JP2024058270A - LAMINATE AND METHOD FOR MANUFACTURING LAMINATE - Google Patents

Abstract

[Problem] To provide a laminate having a resin layer containing a 4-methyl-1-pentene polymer having better storage stability than conventional 4-methyl-1-pentene polymers, and having excellent water repellency. [Solution] A laminate comprising a base layer (I) and a resin layer (II) containing a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (a) to (c), and a method for producing the same: (a) a melting point (Tm) measured by a differential scanning calorimeter (DSC) of more than 180°C and not more than 220°C; (b) an endothermic end temperature (TmE) in a melting (endothermic) curve measured by DSC of 230°C or less; (c) an exothermic start temperature (TcS) in a crystallization (exothermic) curve measured by DSC of 210°C or less. [Selected Figure] None

Description

The present invention relates to a laminate and a method for manufacturing the laminate.

Various coating agents are used for protection, insulation, flattening, heat resistance, light resistance, weather resistance, etc., in display devices, semiconductor devices, optical members, printed circuit boards, etc. Films made using these coating agents are required to have properties such as heat resistance, transparency, electrical insulation, etc., depending on the application.
A 4-methyl-1-pentene polymer has an extremely low surface tension and therefore excellent releasability, and also has high heat resistance. Therefore, a laminate in which a resin layer containing a 4-methyl-1-pentene polymer is laminated on a plastic substrate is often used as an industrial release film or the like.

For example, Patent Documents 1 and 2 disclose a specific 4-methyl-1-pentene copolymer and a composition containing the copolymer and a solvent as a composition that can be used for coating to form a film that exhibits high heat resistance and good electrical insulation. Patent Document 3 discloses a film formation method using a cyclohexene solution of a 4-methyl-1-pentene copolymer maintained at a temperature of 25 to 80°C as a method for producing an extremely thin polymer membrane that has selective permeability to mixed gases.

JP 2013-227421 A JP 2015-34258 A Japanese Patent Application Laid-Open No. 55-41808

However, in applications of industrial release films, particularly high water repellency may be required, and there is room for improvement in the water repellency of the copolymers described in Patent Documents 1 and 2 and release films using the copolymers. Thus, there is a demand for release films with even higher water repellency and 4-methyl-1-pentene polymers that can realize such films.
In addition, the copolymer described in Patent Document 3 has room for improvement in terms of solubility in solvents, and there has been a demand for a 4-methyl-1-pentene polymer that is more soluble and has excellent storage stability when made into a varnish.

The problem that one embodiment of the present invention aims to solve is to provide a laminate that has a resin layer containing a 4-methyl-1-pentene polymer that has better storage stability than conventional 4-methyl-1-pentene polymers and has excellent water repellency, and a method for producing the laminate.

As a result of further investigations, the inventors discovered that the above problems could be solved by a laminate including a base layer (I) and a resin layer (II) containing a 4-methyl-1-pentene polymer (A) that satisfies certain requirements, and thus completed the present invention.

That is, the means for solving the above problems include the following aspects.
<1> A substrate layer (I),
a resin layer (II) containing a 4-methyl-1-pentene polymer (A) satisfying the following requirements (a) to (c);
A laminate comprising:
(a) a melting point (Tm) measured by differential scanning calorimetry (DSC) of more than 180°C and not more than 220°C;
(b) the endothermic end temperature (TmE) in the melting (endothermic) curve measured by differential scanning calorimetry (DSC) is 230° C. or lower;
(c) The heat generation onset temperature (TcS) in the crystallization (heat generation) curve measured by a differential scanning calorimeter (DSC) is 210° C. or lower.
<2> The laminate according to <1>, wherein the base layer (I) contains a polyolefin having a melting point of 200° C. or less as measured by a differential scanning calorimeter (DSC).
<3> The laminate according to <2>, wherein the polyolefin having a melting point of 200° C. or less is at least one resin selected from the group consisting of polypropylene, low-density polyethylene, and high-density polyethylene.
<4> The laminate according to any one of <1> to <3>, wherein the resin layer (II) has a surface free energy of 32 mN/m or less.
<5> The laminate according to any one of <1> to <4>, wherein the resin layer (II) has a water contact angle of 97° or more.
<6> The laminate according to any one of <1> to <5>, wherein the 4-methyl-1-pentene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.5 to 4.5 dl/g.
<7> The amount of structural units (U1) derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) is 84 to 100 mol %,
The laminate according to any one of <1> to <6>, wherein the amount (U2) of structural units derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 16 mol % (wherein the total of U1 and U2 is 100 mol %).
<8> The laminate according to <7>, wherein the α-olefin is an α-olefin having 6 to 18 carbon atoms (excluding 4-methyl-1-pentene).
<9> The laminate according to any one of <1> to <8>, wherein the resin layer (II) has a thickness of 25 μm or less.
<10> The laminate according to any one of <1> to <9>, wherein the 4-methyl-1-pentene polymer (A) is an unmodified polymer.
<11> A method for producing a laminate according to any one of <1> to <10>,
A step (1) of preparing a composition (X) containing the 4-methyl-1-pentene polymer (A) and an organic solvent (B);
(2) applying the composition (X) to at least one surface of the base layer (I) to form a resin layer (II) containing the 4-methyl-1-pentene polymer (A);
A method for producing a laminate, comprising:
<12> The method for producing a laminate according to <11>, wherein the 4-methyl-1-pentene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.5 to 4.5 dl/g.

According to one embodiment of the present invention, it is possible to provide a laminate having a resin layer containing a 4-methyl-1-pentene polymer that has better storage stability than conventional 4-methyl-1-pentene polymers and has excellent water repellency, and a method for producing the laminate.

