JP7449744B2 - Resin film, laminate and release paper containing the same - Google Patents

Description

The present invention relates to a resin film, a laminate containing the same, and a release paper, and more particularly, a resin film containing 4-methyl-1-pentene resin, and a laminate and release paper containing the same.

When manufacturing synthetic leather parts, for example, process paper for embossing (hereinafter also referred to as ``process paper'' or ``release paper'') is made by melt-bonding a high-melting point resin with excellent mold release properties to the surface of paper. ) is used. The resin layer of this process paper has an embossed pattern, and PVC (polyvinyl chloride) sol or polyurethane solution, which is a raw material for synthetic leather, is applied to the surface of the resin layer, heated and cured, and the process paper is peeled off. By doing so, a PVC or polyurethane synthetic leather member having an embossed pattern transferred onto its surface is obtained.

4-Methyl-1-pentene polymers have very low surface tension, high heat resistance, and excellent mold releasability from PVC or polyurethane. Therefore, it is used as a high melting point resin for process paper for embossing or release paper. On the other hand, 4-methyl-1-pentene polymers with a high melting point do not easily penetrate paper even when heated and melted during the production of release paper, and the 4-methyl-1-pentene resin layer that makes up the release paper is difficult to penetrate. It tends to be difficult to obtain sufficient interlayer adhesion strength between the paper and the paper. For this reason, even if you try to peel off the PVC layer or polyurethane layer on which the embossed pattern has been transferred from the release paper, the PVC layer or polyurethane layer will not peel off, and the 4-methyl-1-pentene resin that makes up the release paper will not peel off. Peeling may occur between the layer and the paper. Therefore, various attempts have been made to overcome these problems.

Patent Document 1 discloses that 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. A release paper for artificial leather is disclosed. Here, in the example of Patent Document 1, a 4-methyl-1-pentene/1-decene copolymer is used as the 4-methyl-1-pentene resin layer (A), and a 4-methyl-1-pentene resin is used. A 4-methyl-1-pentene homopolymer or a 4-methyl-1-pentene/1-decene copolymer having a lower 1-decene content than the 4-methyl-1-pentene resin layer (A) is used as the layer (B). When PVC sol was applied to release paper, heated and cured, and then peeled from the release paper, the cured PVC was easily peeled off from the release paper, and no delamination occurred on the release paper itself. It is shown.

On the other hand, attempts have been made to employ compositions made by combining 4-methyl-1-pentene polymers with other resins such as high-pressure low-density polyethylene as high-melting point resins for process papers.

For example, Patent Document 2 describes a 4-methyl-1-pentene polymer composition containing a 4-methyl-1-pentene polymer, an unsaturated carboxylic acid-modified 4-methyl-1-pentene polymer, and a high-pressure A composition comprising a specific ratio of low density polyethylene is disclosed. Here, Patent Document 2 discloses that by adding an unsaturated carboxylic acid-modified 4-methyl-1-pentene polymer to a 4-methyl-1-pentene polymer, an appropriate release weight is imparted to the composition. It is also disclosed that good lamination moldability can be imparted by adding high-pressure low density polyethylene to a 4-methyl-1-pentene polymer.

Patent Document 3 discloses, as a highly heat-resistant and flexible synthetic leather release paper, a release paper formed by coextrusion laminating or single-layer extrusion lamination of a thermoplastic resin layer on a base paper. Here, Patent Document 3 discloses that a copolymer of 4-methyl-1-pentene and an α-olefin having 12 to 20 carbon atoms and a high-pressure process resin are used as thermoplastic resins constituting the highly heat-resistant and flexible synthetic leather release paper. It is also described that a 4-methyl-1-pentene polymer composition consisting of density polyethylene can be used.

Patent Document 4 describes a 4-methyl-1-pentene copolymer consisting of a copolymer of 4-methyl-1-pentene and an α-olefin having 16 to 20 carbon atoms as a highly heat-resistant and flexible synthetic leather release paper. A release paper is disclosed that includes a layer and a base paper. Here, Patent Document 4 discloses that a 4-methyl-1-pentene copolymer composition layer is interposed as an intermediate layer between the 4-methyl-1-pentene copolymer layer and the base paper. Even if this 4-methyl-1-pentene copolymer composition layer is composed of a 4-methyl-1-pentene polymer and high-pressure low-density polyethylene, Good things are also mentioned.

On the other hand, since high heat resistance is required for electronic components, cured products of electron beam curable resin compositions are sometimes employed as constituent materials of electronic components in order to ensure high heat deformation resistance.

As such an electron beam curable resin composition, Patent Document 5 discloses a composition containing an olefin resin and a specific crosslinking agent. Here, the examples of Patent Document 5 include a composition containing an olefin resin such as polymethylpentene resin or polyethylene and an isocyanurate compound, and a molded product formed by irradiating an electron beam to a molded product made of this composition. The body is revealed. In connection with this, Patent Document 6 discloses a reflector formed by molding a resin composition containing an olefin resin such as a polymethylpentene resin or polyethylene and a crosslinking agent such as an isocyanurate compound.

Further, Patent Document 7 discloses a crosslinked olefin elastomer composed of a chain olefin-cyclic olefin copolymer. Patent Document 7 also discloses that both flexibility and heat resistance are achieved by crosslinking an olefin elastomer composed of a chain olefin-cyclic olefin copolymer by electron beam irradiation.

Note that Patent Documents 1 to 4 do not indicate that a 4-methyl-1-pentene polymer or a composition containing a 4-methyl-1-pentene polymer is crosslinked by electron beam irradiation. Not yet.

Patent No. 2728138 Japanese Patent Application Publication No. 07-133390 JP 2002-292716 JP 2003-127284 WO2014/119693 JP2016-36028 JP2012-102211

An object of the present invention is to provide a resin film for release paper that can maintain its shape even at high temperatures and has both excellent mold release properties and transferability during embossing.

The present inventors have discovered that when a crosslinked precursor containing a specific 4-methyl-1-pentene copolymer is irradiated with radiation such as an electron beam, it exhibits high heat resistance and good mold release properties when used as a release paper. The present invention was completed based on the knowledge that a resin film having both of these characteristics could be obtained.

That is, the present invention relates to the following [1] to [19].
[1]
A resin film (F0) made of a crosslinked precursor (PX) containing a 4-methyl-1-pentene resin (X) that satisfies the following requirements (X-a), (X-b) and (X-c)
It is a resin film obtained by irradiating radiation to
The gel fraction by xylene extraction at 140°C is 70 to 90% by mass,
The storage modulus at 220°C is 0.5 to 10 MPa as measured by a dynamic viscoelasticity measurement device.
Resin film (F1):
(Xa) The content of the structural unit derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene The content of the structural unit derived from at least one α-olefin selected from the following is 0.3 to 70.0 mol%.
(X-b) When measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part, there is at least one peak A of the amount of eluted components in the range of 100 to 140 ° C., In addition, at least one peak B of the amount of eluted components exists below 100°C.
The meso diad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 95.0 to 100%.

[2]
The resin film (F1) according to the above [1], wherein the radiation is an electron beam.
[3]
The resin film (F1) according to [1] or [2], wherein the crosslinking precursor (PX) does not contain a crosslinking agent.

[4]
The 4-methyl-1-pentene resin (X) is
10.0 to 95.0 parts by mass of a 4-methyl-1-pentene polymer (x1) that satisfies the following requirement (x1-a),
5.0 to 90.0 parts by mass of 4-methyl-1-pentene copolymer (x2) that satisfies the following requirement (x2-a) (however, the total of the above polymer (x1) and the above copolymer (x2) The resin film (F1) according to any one of [1] to [3] above, comprising:
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The content of structural units derived from at least one α-olefin selected from .) is 0 to 20.0 mol%.
(x2-a) The content of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene ) is 2.0 to 80.0 mol% of the structural unit derived from at least one α-olefin selected from The content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene) is greater than the content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene).

[5]
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 It is in the range of 220-260℃,
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 below 220°C, or a peak indicating the melting point does not appear in DSC measurement,
The resin film (F1) described in [4] above.

[6]
The resin film (F1) according to any one of [1] to [5] above, which has a thermal deformation rate of 0 to 10% at 250° C. as measured by a dynamic viscoelasticity measuring device.

[7]
[1] to [6], wherein the 4-methyl-1-pentene resin (X) has an intrinsic viscosity [η] of 0.5 to 10.0 dl/g as measured in decalin at 135°C. The resin film (F1) according to any one of the above.

[8]
The resin film (F1) according to any one of [1] to [7], wherein in the requirement (Xc), the mesodiad fraction (m) is in the range of 98.0 to 100%.

[9]
Furthermore, it contains a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (A-a) to (A-f),
In the total amount of 100 parts by mass of the 4-methyl-1-pentene resin (X) and the 4-methyl-1-pentene polymer (A),
1 to 99 parts by mass of the 4-methyl-1-pentene resin (X),
Containing 1 to 99 parts by mass of the 4-methyl-1-pentene polymer (A),
The resin film (F1) according to any one of [1] to [8] above.
(A-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) is The content of the structural unit (AQ) derived from at least one α-olefin selected from the following is 0 to 10 mol%.
(A-b) The intrinsic viscosity [η] measured in decalin at 135°C is
It is 1.0 to 4.0 dl/g.
(A-c) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(A-d) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820 to 850 kg/m ³ .
(A-f) When measured with a cross fractionation chromatography device (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. Moreover, there is no peak B of the amount of eluted components in the range below 100°C.

[10]
A laminate comprising a layer (LR1) made of the resin film (F1) according to any one of [1] to [9] above, and a base paper layer (LP).

[11]
A second compound containing a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (A-a) to (A-f) and not containing the 4-methyl-1-pentene resin (X) The laminate according to [10], further comprising a layer (LR2) between the base paper layer (LP) and the layer (LR1):
(A-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) is The content of the structural unit (AQ) derived from at least one α-olefin selected from the following is 0 to 10 mol%.
(A-b) The intrinsic viscosity [η] measured in decalin at 135°C is 1.0 to 4.0 dl/g.
(A-c) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(A-d) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820 to 850 kg/m ³ .
(A-f) When measured with a cross fractionation chromatography device (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. Moreover, there is no peak B of the amount of eluted components in the range below 100°C.

[12]
The laminate according to [10] or [11], wherein the layer (LR1) is located on the outermost surface.

[13]
A release paper comprising a layer (LR1) made of the resin film (F1) according to any one of [1] to [9] above.
[14]
A release paper comprising the laminate according to any one of [10] to [12] above.

[15]
A step of irradiating a crosslinked precursor (PX) containing a 4-methyl-1-pentene resin (X) that satisfies the following requirements (X-a), (X-b) and (X-c) with radiation, Method for manufacturing resin film.
(Xa) The content of the structural unit derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene The content of the structural unit derived from at least one kind of α-olefin selected from ) is 0.3 to 70.0 mol%.
(X-b) When measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part, there is at least one peak A of the amount of eluted components in the range of 100 to 140 ° C., Moreover, at least one peak B of the amount of eluted components exists below 100°C.
The meso diad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 95.0 to 100%.

[16]
The manufacturing method according to the above [15], wherein the irradiation dose of the radiation is 50 to 700 kGy.
[17]
The manufacturing method according to the above [15] or [16], wherein the radiation is an electron beam.

[18]
The 4-methyl-1-pentene resin (X) is
10.0 to 95.0 parts by mass of 4-methyl-1-pentene polymer (x1) that meets the following requirement (x1-a) and 4-methyl-1-pentene copolymer that meets the following requirement (x2-a) The above [15]- containing 5.0 to 90.0 parts by mass of the polymer (x2) (however, the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass) The manufacturing method according to any one of [17].
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The content of structural units derived from at least one α-olefin selected from .) is 0 to 20.0 mol%.
(x2-a) The content of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene ) is 2.0 to 80.0 mol% of the structural unit derived from at least one α-olefin selected from The content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene) is greater than the content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene).

[19]
In the release paper according to [13] or [14], a step (S-1) of embossing the layer (LR1) made of the resin film (F1);
After the step (S-1), a material for forming a synthetic leather member is applied to the surface of the layer (LR1) made of the embossed resin film (F1), and then cured to form a synthetic leather having an embossed pattern. Step (S-2) of forming a leather member;
After the step (S-2), a method for producing a synthetic leather member having an embossed pattern, including a step (S-3) of peeling off the release paper from the synthetic leather member.

