into a predetermined size.
(2) Particles (x) and other optional ingredients are dissolved in a suitable good solvent (e.g., hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is A method of removing, then melt-kneading using an extruder, kneader, etc., and cutting into a predetermined size.

The polymer (X) has high stereoregularity and is characterized by having both excellent heat resistance and relatively low rigidity or flexibility. Due to the component (usually polymer (x1)) having an eluted component amount peak in the range of 100 to 140 ° C. by CFC, the characteristic of high heat resistance that can maintain the embossed shape even after heating is obtained, and at 100 ° C. The flexibility property is obtained by the component (usually copolymer (x2)) having an eluted component amount peak of less than. This is a feature that is preferably provided by particles (x) containing polymer (x1) and copolymer (x2) in the same particle.

For example, it is a preferred embodiment compared to a resin that is a mixture of polymers obtained by separately polymerizing the polymer (x1) and the copolymer (x2), for example, a resin obtained by melt-kneading individual polymers. , The polymer (X) formed from the particles (x) has high heat resistance, and therefore by using the polymer (X), it is possible to obtain a laminate that can maintain an embossed shape even after heating. This is because polymer (X) is preferably obtained from particles (x) containing polymer (x1) and copolymer (x2) in each particle, so that polymer (x1) and This is probably because the copolymer (x2) has good dispersibility and the size of the phase separation structure between the polymer (x1) and the copolymer (x2) is uniform. The phase separation structure can be confirmed by, for example, a transmission electron microscope, an X-ray scattering method, a light scattering method, or the like. When the phase separation structure is small or the compatibility between the polymer (x1) and the copolymer (x2) is high, the phase separation structure may not be observed by these methods. The phase separation structure is not particularly limited, but it is presumed that it depends on the volume ratio of the polymer (x1) and the copolymer (x2), and it is thought that a co-continuous structure or a sea-island structure is likely to be obtained. , depending on the case, it is presumed that a structure such as a lamellar structure (layered structure) or a cylinder can also be taken.

In one embodiment, the molded article molded from the resin composition containing the polymer (X) preferably has a tensile modulus that satisfies Formula 1 below, and more preferably satisfies Formula 2 below.
Formula 1: Tensile modulus (MPa) < Tm (°C) x 49.6-10400
Formula 2: Tensile modulus (MPa) < Tm (°C) x 49.6-10800
Here, the tensile modulus is a value measured according to ASTM D638, and the melting point (Tm) is a value measured by a differential scanning calorimeter (DSC), which usually corresponds to the melting point of the polymer (X). , details are described in the Examples section. The composition of the resin composition, manufacturing conditions, and molding conditions for the molded body (press sheet) are described in Examples.

When the molded article satisfies Formula 1, it can be determined that the molded article has high heat resistance and excellent flexibility. When the molded article satisfies Formula 2, it can be determined that the molded article has a better balance between heat resistance and flexibility.

That is, by using the polymer (X), a polymer (X) layer having excellent heat resistance and flexibility can be obtained. Therefore, a laminate exhibiting excellent curl suppression, excellent crack resistance after embossing, and excellent heat resistance capable of maintaining the embossed shape even after heating can be obtained.
In addition, when the polymer (X) is used, molding defects such as necking and ear swaying of the polymer (X) layer are less likely to occur during molding by extrusion lamination.

[Other ingredients]
The polymer (X) layer can contain other components not applicable to the polymer (X), such as resins other than the polymer (X) and various additives.
Examples of resins other than polymer (X) include thermoplastic resins such as thermoplastic polyolefin resins other than polymer (X), thermoplastic polyamide resins, thermoplastic polyester resins, and thermoplastic vinyl aromatic resins.

[4-methyl-1-pentene polymer (A)]
As a resin other than the polymer (X), a 4-methyl-1-pentene polymer (A) satisfying the following requirements (Aa) to (Ae) (hereinafter simply referred to as "polymer (A)" ) is preferred.
(Aa) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1- The content of structural units (AQ) derived from at least one olefin selected from (excluding pentene) is 0 to 10 mol %.
(Ab) The intrinsic viscosity [η] measured in decalin at 135°C is
1.0 to 4.0 dl/g.
(Ac) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(Ad) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820-850 kg/m ³ .

In one embodiment, the polymer (X) layer contains 1 to 99 parts by mass of the polymer (X) in 100 parts by mass of the total amount of the polymer (X) and the polymer (A). It is preferable to contain 1 to 99 parts by mass of, more preferably 30 to 70 parts by mass of polymer (X) and 30 to 70 parts by mass of polymer (A).

<Requirements (A-a)>
Requirement (Aa): The content of structural units (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, preferably 95 to 100 mol%, and ethylene and C 3-20 The content of structural units (AQ) derived from at least one olefin selected from α-olefins (excluding 4-methyl-1-pentene) is 0 to 10 mol%, preferably 0 to 5 mol%. .

When the content of the structural unit (P) in the polymer (A) is 90 mol% or more, the advantage of obtaining heat resistance as a laminate and the advantage of obtaining an elastic modulus of the layer suitable for handling are obtained. There is

Examples of the olefins forming the structural unit (AQ) include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, and 1-heptadecene. , 1-octadecene, and 1-eicosene. As the olefin forming the structural unit (AQ), α- Olefins such as 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene are preferred.

The polymer (A) may have structural units other than the structural unit (P) and the structural unit (AQ) within a range that does not impair the effects of the present invention. The content of other structural units is, for example, 0 to 10 mol %.
Specific examples of the monomers leading to the other structural units are the same as the specific examples of the monomers leading to the other structural units exemplified in the explanation of the polymer (X).