<Laminate>
The laminate of the present invention includes a substrate layer (I) and a resin layer (II) containing a 4-methyl-1-pentene polymer (A) that satisfies the requirements (a) to (c).
Each component of the laminate of the present invention will be described below.

<Resin layer (II)>
[4-Methyl-1-pentene polymer (A)]
The resin layer (II) contains a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (a) to (c).
In the following description, a structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) may be referred to as a "structural unit (i)." Similarly, a structural unit derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the 4-methyl-1-pentene polymer (A) may be referred to as a "structural unit (ii)."

[Requirement (a)]
The 4-methyl-1-pentene polymer (A) has a melting point (Tm) measured by a differential scanning calorimeter (DSC) of more than 180°C and not more than 220°C, preferably 184 to 217°C, more preferably 188 to 215°C.
When the melting point (Tm) measured by a differential scanning calorimeter (DSC) is within the above range, the resin layer (II) containing the 4-methyl-1-pentene polymer (A) has good water repellency and oil repellency.
The melting point (Tm) is determined by the method described in the Examples below.
The melting point (Tm) value tends to depend on the stereoregularity of the 4-methyl-1-pentene polymer (A) and the content of the structural unit (ii) in the 4-methyl-1-pentene polymer (A). For this reason, the melting point (Tm) can be adjusted by using an olefin polymerization catalyst described later and further controlling the content of the structural unit (ii).

[Requirement (b)]
The 4-methyl-1-pentene polymer (A) has an endothermic end temperature (TmE) in a melting (endothermic) curve measured by a differential scanning calorimeter (DSC) of 230° C. or lower, preferably lower than 230° C., more preferably lower than 228° C., and further preferably lower than 228° C.
Here, the endothermic end temperature (TmE) means the temperature at which melting is completed. The endothermic end temperature (TmE) and the exothermic start temperature (TcS) described later are indicators different from the onset and offset, which are generally the intersection points between the baseline and the tangent to the steady line.
The endothermic end temperature (TmE) can be adjusted to a desired value by, for example, adjusting the type of olefin polymerization catalyst used in polymerizing the 4-methyl-1-pentene polymer (A) and the content of the structural unit (ii).
The endothermic end temperature (TmE) is determined by the method described in the Examples below.

4-methyl-1-pentene polymer (A) having an endothermic end temperature (TmE) in the above range has excellent water repellency and oil repellency. Therefore, the resin layer formed from the coating agent obtained from the composition containing 4-methyl-1-pentene polymer (A) having an endothermic end temperature (TmE) in the above range also tends to have excellent water repellency and oil repellency. In addition, 4-methyl-1-pentene polymer (A) having an endothermic end temperature (TmE) in the above range is more easily dissolved in a solvent that can be used when preparing the coating agent than 4-methyl-1-pentene polymers having an endothermic end temperature (TmE) outside the above range. Therefore, when the endothermic end temperature (TmE) is in the above range, the properties of the coating agent obtained from the composition containing 4-methyl-1-pentene polymer (A) tend to be uniform.

[Requirement (c)]
The 4-methyl-1-pentene polymer (A) has an exothermic onset temperature (TcS) in a crystallization (exothermic) curve measured by a differential scanning calorimeter (DSC) of 210° C. or lower, preferably lower than 210° C., more preferably lower than 200° C., and further preferably lower than 200° C.
The exotherm onset temperature (TcS) can be adjusted to a desired value, for example, by appropriately selecting an olefin polymerization catalyst for polymerizing the 4-methyl-1-pentene polymer (A) or by controlling the content of the structural unit (ii).

4-methyl-1-pentene polymer (A) having a heat generation onset temperature (TcS) within the above range has excellent water repellency and oil repellency. Therefore, the resin layer formed from the coating agent obtained from the composition containing 4-methyl-1-pentene polymer (A) having a heat generation onset temperature within the above range also tends to have excellent water repellency and oil repellency. In addition, 4-methyl-1-pentene polymer (A) having a heat generation onset temperature within the above range is more easily dissolved in the organic solvent (B) described below than 4-methyl-1-pentene polymers having a heat generation onset temperature outside the above range. Therefore, the properties of the coating agent prepared using 4-methyl-1-pentene polymer (A) having a heat generation onset temperature (TcS) within the above range tend to be uniform.

The 4-methyl-1-pentene polymer (A) contained in the laminate of the present invention satisfies the requirements (a) to (c), and therefore has excellent solubility in solvents while maintaining water repellency and oil repellency. In addition, the 4-methyl-1-pentene polymer (A) that satisfies the requirements (a) to (c) has excellent solubility in solvents and is therefore likely to remain dissolved in the solvent, and therefore has excellent storage stability. Therefore, the 4-methyl-1-pentene polymer (A) that satisfies the requirements (a) to (c) has good storage stability when dissolved in a solvent, compared with a 4-methyl-1-pentene polymer that does not satisfy one or more of the requirements (a) to (c).

The 4-methyl-1-pentene polymer (A) contained in the resin layer (II) may further satisfy one or more of the following requirements (d) to (g), and preferably satisfies one or more of the following requirements (d) to (g).

[Requirement (d)]
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A) measured in decalin at 135° C. is preferably 0.5 to 4.5 dl/g, more preferably 0.65 to 4.4 dl/g, and further preferably 0.8 to 4.3 dl/g.
The 4-methyl-1-pentene polymer (A) having an intrinsic viscosity [η] within the above range has good water repellency and oil repellency. Moreover, a coating agent containing the 4-methyl-1-pentene polymer (A) having an intrinsic viscosity [η] within the above range has good coatability and is suitable for forming a resin layer of the 4-methyl-1-pentene polymer (A).
The intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added in the polymerization step for producing the 4-methyl-1-pentene polymer (A). The intrinsic viscosity [η] can be determined by the method described in the examples below.