The present invention can provide a resin film for release paper that can maintain its shape even at high temperatures and has both excellent mold release properties and transferability during embossing.

[Resin film]
The resin film according to the present invention is
A resin film (F0) made of a crosslinked precursor (PX) containing 4-methyl-1-pentene resin (X) (hereinafter referred to as "resin (X)")
This is a resin film (F1) obtained by irradiating radiation.

Hereinafter, the resin film (F1) according to the present invention will be explained in detail.
Here, in this specification, "a structural unit derived from 4-methyl-1-pentene" refers to a structural unit corresponding to 4-methyl-1-pentene, that is, -CH ₂ -CH(-CH ₂ - It means a structural unit represented by CH(CH ₃ ) ₂ )-. "Constituent unit derived from α-olefin" is interpreted in the same way, and refers to a constitutional unit corresponding to α-olefin, that is, a constitutional unit represented by -CH ₂ -CHR- (R is a hydrogen atom or an alkyl group). means.
Furthermore, in this specification, the term "polymer" includes both homopolymers and copolymers, unless otherwise specified.

[4-Methyl-1-pentene resin (X)]
In the present invention, the crosslinked precursor (PX) that provides the resin film (F1) contains 4-methyl-1-pentene resin (X).
The 4-methyl-1-pentene resin (X) used in the present invention satisfies the following requirements (Xa), (Xb) and (Xc).

<Requirements (X-a)>
Requirement (Xa): The content of structural units derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and α-olefin having 2 to 20 carbon atoms (4-methyl-1 - Excluding pentene) is 0.3 to 70.0 mol%.

The content of the structural unit derived from 4-methyl-1-pentene is preferably 40.0 to 99.5 mol%, more preferably 50.0 to 99.0 mol%, even more preferably 70.0 to 99.5 mol%. 97.0 mol%, 75.0 to 96.0 mol%, or 80.0 to 95.0 mol%. Further, the content of structural units derived from at least one α-olefin selected from α-olefins having 2 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%, even more preferably 3.0 to 30.0 mol%, 4.0 to 25.0 mol%, or 5.0 to 20.0 mol% It is mole%.

Examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 - Examples include eicosene. The α-olefin can be appropriately selected depending on the use and required physical properties of the resin (X). For example, the α-olefin is preferably an α-olefin having 8 to 18 carbon atoms, and 1-octene. , 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene.

The resin (X) may contain structural units other than the structural units derived from 4-methyl-1-pentene and the structural units derived from the α-olefin (hereinafter referred to as "other structural units"), to the extent that 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 that lead 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. Examples of cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins include those described in paragraphs [0035] to [0041] of JP-A No. 2013-169685. Compounds can be used.
When the resin (X) has other structural units, only one type of other structural units may be contained, or two or more types of other structural units may be contained.

<Requirements (X-b)>
Requirement (X-b): At least one peak A of the amount of eluted components exists in the range of 100 to 140°C when measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part However, at least one peak B of the amount of eluted components exists in the range of less than 100°C, preferably 0°C or more and less than 100°C. The peak A may be a single peak or multiple peaks. Moreover, the peak B may be a single peak or may be a multi-peak.

By using a polymer in which peaks A and B of the eluted component amount are present in the above ranges, a molded article having low rigidity (high flexibility) can be obtained while maintaining high heat resistance, which is an advantage.

For example, in the method for producing 4-methyl-1-pentene resin (X) described below, peak A is derived from the polymer (x1) produced in step (1), and peak B is derived from the polymer produced in step (2). Derived from polymer (x2).

<Requirements (X-c)>
Requirement (Xc): The mesodiad fraction (m) measured by ¹³ C-NMR is in the range of 95.0 to 100%. The meso diad 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 4-methyl-1-pentene resin (X) and its resin composition are less likely to occur. This is presumed to be because the uniformity of the composition distribution is improved by narrowing the melting point distribution.

<Other requirements>
In addition to the above requirements (Xa) to (Xc), the resin (X) used in the present invention preferably satisfies the following requirements.

Requirement (X-d): Intrinsic viscosity [η] measured in decalin at 135°C is preferably 0.5 to 10.0 dl/g, more preferably 0.5 to 5.0 dl/g, even more preferably It is in the range of 1.0 to 5.0 dl/g.

The intrinsic viscosity [η] of the 4-methyl-1-pentene resin (X) is adjusted, for example, by the value of [η] and the content ratio of the polymer (x1) and copolymer (x2), which will be described later. sell.
Details of the measurement conditions for the above requirements are described in the Examples column.

<Polymer component contained in 4-methyl-1-pentene resin (X)>
The 4-methyl-1-pentene resin (X) contains 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 4-methyl-1-pentene copolymer (x2) that satisfies a). However, the total amount of the polymer (x1) and copolymer (x2) is 100 parts by mass. The resin (X) is usually preferably a resin obtained by melting particles (x) containing the polymer (x1) and the copolymer (x2) in the same particle.

The amount of polymer (x1) is preferably 20.0 to 90.0 parts by weight, more preferably 30.0 to 85.0 parts by weight. The amount of copolymer (x2) is preferably 10.0 to 80.0 parts by weight, more preferably 15.0 to 70.0 parts by weight. However, the total amount of the 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%. 100 mol%, more preferably 95.0 to 100 mol%, at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter referred to as (Also referred to as "comonomer 1." is 0 to 5.0 mol%.

Note that the content of the above-mentioned structural units is based on the total amount of repeating structural units being 100 mol%.
Examples of the comonomer 1 include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene. can be mentioned. Comonomer 1 can be appropriately selected depending on the use and required physical properties of the 4-methyl-1-pentene resin (X). For example, the comonomer 1 is preferably an α-olefin having 8 to 18 carbon atoms, such as 1-octene, 1 At least one selected from -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 of the structural unit may be contained.
The polymer (x1) may contain structural units derived from other monomers 1 other than 4-methyl-1-pentene and comonomer 1 (hereinafter also referred to as "other structural units 1") within a range that does not impair the effects of the present invention. ). The content of other structural units 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. Examples of cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins include those described in paragraphs [0035] to [0041] of JP-A No. 2013-169685. Compounds can be used.

When the polymer (x1) has other structural units 1, only one type of other structural units 1 may be contained, or two or more types of other structural units 1 may be contained.
It is preferable that the polymer (x1) further satisfies the requirements for at least one physical property selected from the physical properties ([η], melting point) described below.

The intrinsic viscosity [η] of the polymer (x1) measured in decalin at 135° C. is preferably in the range of 0.5 to 20 dl/g, more preferably 0.5 to 5.0 dl/g.
The polymer (x1) has a melting point (Tm) measured by a differential scanning calorimeter (DSC) of preferably 220°C or higher, more preferably 220 to 260°C, and even more preferably 225 to 260°C. When the melting point of the polymer (x1) is within the above range, the resulting resin (X) has excellent heat resistance.
Details of the above structure, methods of measuring physical properties, etc. are described in the Examples column.

《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 the structural unit 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%, at least selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The content of the structural unit derived from one type of α-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 structural units derived from comonomer 2 in the copolymer (x2) is larger than the content (mol%) of structural units derived from comonomer 1 in the polymer (x1).

Note that the content of the above-mentioned structural units is based on the total amount of repeating structural units being 100 mol%.
Examples of comonomer 2 include the olefins exemplified as comonomer 1 in requirement (x1-a). The comonomer 2 can be appropriately selected depending on the use and required physical properties of the resin (X).

In the copolymer (x2), only one type of structural unit derived from comonomer 2 may be included, or two or more types may be included. Further, when the polymer (x1) has a structural unit derived from the comonomer 1, the comonomer 1 of the polymer (x1) and the comonomer 2 of the copolymer (x2) may be the same or different.

The copolymer (x2) may contain structural units derived from other monomers 2 other than 4-methyl-1-pentene and comonomer 2 (hereinafter also referred to as "other structural units 2"), within a range that does not impair the effects of the present invention. ). The content of other structural units 2 is, for example, 0 to 10.0 mol%.

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

It is preferable that the copolymer (x2) further satisfies the requirements for at least one physical property selected from the physical properties ([η], melting point) described below.
The intrinsic viscosity [η] of the copolymer (x2) measured in decalin at 135° C. is preferably in the range of 0.5 to 20 dl/g, more preferably 1.0 to 7.0 dl/g.

The melting point (Tm) of the copolymer (x2) measured by differential scanning calorimetry (DSC) is preferably in a range of less than 220° C., or a peak indicating the melting point does not appear in the DSC measurement. More preferably, the melting point (Tm) is in the range below 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 an embodiment is preferable in that a 4-methyl-1-pentene polymer having a high content of structural units derived from the comonomer can be obtained. In one of the preferred and exemplary embodiments of the present invention, as shown in the examples below, the copolymer (x2) does not exhibit a peak indicating a melting point in DSC measurement.

Details of the above structure, methods of measuring physical properties, etc. are described in the Examples section. The content of the constituent units of the copolymer (x2), [η] and Tm are determined from the measurement results of the polymer (x1) and the resin (X), and the mass of the polymer (x1) and copolymer (x2). It is possible to calculate from the ratio.

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

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

《Process (1)》
In step (1), 4-methyl-1-pentene polymer (x1) is produced by slurry polymerization.

In step (1), when comonomer 1 is used, the feed ratio of 4-methyl-1-pentene and comonomer 1 is set so that the content of the constituent units derived from each is within the above range, and Although it varies depending on the reactivity, for example, the supply ratio 4-methyl-1-pentene/comonomer 1 (mole ratio) is 100/0 to 80/20, preferably 100/0 to 90/10, more preferably 100/ The range is from 0 to 95/5, more preferably from 100/0 to 97/3, particularly preferably from 100/0 to 98/2, which is a range that allows slurry polymerization.

In step (1), a slurry containing the 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.

《Process (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 feed ratio of 4-methyl-1-pentene and comonomer 2 is set so that the content of the structural units derived from each is within the above range, and it varies depending on the reactivity of comonomer 2. , for example, the supply ratio 4-methyl-1-pentene/comonomer 2 (molar ratio) is 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 step (2), when the total amount of the polymer (x1) obtained in step (1) and the copolymer (x2) obtained in step (2) is 100 parts by mass, copolymer (x2) Copolymer (x2) is produced in an 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. do. When these polymers are produced in such a quantitative ratio, a 4-methyl-1-pentene polymer with a high content of structural units derived from the comonomer (comonomer 1 and comonomer 2 are collectively referred to in this way) is produced. It is preferable in that it can be obtained.

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

In step (2), the amounts of 4-methyl-1-pentene and comonomer 2 to be supplied are selected such that the quantitative 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 are added to a slurry containing polymer (x1), and slurry polymerization of these monomers can be performed.

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

《Polymerization conditions》
The polymerization conditions in steps (1) and (2) are described below.
Examples of the polymerization solvent include hydrocarbon media, specifically aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane; or a mixture of two or more selected from these. Further, olefins themselves such as 4-methyl-1-pentene and other α-olefins can also be used as the polymerization solvent. As described above, 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.

The above production method employs slurry polymerization, and "slurry polymerization" means that the polymer produced by polymerization is dispersed in the medium as fine particles without being substantially dissolved in the medium used during polymerization. refers to polymerization characterized by the presence of

In steps (1) and (2), the polymerization temperature of the olefin 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 The pressure was 5 MPa gauge. The polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. These conditions in 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 a catalyst that can be used in olefin polymerization and the effect of increasing or decreasing the molecular weight of a 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 determined by various methods, such as conducting a reaction that generates or consumes hydrogen within the system, separating hydrogen using a membrane, and using some methods that contain hydrogen. Adjustment can also be made by releasing gas out of the system.

The molecular weight of the resulting polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature in each of step (1) and step (2). Furthermore, it can also be adjusted by changing the carrier (D) described below 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), it is preferable that the polymer (x1) and the copolymer (x2) are each produced using a metallocene catalyst. Compared to the case of using a Ziegler catalyst, the use of a metallocene catalyst reduces the amount of solvent-soluble parts of the obtained polymer and improves the properties of the slurry. The properties become better. Therefore, target 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 include a carrier (D).
The metallocene catalyst is preferably a particulate catalyst having a volumetric D50 in the range of 1 to 500 μm, more preferably in the range of 2 to 200 μm, even more preferably in the range of 5 to 50 μm. D50 as a volume statistical value can be determined by a 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 support (D) described below, that is, it is usually in the range of 0.90 to 1.10 times, preferably 0.95 to 1.05. It is in the range of 1.0 to 1.03 times, more preferably 1.0 to 1.03 times.