<Requirements (A-b)>
Requirement (Ab): Intrinsic viscosity [η] of polymer (A) measured at 135° C. in decalin solvent is 1.0 to 4.0 dl/g, preferably 1.0 to 3 .5 dl/g, more preferably 1.0 to 3.0 dl/g. When the intrinsic viscosity [η] of the polymer (A) is within the above range, the amount of low-molecular-weight substances is small, so the layer containing the polymer (A) is less sticky, and the laminate obtained by the extrusion lamination method Molding becomes possible.

<Requirements (A-c)>
Requirement (Ac): The melting point (Tm) of polymer (A) measured by DSC is in the range of 200-250°C, preferably 200-245°C, more preferably 200-240°C. Since the melting point (Tm) of the polymer (A) is within the above range, the laminate has a moderate elastic modulus compared to the case where the melting point (Tm) is higher than the above range, and heat resistance compared to the case where it is lower than the above range. is good.

<Requirements (A-d)>
Requirement (Ad): The crystallization temperature (Tc) of polymer (A) measured by DSC is in the range of 150-220°C, preferably 180-220°C, more preferably 190-220°C. When the crystallization temperature (Tc) of the polymer (A) is within the above range, the laminate has moderate flexibility as compared with the case where it is higher than the above range. Cracks are less likely to occur, and the rigidity and crystallinity are higher than when the thickness is lower than the above range, so that the layer containing the polymer (A) has good releasability even at high temperatures.

<Requirements (Ae)>
Requirement (Ae): The density of polymer (A) measured according to JIS K7112 (density gradient tube method) is 820 to 850 kg/m ³ , preferably 825 to 840 kg/m ³ . , more preferably 830-835 kg/m ³ . When the density is within the range, the mechanical strength of the layer containing the polymer (A) is higher than when the density is lower than the range, and the polymer (A) is higher than when the density is higher than the range. The impact strength of the containing layer tends to be higher.
Details of the measurement conditions for the above requirements are described in Examples.

<Other requirements>
In addition to the requirements (Aa) to (Ae) above, the polymer (A) preferably satisfies any one of the following requirements.
Requirement (Af): Melt flow rate (MFR) of polymer (A) measured at 260° C. under a load of 5.0 kg in accordance with ASTM D1238 is not particularly specified as long as it is within a range that allows co-extrusion. is usually 0.5 to 200 g/10 min, preferably 1 to 150 g/10 min, more preferably 1 to 100 g/10 min. When the MFR is within the above range, it is easy to extrude the composition containing the polymer (A) into a relatively uniform film thickness.
Requirement (Ag): The molecular weight distribution (Mw/Mn) of the polymer (A) is usually 1.0 to 7.0, preferably 2.0 to 6.0. The molecular weight distribution (Mw/Mn) of the polymer (A) is a value calculated by the method described in Examples.
Requirement (Ah): The polymer (A) is preferably a highly crystalline polymer from the viewpoint of obtaining a tear-resistant layer. The highly crystalline polymer may be either a polymer having an isotactic structure or a polymer having a syndiotactic structure, but a polymer having an isotactic structure is particularly preferred, and is also readily available. Easy. Further, if the polymer (A) can form a layer containing the polymer (A) into a film and has the strength to withstand the intended use when formed into a laminate, the stereoregularity is particularly Not restricted.

<Method for producing polymer (A)>
The polymer (A) may be produced by polymerizing olefins or by pyrolyzing a high-molecular-weight 4-methyl-1-pentene polymer. Further, the polymer (A) may be purified by a method such as solvent fractionation for fractionation based on the difference in solubility in a solvent, or molecular distillation for fractionation based on the difference in boiling point.

When the polymer (A) is produced by a polymerization reaction, for example, the amount of 4-methyl-1-pentene and, if necessary, the olefin to be copolymerized, the type of polymerization catalyst, the polymerization temperature, the amount of hydrogen added during polymerization, etc. By adjusting the melting point, stereoregularity, molecular weight and the like are controlled. A method for producing the polymer (A) by a polymerization reaction may be a known method. Polymer (A) can be produced, for example, by a method using a known catalyst such as a Ziegranatta catalyst or a metallocene catalyst, preferably using a metallocene catalyst. On the other hand, when the polymer (A) is produced by thermal decomposition of a 4-methyl-1-pentene polymer having a higher molecular weight, the molecular weight can be adjusted to a desired value by controlling the thermal decomposition temperature and time. Control.
Polymer (A) may be a commercially available polymer such as TPX manufactured by Mitsui Chemicals, Inc., in addition to the one produced as described above.

[Additive]
Various additives include, for example, weather stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, pigments, dyes, aging Inhibitors, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, cross-linking aids, pressure-sensitive adhesives, softeners, flame retardants and the like.

In the polymer (X) layer, the content of components other than the polymer (X) and the polymer (A) (for example, resins other than these and the additives) is ) to a total of 100 parts by mass, preferably 50 parts by mass or less, more preferably 30 parts by mass or less. Here, the content of the polymer (A) may be 0 parts by mass.

The polymer (X) layer may be formed only from the polymer (X) or the particles (x), or may be formed using a resin composition containing the polymer (X) or the particles (x). good too. The resin composition for forming the polymer (X) layer may further contain other components such as the polymer (A) and various additives as described above. For example, it can be obtained by mixing the polymer (X) or particles (x) with other components, and the mixing method is not particularly limited. A method of mixing can be mentioned.