[Requirement (e)]
In the 4-methyl-1-pentene polymer (A), the amount (U1) of the structural unit (structural unit (i)) derived from 4-methyl-1-pentene is preferably 84 to 100 mol%, more preferably 87 to 99.0 mol%, and even more preferably 90 to 98.5 mol%.
In the 4-methyl-1-pentene polymer (A), the amount (U2) of the structural unit (structural unit (ii)) derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 0 to 16 mol %, more preferably 1.0 to 13 mol %, and even more preferably 1.5 to 10 mol %, with the total of U1 and U2 being 100 mol %.
The present inventors presume that when the amount (U2) of the structural unit (ii)) in the 4-methyl-1-pentene polymer (A) is in the range of 0 to 16 mol %, the temperature at which the polymer starts to crystallize and the temperature at which the crystals completely melt can be more easily lowered, and therefore, storage stability when the polymer is dissolved in a solvent can be ensured.
U1 and U2 are determined by the measurement method described in the Examples below. A 4-methyl-1-pentene polymer (A) having U1 and U2 in the above ranges is excellent in water repellency and oil repellency. Therefore, a resin layer formed using a coating agent obtained from a composition containing a 4-methyl-1-pentene polymer (A) having U1 and U2 in the above ranges also tends to be excellent in water repellency and oil repellency.

The α-olefin from which the structural unit (ii) is derived may be a linear α-olefin, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
Among these, from the viewpoint of water repellency and oil repellency, the α-olefin (excluding 4-methyl-1-pentene) is preferably an α-olefin having 6 to 18 carbon atoms, and more preferably a linear α-olefin having 6 to 18 carbon atoms. Specifically, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, and 1-octadecene are more preferable, and 1-decene, 1-hexadecene, and 1-octadecene are particularly preferable.

The structural unit (ii) may be derived from only one type selected from the group consisting of ethylene or α-olefins having 3 to 20 carbon atoms, or may be derived from two or more types selected from the group consisting of ethylene or α-olefins having 3 to 20 carbon atoms.

The 4-methyl-1-pentene polymer (A) may be a copolymer consisting of only the structural unit (i) and the structural unit (ii), or may contain, in addition to the structural unit (i) and the structural unit (ii), a structural unit (hereinafter also referred to as "other structural unit") derived from a polymerizable monomer (hereinafter also referred to as "other polymerizable monomer") other than 4-methyl-1-pentene, ethylene, and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). In this case, the total amount of the structural unit (i) and the structural unit (ii) (U1+U2) is 100 mol%.

When the 4-methyl-1-pentene polymer (A) contains other structural units, the other structural units are preferably contained in such a small amount that the object of the present invention is not impaired. Specifically, the content of the other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and further preferably 3 mol % or less, based on the total structural units of the 4-methyl-1-pentene polymer (A).
The other structural units may be of one type alone or of two or more types.

Specific preferred examples of the other polymerizable monomers include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentane, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or derivatives thereof such as maleic anhydride; conjugated dienes such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene. Non-conjugated polyenes such as dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene are examples of such non-conjugated polyenes.

Here, when the 4-methyl-1-pentene polymer (A) contains other structural units, it is preferable that the total content of the structural unit (ii) and the other structural units satisfies the content of the structural unit (ii) of 0 to 16 mol %. In this case, the total amount of the structural unit (i), the structural unit (ii), and the other structural units is 100 mol %.

[Requirement (f)]
The 4-methyl-1-pentene polymer (A) is preferably an unmodified polymer. The 4-methyl-1-pentene polymer (A) being an unmodified polymer means, for example, that it is a polymer that has not been graft-modified with a polar functional group such as a carboxy group.
When the 4-methyl-1-pentene polymer (A) is an unmodified polymer, it tends to have excellent releasability from a release material (a counter material laminated on the release material).

[Requirement (g)]
The crystallization temperature (Tc) measured by differential scanning calorimetry (DSC) is preferably from 110 to 220°C, more preferably from 120 to 210°C, and even more preferably from 130 to 200°C.
A 4-methyl-1-pentene polymer (A) having a crystallization temperature (Tc) within the above range is preferable from the viewpoints of water repellency, oil repellency, and moldability. Therefore, a coating agent or the like obtained from a composition containing a 4-methyl-1-pentene polymer (A) having a crystallization temperature (Tc) within the above range tends to have good properties and storage stability.
The crystallization temperature (Tc) can be determined by the measurement method described in the Examples section below.

[Method for producing 4-methyl-1-pentene polymer (A)]
The method for producing the 4-methyl-1-pentene polymer (A) is not particularly limited, and may be any known method, such as a method for producing 4-methyl-1-pentene, a specific olefin from which the above-mentioned structural unit (ii) is derived, and, if necessary, the above-mentioned other polymerizable monomers by a known polymerization method in the presence of an olefin polymerization catalyst.

An example of an olefin polymerization catalyst that can be used in the production of the 4-methyl-1-pentene polymer (A) is a metallocene catalyst. Preferred metallocene catalysts include those described in WO 2001/53369, WO 2001/27124, JP-A 3-193796, JP-A 02-41303, WO 2006/025540, or WO 2014/123212.

The 4-methyl-1-pentene polymer (A) may be prepared by heat-treating a 4-methyl-1-pentene polymer once produced with the above catalyst or the like in an extruder, mixer, or the like to prepare the 4-methyl-1-pentene polymer (A) so as to satisfy requirements (a) to (c). The 4-methyl-1-pentene polymer (A) may also be prepared by heat-treating a commercially available 4-methyl-1-pentene polymer (for example, product name: TPX, manufactured by Mitsui Chemicals, Inc.) in an extruder, mixer, or the like to prepare the 4-methyl-1-pentene polymer (A) so as to satisfy requirements (a) to (c).