<Metallocene compound (C)>
Examples of the metallocene compound (C) include compounds disclosed in International Publication No. 2005/121192, International Publication No. 2014/050817, International Publication No. 2014/123212, International Publication No. 2017/150265, etc. . Preferred examples include crosslinked metallocene compounds disclosed in International Publication No. 2014/050817, International Publication No. 2017/150265, etc., but the scope of the present invention is not limited thereby.

The metallocene compound (C) is preferably a compound represented by the general formula [C1].

In formula [C1], R ¹ is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group, and 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. Each of the substituents may be the same or different, and the substituents may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene with 10 or less carbon atoms, an anionic ligand, and a neutral compound capable of coordination with a lone pair of electrons. The same or different combinations of ligands are selected, and j is an integer from 1 to 4.

A particularly preferred metallocene compound (C) is one that exhibits little decrease in polymerization activity through steps (1) and (2), enables highly stereoregular polymerization, has excellent comonomer copolymerization performance, and has high molecular weight copolymerization. Complex compounds that can be combined are preferably used. Since highly stereoregular polymerization is possible, the elution of polymer components during slurry polymerization can be suppressed, and the melting point of the polymer (x1) can be adjusted to a high range, so that the resulting resin (X) can be Heat resistance can be highly adjusted. In addition, the excellent comonomer copolymerization performance makes it possible to freely change the copolymerization composition of polymer (x1) and copolymer (x2), and to appropriately increase the flexibility of resin (X) according to its use. Can be set. 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 value, making it possible to increase the strength and toughness of the resulting resin (X). preferred for.

From this point of view, among the compounds represented by the general formula [C1], the compounds represented by the general formula [C2] described in International Publication No. 2014-050817 and the like are particularly preferable.

In formula [C2], R ^1b is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group, and 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. Each of the substituents may be the same or different, and the substituents may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, n is an integer of 1 to 3, and Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and The same or different combinations are selected from neutral ligands capable of coordinating with lone pairs of electrons, and j is an integer from 1 to 4.

(R ¹ to R ¹⁰ , R ^1b to R ^12b )
Examples of the hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. Examples include a group in which one or more hydrogen atoms possessed by are substituted with a cyclic unsaturated hydrocarbon group. The hydrocarbon group usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

Examples of linear hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group. linear alkyl groups such as n-decanyl group; linear alkenyl groups such as allyl group.

Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group are mentioned.

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

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

Examples of groups 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, etc. Examples include a group in which one or more hydrogen atoms of an alkyl group are substituted with an aryl group.

The silicon-containing groups in R ¹ to R ¹⁰ and R ^1b to R ^12b include, for example, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, _{triphenylsilyl} , etc. , each of the plurality of R's is independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.

The halogen-containing hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b is, for example, a trifluoromethyl group or the like, in which one or more hydrogen atoms possessed by the above hydrocarbon group are replaced with a halogen atom. Examples include groups.

Examples of the halogen atom in R ² to R ¹⁰ and R ^2b to R ^12b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among 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 , R ^11b and R ^12b ) may be bonded to each other to form a ring, and the ring formation is present at two or more locations in the molecule. It's okay.

In the present invention, examples of the ring formed by bonding two substituents to each other (spiro ring, additional ring) include an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and 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, even more preferably not an aryl group, and R 1b is a linear hydrocarbon group. substituents in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon are particularly preferred. preferable.

Specific examples of R ^1b include methyl group, ethyl group, isopropyl group, tert-butyl group, tert-pentyl group, tert-amyl group, 1-methylcyclohexyl group, and 1-adamantyl group, and more preferably is a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, a 1-adamantyl group, and particularly preferably a tert-butyl group, a 1- It is an adamantyl group.

In general formula [C2], the fluorene ring moiety 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 a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, still more preferably a hydrocarbon group having 1 to 20 carbon atoms. Furthermore, R ^2b and R ^3b may be bonded to each other to form a ring, and R ^6b and R ^7b may be bonded to each other to form a ring. Such substituted fluorenyl groups include, for example, 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 is mentioned, 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, and more preferably R ^9b is 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, It is particularly preferable that R ^9b is an alkyl group having 2 or more carbon atoms. Furthermore, from a synthetic viewpoint, it is also preferable that R ^10b and R ^11b are hydrogen atoms.

Alternatively, when n=1, it is more preferable that R ^9b and R ^10b are bonded to 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 transition metal of group 4 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 coordination with a lone pair of electrons.
Examples of the halogen atom for Q include fluorine, chlorine, bromine, and iodine.

The hydrocarbon group for Q is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Examples of the alkyl group 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 a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. The number of carbon atoms in the hydrocarbon group is more preferably 5 or less.

Neutral conjugated or nonconjugated 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 ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene are exemplified.

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.

Examples of neutral ligands that can coordinate with a lone pair of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, and 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 from 1 to 3, preferably 1 or 2, and more preferably 1. It is preferable for n to have the above value from the viewpoint of efficiently obtaining the produced polymer.

j is an integer from 1 to 4, preferably 2.
Preferred embodiments of the structure of the compound represented by the general 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 the respective preferred embodiments is also a preferred embodiment. Such a crosslinked metallocene compound can be suitably used to obtain a 4-methyl-1-pentene resin (X) having the above physical properties.

Compounds represented by the general formula [C2] include (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 above 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 in the form of particles, and the metallocene catalyst is formed by immobilizing the metallocene compound (C) on its surface and inside. This type of catalyst is generally called a metallocene supported catalyst.

The carrier (D) is mainly composed of an organic aluminum compound (D-1), an organic boron compound (D-2), an inorganic compound (D-3), or a composite of two or more selected from these.

Examples of the organoaluminum compound (D-1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trin-octylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, tricycloalkylaluminum, and aluminoxane. Representative examples include organoaluminumoxy compounds. Further, as the organoaluminum compound (D-1), for example, an organoaluminum oxy compound containing a boron atom, or a halogen-containing compound as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010. Aluminoxane, ionic aluminoxane as exemplified in International Publication No. 2003/082879 can also be mentioned.

Examples of the organic boron compound (D-2) include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, and trimethylammonium tetrakis. (o-tolyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(2, 4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium Tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammoniumtetrakis(p-tolyl)borate, dioctadecyl Methyl ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammoniumtetrakis(pentafluorophenyl)borate, dioctadecylmethylammoniumtetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammoniumtetrakis(3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammoniumtetrakis(3,5-ditrifluoromethylphenyl)borate, dioctadecylmethylammonium, N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N- Diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N , N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

Examples of the inorganic compound (D-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds.
Porous oxides include, for example, oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or composites containing these. Mixtures may be mentioned. _For example, natural or synthetic zeolites, SiO2 _- MgO, _{SiO2 - Al2O3} , _SiO2 - _TiO2 , _SiO2 - _V2O5 , _{SiO2 - Cr2O3} , _SiO2 - _TiO2 -MgO, etc. can be exemplified.

Examples of the inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is, or after being pulverized using a ball mill or a vibration mill. Alternatively, an inorganic halide may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds or the like are stacked in parallel with each other with weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion exchange layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificially synthesized ones can also be used. In addition, as the clay, clay mineral, or ion exchange layered compound, clay, clay mineral, or an ionic crystalline compound having a layered crystal structure such as a hexagonal close-packed packing type, an antimony type, a CdCl ₂ type, a CdI ₂ type, etc. I can give an example.

It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of surface treatment to remove impurities adhering to the surface, treatment to affect the crystal structure of clay, etc. can be used. 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 aluminum atoms is preferable from the viewpoint of high activity and further suppressing the amount of solvent-soluble parts. The content of aluminum atoms in the support (D) is preferably 20% by mass or more, more preferably 20 to 60% by mass, even more preferably 30 to 50% by mass, particularly preferably 35 to 47% by mass.

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

As such a carrier (D), solid aluminoxane is suitably used, for example, as disclosed in International Publication No. 2010/055652, International Publication No. 2013/146337, or International Publication No. 2014-123212. Solid aluminoxane is particularly preferably used.

"Solid state" means that the solid aluminoxane maintains a substantially solid state under the reaction environment in which the solid aluminoxane is used. More specifically, for example, when preparing an olefin polymerization solid catalyst component by bringing the components constituting the olefin polymerization catalyst into contact with each other, a specific temperature and pressure may be used in an inert hydrocarbon medium such as hexane or toluene used in the reaction. This indicates that the aluminoxane is in a solid state in the environment.

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

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, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include 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 solid aluminoxane is not necessarily clarified, and it is usually estimated that it has 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 modes of the constituent units are various, for example, linear, cyclic, or cluster-like, and aluminoxane is estimated to usually consist of one of these or a mixture thereof. . Moreover, aluminoxane may consist only of the structural unit represented by Formula (1) or Formula (2).

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

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

The solid aluminoxane functions as a catalyst support. Therefore, in addition to solid aluminoxane, it is not necessary to use, as a catalyst carrier, a solid inorganic carrier such as silica, alumina, silica-alumina, magnesium chloride, or a solid organic carrier such as polystyrene beads.
Solid aluminoxane can be prepared, for example, by the method described in International Publication No. 2010/055652 and International Publication No. 2014/123212.

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

<How to use each ingredient and order of addition>
At the time of olefin polymerization, the usage method and addition order of each component 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 component (C) and component (D) to a polymerization vessel in any order.
(ii) A method in which a catalyst component in which component (C) is supported on component (D) is added to a polymerization vessel.

In each of the above methods (i) to (ii), component (E) may be further added at any stage. Furthermore, at least two of each catalyst component may be contacted in advance.
In addition, 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 catalyst component may be further supported on the solid catalyst component.

In the present invention, it is preferable to prepare a metallocene catalyst from a metallocene compound (C), a carrier (D), and optionally other components, and to polymerize an olefin containing 4-methyl-1-pentene in the presence of this catalyst. That is, it is preferable to perform steps (1) and (2). "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, as in each of the above methods, to form an olefin. Includes embodiments in which polymerization occurs.

In steps (1) and (2), when polymerizing an olefin using a metallocene catalyst, the amounts of each component that can constitute the metallocene catalyst are as follows. Further, in the metallocene catalyst, the content of each component can be adjusted as follows.

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

When using component (E), if 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)] is usually 0.002 to 500, preferably 0.01 to 60. is used in an amount such that the molar ratio [(D-3)/(E)] of component (D-3) and 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, by filtration. By doing so, the particles (x) can be separated and recovered. Through this solid-liquid separation step, particles (x) can be efficiently recovered.

《Post-processing process》
For the particles (x) obtained by the above production method, after production by the above method, a known post-treatment process such as a catalyst deactivation process, a catalyst residue removal process, a drying process, etc. is performed as necessary. good.

The 4-methyl-1-pentene resin (X) is preferably a resin obtained by melting (preferably melt-kneading) the particles (x). The melting temperature is usually in the range of 180 to 350°C, preferably 200 to 320°C, more preferably 250 to 320°C.

Although the shape of the resin (X) is not limited, it is usually preferable to be in the form of pellets for ease of handling. At this time, various additives described below may be added as necessary.
Examples of the pelletizing method include the following methods (1) and (2).
(1) A method in which particles (x) and other components added as desired are melt-kneaded using an extruder, kneader, etc., and then cut into a predetermined size.
(2) Particles (x) and other components added as desired are dissolved in a suitable good solvent (e.g., a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene), and then the solvent is removed. A method of removing, then melt-kneading using an extruder, kneader, etc., and cutting into a predetermined size.

The resin (X) has high stereoregularity and is characterized by having both excellent heat resistance and relatively low rigidity, that is, flexibility. Due to the component (usually polymer (x1)) whose elution component amount peaks in the range of 100 to 140°C by CFC, it has the property of high heat resistance that can maintain the embossed shape even after heating. The property of flexibility is obtained by a component (usually a copolymer (x2)) having a peak in the amount of eluted component below . Heat resistance can be further improved by irradiating a molded article formed from a crosslinked precursor (PX) containing resin (X) with an electron beam. Such characteristics are significantly brought about in particles (x) containing polymer (x1) and copolymer (x2) in the same particle.