[Base paper layer]
Materials for the base paper layer constituting the laminate of the present invention include, for example, natural pulp, that is, aggregates of cellulose fibers extracted from plants, such as high-quality processed base paper, kraft paper, bleached kraft paper, white paperboard, In addition to glassine and Japanese paper, organic fibers such as rayon and acetate fibers, inorganic fibers such as glass fibers, asbestos fibers and carbon fibers, and synthetic pulps can be used. Among these, aggregates of cellulose fibers are preferably used. A base paper layer made of such materials may contain pigments, dyes, binders, and the like.

[Manufacturing Method and Configuration of Laminate]
The laminate of the present invention is formed by laminating a base paper layer and a layer containing a 4-methyl-1-pentene polymer (X) (polymer (X) layer). A material paper layer, a polymer (X) layer, and a second layer described later are laminated in this order. Lamination of the base paper layer and the polymer (X) layer, and lamination of the base paper layer, the polymer (X) layer and the second layer can be performed by a conventional method such as extrusion lamination. If the conditions are such that the particles (x) are melted to form the polymer (X), the particles (x) or the resin composition containing the particles (x) is used to form the polymer (X) layer. may be formed.

Then, an embossed pattern may be formed on the polymer (X) layer or (when the laminate has a second layer described later on the outermost surface) on the second layer by a conventional method. That is, a laminate obtained by an extrusion lamination method or the like is passed between a metal roll having a predetermined embossed pattern and a rubber roll, or is embossed through male and female metal embossing rolls having a predetermined embossed pattern. Processing may be performed, and embossing may be performed by hot-pressing a metal plate having an embossed pattern.

Thus, according to the present invention, since the polymer (X) layer is formed using at least the specific 4-methyl-1-pentene polymer (X), crack resistance and heat resistance are excellent. A laminate is obtained.

The thickness of the laminate of the present invention is generally 25-650 μm, preferably 40-520 μm, more preferably 110-400 μm.
The thickness of the polymer (X) layer is generally 5-150 μm, preferably 10-120 μm, more preferably 10-100 μm.

The thickness of the base paper layer is generally 20-500 μm, preferably 30-400 μm, more preferably 100-300 μm.
The thickness ratio of the polymer (X) layer to the base paper layer (thickness of the polymer (X) layer/thickness of the base paper layer) is generally 1/1 to 1/100, It is preferably 1/2 to 1/20.

The laminate of the present invention may contain layers other than the polymer (X) layer and the base paper layer as long as the effects of the present invention are not impaired. Layers other than the polymer (X) layer and the base paper layer contain a 4-methyl-1-pentene polymer (A) that satisfies the above requirements (Aa) to (Ae). and the second layer not containing the 4-methyl-1-pentene polymer (X) described above is preferred. Preferred aspects of the polymer (A) are as described above.

When the laminate of the present invention has the second layer, it is preferable that the base paper layer, the polymer (X) layer, and the second layer are laminated in this order, and the second layer is the outermost layer. more preferably located.

The thickness ratio of the polymer (X) layer and the second layer (thickness of the polymer (X) layer/thickness of the second layer) is preferably 1/99 to 99/1, more preferably is 1/4 to 4/1.
Further, the laminate of the present invention may have a base layer between the base paper layer and the polymer (X) layer.

When the laminate of the present invention has layers other than the base paper layer, the polymer (X) layer and the second layer, the thickness of the other layers is preferably It is 50% or less, more preferably 20% or less.

Furthermore, a coating layer containing resin or the like may be provided on the surface of the base paper layer opposite to the surface on which the polymer (X) layer is formed. A base paper layer having a coat layer formed in advance may also be used. Having a coat layer tends to suppress curling of the laminate.

Although the use of the laminate of the present invention is not particularly limited, it can be suitably used as various process papers such as release paper, photographic paper, and tape separators. For example, release paper for synthetic leather, rubber production paper, urethane curing release paper, epoxy curing release paper, solar cell manufacturing process paper, semiconductor manufacturing process paper, fuel cell manufacturing process paper, electrical and electronic component manufacturing casting paper, casting paper for semiconductor product manufacturing, casting paper for circuit board manufacturing, release liner for flexible printed circuit boards, release liner for rigid substrates, release liner for rigid flexible substrates, casting paper for manufacturing advanced composite materials, carbon fiber composite materials Release liner for curing, release liner for curing glass fiber composite material, release liner for curing aramid fiber composite material, release liner for curing nanocomposite material, release liner for curing filler filler, heat and water resistant photographic paper, OA paper, adhesive tape separator , silicone tape separators, adhesive separators, and the like, and among these, it is preferably used as a release paper for synthetic leather, which is particularly excellent in embossability.

In general, in a laminate obtained by laminating a resin layer containing a 4-methyl-1-pentene polymer and a paper that does not stretch, the resin layer cannot be greatly deformed in the thickness direction during embossing, so the resin It is more likely that cracks will form in the layers. In addition, if a flexible component is added to the resin layer so that the resin layer can be deformed in the thickness direction, the heat resistance is lowered and the release force is also lowered.

On the other hand, since the resin layer is the polymer (X) layer described above, the laminate of the present invention is excellent in heat resistance and flexibility, and is also excellent in crack resistance and embossed shape retention after embossing. Therefore, it is preferable that the polymer (X) layer and the base paper layer are in contact with each other.