[Thickness of resin layer (II)]
The thickness of the resin layer (II) is not particularly limited and can be appropriately set depending on the purpose. From the viewpoint of suppressing the occurrence of curling in the obtained laminate, the thickness of the resin layer (II) is preferably 25 μm or less, more preferably 20 μm or less, preferably 0.01 to 20 μm, and further preferably 0.03 to 10 μm.
When the thickness of the resin layer (II) is within the above range, the resulting laminate is less likely to curl even when the resin layer (II) is formed on only one side of the base layer (I). Also, when the thickness of the resin layer (II) is within the above range, the laminate is less likely to curl even when the base layer (I) does not have a multilayer structure provided with an intermediate layer for suppressing curl.

[Physical Properties of Resin Layer (II)]
The surface free energy of the resin layer (II) is preferably 32 mN/m or less, more preferably 29 mN/m or less, and even more preferably 26 mN/m or less. The lower limit of the surface free energy is not particularly limited, but can be, for example, more than 0 mN/m.
When the surface free energy of the resin layer (II) is within the above range, the water repellency and oil repellency of the laminate are superior. For example, when the laminate of the present invention is used as the innermost layer of a package, water-soluble or lipophilic contents can be easily released, and the inner layer of the package can be less likely to become soiled by the contents.
The surface free energy of the resin layer (II) can be controlled by the composition of the 4-methyl-1-pentene polymer (A) contained in the resin layer (II) (for example, the amount of structural units derived from 4-methyl-1-pentene, and the types and amounts of structural units other than the structural units derived from 4-methyl-1-pentene).
The surface free energy can be determined by the method described in the Examples below.

The water contact angle of the resin layer (II) is preferably 97° or more, more preferably 100° or more, and even more preferably 101° or more. The upper limit of the water contact angle is not particularly limited, but can be, for example, less than 180°.
When the water contact angle of the resin layer (II) is within the above range, the laminate has excellent water repellency. Therefore, for example, when the laminate is used as the inner layer of a package, water-soluble contents are easily taken out and the inner layer is less likely to be soiled by the contents.
The water contact angle of the resin layer (II) can be controlled by the composition of the 4-methyl-1-pentene polymer (A) contained in the resin layer (II) (for example, the amount of structural units derived from 4-methyl-1-pentene, and the types and amounts of structural units other than the structural units derived from 4-methyl-1-pentene). The water contact angle is determined by the method described in the examples below.

The resin layer (II) may be one layer or two or more layers. When the laminate has two or more resin layers (II), these resin layers (II) may be the same or different as long as the above-mentioned resin layers (II) satisfy the requirements (a) to (c).

<Substrate layer (I)>
The laminate of the present invention comprises a substrate layer (I).
The base layer (I) preferably contains a polyolefin having a melting point of 200° C. or less as measured by a differential scanning calorimeter (DSC), and more preferably is a layer made of a polyolefin having a melting point of 200° C. or less as measured by a differential scanning calorimeter (DSC).
The substrate layer (I) may be a single layer or a multi-layer. The substrate layer (I) may be a film containing a polyolefin having a melting point of 200° C. or less, or may be a molded product such as a bottle molded by a known method such as injection molding or blow molding. The substrate layer (I) may be a layer laminated to paper, nonwoven fabric, metal, or a gas barrier layer described later.

The polyolefin having a melting point of 200° C. or less is not particularly limited, and examples thereof include high-density polyethylene, low-density polyethylene, linear low-density polyethylene such as ethylene-α-olefin copolymer, polypropylene, 4-methyl-1-pentene polymers (excluding those corresponding to 4-methyl-1-pentene polymer (A)), polybutene, and the like.
The "high density polyethylene" is preferably polyethylene having a density of more than 0.940 g/cm ³ .
Furthermore, the "low density polyethylene" preferably has a density of 0.940 g/cm ³ or less.

Among these, the polyolefin having a melting point of 200°C or less is preferably at least one resin selected from the group consisting of polypropylene, low-density polyethylene, and high-density polyethylene, and more preferably at least one resin selected from the group consisting of polypropylene and low-density polyethylene.

The method for forming the substrate layer (I) is not particularly limited and may be a common method such as extrusion, uniaxial or biaxial stretching, or the like.
The base layer (I) may also contain various additives that are usually used in polyolefins, such as a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a lubricant, a slipping agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, a dye, and an inorganic or organic filler, within the range that does not impair the object of the present invention.
Furthermore, the substrate layer (I) may contain a polyolefin having a melting point of more than 200° C. as measured by a differential scanning calorimeter (DSC) within a range that does not impair the object of the present invention.
The thickness of the substrate layer (I) is usually 10 to 100 μm, but is not particularly limited.

<<Other layers>>
The laminate of the present invention may include layers other than the substrate layer (I) and the resin layer (II) (hereinafter, also referred to as "other layers").
Examples of the other layers include a protective layer, a primer layer, a gas barrier layer, etc. The laminate may be, for example, a laminate in which the base layer (I) and the primer layer are laminated so as to be in contact with each other, and the primer layer side of the base layer (I) is laminated so as to be in contact with the resin layer (II).
When the laminate of the present invention is used as a release paper, a release film, or the like as described below, a preferred embodiment of the laminate of the present invention is one in which the outermost layer of the laminate comprises at least one resin layer (II).
The laminate may be formed by laminating a layer selected from the group consisting of paper, nonwoven fabric, metal, and a gas barrier layer so as to be in contact with the base layer (I). The gas barrier layer is not particularly limited as long as it is a layer that suppresses the permeation of a desired gas, and examples of the gas barrier layer include layers formed from nylon, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, silicon oxide, etc.