For example, it is a preferable embodiment compared to a resin that is a mixture of polymers obtained by individually polymerizing the polymer (x1) and the copolymer (x2), for example, a resin obtained by melt-kneading the individual polymers. , the resin (X) formed from the particles (x) has high heat resistance. By using the resin (X) formed from the particles (x) in this way, it is possible to obtain a laminate that can maintain the embossed shape even after heating, and from the crosslinked precursor (PX) containing the resin (X). Heat resistance can be further improved by irradiating the molded body with an electron beam. That is, when the resin (X) formed from the particles (x) is used, when it is made into a resin film (F1), the elastic modulus can be maintained without melting even at high temperatures, and the surface shape of the resin film can be maintained. From this, when the release paper containing the resin film (F1) obtained using the resin (X) formed from the particles (x) is used as a release paper for synthetic leather whose surface is embossed, for example, Since the embossed shape on the surface can be maintained even at high temperatures, the surface shape of the synthetic leather can be transferred as designed, which also has the advantage of increasing the number of times it can be used repeatedly. Such an effect is obtained because the resin (X) is preferably obtained from particles (x) each of which contains a polymer (x1) and a copolymer (x2). ) and copolymer (x2) were improved, and the size of the phase separation structure of polymer (x1) and copolymer (x2) was 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. Note that if the phase separation structure is small or the compatibility between the polymer (x1) and the copolymer (x2) is high, it may not be possible to observe the phase separation structure using these methods. Although the phase separation structure is not particularly limited, it is assumed 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 formed. It is presumed that in some cases, a lamellar structure (layered structure), a cylindrical structure, etc. may also be possible.

In one embodiment, the molded article formed from the crosslinked precursor (PX) containing resin (X) preferably has a tensile modulus that satisfies the following formula 1, and more preferably satisfies formula 2.

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 in accordance with 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 resin (X), Details are described in the Examples column. The composition of the crosslinked precursor (PX), manufacturing conditions, and molding conditions of the molded body (press sheet) are described in the Examples column.

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 an even better balance between heat resistance and flexibility.

That is, by using resin (X), a resin film (F1) with excellent heat resistance and flexibility can be obtained, and a molded article formed from a crosslinked precursor (PX) containing resin (X) can be obtained. Heat resistance can be further improved by irradiating with an electron beam. Therefore, a laminate can be obtained that exhibits excellent curl control, excellent crack resistance after embossing, and excellent heat resistance that allows the embossed shape to be maintained even after heating.
In addition, when resin (X) is used, molding defects such as necking and ear shaking of the resin film (F1) are less likely to occur during molding by extrusion lamination.

[4-Methyl-1-pentene polymer (A)]
In addition to the above-mentioned 4-methyl-1-pentene resin (X), the crosslinked precursor (PX) used in the present invention is a 4-methyl-1-pentene resin that satisfies the following requirements (A-a) to (A-f). - It is preferable to further include a pentene polymer (A) (hereinafter simply referred to as "polymer (A)").

(A-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) is The content of the structural unit (AQ) derived from at least one α-olefin selected from the following is 0 to 10 mol%.

(A-b) The intrinsic viscosity [η] measured in decalin at 135°C is 1.0 to 4.0 dl/g.
(A-c) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.

(A-d) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820 to 850 kg/m ³ .
(A-f) When measured with a cross fractionation chromatography device (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. Moreover, there is no peak B of the amount of eluted components in the range below 100°C.

<Requirements (A-a)>
Requirement (A-a): The content of the structural unit (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, preferably 95 to 100 mol%, and α- The content of the structural unit (AQ) derived from at least one α-olefin selected from olefins (excluding 4-methyl-1-pentene) is 0 to 10 mol%, preferably 0 to 5 mol%. . That is, the polymer (A) that can be used in the present invention may be a 4-methyl-1-pentene homopolymer, or a 4-methyl-1-pentene and α-carbon number 2 to 20 polymer. It may also be a copolymer with at least one α-olefin selected from olefins (excluding 4-methyl-1-pentene).

When the content of the structural unit (P) in the polymer (A) is 90 mol% or more, the advantage is that heat resistance as a laminate can be obtained, and the advantage that the elastic modulus of the layer suitable for handling can be obtained. There is. Further, when it is combined with the resin (X) to form a crosslinked precursor (PX), it has the advantage that a laminate that can ensure a certain level of mold releasability can be provided.

Examples of the α-olefin forming the structural unit (AQ) include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1 -Heptadecene, 1-octadecene, 1-eicosene. The α-olefin forming the structural unit (AQ) is preferably one having a carbon number of 8 to 18 from the viewpoint of imparting appropriate elastic modulus, flexibility, and flexibility to the layer containing the polymer (A). α-olefins such as 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene are preferred.

The polymer (A) may contain other structural units other than the structural unit (P) and the structural unit (AQ) (hereinafter referred to as 4-methyl-1-pentene polymer (A)) to the extent that the effects of the present invention are not impaired. ``Other structural units''). The content of other structural units is, for example, 0 to 10 mol%.
Specific examples of monomers leading to other structural units are the same as the specific examples of monomers leading to other structural units described above in the section of "4-methyl-1-pentene resin (X)".

<Requirements (A-b)>
Requirement (A-b): The intrinsic viscosity [η] of the polymer (A) measured at 135°C in a 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) will have less stickiness, and the laminate produced by extrusion lamination will be less sticky. Molding becomes possible.

<Requirements (A-c)>
Requirement (A-c): The melting point (Tm) of the polymer (A) measured by DSC is in the range of 200 to 250°C, preferably 200 to 245°C, more preferably 200 to 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 when it is higher than the above range, and has better heat resistance than when it is lower than the above range. is good.

<Requirements (A-d)>
Requirement (A-d): The crystallization temperature (Tc) of the polymer (A) measured by DSC is in the range of 150 to 220°C, preferably 180 to 220°C, more preferably 190 to 220°C. When the crystallization temperature (Tc) of the polymer (A) is within the above range, the laminate has appropriate flexibility compared to when it is higher than the above range, so the layer containing the polymer (A) is less prone to cracking and has higher rigidity and crystallinity than those lower than the above range, so the layer containing the polymer (A) has good mold releasability even at high temperatures.

<Requirements (A-e)>
Requirements (A-e): The density of the polymer (A) measured in accordance with JIS K7112 (density gradient tube method) is 820 to 850 kg/m ³ , preferably 825 to 840 kg/m ³ , more preferably 830 to 835 kg/m ³ . When the density is within the above range, the mechanical strength of the layer containing the polymer (A) is higher than when the density is smaller than the above range, and when the density is higher than the above range, the mechanical strength of the layer containing the polymer (A) is higher than when the density is smaller than the above range. The impact strength of the containing layer tends to be high.

<Requirements (A-f)>
Requirement (A-f): At least one peak A of the amount of eluted components exists in the range of 100 to 140°C when measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part Moreover, there is no peak B of the amount of eluted components in the range below 100°C. The peak A may be a single peak or multiple peaks.

Polymer (A) can be distinguished from the above 4-methyl-1-pentene resin (X) in that peak B of the amount of eluted components does not exist, that is, it does not satisfy the above requirement (Xb). can.
Details of the measurement conditions for the above requirements are described in the Examples section.

<Other requirements>
In addition to the above requirements (A-a) to (A-f), the polymer (A) preferably satisfies any one or more of the following requirements (A-g) to (A-i). .

Requirements (A-g): The melt flow rate (MFR) of the polymer (A) measured at 260°C and a load of 5.0 kg in accordance with ASTM D1238 is not particularly specified as long as it can be coextruded. However, it is usually 0.5 to 300 g/10 minutes, preferably 1 to 250 g/10 minutes, and more preferably 1 to 200 g/10 minutes. 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 (Ah): 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 (A-i): 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 with an isotactic structure or a polymer with a syndiotactic structure, but a polymer with an isotactic structure is particularly preferred, and it is also difficult to obtain. It's easy. Whether the polymer (A) has high crystallinity can be confirmed by the mesodiad fraction. This meso diad fraction is an index indicating the structural stereoregularity of the polymer, and can be determined by the method described in the Examples below. In the present invention, the mesodiad fraction of the polymer (A) is preferably 95 to 100%. However, the stereoregularity of the polymer (A) is particularly limited as long as the layer containing the polymer (A) can be formed into a film and the laminate has the strength to withstand the intended use. Not restricted.

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

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

[Crosslinked precursor (PX)]
The crosslinked precursor (PX) that provides the resin film (F1) of the present invention contains the above-mentioned 4-methyl-1-pentene resin (X).

Here, the crosslinked precursor (PX) may be composed of the above-mentioned 4-methyl-1-pentene resin (X), and in addition to the above-mentioned 4-methyl-1-pentene resin (X), the above-mentioned 4-methyl-1-pentene resin (X) may be used. It may further contain a methyl-1-pentene polymer (A). Here, when the crosslinked precursor (PX) contains the above polymer (A), 1 to 99 parts of the above resin (X) is contained in 100 parts by mass of the total amount of the above resin (X) and the above polymer (A). It is preferable to contain 1 to 99 parts by mass of the polymer (A), more preferably 30 to 70 parts by mass of the resin (X), and 30 to 70 parts by mass of the polymer (A). preferable.

In addition, the crosslinked precursor (PX) may contain other components that do not fall under either the resin (X) or the polymer (A) (hereinafter referred to as "other"), regardless of whether it contains the polymer (A) or not. It may contain "components"). Examples of "other components" include resins that do not fall under either the resin (X) or the polymer (A) (hereinafter referred to as "other resins"), and various additives.

Examples of "other resins" include thermoplastic polyolefin resins, thermoplastic polyamide resins, thermoplastic polyester resins, and thermoplastic vinyl aromatic resins that do not fall under either the resin (X) or the polymer (A). Examples include resin.

As a specific example of a thermoplastic polyolefin resin that does not fall under either the resin (X) or the polymer (A),
Polyethylene, polypropylene, polybutene-1, ethylene propylene copolymer, ethylene butene-1 copolymer, propylene butene-1 copolymer, ethylene propylene butene-1 copolymer, ethylene propylene hexene 1 copolymer, ethylene/propylene/octene-1 copolymer, ethylene/butene-1/hexene-1 copolymer, ethylene/butene-1/octene-1 copolymer, ethylene/α-olefin/nonconjugated Various olefin polymers other than 4-methyl-1-pentene polymers, such as diene copolymers; and
Examples include thermoplastic halogen-containing resins such as chlorinated polyethylene, polyvinyl chloride, and polyvinylidene chloride.

Specific examples of thermoplastic polyamide resins include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 6T/66 copolymer, polyamide 6T/6I copolymer, polyamide 9T, polyamide 10T, etc. can be mentioned.

Specific examples of thermoplastic polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyarylate, and the like.
Specific examples of the thermoplastic vinyl aromatic resin include polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and the like.

Specific examples of other thermoplastic resins that can be used as "other resins" include:
Examples include polyvinyl alcohol, acrylic resin, thermoplastic polyurethane, polycarbonate resin, polyphenylene ether, polyphenylene sulfide, polyimide, polysulfone, and polyether sulfone.

Other examples that can be used as "other resins" include thermosetting resins such as unsaturated polyester resins, epoxy resins, phenol resins, urea resins, melamine resins, diallyl phthalate resins, and silicone resins.

Further, other examples of the above-mentioned "other components" include various additives commonly used as additives in the field of resins. Various additives include, for example, weather stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fog agents, nucleating agents, lubricants, pigments, dyes, aging agents, etc. Examples include inhibitors, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic blowing agents, crosslinking agents, crosslinking aids, adhesives, softeners, flame retardants, and the like.

Here, the crosslinking precursor (PX) may or may not contain a crosslinking agent. However, in a preferred embodiment of the present invention, the crosslinking precursor (PX) does not contain a crosslinking agent.