[How to use release paper for synthetic leather]
In order to use the laminate of the present invention as a release paper for synthetic leather, for example, to apply embossing or texturing to a member for synthetic leather, first, for example, by the method described above, the polymer (X ) layer, or the surface of the second layer (if the laminate has a second layer on top), is embossed with an embossed pattern.

A synthetic leather member forming material (PVC dispersion, polyurethane solution, etc.) is applied to the surface of the polymer (X) layer having an embossed pattern on the surface or the surface of the second layer, and then cured by heating or drying. A synthetic leather member made of PVC, polyurethane or the like is formed on the polymer (X) layer or the second layer. The temperature during heating is usually about 180 to 230° C. when forming a PVC film, and usually about 130 to 180° C. when forming a polyurethane film.
Next, when the laminate (release paper) of the present invention is peeled off from the synthetic leather member, the synthetic leather member having the desired embossed pattern or the like transferred to the surface is obtained.

The present invention will be described in more detail below based on examples. However, the present invention is not limited to these examples.
[Methods for measuring various physical properties]
<Catalyst carrier, catalyst particle size (D50)>
D50 in volume statistics was obtained by laser diffraction/scattering method using MT3300EX II manufactured by Microtrac.

<Elemental analysis (Al content in carrier)>
Measurement was performed using an ICP (inductively coupled plasma) emission spectrometer: ICPS-8100 model manufactured by Shimadzu Corporation. For the quantitative and qualitative analysis of aluminum and zirconium, the sample was subjected to wet decomposition with sulfuric acid and nitric acid, and then the constant volume (including filtration and dilution as necessary) was used as the test solution.

<Slurry properties>
Regarding the resulting polymer solution, "good" means that it was a slurry with good solid-liquid separability in the filtration process. The case was described as "bad", and the case where it was a solution rather than a slurry was described as "solution".

[Measurement method of polymer physical properties]
<Mass ratio of polymer produced in step (1) and step (2)>
At the end of the polymerization in step (1), the polymer slurry was extracted and the slurry concentration was measured to calculate the amount of polymer produced in step (1). Based on this amount and the amount of the polymer finally obtained, the mass ratio of the polymer produced in each step was determined. Filtration temperature: Room temperature (25° C.), Filtration method: Filtration was carried out using Kiriyama filter paper (mesh opening: 1 μm) while washing with hexane, and the concentration of the slurry was calculated. Filtration was carried out under these conditions in the following examples.

<Comonomer content in 4-methyl-1-pentene copolymer>
The content of structural units derived from 4-methyl-1-pentene and structural units derived from a comonomer (comonomer content) was calculated from ¹³ C-NMR spectrum using the following equipment and conditions.

Using a Bruker Biospin AVANCE IIIcryo-500 nuclear magnetic resonance apparatus, the solvent is o-dichlorobenzene/benzene-d ₆ (4/1 v/v) mixed solvent, the sample concentration is 55 mg/0.6 mL, the measurement temperature is is 120°C, the observation nucleus is ¹³ C (125 MHz), the sequence is single-pulse fronton broadband decoupling, the pulse width is 5.0 μs (45° pulse), the repetition time is 5.5 seconds, and the number of integrations is 64. , 128 ppm for benzene-d ₆ was measured as a chemical shift reference. Using the integrated value of the main chain methine signal, the comonomer content was calculated by the following formula.
Comonomer content (%) = [P/(P+M)] x 100
where P denotes the total peak area of the comonomer backbone methine signal,
M indicates the total peak area of the 4-methyl-1-pentene backbone methine signal.

The comonomer content in the polymer produced in step (1) is determined using the polymer obtained from the polymer slurry extracted at the end of the polymerization in step (1). The comonomer content of is the comonomer content in the polymer obtained in step (1), the comonomer content in the final polymer (step (1) + step (2)), and the proportion of the polymer produced in each step was obtained using Specifically, the comonomer contents in the polymer produced in steps (1) and (2) and the final polymer are respectively m ₁ , m ₂ and m _f , and the polymer produced in steps (1) and (2) If the coalescence ratios are w ₁ and w ₂ respectively, then m ₂ =(m _f −w ₁ ·m ₁ )/w ₂ .

<Meso diad fraction>
The mesodiad isotacticity (mesodiad fraction) (m) of a 4-methyl-1-pentene polymer is a planar When expressed as a zigzag structure, it was defined as the ratio of isobutyl branching directions that were the same, and was calculated from the ¹³ C-NMR spectrum by the following formula.

Mesodiad isotacticity (m) (%) = [m/(m+r)] x 100
[In the formula, m and r represent the absorption intensity derived from the main chain methylene of the 4-methyl-1-pentene units bonded head-to-tail represented by the following formula. ]

¹³Ｃ－ＮＭＲスペクトルは、ブルカー・バイオスピン製ＡＶＡＮＣＥＩＩＩｃｒｙｏ－５００型核磁気共鳴装置を用いて、溶媒はｏ－ジクロロベンゼン／ベンゼン－ｄ６（４／１ ｖ／ｖ）混合溶媒、試料濃度は６０ｍｇ／０．６ｍＬ、測定温度は１２０℃、観測核は¹³Ｃ（１２５ＭＨｚ）、シーケンスはシングルパルスプロトンブロードバンドデカップリング、パルス幅は５．０μ秒（４５°パルス）、繰返し時間は５．５秒、ベンゼン－ｄ６の１２８ｐｐｍをケミカルシフトの基準値として測定した。

The ¹³ C-NMR spectrum was obtained using a Bruker Biospin AVANCEIIIcryo-500 nuclear magnetic resonance spectrometer, the solvent was o-dichlorobenzene/benzene-d6 (4/1 v/v) mixed solvent, and the sample concentration was 60 mg/ 0.6 mL, measurement temperature 120° C., observation nucleus ¹³ C (125 MHz), sequence single-pulse proton broadband decoupling, pulse width 5.0 μs (45° pulse), repetition time 5.5 s, benzene -d6 of 128 ppm was measured as a reference value for chemical shift.