<<Method of manufacturing laminate>>
The method for producing the laminate of the present invention is not particularly limited, and a known production method can be used. For example, the laminate of the present invention can be suitably produced by the following production method. That is, the production method for the laminate of the present invention preferably includes a step (1) of preparing a composition (X) containing the 4-methyl-1-pentene polymer (A) and an organic solvent (B), and a step (2) of applying the composition (X) to at least one surface of a base layer (I) to form a resin layer (II) containing the 4-methyl-1-pentene polymer (A).
The laminate of the present invention may have the resin layer (II) on only one side of the base layer (I), or may have the resin layer (II) on both sides of the base layer (I). Furthermore, the base layer (I) may have another layer such as a primer layer on the surface side on which the resin layer (II) is formed.
In the method for producing the laminate, the base material layer (I) and the base material layer (II), and the 4-methyl-1-pentene polymer (A) contained in the base material layer (II) have the same meanings as the base material layer (I), the base material layer (II), and the 4-methyl-1-pentene polymer (A) in the laminate, and preferred embodiments are also the same.

[Step (1) of preparing composition (X)]
Step (1) is a step of preparing a composition (X) containing a 4-methyl-1-pentene polymer (A) and an organic solvent (B). The composition (X) may be used as a coating agent in which the 4-methyl-1-pentene polymer (A) is dissolved in the organic solvent (B).

The content of the 4-methyl-1-pentene polymer (A) is usually 0.01 to 50 mass%, preferably 0.05 to 30 mass%, more preferably 0.07 to 25 mass%, even more preferably 0.1 to 20 mass%, particularly preferably 1.0 to 20 mass%, and most preferably 3.0 to 20 mass%, based on the total mass of the composition (X). The content of the organic solvent (B) is usually 50 to 99.99 mass%, preferably 70 to 99.95 mass%, more preferably 75 to 99.93 mass%, even more preferably 80 to 99.90 mass%, particularly preferably 80.0 to 99.0 mass%, and most preferably 80.0 to 97.0 mass%, based on the total mass of the composition (X).

When the content of the 4-methyl-1-pentene polymer (A) and the organic solvent (B) relative to the total mass of the composition (X) is within the above range, when the composition (X) is used as a coating agent or the like, a good balance is achieved between the handleability and the ease of removing the solvent when forming the resin layer (II) from the coating agent.

[Organic solvent (B)]
The organic solvent (B) is not particularly limited as long as it can dissolve the 4-methyl-1-pentene polymer (A). Examples of the organic solvent (B) include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons such as toluene and xylene. Among these, toluene, cyclohexane, and methylcyclohexane can be preferably used as the organic solvent (B).

[Other components contained in composition (X)]
The composition (X) may further contain, as necessary, components other than the 4-methyl-1-pentene polymer (A) and the organic solvent (B) (hereinafter also referred to as "other components"), provided that the object of the present invention is not impaired. Examples of the other components include antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, leveling agents, reinforcing agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, and fillers.
The resin layer (II) produced using the composition (X) may also contain other components contained in the composition (X).
The other components may be one type alone or two or more types.
The content of the other components may be any amount that does not impair the object of the present invention, but the total content of the other components is usually about 0.005 to 5 parts by mass, and preferably about 0.01 to 3 parts by mass, per 100 parts by mass of the composition (X).

As the antioxidant, known antioxidants can be used. Specific examples include hindered phenol compounds, sulfur-based antioxidants, lactone-based antioxidants, organic phosphite compounds, and organic phosphonite compounds. The antioxidant may be a single type, or a combination of several types.

Examples of lubricants include sodium, calcium, and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid, which can be used alone or in combination of two or more. The content of such lubricants is usually 0.1 to 3 parts by mass, and preferably 0.1 to 2 parts by mass, per 100 parts by mass of composition (X).

Examples of slip agents include amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and hebenic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred as slip agents. The content of the slip agent is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the 4-methyl-1-pentene polymer (A).

Examples of antiblocking agents include finely divided silica, finely divided aluminum oxide, finely divided clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely divided crosslinked resin, such as crosslinked acrylic or methacrylic resin powder. Of these, finely divided silica and crosslinked acrylic and methacrylic resin powder are preferred as antiblocking agents.

As described below, when the composition (X) is used as a coating agent, it is also a preferred embodiment to add a leveling agent to the composition (X). Examples of leveling agents for reducing the surface roughness of the resin layer (II) formed from the composition (X) include fluorine-based nonionic surfactants, special acrylic resin-based leveling agents, silicone-based leveling agents, etc. As the leveling agent, one that has good compatibility with the organic solvent (B) is preferred, and the content of the leveling agent is preferably in the range of 1 to 50,000 ppm relative to the 4-methyl-1-pentene polymer (A) in the composition (X).

Examples of the reinforcing agent include oxides of metals such as silicon, titanium, aluminum and zirconium, polyfunctional alkoxy compounds or oligomers thereof, clay minerals, etc. The content of the reinforcing agent is preferably 5 to 50 parts by mass per 100 parts by mass of the 4-methyl-1-pentene polymer (A) in the composition (X).
When the content of the reinforcing agent is within the above range, the hardness and elastic modulus of the resin layer (II) formed from the composition (X) used as a coating agent can be increased.