When the crosslinked precursor (PX) contains the above-mentioned "other components", the total content of the above-mentioned "other components" is based on the total of 100 parts by mass of the above-mentioned resin (X) and the above-mentioned polymer (A). The amount is 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 resin film (F1) may be formed only from the above resin (X), or may be formed using a resin composition containing the above resin (X). That is, the crosslinked precursor (PX) may consist only of the above-mentioned resin (X), or may be a resin composition containing the above-mentioned resin (X). The resin composition for forming the resin film (F1), that is, the resin composition containing the resin (X), contains the polymer (A) and/or various additives as described above. It may further contain other components. Such a resin composition can be obtained, for example, by mixing the resin (X), the polymer (A), and/or the "other components". The method for performing the mixing is not particularly limited, and examples thereof include a method of compounding using a twin-screw extruder, a method of mixing by dry blending, and the like.

[Structure and manufacturing method of resin film (F1)]
The resin film (F1) according to the present invention is obtained by irradiating the resin film (F0) made of the crosslinked precursor (PX) with radiation. From a different perspective, the resin film (F1) can also be said to be a resin film made of a crosslinked product of the above-mentioned crosslinked precursor (PX). When the crosslinking precursor (PX) is irradiated with radiation, the molecular chains of the resin (X) and the optional polymer (A) are cut and crosslinked, and as a result, the molecular chains are linked together at crosslinking points. From this, when the crosslinked precursor (PX) changes into the corresponding crosslinked product, the molecular chains are no longer able to flow freely even above the glass transition temperature or melting point, and the high temperature properties are improved. This also leads to a small thermal deformation rate of the resin film (F1) at high temperatures. In a typical embodiment of the present invention, the resin film (F1) has a thermal deformation rate at 250° C. of 0 to 10%. This thermal deformation rate can be measured with a dynamic viscoelasticity measurement device as shown in the Examples described later. Furthermore, the resin film (F1) can maintain its shape even when subjected to stress, and can maintain its mechanical properties.

Examples of the radiation used for the irradiation include α rays, β rays, γ rays, electron beams, and ion beams, and any of these can be used. However, in the present invention, among these radiations, electron beams or gamma rays are suitable, and among them, electron beams are particularly preferable.

Here, crosslinking of α-olefin resin using electron beam is easy to occur with linear resins such as polyethylene (no tertiary carbon), but with branched resins such as 4-methyl-1-pentene. Olefin resins (with tertiary carbon) tend to be difficult to crosslink. This is because branched (having tertiary carbon) olefin resins such as 4-methyl-1-pentene are likely to have their branched parts cut off by electron beam irradiation. However, even if the resin is an olefin resin whose main component is a branched component such as 4-methyl-1-pentene, if it contains linear components to an extent that increases the probability of crosslinking, crosslinking by electron beams will proceed. It tends to be easy. Here, a method for introducing a linear component into an olefin resin whose main component is a branched component such as 4-methyl-1-pentene is to copolymerize an α-olefin with a large number of carbon atoms as a comonomer. Another method is to mix an easily crosslinkable resin (such as a polyethylene polymer) with an olefin resin whose main component is a branched component such as 4-methyl-1-pentene. By using an olefin resin whose main component is a branched component such as 4-methyl-1-pentene that contains a component that easily crosslinks, it has the advantage of being able to be crosslinked without a crosslinking agent. . This is the reason why, in the present invention, a crosslinking precursor (PX) containing the resin (X) is used.

Here, the heat resistance of the resin film (F1) can be expressed by the storage modulus E' at 220°C. Specifically, the storage modulus E' at 220°C is 0.5 to 10 MPa, preferably 0.5 to 7.0 MPa, and more preferably 0.5 to 5.0 MPa. This storage elastic modulus E' is a value measured using a dynamic viscoelasticity measuring device. Specifically, it is measured at a measurement frequency of 1 Hz while increasing the temperature from -50°C to 250°C at a rate of 3°C/min. It can be determined by measuring the elastic modulus of the film in the MD direction and from the measurement results at 220°C. In the present invention, the crosslinked material exhibits a low storage modulus E' even at a high temperature of 220°C, and maintains excellent heat resistance.

Further, the resin film (F1) is appropriately crosslinked in order to achieve both good mold releasability and good heat resistance. The degree of crosslinking in the resin film (F1) is shown by the gel fraction obtained by xylene extraction at 140 °C, more specifically, by the gel fraction measured as the ratio of the xylene insoluble matter at 140 °C to the entire resin film (F1). be able to. The gel fraction of the resin film (F1) is 70 to 90% by mass, preferably 70 to 85% by mass, and more preferably 70 to 80% by mass. Specifically, the gel fraction can be measured by the measuring method described in Examples.

Such a resin film (F1) can be obtained by a manufacturing method including a step of irradiating a crosslinked precursor (PX) with radiation.
Here, in a typical embodiment of the present invention, the resin film (F1) is
A step (S-F1) of molding the crosslinked precursor (PX) to lead to a resin film (F0);
It can be obtained by a manufacturing method including a step (S-F2) of irradiating the resin film (F0) obtained in the step (S-F1) with radiation.

Here, in the step (S-F1), the molding can be performed by a method generally used for film molding, for example, by using a general T-die extrusion molding machine. For example, a resin film (F0) can be obtained in the form of an extruded film or sheet using a single-screw extruder and a cast roll, in which case the cylinder temperature of the single-screw extruder is 250-320°C, and the cast roll temperature is 0. -80°C. This resin film (F0) serves as a precursor resin film that provides the resin film (F1) of the present invention by radiation irradiation performed in the step (S-F2).

On the other hand, in the step (S-F2), the irradiation dose of the radiation is usually 50 to 700 kGy, preferably 100 to 500 kGy is desired.

When the irradiation dose is within the above range, the crosslinking reaction of the resin (X) and the optional polymer (A) proceeds efficiently, and a cured product of the crosslinked precursor (PX) thus obtained is synthesized. When used in release paper for leather, it has excellent crack resistance and maintainability of the embossed shape after embossing.

On the other hand, if the irradiation dose is 700 kGy or more, polymer deterioration will be severe, and if the irradiation dose is 50 kGy or less, the crosslinking of the polymer chains will not proceed or even if it does, the crosslinking rate will be slow. It may be stored away.

The types of radiation used in the step (S-F2) include those exemplified above, such as an electron beam.
As described above, in a typical embodiment of the present invention, the resin film (F1) is produced through the steps (S-F1) and (S-F2), which means that the resin film (F1) of the present invention ( This does not exclude the possibility that F1) can be obtained by other manufacturing methods. The resin film (F1) may be obtained, for example, by irradiating the granular crosslinked precursor (PX) with the radiation and then molding it into a film.

[Laminated body and release paper]
The resin film (F1) can be used in the form of a laminate in combination with a base paper.

The laminate of the present invention includes a layer (LR1) made of the resin film (F1) and a base paper layer (LP). Here, in the laminate of the present invention, the layer (LR1) made of the resin film (F1) is often located at the outermost surface. The layer (LR1) made of the resin film (F1) can also be seen as a layer made of a crosslinked product of the crosslinked precursor (PX).

The above-mentioned laminate can be used as a release paper, as described below. In other words, the release paper according to the present invention consists of the above-mentioned laminate. From a different perspective, it can be said that the release paper according to the present invention includes a layer (LR1) made of the resin film (F1).

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

[Manufacturing method and specific configuration of laminate]
The laminate of the present invention includes a layer (LR1) made of the resin film (F1) and a base paper layer (LP).

Here, in the first preferred embodiment of the present invention, the laminate of the present invention is formed by laminating a base paper layer (LP) and a layer (LR1) made of the resin film (F1). In this embodiment, the laminate of the present invention consists of a base paper layer (LP) and a layer (LR1) made of the resin film (F1).

However, the laminate of the present invention may include an optional layer in addition to the layer (LR1) made of the resin film (F1) and the base paper layer (LP) as long as the effects of the present invention are not impaired. I do not care. An example of such an optional layer that may be included in the laminate of the present invention is the second layer (LR2) described below. Here, in one of the preferred embodiments of the present invention, the laminate of the present invention includes, in addition to the base paper layer (LP) and the layer (LR1) consisting of the resin film (F1), the base paper layer (LP) and the layer (LR1) made of the resin film (F1), a second layer (LR2) described below is further provided.

<Second layer (LR2)>
The laminate of the present invention contains, in addition to the base paper layer (LP) and the layer (LR1), the 4-methyl-1-pentene polymer (A), and the 4-methyl-1-pentene polymer (A) described above. It may further include a layer not containing 1-pentene resin (X) (hereinafter referred to as "second layer (LR2)"). Such a second layer (LR2) tends to be softer than the layer (LR1) made of the resin film (F1). It is preferable for the laminate of the present invention to have the second layer (LR2) because the resulting laminate tends to have good curling properties and good crack resistance. As a component constituting the "second layer (LR2)", the above polymer (A) can be mentioned. Preferred embodiments of the 4-methyl-1-pentene polymer (A) are as described above in the "4-methyl-1-pentene polymer (A)" section. The "second layer (LR2)" may further contain polypropylene, polyethylene, a compound containing them, etc. in addition to the polymer (A). However, the above-mentioned 4-methyl-1-pentene resin (X) is not included.

In the "second layer (LR2)", these components may be present in a corresponding crosslinked state.
When the laminate of the present invention has a second layer (LR2), it is preferable that the base paper layer (LP), the second layer (LR2), and the layer (LR1) are laminated in this order, It is more preferable that the layer (LR1) is located on the outermost surface. In this embodiment, the laminate of the present invention will have a second layer (LR2) between the base paper layer (LP) and the layer (LR1). On the other hand, when the laminate of the present invention does not have the second layer (LR2), the layer (LR1) made of the resin film (F1) is often located on the outermost surface.

<Other layers (LO)>
In addition to the base paper layer (LP), the layer (LR1), and the optional second layer (LR2), the laminate of the present invention includes an optional layer other than the second layer (LR2). (hereinafter referred to as other layers (LO)) may further be included.

An example of such "other layers (LO)" is the underlayer (LU). In one of the preferred embodiments of the present invention, in the laminate of the present invention, when the second layer (LR2) is present between the base paper layer (LP) and the layer (LR1), A base layer (LU) is further provided between the base paper layer (LP) and the second layer (LR2). This underlayer (LU) may be provided to further strengthen the bond between the base paper layer (LP) and the layer (LR1). Examples of materials for this underlayer (LU) include emulsions or dispersions of polypropylene, modified polyolefin, ethylene-vinyl acetate copolymer, polyethyleneimine, polybutadiene, polyurethane, and polyester resins, as well as polychloride resins. Vinyl emulsions, urethane acrylic resin emulsions, silicone acrylic resin emulsions, vinyl acetate acrylic resin emulsions, other acrylic resin emulsions, and styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer Latex, rubber latex such as chloroprene latex, polybutadiene latex, polyacrylic acid ester latex, polyvinylidene chloride latex, or carboxyl modified products of these latexes.As water-soluble anchor coating agents, polyvinyl alcohol, water-soluble ethylene-acetic acid Examples include aqueous solutions of vinyl copolymers, polyethylene oxide, water-soluble acrylic resins, water-soluble epoxy resins, water-soluble cellulose derivatives, water-soluble polyesters, water-soluble isocyanates, water-soluble lignin derivatives, and the like.

Furthermore, in the laminate of the present invention, a coating layer containing resin or the like is provided on the surface of the base paper layer (LP) opposite to the surface on which the layer (LR1) made of the resin film (F1) is formed. It may have. Further, as the base paper layer (LP), a base paper layer on which a coating layer has been formed in advance may be used. When the base paper layer (LP) has a coating layer, curling of the laminate can be easily suppressed.

<Method for manufacturing laminate>
The laminate of the present invention as described above is
A step (S-L1) of forming a precursor laminate (LmP) including a layer (LRP1) made of the crosslinked precursor (PX) and a base paper layer (LP);
It can be obtained by a manufacturing method including a step (S-L2) of irradiating the precursor laminate (LmP) obtained in the step (S-L1) with radiation.