As for the peak region, the region of 41.5 to 43.3 ppm was separated by the minimum point of the peak profile, and the high magnetic field side was classified into the first region and the low magnetic field side into the second region.
In the first region, the main chain methylene in the two chains of 4-methyl-1-pentene units shown by (m) resonates, but the integrated value assuming that it is a 4-methyl-1-pentene homopolymer is "m". and In the second region, main chain methylene in two chains of 4-methyl-1-pentene units represented by (r) resonated, and the integrated value was defined as "r". In addition, less than 0.01% was defined as below the detection limit.

<Intrinsic viscosity [η]>
Using an automatic kinematic viscometer VMR-053PC manufactured by Rigosha and an improved Ubbelohde-type capillary viscometer, the specific viscosity ηsp of decalin at 135° C. was determined, and the intrinsic viscosity ([η]) was calculated from the following formula.
[η]=ηsp/{c(1+K·ηsp)}
(c: solution concentration [g/dl], K: constant)
The intrinsic viscosity [η] of the polymer produced in step (1) was determined using the polymer obtained from the polymer slurry extracted at the end of the polymerization in step (1), and the polymer produced in step (2) was The intrinsic viscosity [η] of the coalescence is the intrinsic viscosity [η] of the polymer obtained in step (1), the intrinsic viscosity [η] of the final polymer (step (1) + step (2)), and each It was determined using the percentage of polymer produced in the process. Specifically, the [η] of the polymer produced in steps (1) and (2) and the final polymer are [η] ₁ , [η] ₂ and [η] _f respectively, and step (1), ( [η] ₂ =([η] _f −w ₁ ·[η] ₁ )/w ₂ where w ₁ and w ₂ are the proportions of the polymer produced in 2).

<Melting point (Tm), crystallization temperature (Tc), heat of fusion (ΔH)>
About 4 mg of sample was heated from 30° C. to 280° C. in a nitrogen atmosphere (30 ml/min) using EXSTAR DSC6220 manufactured by SII Nano Technology Co., Ltd. After holding at 280°C for 5 minutes, it was cooled to -50°C at 10°C/min. After holding at -50°C for 5 minutes, the temperature was raised to 280°C at 10°C/min. The apex temperature of the crystallization peak observed during cooling was defined as the crystallization temperature (Tc), and the apex temperature of the crystal melting peak observed during the second heating was defined as the melting point (Tm). Also, the amount of heat of fusion accompanying melting was defined as ΔH. When multiple peaks were detected for the polymer produced in each stage, the maximum temperature was taken as the melting point (Tm). The melting point (Tm) of the polymer produced in step (2) was determined by analyzing the polymer produced in step (1) and the final polymer.

<CFC measurement>
CFC measurement was performed under the following conditions.
Apparatus: CFC2-type Cross Fractionation Chromatograph (Polymer Char)
Detector (built-in): IR4 infrared spectrophotometer (Polymer Char)
Detection wavelength: 3.42 μm (2,920 cm ^-1 ); Fixed sample concentration: Sample: 30 mg/30 mL (diluted with o-dichlorobenzene (ODCB))
Injection Volume: 0.5mL
Temperature conditions: Raise temperature to 145°C at 40°C/min and hold for 30 minutes. After cooling to 0°C at 1°C/min and holding for 60 minutes, the elution amount was evaluated for each of the following elution categories. The temperature change between sections was 40°C/min.
Elution division: 0, 5, 10, 15, 20, 25, 30, 35, 50, 70, 90, 95, 100, 102, 104, 106℃, and from 108℃ to 135℃ in increments of 1℃, Evaluate the amount of elution at 140 and 145°C.
GPC column: Shodex HT-806M x 3 (Showa Denko)
GPC column temperature: 145°C
GPC column calibration: monodisperse polystyrene (Tosoh)
Molecular weight calibration method: Standard calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (ODCB), BHT Addition flow rate: 1.0 mL/min

<Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw/Mn)>
Liquid chromatograph: Waters ALC/GPC 150-C plus type (differential refractometer detector integrated type) is used, and Tosoh Corporation GMH6-HT × 2 and GMH6-HTL × 2 are connected in series as columns, Gel permeation chromatography (GPC) measurement was performed at a flow rate of 1.0 ml/min and 140° C. using o-dichlorobenzene as a mobile phase medium. The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were obtained by analyzing the obtained chromatogram using a calibration curve using a standard polystyrene sample by a known method.

<Melt flow rate (MFR)>
A melt flow rate (MFR) measured at 260° C. under a load of 5.0 kg was determined according to ASTM D1238.

<Density>
Density was determined according to JIS K7112 (density gradient tube method).
[Synthesis of transition metal complex (metallocene compound (C))]
According to Synthesis Example 4 of WO 2014/050817, (8-octamethylfluorene-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6, 7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride (metallocene compound (c1)) was synthesized.