[Method for producing composition (X)]
Step (1) may include a step of producing the composition (X). The method of producing the composition (X) is not particularly limited, and the composition (X) may be produced by a commonly used method. For example, the composition (X) may be produced by adding the 4-methyl-1-pentene polymer (A) to the organic solvent (B) and stirring the mixture for a predetermined time at a temperature equal to or lower than the boiling point of the organic solvent (B). The composition (X) may also be produced by heat-treating a separately prepared 4-methyl-1-pentene polymer (A) to prepare the 4-methyl-1-pentene polymer (A), adding the obtained 4-methyl-1-pentene polymer (A) to the organic solvent (B), and stirring the mixture for a predetermined time at a temperature equal to or lower than the boiling point of the organic solvent (B).

[Step (2) of forming resin layer (II)]
The step of forming the resin layer (II) (step (2)) is a step of applying the composition (X) to at least one surface of the base layer (I) to form a resin layer (II) containing the 4-methyl-1-pentene polymer (A).
An example of the process carried out in step (2) will now be described.
Specifically, in the step (2), it is preferable to apply the composition (X) prepared in the above step (1) to one surface of the base layer (I) and heat the composition (X) to a temperature close to the boiling point of the organic solvent (B) in the composition (X) to remove the organic solvent (B) in the composition (X) to a certain extent.
The method for applying the composition (X) to the surface of the base layer (I) is not particularly limited, and examples thereof include application using a brush or paintbrush, spraying, screen printing, flow coating, spin coating, dipping, and application to a roll or a flat plate using a bar coater, a T-die, a T-die with a bar, a doctor knife, a roll coater, a die coater, etc.

When the step (2) includes a step of removing the organic solvent (B) from the composition (X), it is preferable that the organic solvent (B) is completely removed from the composition (X), but there is no particular limitation as long as the solvent (B) is removed to an extent that the 4-methyl-1-pentene polymer (A) contained in the composition (X) can be formed as the resin layer (II). Specifically, it is preferable that the organic solvent (B) is removed until the organic solvent (B) is about 0.001 to 0.5 mass % relative to 100% mass of the resin layer (II) formed using the composition (X).
The method for removing the organic solvent (B) is not particularly limited, and although natural drying may be used, it is generally removed by drying under heating at 30 to 220°C.
In order to prevent thermal deterioration or thermal decomposition of the 4-methyl-1-pentene polymer (A), improve productivity, and suppress foaming or deterioration, it is preferable to remove the organic solvent (B) at a temperature equal to or lower than the melting point (Tm) of the 4-methyl-1-pentene polymer (A). In order to dry in a short time while preventing foaming, the temperature may be increased in two or more stages or continuously during drying. In addition, the amount of solvent remaining in the resin layer (II) can be reduced by carrying out a step of immersing the resin layer (II) in a solvent in which the 4-methyl-1-pentene polymer (A) is difficult to dissolve, such as water, methanol, ethanol, acetone, or methylene chloride, or a step of exposing the resin layer (II) to a vapor atmosphere of the solvent, after the drying step.
The content of the organic solvent (B) remaining in the resin layer (II) after drying is 0.5% by mass or less, preferably 0.05% by mass or less, and more preferably 0.01% by mass or less.

<<Applications of the laminate>>
The laminate of the present invention is preferably used as various process papers such as release paper, photographic paper, tape separator, etc., when the base layer (I) is, for example, a polyolefin having a melting point of 200° C. or less laminated on paper. For example, there are applications such as release paper for synthetic leather, release paper for rubber manufacturing, release paper for urethane curing, release paper for epoxy curing, release paper for solar cell manufacturing, release paper for semiconductor manufacturing, release paper for fuel cell manufacturing, release paper for electric and electronic parts manufacturing, release paper for semiconductor product manufacturing, release paper for circuit board manufacturing, release paper for flexible printed circuit boards, release paper for rigid boards, release paper for rigid flexible boards, release paper for advanced composite material manufacturing, release paper for carbon fiber composite curing, release paper for glass fiber composite curing, release paper for aramid fiber composite curing, release paper for nanocomposite curing, release paper for filler filler curing, heat-resistant and water-resistant photographic paper, OA paper, adhesive tape separator, silicon tape separator, adhesive separator, etc.

Since the laminate of the present invention has excellent water repellency as described above, when a base film (preferably a polyolefin having a melting point of 200° C. or less) is used as the base layer (I), it can also be suitably used as a protective film for various display devices, semiconductor devices, optical members, printed circuit boards, capacitors, etc., daily necessities packaging materials, food packaging materials, food containers, retort containers, protective films, decorative films and sheets, shrink films, infusion bags, heat-sealing films, medical containers, release films or release layers of release films, etc.
The laminate of the present invention can also be suitably used for other purposes such as bottles, for example, to enhance water repellency.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

<Method of measuring physical properties of polymer>
[composition]
The amount (U1) of the structural unit (i) derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) and the amount (U2) of the structural unit (ii) derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) were calculated from a ^13C -NMR spectrum using the following apparatus and conditions.

The measurements were performed using an ECP500 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., with a mixed solvent of o-dichlorobenzene/heavy benzene (80/20% by volume) as the solvent, a sample concentration of 55 mg/0.6 mL, a measurement temperature of 120°C, an observation nucleus of ¹³ C (125 MHz), a sequence of single pulse proton decoupling, a pulse width of 4.7 μsec (45° pulse), a repetition time of 5.5 sec, an accumulation count of 10,000 or more, and a chemical shift reference value of 27.50 ppm. The compositions of 4-methyl-1-pentene and α-olefins were quantified from the obtained ¹³ C-NMR spectrum.
The amounts of the structural units (i) and (ii) were determined in the same manner for the 4-methyl-1-pentene polymer used in the comparative example described below.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] was measured at 135°C using decalin solvent. That is, about 20 mg of the sample 4-methyl-1-pentene polymer (A) was weighed out and dissolved in 15 mL of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 mL of decalin solvent, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was calculated as the intrinsic viscosity (see the formula below).
[η] = lim (η _sp / C) (C → 0)
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer used in the comparative examples described later was also determined in the same manner.