Here, the step (S-L1) can be performed by a conventional method such as an extrusion lamination method. For example, when obtaining the laminate of the first preferred embodiment, the step (S-L1) is performed by using a conventional method such as an extrusion lamination method to laminate the base paper layer (LP) and the crosslinked precursor (PX). ) (LRP1). In addition, when obtaining a laminate having the second layer (LR2), the same method is used to prepare the base paper layer (LP) and the second precursor that becomes the precursor of the second layer (LR2). It can be obtained by performing a step including a step of laminating a layer (LRP2) and a step of laminating a second layer (LR2) and a layer (LRP1) made of the crosslinked precursor (PX). In this embodiment, these steps include:
a step of laminating the base paper layer (LP) and the second precursor layer (LRP2) to obtain a first intermediate laminate (LmIPA1);
The first intermediate laminate (LmIPA1) and the layer (LRP1) made of the crosslinked precursor (PX) may be laminated;
a step of laminating the second precursor layer (LRP2) and a layer (LRP1) made of the crosslinked precursor (PX) to obtain a first intermediate laminate (LmIPB1);
The step may be performed as a step including a step of laminating the base paper layer (LP) and the first intermediate laminate (LmIPB1); or,
This may be performed as a step of laminating the base paper layer (LP), the second precursor layer (LRP2), and the layer (LRP1) made of the crosslinked precursor (PX).

The components constituting the second precursor layer (LRP2) include the above-mentioned 4-methyl-1-pentene polymer (A), and the second precursor layer (LRP2) includes polypropylene, polyethylene, and the like. It may further contain a compound product or the like. However, the above-mentioned crosslinked precursor (PX) is not included.

Note that the layer (LRP1) made of the crosslinked precursor (PX) corresponds to the layer made of the resin film (F0).
Further, the radiation irradiation performed in the step (S-L2) can be performed in the same manner as the step (S-F2) described in the above "Structure and manufacturing method of resin film (F1)". That is, the irradiation dose of the radiation is usually 50 to 700 kGy, preferably 100 to 500 kGy, although it varies depending on the type of monomer constituting the resin component (for example, resin (X)) constituting the crosslinked precursor (PX). be. Further, types of radiation include α rays, β rays, γ rays, electron beams, ion beams, etc., and any of these can be used. However, in the present invention, among these radiations, electron beams or gamma rays are suitable, and among them, electron beams are particularly preferable.

By the radiation irradiation in this step (S-L2), the layer (LRP1) made of the crosslinked precursor (PX) changes into the layer (LR1) made of the resin film (F1), and the second precursor layer (LRP2) changes to the second layer (LR2).

The laminate obtained in the step (S-L2) may be used as it is as the laminate of the present invention, but after performing the step (S-L2), an embossed pattern (embossed pattern) can be formed by a conventional method. may be formed. That is, a precursor laminate (LmP) obtained by an extrusion lamination method or the like is passed between a metal roll with a predetermined embossed pattern and a rubber roll, or a male and female metal roll with a predetermined embossed pattern is passed between the metal roll and the rubber roll. Embossing may be performed through an embossing roll, or may be performed by hot pressing a metal plate with an embossed pattern.

The thickness of the laminate of the present invention is generally 25 to 650 μm, preferably 40 to 520 μm, and more preferably 110 to 400 μm.
The thickness (Th1) of the layer (LR1) made of the resin film (F1) is generally 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

The thickness (Thp) of the base paper layer (LP) is generally 20 to 500 μm, preferably 30 to 400 μm, and more preferably 100 to 300 μm.
The ratio (Th1/Thp) of the thickness (Th1) of the layer (LR1) made of the resin film (F1) and the thickness (Thp) of the base paper layer (LP) is generally 1/1. ~1/100, preferably 1/2 ~ 1/20.

Further, when the laminate of the present invention has the second layer (LR2), the thickness (Th2) of the second layer (LR2) is generally 5 to 150 μm, preferably 10 to 120 μm, and further Preferably it is 10 to 100 μm. Here, the ratio (Th2/Th1) of the thickness (Th2) of the second layer (LR2) and the thickness (Th1) of the layer (LR1) made of the resin film (F1) is preferably 1/ 99 to 99/1, more preferably 1/4 to 4/1.

In addition, when the laminate of the present invention has other layers other than the base paper layer (LP), the layer (LR1) made of the resin film (F1), and the second layer (LR2), the other layer The thickness is preferably 50% or less, more preferably 20% or less of the total thickness of the laminate.

[Applications of laminate]
The use of the laminate of the present invention is not particularly limited, but 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, process paper for rubber manufacturing, release paper for urethane curing, release paper for epoxy curing, process paper for solar cell manufacturing, process paper for semiconductor manufacturing, process paper for fuel cell manufacturing, process paper for electrical and electronic component manufacturing. Process paper, process paper for semiconductor product manufacturing, process paper for circuit board manufacturing, release paper for flexible printed circuit boards, release paper for rigid circuit boards, release paper for rigid-flexible boards, process paper for manufacturing advanced composite materials, carbon fiber composite materials Release paper for curing, release paper for curing glass fiber composites, release paper for curing aramid fiber composites, release paper for curing nanocomposites, release paper for curing fillers, heat-resistant and water-resistant photographic paper, OA paper, adhesive tape separator , silicone tape separators, adhesive separators, etc. Among these, it is preferably used as a release paper for synthetic leather because of its excellent embossing properties.

Generally, in a laminate in which a resin layer containing 4-methyl-1-pentene polymer and non-stretch paper are laminated, the resin layer cannot be deformed significantly in the thickness direction during embossing. cracks are more likely to occur. Furthermore, 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 will decrease and the mold release force will also decrease.

On the other hand, the laminate of the present invention has a layer (LR1) made of the resin film (F1) as the resin layer, that is, a crosslinked layer obtained by crosslinking the crosslinked precursor (PX) by irradiation with radiation such as an electron beam. It has excellent heat resistance and flexibility. Therefore, when used as a release paper, it has excellent crack resistance and maintainability of the embossed shape. Therefore, it is preferable that the layer (LR1) made of the resin film (F1) is a surface layer.

[How to use release paper for synthetic leather]
As described above, the laminate of the present invention is preferably used as a release paper for synthetic leather that has excellent embossing properties. From this point of view, the present invention
In the release paper, a step (S-1) of embossing the layer (LR1) made of the resin film (F1);
After the step (S-1), a material for forming a synthetic leather member is applied to the surface of the layer (LR1) made of the embossed resin film (F1), and then cured to form a synthetic leather having an embossed pattern. Step (S-2) of forming a leather member;
There is also provided a method for manufacturing a synthetic leather member having an embossed pattern, which includes a step (S-3) of peeling off the release paper from the synthetic leather member after the step (S-2).

In order to use the laminate of the present invention as a release paper for synthetic leather to emboss or texture a member for synthetic leather, first, the release paper is made of the resin film (F1). A step (S-1) of embossing the layer (LR1) is performed. Specifically, this step (S-1) is performed by applying an embossed pattern to the surface of the layer (LR1) made of the resin film (F1) in the laminate by embossing, for example, by the method described above. be able to.

After the step (S-1), a material for forming a synthetic leather member is applied to the surface of the layer (LR1) made of the embossed resin film (F1), and then cured to form a synthetic leather having an embossed pattern. A step (S-2) of forming a leather member is performed. Specifically, in this step (S-2), a synthetic leather member forming material (PVC dispersion, polyurethane solution, etc.) is applied to the layer (LR1) whose surface has an embossed pattern, and then heated. Alternatively, a synthetic leather member made of PVC, polyurethane, or the like is formed on the layer (LR1) by curing by drying or the like. The heating temperature is usually about 180 to 230°C when forming a PVC film, and usually about 130 to 180°C when forming a polyurethane film.

After the step (S-2), a step (S-3) of peeling off the release paper from the synthetic leather member is performed. Through this step (S-3), a synthetic leather member having a desired embossed pattern etc. transferred onto its surface is obtained.

Hereinafter, the present invention will be explained in more detail based on Examples. However, the present invention is not limited to these examples.
[Measurement methods for various physical properties]
<Catalyst carrier, catalyst particle size (D50)>
D50 as a volume statistical value was determined by a laser diffraction/scattering method using MT3300EX II manufactured by Microtrac.

<Elemental analysis (Al content in carrier)>
Measurements were performed using an ICP (inductively coupled plasma) emission spectrometry device: ICPS-8100 manufactured by Shimadzu Corporation. For quantitative and qualitative analysis of aluminum and zirconium, the sample was wet decomposed with sulfuric acid and nitric acid, and then the sample was diluted to a fixed volume (including filtration and dilution as necessary) and used as a test solution.

<Slurry properties>
Regarding the obtained polymerization liquid, if the slurry had good solid-liquid separation in the filtration process, it was considered "good", and although it was a slurry, it was porridge-like and the solid-liquid separation in the filtration process was poor. The case was described as "poor", and the case where it was not a slurry but a solution was described as "solution".

[Measurement method for polymer physical properties, etc.]
<Mass percentage of the polymer produced in step (1) and step (2)>
At the end of the polymerization in step (1), the polymer slurry was extracted, the slurry concentration was measured, and the amount of the polymer produced in step (1) was calculated. From this amount and the amount of the polymer finally obtained, the mass percentage of the polymer produced in each step was determined. Temperature during filtration: room temperature (25°C), filtration method: Filtering was performed using Kiriyama filter paper (mesh opening: 1 μm) while washing with hexane, and the slurry concentration was calculated. In the following examples, filtration was performed under these conditions.

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

Using a Bruker Biospin AVANCE III cryo-500 nuclear magnetic resonance apparatus, the solvent was an o-dichlorobenzene/benzene-d ₆ (4/1 v/v) mixed solvent, the sample concentration was 55 mg/0.6 mL, and the measurement temperature was The temperature was 120℃, the observation core was ^13C (125MHz), the sequence was single-pulse proton broadband decoupling, the pulse width was 5.0 μs (45° pulse), the repetition time was 5.5 seconds, and the number of integrations was 64. 128 ppm of benzene-d ₆ was measured as a reference value for chemical shift. The comonomer content was calculated using the following formula using the integral value of the main chain methine signal.

Comonomer content (%) = [P/(P+M)] x 100
Here, P indicates the total peak area of the comonomer main chain methine signal,
M indicates the total peak area of the 4-methyl-1-pentene main chain methine signal.

The comonomer content in 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 comonomer content in the polymer produced in step (2) The comonomer content is determined by 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. It was calculated using Specifically, the comonomer contents in the polymers produced in steps (1) and (2) and the final polymer are respectively m ₁ , m ₂ and m _f , and the polymers produced in steps (1) and (2) are Let w ₁ and w ₂ be the rate of coalescence, respectively, then m ₂ =(m _f −w ₁ ·m ₁ )/w ₂ .

<Meso diad fraction>
The meso diad isotacticity (meso diad fraction) (m) of a 4-methyl-1-pentene polymer is defined as the plane of any two head-to-tail bonded 4-methyl-1-pentene unit chains in the polymer chain. When expressed as a zigzag structure, it is defined as the proportion of isobutyl branches in the same direction, and was determined from the ¹³ C-NMR spectrum using the following formula.

Meso-dyad isotacticity (m) (%) = [m/(m+r)] x 100
[Wherein, m and r represent the absorption intensity derived from the main chain methylene of the 4-methyl-1-pentene unit bonded head-to-tail as shown in the following formula. ]

^13C -NMR spectra were performed using a Bruker Biospin AVANCE III cryo-500 nuclear magnetic resonance apparatus, the solvent was an o-dichlorobenzene/benzene-d6 (4/1 v/v) mixed solvent, and the sample concentration was 60 mg/v. 0.6 mL, measurement temperature is 120 °C, observation nucleus is ¹³ C (125 MHz), sequence is single pulse proton broadband decoupling, pulse width is 5.0 μ seconds (45° pulse), repetition time is 5.5 seconds, benzene -d6 of 128 ppm was measured as a reference value of chemical shift.

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

<Intrinsic viscosity [η]>
The specific viscosity ηsp of decalin at 135° C. was determined using an automatic kinematic viscosity measuring device VMR-053PC manufactured by Rigosha and an improved Ubbelohde capillary viscometer, 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 intrinsic viscosity of the coalescence [η] 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 the It was determined using the proportion of polymer produced in the process. Specifically, [η] of the polymer produced in steps (1) and (2) and the final polymer are respectively [η] ₁ , [η] ₂ and [η] _f , and steps (1) and ( Letting w ₁ and w ₂ be the proportions of the polymers produced in 2), respectively, [η] ₂ = ([η] _f −w ₁ ·[η] ₁ )/w ₂ .