[Preparation of solid catalyst component (metallocene catalyst)]
As the carrier (D), a particulate solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) having a D50 of 8 μm and an aluminum atom content of 42% by mass was used. 29.9 mL of purified decane and 7.26 mL of a hexane/decane solution of the solid polymethylaluminoxane (aluminum atom 14.3 mmol in terms of conversion) was charged to form a suspension. To the suspension, 12.8 mL of a 4.59 mmol/L toluene solution of 50 mg (0.0586 mmol in terms of zirconium atom) of the previously synthesized metallocene compound (c1) was added while stirring. Stirring was stopped after 1.5 hours, and decantation washing was performed with decane (washing efficiency: 98%) to obtain a slurry liquid of 50 mL (Zr loading rate: 96%). The obtained solid catalyst component (metallocene catalyst) was particulate and its D50 was 8 μm.

[Preparation of prepolymerization catalyst component]
4.0 mL of a decane solution of diisobutylaluminum hydride (1 mol/L in terms of aluminum atoms) and 15 mL (10.0 g) of 3-methyl-1-pentene were added to the slurry liquid prepared as described above under a nitrogen stream. did. Stirring was stopped after 1.5 hours, and decantation washing was performed with decane (washing efficiency 95%) to obtain 100 mL of decane slurry (Zr recovery rate 93%, 0.548 mmol/L in terms of zirconium atom).

[Polymer particles (x-1)]
At room temperature (25° C.) under a nitrogen stream, 425 mL of purified decane and 0.4 mL of triethylaluminum solution (1.0 mmol/mL in terms of aluminum atoms) were placed in a SUS polymerization vessel with an internal volume of 1 L and equipped with a stirrer. 0.4 mmol in atomic terms) was charged. Next, 0.0014 mmol of the previously prepared decane slurry of the prepolymerized catalyst component in terms of zirconium atoms was added, and the temperature was raised to 40°C. After reaching 40° C., 30 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene (4MP-1) was continuously charged into the polymerization vessel over 30 minutes at a constant rate. The polymerization was started at the time when the charging was started, and the temperature was kept at 45° C. for 3 hours (step (1)). After 3 hours, the inside of the system was depressurized at 45° C., and pressurization and depressurization with nitrogen (0.6 MPa) were performed three times in order to discharge residual hydrogen outside the system. Thereafter, 30 NmL of hydrogen was charged at 45° C. under a nitrogen stream, and then a mixed solution of 79.4 mL of 4-methyl-1-pentene and 7.4 mL of 1-decene was continuously introduced into the polymerization vessel over 30 minutes. charged at a relatively constant speed. The polymerization was started at the time when the charging was started, and the temperature was kept at 45° C. for 3 hours (step (2)). After 3 hours from the initiation of polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization liquid (slurry) containing white solids was immediately filtered to obtain a solid substance. This solid substance was dried at 80° C. for 8 hours under reduced pressure to obtain 105.4 g of polymer particles (x-1). Various results are shown in Tables 1 and 2. These results (e.g., content of constituent units, DSC and CFC measurement results, meso diad fraction, [η]) are obtained by melting the polymer particles (x-1) (polymer ( Similar results are obtained for X-1)).

[Polymer particles (x-2)]
Polymer particles (x-2) were obtained in the same manner as for polymer particles (x-1) except that the polymerization conditions were changed as shown in Table 1. Various results are shown in Tables 1 and 2. These results are the same for the resin obtained by melting the polymer particles (x-2) (polymer (X-2)).

[4-methyl-1-pentene polymer (A)]
4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene and hydrogen are changed according to the polymerization method described in Comparative Example 7 and Comparative Example 9 of WO 2006/054613. Thus, 4-methyl-1-pentene copolymers (A-1) and (A-2) having physical properties shown in Table 2 were obtained. In Table 2, L168 is a 1-hexadecene/1-octadecene mixture (mixing molar ratio 60:40).

Physical properties other than those listed in Table 2 are as follows. The copolymer (A-1) had a crystallization temperature of 207° C., a density of 833 kg/m ³ , an MFR of 100 g/10 min, an Mw of 322,000, and an Mw/Mn of 5.5. The copolymer (A-2) had a crystallization temperature of 205° C., a density of 834 kg/m ³ , an MFR of 100 g/10 min, an Mw of 330,000, and an Mw/Mn of 4.1.

[Copolymer (F-1)]
300 ml of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a fully nitrogen-substituted 1.5 L SUS autoclave equipped with a stirring blade. 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 to an internal temperature of 60° C., and pressurized with propylene to a total pressure (gauge pressure) of 0.19 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t- 0.34 ml of a toluene solution containing butyl-fluorenyl)zirconium dichloride was injected into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C.

After 60 minutes from the initiation of polymerization, 5 ml of methanol was injected into the autoclave under pressure with nitrogen to stop the polymerization reaction, and then the pressure inside the autoclave was released 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. Next, the obtained polymerization reaction product containing the solvent was dried at 130° C. for 12 hours under reduced pressure to obtain 44.0 g of powdery copolymer (F-1).

Table 2 shows the measurement results of various physical properties of the copolymer (F-1). The measurement method is the same as the measurement method for polymer (A), except that the melt flow rate (MFR) measurement conditions are changed to 230° C. and a load of 2.16 kg. Physical properties other than those listed in Table 2 are as follows. Copolymer (F-1) had a crystallization temperature of 60° C., a density of 838 kg/m ³ , an MFR of 11 g/10 min, an Mw of 340,000, and an Mw/Mn of 2.1.