[Melting point (Tm), endothermic end temperature (TmE), exothermic start temperature (TcS), and crystallization temperature (Tc)]
Using a differential scanning calorimeter (DSC) measuring device (model: DSC220C) manufactured by Seiko Instruments Inc., an exothermic/endothermic curve was obtained in accordance with ASTM D3418, and the melting point (Tm) and crystallization temperature (Tc) were determined as follows.

Approximately 5 mg of the sample was placed in a measurement aluminum pan, heated from 20°C to 280°C at a heating rate of 10°C/min, held at 280°C for 5 minutes, cooled to 20°C at a cooling rate of 10°C/min, held at 20°C for 5 minutes, and then heated again from 20°C to 280°C at a heating rate of 10°C/min. The crystallization peak that appeared during the first cooling was taken as the crystallization temperature (Tc). If multiple crystallization peaks were detected, the one with the highest temperature was taken as the crystallization temperature (Tc). The melting peak that appeared during the second heating was taken as the melting point (Tm). If multiple melting peaks were detected, the one with the highest temperature was taken as the melting point (Tm).

The temperature at which the endotherm of the melting (endotherm) curve ended was taken as the endotherm temperature (TmE). Also, the temperature at which the heat generation began of the crystallization (exotherm) curve was taken as the heat generation start temperature (TcS).

The above start and end points are the points where it can be confirmed that the curve deviates from the baseline and a difference in the amount of heat begins to appear, as opposed to the baseline where the amount of heat is constant at the start or end of the endothermic or exothermic reaction.

<Preparation Example 1: Preparation of (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride>
Using the method described in Preliminary Experiment 5 (paragraphs [0346] to [0348]) of WO 2014/123212, (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride was synthesized.

<Production Example 1: Production of Polymer 1>
500 mL of 4-methyl-1-pentene and 220 mL of heptane were charged at 23°C into a 1.5 L capacity SUS autoclave equipped with an agitator and thoroughly purged with nitrogen. 30 mL of 1-decene and 0.3 mL of a 1.0 mmol/mL toluene solution of triisobutylaluminum (TIBAL) were successively charged into the autoclave, and stirring was started. Next, 140 mL of hydrogen was charged into the autoclave, and the autoclave was heated to an internal temperature of 60°C.
Thereafter, 2 mL of a toluene solution containing liquid methylaluminoxane in terms of aluminum atom at 0.039 mmol and further containing the (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 above at 0.00013 mmol was injected into the autoclave with nitrogen to initiate polymerization.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60° C. Ten minutes after the start of polymerization, 5 mL of methanol was injected into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone with stirring to precipitate Polymer 1. The obtained Polymer 1 was dried at 130° C. under reduced pressure for 10 hours. Various physical properties of Polymer 1 are shown in Table 1.

<Production Example 2: Production of Polymer 2>
[Synthesis Example 2-1: Production of olefin polymerization catalyst]
At 30°C, in a 200 mL three-necked flask equipped with a stirrer and thoroughly purged with nitrogen, 30 mL of purified decane and 14.65 mmol of particulate solid polymethylaluminoxane having a D50 of 28 μm and an aluminum atom content of 43 mass% (synthesized using the method described in WO 2014/123212) were charged under a nitrogen stream to prepare a suspension. 50.0 mg (0.0586 mmol) of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 above was added to the suspension as a 4.58 mmol/L toluene solution while stirring. After 1 hour, the stirring was stopped, and the resulting mixture was washed with 100 mL of decane by decantation, and then decane was added to make 50 mL of a slurry liquid (zirconium atom carrying rate: 98%).

[Synthesis Example 2-2: Preparation of prepolymerized catalyst component]
To the slurry liquid prepared in Synthesis Example 2-1, 1.0 mL of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol/mL in terms of aluminum atom) was charged under a nitrogen gas flow at 25°C. After cooling to 15°C, 10 mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start of the charging of 4-methyl-1-pentene was regarded as the start of prepolymerization. Stirring was stopped 2.0 hours after the start of prepolymerization, and the resulting mixture was washed three times with 100 mL of decane by decantation. The prepolymerization catalyst component was a decane slurry (9.5 g/L, 0.56 mmol/L in terms of zirconium atom).

[Production of Polymer 2a]
At room temperature and under a nitrogen stream, 425 mL of purified decane was charged into a 1 L SUS polymerization vessel equipped with a stirrer, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol/mL in terms of aluminum atoms) was charged, and then 0.00175 mmol in terms of zirconium atoms of the decane slurry of the prepolymerized catalyst component of Synthesis Example 2-2 was charged. 23.75 NmL of hydrogen was charged, and then a mixture of 230 mL of 4-methyl-1-pentene and 22.4 mL of Linearene 168 (product name: mixture of 1-hexadecene and 1-octadecene, manufactured by Idemitsu Kosan Co., Ltd.) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start of charging the above mixture was regarded as the start of polymerization, and the temperature was maintained at 45°C for 4.5 hours. One hour and two hours after the start of polymerization, 23.75 NmL of hydrogen was charged. 4.5 hours after the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization liquid containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain polymer 2a. The yield was 142 g. The contents of the structural units contained in polymer 2a were determined to be 4-methyl-1-pentene content (U1) of 96.5 mol% and α-olefin content (U2) of 3.5 mol%. The melting point (Tm) of polymer 2a was 201°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 4.2 dl/g.