<Melting point (Tm), crystallization temperature (Tc), heat of fusion (ΔH)>
About 4 mg of the sample was heated from 30° C. to 280° C. under a nitrogen atmosphere (30 ml/min) using EXSTAR DSC6220 manufactured by SII Nano Technology Co., Ltd. After being held at 280°C for 5 minutes, it was cooled to -50°C at a rate of 10°C/min. After being held at -50°C for 5 minutes, the temperature was raised to 280°C at a rate of 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). Further, the amount of heat of fusion accompanying melting was defined as ΔH. When multiple peaks were detected for the polymer produced at each stage, the one with the highest 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.
Equipment: CFC2 type cross fractionation chromatograph (Polymer Char)
Detector (built-in): IR4 type infrared spectrophotometer (Polymer Char)
Detection wavelength: 3.42μm (2,920cm ^-1 ); Fixed Sample concentration: Sample: 30mg/30mL (diluted with o-dichlorobenzene (ODCB))
Injection volume: 0.5mL
Temperature conditions: Raise the 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 for each elution category was evaluated. The temperature change between sections was 40℃/min.

Elution classification: 0, 5, 10, 15, 20, 25, 30, 35, 50, 70, 90, 95, 100, 102, 104, 106℃, and in 1℃ increments from 108℃ to 135℃, Evaluate the elution amount at 140 and 145℃.
GPC column: Shodex HT-806M x 3 (Showa Denko)
GPC column temperature: 145℃
GPC column calibration: Monodisperse polystyrene (Tosoh)
Molecular weight calibration method: Standard calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (ODCB), BHT added Flow rate: 1.0mL/min

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

<Melt flow rate (MFR)>
The melt flow rate (MFR) measured at 260° C. and a load of 5.0 kg was determined in accordance with ASTM D1238.

<Density>
The density was determined in accordance with JIS K7112 (density gradient tube method).
[Synthesis of transition metal complex (metallocene compound (C))]
According to Synthesis Example 4 of International Publication No. 2014/050817, (8-octamethylfluoren-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.

<Manufacturing example>
[Preparation of solid catalyst component (metallocene catalyst)]
As the carrier (D), solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.), which is particulate and has a D50 of 8 μm and an aluminum atom content of 42% by mass, was used. At 30°C, in a 100 mL three-necked flask equipped with a stirrer and sufficiently purged with nitrogen, 29.9 mL of purified decane and 7.26 mL of the hexane/decane solution of the solid polymethylaluminoxane (aluminum atoms) were added under a nitrogen stream. 14.3 mmol) was added to form a suspension. To the suspension, 50 mg (0.0586 mmol in terms of zirconium atoms) of the previously synthesized metallocene compound (c1) was added as a 4.59 mmol/L toluene solution in 12.8 mL with stirring. After 1.5 hours, stirring was stopped, and decantation cleaning was performed with decane (cleaning efficiency 98%) to obtain 50 mL of slurry liquid (Zr loading rate 96%). The obtained solid catalyst component (metallocene catalyst) was in the form of particles, and its D50 was 8 μm.

[Preparation of prepolymerization catalyst component]
To the slurry liquid prepared as above, 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 charged under a nitrogen stream. did. After 1.5 hours, stirring was stopped 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 atoms).

[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 1 L internal volume SUS polymerization vessel equipped with a stirrer. 0.4 mmol (in terms of atoms) was charged. Next, 0.0014 mmol in terms of zirconium atoms of the previously prepared decane slurry of the prepolymerized catalyst component 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 at a constant rate over 30 minutes. The polymerization was started at the start of this charge, and the temperature was maintained at 45° C. for 3 hours (step (1)). After 3 hours, the system was depressurized at 45° C., and in order to discharge residual hydrogen from the system, pressurization and depressurization with nitrogen (0.6 MPa) were performed three times. 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 8.0 mL of 1-decene was continuously poured into the polymerization vessel over 30 minutes. It was charged at a constant speed. The polymerization was started at the start of this charge, and the temperature was maintained at 45° C. for 3 hours (step (2)). After 3 hours from the start of polymerization, the temperature was lowered to room temperature, the pressure was removed, and the polymerization liquid (slurry) containing a white solid 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). The physical properties of the obtained polymer particles are shown in Table 1 below. Note that these results (for example, content of structural units, DSC and CFC measurement results, mesodiad fraction, [η]) are based on the resin obtained by melting the polymer particles (x-1) (resin (X The same result is obtained for -1)). Therefore, in Table 1 below, the physical properties of polymer particles (x-1) are described as the physical properties of "resin (X-1)".

[Polymer particles (x-2)]
Polymer particles (x-2) were obtained by performing the same operation as for polymer particles (x-1) except that the comonomer was changed to 14.5 mL of a 1-hexadecene/1-octadecene mixture. Table 1 shows the physical properties of the obtained polymer particles. Note that similar results are obtained for the resin obtained by melting the polymer particles (x-2) (resin (X-2)). Therefore, in Table 1 below, the physical properties of the polymer particles (x-2) are described as the physical properties of "resin (X-2)".

[4-Methyl-1-pentene polymer (A)]
According to the polymerization method described in Comparative Example 7 and Comparative Example 9 of International Publication No. 2006/054613, the proportions of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, and hydrogen are changed. As a result, 4-methyl-1-pentene copolymers (A-1), (A-2), and (A-3) having the physical properties shown in Table 1 below were obtained.

Physical properties other than those listed in Table 1 are as follows. Copolymer (A-1) had a crystallization temperature of 212° C., a density of 832 kg/m ³ , an MFR of 180 g/10 min, an Mw of 238,000, and an Mw/Mn of 3.3. Copolymer (A-2) 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. Further, the copolymer (A-3) 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.

[Preparation of press sheet]
To 100 parts by mass of the above polymer particles (x-1), 0.1 part by mass of tri(2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl as a heat stabilizer. 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 Research Institute Co., Ltd., the conditions were set at a temperature of 260°C, a resin extrusion rate of 60 g/min, and a rotation speed of 200 rpm. The above mixture was granulated to obtain a resin composition.

A 1 mm thick iron plate hollowed out in 8 cm squares was placed between two iron plates, and 5.2 g of the above resin composition was charged into the hollowed out area. A compression molding machine manufactured by Shindo Metal Industry Co., Ltd. (50 tons of mold clamping) was heated to 270° C., and the above-mentioned 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, held for 3 minutes, taken out, inserted into the compression molding machine set at 23°C, and compressed at a pressure of 10 MPa for 3 minutes. Cooled over a period of minutes. A 1 mm thick molded body was taken out from the hollowed out part and used as a press sheet for evaluation.

Also regarding the case where the above polymer particles (x-2), the above copolymers (A-1), (A-2), and (A-3) are used in place of the above polymer particles (x-1). , and press sheets for evaluation were similarly produced. Here, in Table 2, the results when using the above polymer particles (x-1) and (x-2) are the results of "resin (X-1)" and "resin (X-2)", respectively. The results are listed.

<Tensile modulus>
The elastic modulus, which is a tensile property, was measured in accordance with ASTM D638 using a test piece punched from the 1 mm thick press sheet prepared above using a universal tensile tester 3380 manufactured by Instron, with a distance between chucks of 65 mm, A tensile test was conducted at a tensile speed of 50 mm/min for evaluation. The evaluation results are shown in Table 2 below.

<Indicator of high heat resistance and low rigidity (flexibility)>
As an index of heat resistance, the case where the melting point (Tm) of the sample was 220°C or higher was shown as "A", and the case where it was not was shown as "C". Here, when a sample has a plurality of melting point peaks, if at least one of the melting point peaks is at 220°C or higher, it was rated as "A".

In addition, as an index of high heat resistance and low rigidity (flexibility), the heat resistance evaluation is "A" and the tensile modulus (MPa) is smaller than Tm (℃) × 49.6-10400 The case was designated as "A", and the case where the tensile modulus (MPa) was smaller than Tm (°C) x 49.6-10800 was designated as "AA". If these conditions are not met, it is marked as "C".

The evaluation results are shown in Table 2 below. Here, in Table 2 below, the evaluation results as to whether the material has high heat resistance and low rigidity (flexibility) are shown in the item "high melting point and flexibility."

[Production of film]
<Example 1A>
The resin (X-1) obtained in the above production example was molded to produce a film. Specifically, using a single-screw extruder (TP20 type) manufactured by Thermo Plastics Industries Co., Ltd., resin (X-1) was extruded into a T-die under conditions of a cylinder temperature of 280°C, a die temperature of 280°C, and a roll temperature of 60°C. Film molding was performed to obtain an extruded film with a thickness of about 50 μm.

The extruded film obtained above was irradiated with an electron beam at a dose of 200 kGy to obtain a crosslinked film.
<Example 2A, Comparative Examples 1A to 3A>
A film was produced in the same manner as in Example 1A, except that the structure was changed to the one shown in Table 3 below.
<Comparative example 4A>
The resin (X-1) obtained in the above production example was molded to produce a film. Specifically, using a single-screw extruder (TP20 type) manufactured by Thermo Plastics Industries Co., Ltd., resin (X-1) was extruded into a T-die under conditions of a cylinder temperature of 280°C, a die temperature of 280°C, and a roll temperature of 60°C. Film molding was performed to obtain an extruded film with a thickness of about 50 μm.

This film was not irradiated with an electron beam.
That is, this comparative example 4A corresponds to a comparative example conducted in the same manner as Example 1A except that the electron beam was not irradiated.

<Comparative example 5A>
A film was produced in the same manner as Comparative Example 4A except for changing the structure shown in Table 3 below.

That is, this comparative example 5A corresponds to a comparative example conducted in the same manner as Example 2A except that the electron beam was not irradiated.
[Film evaluation]
The following measurements and evaluations were carried out for each of the films obtained in Examples 1A to 2A and Comparative Examples 1A to 5A. The measurement and evaluation methods are shown below. The results are also shown in Table 3 below.

<Gel fraction>
The gel content of each of the films obtained in Examples 1A to 2A and Comparative Examples 1A to 5A was measured by a method based on JIS K6796. Specifically, about 0.6 g of a test piece was placed in a wire mesh with a 125 μm mesh, and immersed at 140° C. for 8 hours in a sufficient amount of solvent (xylene) to ensure continued immersion of the test piece. The mass of the sample before and after immersion in the solvent was measured, and the gel fraction was calculated using the following formula.

G=100×( _m2 / _m1 )
G: Gel fraction (%)
m ₁ : Mass of test piece before immersion in solvent (mg)
m ₂ : Mass of residue after solvent immersion (mg)
<Storage modulus, thermal deformation length>
For each of the films obtained in Examples 1A to 2A and Comparative Examples 1A to 5A, using a dynamic viscoelasticity measuring device (trade name "RSA-III", manufactured by TA Instruments), - The elastic modulus of the film in the MD direction was measured at a measurement frequency of 1 Hz while increasing the temperature from 50 °C to 250 °C at a rate of 3 °C/min, and the storage modulus (E') was calculated from the measurement results at 220 °C. The thermal deformation length and thermal deformation rate were calculated from the measurement results at 250°C. Here, the sample shape was a rectangular shape with a width of 3 mm. Moreover, the said measurement was performed by setting the distance between chucks to 20 mm, and holding both end portions of the sample in the longitudinal direction with chucks. The length of the sample was set so that it could be sufficiently gripped by the chuck. The difference between the length between the chucks and the distance between the chucks measured at 250° C. in the sample was defined as the thermal deformation length, and the ratio of the thermal deformation length to the distance between the chucks was defined as the thermal deformation rate.

[Preparation of laminate]
<Example 1B>
A layer made of the resin (X-1) was formed on a base paper by extrusion lamination molding using a thermoplastic coextrusion laminator with a diameter of 30 mm to produce a laminate. As the base paper, high-quality release paper for synthetic leather (thickness 200 μm) is used, and the die temperature is set to 310°C, the die width is 400 mm, and the line speed is 10 m/min to form on the base paper. The screw rotation speed was adjusted so that the layer thickness was a predetermined thickness.

A crosslinked laminate was obtained by irradiating the laminate obtained above with an electron beam at a dose of 200 kGy. This laminate consists of a base paper layer made of the above-mentioned base paper and a layer (hereinafter referred to as "surface layer") made of a crosslinked product of the above-mentioned resin (X-1), and this surface layer is This corresponds to "a layer (LR1) made of a resin film (F1)".