[Preparation of press sheet]
100 parts by mass of polymer particles (x-1), 0.1 part by mass of tri(2,4-di-t-butylphenyl) phosphate as a secondary antioxidant, n-octadecyl- 0.1 part by mass of 3-(4'-hydroxy-3',5'-di-t-butylphenyl)propinate was blended to obtain a mixture. After that, using a twin-screw extruder BT-30 (screw system 30 mmφ, L/D 46) manufactured by Plastic Engineering Laboratory Co., Ltd., set temperature 260 ° C., resin extrusion rate 60 g / min and rotation speed 200 rpm. to granulate the above mixture to obtain a resin composition.

A 1 mm-thick iron plate with a 8-cm square cutout was placed between two iron plates, and 5.2 g of the above resin composition was charged in the cut-out portion. A compression molding machine (mold clamping 50 tons) manufactured by Shindo Kinzoku Kogyo Co., Ltd. was heated to 270° C., and the iron plate was inserted. After standing for 7 minutes to melt the resin composition, the iron plate was compressed at a pressure of 10 MPa and held for 3 minutes, then taken out, inserted into the compression molding machine set at 23 ° C., and subjected to a pressure of 10 MPa for 3 minutes. Cooled over a period of minutes. A molded article having a thickness of 1 mm was taken out from the cutout portion and used as a press sheet for evaluation.
Instead of the polymer particles (x-1), polymer particles (x-2), copolymers (A-1), (A-2), and (F-1) were similarly used for evaluation. A press sheet was made.

<Tensile modulus>
The elastic modulus, which is a tensile property, was measured in accordance with ASTM D638 using a test piece punched out from the 1 mm thick press sheet prepared above, using a universal tensile tester 3380 manufactured by Instron, with a chuck distance of 65 mm, and tensile strength. A tensile test was performed at a speed of 50 mm/min for evaluation.

<Index of high heat resistance and low rigidity (flexibility)>
As an index of high heat resistance and low rigidity (softness), at least one of the melting point peaks is at 220 ° C. or higher, and the tensile elastic modulus (MPa) is smaller than Tm (° C.) × 49.6-10400. Furthermore, when the tensile elastic modulus (MPa) was smaller than Tm (°C) x 49.6-10800, it was evaluated as ⊚. If these conditions are not met, "-" is indicated.

[Preparation of laminate]
<Example 1>
Using a thermoplastic 30 mmΦ co-extrusion laminator, a layer (polymer (X-1) layer) composed of polymer particles (x-1) is formed as an intermediate layer on the base paper by extrusion lamination molding, and further , to prepare a laminate by forming a layer of the copolymer (A-1). As the base paper, high-quality release paper for synthetic leather (thickness: 200 μm) is used, the die temperature is set to 310° C., the die width is 400 mm, and the line speed is 10 m/min. The number of screw rotations was adjusted so that the thickness of the layer would be a predetermined thickness.

<Example 2>
A laminate was produced in the same manner as in Example 1, except that polymer particles (x-1) were changed to polymer particles (x-2).

<Comparative Example 1>
A laminate was produced in the same manner as in Example 1, except that the polymer particles (x-1) were changed to the copolymer (A-2).

<Comparative Example 2>
90 parts by mass of the copolymer (A-1), 10 parts by mass of the copolymer (F-1), and 0.12 phr of a phenolic stabilizer Irganox 1010 (manufactured by Ciba BASF) as a heat stabilizer. A mixture was obtained by mixing with a twin-screw extruder manufactured by Plastics Co., Ltd.
A laminate was produced in the same manner as in Comparative Example 1, except that the copolymer (A-1) was changed to the mixture obtained above.

<Comparative Example 3>
A laminate was produced by forming a layer of the copolymer (A-1) on the base paper by extrusion lamination molding using a thermoplastic 30 mmφ co-extrusion laminator. As the base paper, high-quality release paper for synthetic leather (thickness: 200 μm) is used, the die temperature is set to 310° C., the die width is 400 mm, and the line speed is 10 m/min. The number of screw rotations was adjusted so that the thickness of the layer would be a predetermined thickness.

<Comparative Example 4>
A laminate was produced in the same manner as in Comparative Example 3, except that the copolymer (A-1) was changed to the copolymer (A-2).

<Comparative Example 5>
75 parts by mass of the copolymer (A-1), 25 parts by mass of the copolymer (F-1), and 0.12 phr of a phenolic stabilizer Irganox 1010 (manufactured by Ciba BASF) as a heat stabilizer. A mixture was obtained by mixing with a twin-screw extruder manufactured by Plastics Co., Ltd.
A laminate was produced in the same manner as in Comparative Example 3, except that the copolymer (A-1) was changed to the mixture obtained above.

[Evaluation of laminate]
The obtained laminate was subjected to the following measurements and evaluations. Measurement and evaluation methods are shown below. Table 4 shows the results.

<Moldability>
In Examples 1 and 2 and Comparative Examples 1 and 5, neck-in and ear wobble when the resin layers were formed by extrusion lamination were evaluated according to the following criteria. If the neck-in rate is 30% or less and the ear wobble is 10% or less, there is no practical problem.

In addition, at the time of evaluation, the length of the direction perpendicular to the extrusion direction and thickness direction of the laminated resin layer (hereinafter referred to as "resin lamination width") was measured at 20 points, and the average value, maximum value and minimum value asked for
Neck-in rate (%)
= ((die width (400 mm) - average resin lamination width)/die width (400 mm)) x 100
Ear shaking:
The state of film formation, such as the resin end portion, during extrusion lamination was visually observed, and ear wobble was calculated by the following formula.
Ear shaking (%)
= (((Maximum value of resin lamination width) - (Minimum value of resin lamination width))/(Average value of resin lamination width)) x 100
A: The neck-in rate was 30% or less and the ear wobble was 5% or less.
B: The neck-in rate was 30% or less and the ear wobble was more than 5% and 10% or less.
C: The neck-in rate exceeded 30%, or the ear wobble exceeded 10%.