<Example 2B>
A laminate was produced in the same manner as in Example 1B except that resin (X-1) was changed to resin (X-2).

<Comparative example 1B>
A laminate was produced in the same manner as in Example 1B except that the resin (X-1) was changed to the copolymer (A-1).

<Comparative example 2B>
A laminate was produced in the same manner as in Example 1B except that the resin (X-1) was changed to the copolymer (A-2).

<Comparative example 3B>
A laminate was produced in the same manner as in Example 1B except that the resin (X-1) was changed to the copolymer (A-3).

<Comparative example 4B>
A layer made of the resin (X-1) was formed on a base paper by extrusion lamination molding using a thermoplastic coextrusion laminator with a diameter of 30 mm to produce a laminate. As the base paper, high-quality release paper for synthetic leather (thickness 200 μm) is used, and the die temperature is set to 310°C, the die width is 400 mm, and the line speed is 10 m/min to form on the base paper. The screw rotation speed was adjusted so that the layer thickness was a predetermined thickness.

This laminate was not irradiated with an electron beam.
That is, this Comparative Example 4B corresponds to a comparative example conducted in the same manner as Example 1B except that the electron beam was not irradiated.

<Comparative Example 5B>
A laminate was produced in the same manner as in Comparative Example 4B except that resin (X-1) was changed to resin (X-2).

[Evaluation of laminate]
The following measurements and evaluations were performed on each of the laminates obtained in Examples 1B to 2B and Comparative Examples 1B to 5B. The measurement and evaluation methods are shown below. The results are also shown in Table 4 below.

<Water contact angle>
For each of the laminates obtained in Examples 1B to 2B and Comparative Examples 1B to 5B, an image processing solid-liquid interface analysis system (DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.) was used to test the laminates at 23°C and 50% RH. Below, a test liquid (high performance liquid chromatograph, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped onto the sample surface, and the contact angle was measured. Here, the measurement was performed on the surface of the sample laminate on which the surface layer was present. Measurements were performed on five test samples, and the average value was calculated.

<Releasability from PVC>
A PVC sol having the composition shown below was prepared, and this PVC sol was applied to each of the laminates obtained in Examples 1B to 2B and Comparative Examples 1B to 5B using a knife coater so that the dry thickness was 40 μm. A PVC layer was formed by drying with hot air at 210° C. for 4 minutes. Here, the PVC sol was applied to the surface of the sample laminate where the surface layer was present.

Here, the composition of the PVC sol used to form the PVC layer is as follows:
PVC/bis(2-ethylhexyl phthalate)/stabilizer=100/150/3 parts ・PVC: Manufactured by Tosoh Corporation, trade name: Ryuron Paste 860
・Bis(2-ethylhexyl) phthalate: J-Plus Co., Ltd., product name DOP
・Stabilizer: ADEKA Co., Ltd., product name SC-320
After forming the PVC layer, sensitivity evaluation was performed to determine whether the PVC layer could be peeled off from the laminate.

Peelable: "A", non-peelable: "C"
Here, when an attempt was made to peel the PVC layer from the laminate, if the PVC film corresponding to the PVC layer could be taken out and the PVC film was not torn, it was evaluated as "peelable". . On the other hand, when the PVC layer is stuck to the laminate and the PVC film cannot be taken out, or when the PVC film can be taken out but the PVC film is torn, it will be marked as ``unremovable.'' evaluated.

<Curl amount>
Each of the laminates produced in Examples 1B to 2B and Comparative Examples 1B to 5B was cut out into an A4 size piece, and the surface layer was placed on the upper side under conditions of a temperature of 23° C. and a humidity of 80% RH. It was left to stand for 24 hours, and then placed in an oven set at 200°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 up to varying degrees. Measure the height of the four curled corners of the laminate from the horizontal plane (hereinafter also referred to as "curl amount"), evaluate the curl amount using the following criteria, and evaluate the results as one of the following "A" to "C". It was shown by Moreover, when the laminate was curled one turn or more, it was determined to be "C".

A: Curl amount is less than 5 mm B: Curl amount is 5 mm or more and less than 15 mm C: Curl amount is 15 mm or more, or
The laminate is curled more than once, making it difficult to calculate the amount of curl.

<Crack resistance: thermal cycle test>
A crack resistance test was conducted on each of the laminates produced in Examples 1B to 2B and Comparative Examples 1B to 5B according to the following procedure.

The laminate is cut into A4 size, an embossing mold is placed on the composition layer of the laminate, heated at 160°C for 3 minutes, and then pressurized at 50 kgf for 10 seconds to embossing the laminate. Processed. Here, the embossing was performed using a 50-ton press machine manufactured by Shindo Metal Industry Co., Ltd. and an embossing mold with dimensions of 70 mm in length x 70 mm in width x 15 mm in thickness. An embossing mold in which 140 μm stripes were formed at a pitch of 0.5 mm was used. The embossing was performed in such a manner that the surface of the embossing die having the stripes faced the surface of the laminate where the surface layer was present. Thereafter, the embossed laminate was taken out from the embossing mold, and the embossed laminate was left to stand in an oven set at 220°C for 10 minutes, and then left to stand at room temperature for 10 minutes. This was repeated 10 times as one cycle of the heat cycle test. After repeating the thermal cycle 10 times, the presence or absence of cracks in the surface layer was observed using a scanning electron microscope (SEM), and the results were indicated by one of the following "A" to "C".

A: No cracks were observed.
B: Cracks were confirmed at 1 to 5 locations.
C: Cracks were confirmed at 5 or more locations.

Claims (19)

A resin film (F0) made of a crosslinked precursor (PX) containing a 4-methyl-1-pentene resin (X) that satisfies the following requirements (X-a), (X-b) and (X-c)
It is a resin film obtained by irradiating radiation to
The gel fraction by xylene extraction at 140°C is 70 to 90% by mass,
The storage modulus at 220°C is 0.5 to 10 MPa as measured by a dynamic viscoelasticity measurement device.
Resin film (F1):
(Xa) The content of the structural unit derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene The content of the structural unit derived from at least one α-olefin selected from the following is 0.3 to 70.0 mol%.
(X-b) When measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part, there is at least one peak A of the amount of eluted components in the range of 100 to 140 ° C., In addition, at least one peak B of the amount of eluted components exists below 100°C.
The meso diad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 95.0 to 100%. The resin film (F1) according to claim 1, wherein the radiation is an electron beam. The resin film (F1) according to claim 1 or 2, wherein the crosslinking precursor (PX) does not contain a crosslinking agent. The 4-methyl-1-pentene resin (X) is
10.0 to 95.0 parts by mass of a 4-methyl-1-pentene polymer (x1) that satisfies the following requirement (x1-a),
5.0 to 90.0 parts by mass of 4-methyl-1-pentene copolymer (x2) that satisfies the following requirement (x2-a) (however, the total of the above polymer (x1) and the above copolymer (x2) The resin film (F1) according to any one of claims 1 to 3, comprising:
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The content of structural units derived from at least one α-olefin selected from .) is 0 to 20.0 mol%.
(x2-a) The content of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene ) is 2.0 to 80.0 mol% of the structural unit derived from at least one α-olefin selected from The content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene) is greater than the content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene). 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 It is in the range of 220-260℃,
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 below 220°C, or a peak indicating the melting point does not appear in DSC measurement,
The resin film (F1) according to claim 4. The resin film (F1) according to any one of claims 1 to 5, which has a thermal deformation rate of 0 to 10% at 250°C as measured with a dynamic viscoelasticity measuring device. Any one of claims 1 to 6, wherein the intrinsic viscosity [η] of the 4-methyl-1-pentene resin (X) measured in decalin at 135°C is in the range of 0.5 to 10.0 dl/g. The resin film (F1) according to item 1. The resin film (F1) according to any one of claims 1 to 7, wherein in the requirement (Xc), the mesodiad fraction (m) is in the range of 98.0 to 100%. Furthermore, it contains a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (A-a) to (A-f),
In the total amount of 100 parts by mass of the 4-methyl-1-pentene resin (X) and the 4-methyl-1-pentene polymer (A),
1 to 99 parts by mass of the 4-methyl-1-pentene resin (X),
Containing 1 to 99 parts by mass of the 4-methyl-1-pentene polymer (A),
The resin film (F1) according to any one of claims 1 to 8.
(A-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) is The content of the structural unit (AQ) derived from at least one α-olefin selected from the following is 0 to 10 mol%.
(A-b) The intrinsic viscosity [η] measured in decalin at 135°C is
It is 1.0 to 4.0 dl/g.
(A-c) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(A-d) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820 to 850 kg/m ³ .
(A-f) When measured with a cross fractionation chromatography device (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. Moreover, there is no peak B of the amount of eluted components in the range below 100°C. A laminate comprising a layer (LR1) made of the resin film (F1) according to any one of claims 1 to 9 and a base paper layer (LP). A second compound containing a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (A-a) to (A-f) and not containing the 4-methyl-1-pentene resin (X) The laminate according to claim 10, further comprising a layer (LR2) between the base paper layer (LP) and the layer (LR1):
(A-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 100 to 90 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) is The content of the structural unit (AQ) derived from at least one α-olefin selected from the following is 0 to 10 mol%.
(A-b) The intrinsic viscosity [η] measured in decalin at 135°C is 1.0 to 4.0 dl/g.
(A-c) The melting point (Tm) measured by DSC is in the range of 200 to 250°C.
(A-d) The crystallization temperature (Tc) measured by DSC is in the range of 150 to 220°C.
(Ae) Density is 820 to 850 kg/m ³ .
(A-f) When measured with a cross fractionation chromatography device (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. Moreover, there is no peak B of the amount of eluted components in the range below 100°C. The laminate according to claim 10 or 11, wherein the layer (LR1) is located on the outermost surface. A release paper comprising a layer (LR1) made of the resin film (F1) according to any one of claims 1 to 9. A release paper comprising the laminate according to any one of claims 10 to 12. A step of irradiating a crosslinked precursor (PX) containing a 4-methyl-1-pentene resin (X) that satisfies the following requirements (X-a), (X-b) and (X-c) with radiation, Manufacturing method of resin film:
(Xa) The content of the structural unit derived from 4-methyl-1-pentene is 30.0 to 99.7 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene The content of the structural unit derived from at least one kind of α-olefin selected from ) is 0.3 to 70.0 mol%.
(X-b) When measured with a cross fractionation chromatography device (CFC) using an infrared spectrophotometer in the detection part, there is at least one peak A of the amount of eluted components in the range of 100 to 140 ° C., Moreover, at least one peak B of the amount of eluted components exists below 100°C.
The meso diad fraction (m) measured by (Xc) ¹³ C-NMR is in the range of 95.0 to 100%. The manufacturing method according to claim 15, wherein the irradiation dose of the radiation is 50 to 700 kGy. The manufacturing method according to claim 15 or 16, wherein the radiation is an electron beam. The 4-methyl-1-pentene resin (X) is
10.0 to 95.0 parts by mass of 4-methyl-1-pentene polymer (x1) that meets the following requirement (x1-a) and 4-methyl-1-pentene copolymer that meets the following requirement (x2-a) Claims 15 to 17 containing 5.0 to 90.0 parts by mass of the polymer (x2) (provided that the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass). The manufacturing method according to any one of the above.
(x1-a) The content of structural units derived from 4-methyl-1-pentene is 80.0 to 100 mol%, and α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The content of structural units derived from at least one α-olefin selected from .) is 0 to 20.0 mol%.
(x2-a) The content of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene ) is 2.0 to 80.0 mol% of the structural unit derived from at least one α-olefin selected from The content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene) is greater than the content of structural units derived from at least one α-olefin selected from α-olefins (excluding 4-methyl-1-pentene). In the release paper according to claim 13 or 14, a step (S-1) of embossing the layer (LR1) made of the resin film (F1);
After the step (S-1), a material for forming a synthetic leather member is applied to the surface of the layer (LR1) made of the embossed resin film (F1), and then cured to form a synthetic leather having an embossed pattern. Step (S-2) of forming a leather member;
After the step (S-2), a method for producing a synthetic leather member having an embossed pattern, including a step (S-3) of peeling off the release paper from the synthetic leather member.