<Curl amount>
The laminates prepared in Examples 1 and 2 and Comparative Examples 1 and 5 were cut into A4 size, the surface layer was facing upward, and the temperature was 23° C. and the humidity was 80% RH for 24 hours. Set aside and then place in an oven set at 100° C. for 5 minutes. After the laminate was taken out of the oven and returned to room temperature, the laminate was placed on a horizontal surface with the surface layer facing upward. The four corners of the laminate were curled to varying degrees. The height of the curled four corners of the laminate (hereinafter also referred to as "curling amount") from the horizontal plane was measured, and the curling amount was evaluated according to the following criteria. In addition, when the laminate was curled one round or more, it was judged as C.
A: The amount of curl is less than 5 mm B: The amount of curl is 5 mm or more and less than 15 mm C: The amount of curl is 15 mm or more, or
It is difficult to calculate the amount of curl because the laminate curls up more than once.

<Crack resistance: thermal cycle test>
For embossing, a 50-ton press machine manufactured by Shindo Kinzoku Kogyo Co., Ltd. and an embossing mold with dimensions of 70 mm in length × 70 mm in width × 15 mm in thickness, and stripes of 0.5 mm in width and 140 μm in depth were formed on one side of the embossing mold. were formed at a pitch of 0.5 mm. An embossing die was placed on the surface layer of the laminate cut into A4 size produced in Examples 1 and 2 and Comparative Examples 1 and 5, and heated at 160 ° C. for 3 minutes, and then at 50 kgf. Pressing was performed for 10 seconds, and the embossed laminate was taken out. The embossed laminate was left in an oven set at 200° C. for 10 minutes and then at room temperature for 10 minutes. This was regarded as one cycle of the thermal cycle test, and the same thermal cycle was repeated 10 times and 30 times. The presence or absence of cracks in the surface layer after repeating the heat cycle 10 times and 30 times was observed with a scanning electron microscope (SEM).
A: No cracks were observed.
B: 1 to 5 cracks were observed.
C: Five or more cracks were confirmed.

<Heat resistance>
The laminates prepared in Examples 1 and 2 and Comparative Examples 1 and 5 and subjected to the embossing described above were cut into pieces of 10 cm each, left to stand in an oven set at 200 ° C. for 10 minutes, and then heated at room temperature for 10 minutes. Let stand for a minute. This was regarded as one cycle of the thermal cycle test, and 10 cycles were repeated. The degree of change in embossed height on the surface after 10 cycles was measured with a surface roughness attached to a laser microscope.
A: degree of change 10% or less B: degree of change greater than 10% and less than 30% C: degree of change 30% or more

Claims (6)

a layer containing a 4-methyl-1-pentene polymer component (X) that satisfies the following requirements (Xa), (Xb) and (Xc);
and a base paper layer,
The 4-methyl-1-pentene polymer component (X) is
10.0 to 95.0 parts by mass of a 4-methyl-1-pentene polymer (x1) satisfying the following requirement (x1-a) and a 4-methyl-1-pentene copolymer satisfying the following requirement (x2-a) A laminate containing 5.0 to 90.0 parts by mass of the coalescence (x2) (where the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass).
(Xa) The content of structural units derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 - excluding pentene) is 0.3 to 70.0 mol% of structural units derived from at least one olefin.
(Xb) when measured by a cross-fractionated chromatograph (CFC) using an infrared spectrophotometer in the detection part, at least one peak A of the amount of eluted components exists in the range of 100 to 140 ° C., In addition, at least one peak B of the amount of eluted components is present below 100°C.
The mesodiad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 98.5 to 100%.
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and is derived from at least one olefin selected from α-olefins having 8 to 20 carbon atoms. The content of the structural unit is 0 to 20.0 mol%.
(x2-a) at least one olefin selected from α-olefins having 8 to 20 carbon atoms and having a content of structural units derived from 4-methyl-1-pentene of 20.0 to 98.0 mol%; The content of structural units derived from is 2.0 to 80.0 mol%, provided that at least one olefin selected from α-olefins having 8 to 20 carbon atoms in the polymer (x1) is derived from greater than the content of structural units The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (x1) measured in decalin at 135° C. is in the range of 0.5 to 20 dl/g, and the melting point (Tm) measured by DSC is in the range of 210-260°C,
The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (x2) measured in decalin at 135° C. is in the range of 0.5 to 20 dl/g, and the melting point (Tm) measured by DSC. is in the range of less than 220 ° C, or no peak indicating the melting point appears in the DSC measurement,
The laminate according to claim 1. The 4-methyl-1-pentene polymer component (X) according to claim 1 or 2, wherein the intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 10.0 dl/g. Laminate as described. A release paper comprising the laminate according to any one of claims 1 to 3 . The method for producing a laminate according to any one of claims 1 to 3 , wherein the base paper layer and the layer containing the 4-methyl-1-pentene polymer component (X) are laminated. embossing the layer containing the 4-methyl-1-pentene polymer component (X) of the release paper according to claim 4 ;
A material for forming a synthetic leather member is applied to the embossed surface of the layer containing the 4-methyl-1-pentene polymer component (X) and then cured to form a synthetic leather member having an embossed pattern. A method for producing a member for synthetic leather having an embossed pattern, comprising a step of forming and a step of peeling the release paper from the member for synthetic leather.