[Production of Polymer 2]
Polymer 2a was blended with 0.02 phr of a phenolic stabilizer Irganox 1010 (manufactured by BASF Chiba) as a heat stabilizer, and the mixture was kneaded using a Labo Plastomill mixer manufactured by Toyo Seiki Seisakusho Co., Ltd. at a resin temperature of 280° C. and a screw rotation speed of 150 rpm to obtain Polymer 2. Various physical properties of the obtained Polymer 2 are shown in Table 1. The 4-methyl-1-pentene content (U1) and the α-olefin content (U2) of Polymer 2 were the same as those of Polymer 2a.

<Production Example 3: Production of Polymer 3>
500 mL of 4-methyl-1-pentene and 230 mL of heptane were charged at 23° C. into a 1.5 L capacity SUS autoclave equipped with an agitator and thoroughly purged with nitrogen. 20 mL of Linearene 168 (Idemitsu Kosan Co., Ltd., a mixture of 1-hexadecene and 1-octadecene) and 0.3 mL of a 1.0 mmol/mL toluene solution of triisobutylaluminum (TIBAL) were successively charged into the autoclave, and stirring was started. Next, 140 mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60° C.
Thereafter, 2 mL of a toluene solution containing liquid methylaluminoxane in an amount of 0.033 mmol calculated as aluminum atom and further containing 0.00011 mmol of (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 above was pressurized into the autoclave with nitrogen to initiate polymerization.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60° C. 13 minutes after the start of polymerization, 5 mL of methanol was injected into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone with stirring to precipitate polymer 3. The obtained polymer 3 was dried at 130° C. under reduced pressure for 10 hours. Various physical properties of polymer 3 are shown in Table 1.

<Production Example 4: Production of Polymer 4>
500 mL of 4-methyl-1-pentene and 230 mL of heptane were charged at 23°C into a 1.5 L capacity SUS autoclave equipped with an agitator and thoroughly purged with nitrogen. 15 mL of 1-decene and 0.3 mL of a 1.0 mmol/mL toluene solution of triisobutylaluminum (TIBAL) were successively charged into the autoclave, and stirring was started. Next, 140 mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60°C.
Thereafter, 2 mL of a toluene solution containing 0.06 mmol of previously prepared liquid methylaluminoxane in terms of aluminum atom and 0.0002 mmol of the (8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 above was pressurized into the autoclave with nitrogen to initiate polymerization.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60° C. Thirty minutes after the start of polymerization, 5 mL of methanol was injected into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone with stirring to precipitate Polymer 4. The obtained Polymer 4 was dried at 130° C. under reduced pressure for 10 hours. Various physical properties of the obtained Polymer 4 are shown in Table 1.

<Production Example 5: Production of Polymer 5>
[Synthesis Example 5-1: Production of olefin polymerization catalyst]
At 30°C, 29.9 mL of purified decane and 14.3 mmol of particulate solid polymethylaluminoxane (manufactured by Toso FineChem Co., Ltd.) having a D50 of 8 μm and an aluminum atom content of 42 mass% were charged under a nitrogen gas flow into a 100 mL three-necked flask equipped with a stirrer and thoroughly purged with nitrogen to prepare a suspension. 50.0 mg (0.0586 mmol) of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 above was added to the suspension as a 4.59 mmol/L toluene solution while stirring. Stirring was stopped after 1.5 hours, and the resulting mixture was washed with 100 mL of decane by decantation, after which decane was added to make 50 mL of a slurry (zirconium atom carrying rate: 96%).

[Synthesis Example 5-2: Preparation of prepolymerized catalyst component]
To the slurry liquid prepared in Synthesis Example 5-1, 4.0 mL of a decane solution of diisobutylaluminum hydride (DIBAL-H) (1.0 mmol/mL in terms of aluminum atom) was charged under a nitrogen gas flow, and 15 mL (10.0 g) of 3-methyl-1-pentene was further charged. The start of the charging of 3-methyl-1-pentene was regarded as the start of prepolymerization. 1.5 hours after the start of polymerization, stirring was stopped, and the resulting mixture was washed by a decantation method to a washing efficiency of 95%. The prepolymerization catalyst component was 100 mL of decane slurry (zirconium atom recovery rate 93%, 0.548 mmol/L in terms of zirconium atom).

[Production of Polymer 5]
At room temperature (25°C) and under a nitrogen stream, 425 mL of purified decane and 0.4 mL (0.4 mmol in terms of aluminum atoms) of a triethylaluminum solution (1.0 mmol/mL in terms of aluminum atoms) were charged into a SUS autoclave equipped with a stirrer and having an internal volume of 1 L. Next, 0.0014 mmol in terms of zirconium atoms of the decane slurry of the prepolymerized catalyst component previously prepared in Synthesis Example 5-2 was added, and the temperature was raised to 40°C.
After the temperature reached 40°C, 30 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene was continuously charged into the autoclave at a constant rate over 30 minutes. The start of charging 4-methyl-1-pentene was regarded as the start of polymerization, and the temperature was maintained at 45°C for 3 hours. After 3 hours had elapsed from the start of polymerization, the system was depressurized at 45°C, and pressurization and depressurization with nitrogen (0.6 MPa) were performed three times in order to discharge the remaining hydrogen out of the system.
Thereafter, 30 NmL of hydrogen was charged under a nitrogen stream at 45°C, and then a mixed solution of 79.4 mL of 4-methyl-1-pentene and 7.4 mL of 1-decene was continuously charged into the autoclave at a constant rate over 30 minutes. The start of charging the mixed solution of 4-methyl-1-pentene and 1-decene was set as the start of the second polymerization, and the temperature was maintained at 45°C for 3 hours. After 3 hours had elapsed from the start of the second polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization solution (slurry) containing a white solid was immediately filtered to obtain a solid substance (polymer 5). This solid substance was dried under reduced pressure at 80°C for 8 hours. Various physical properties of the obtained polymer 5 are shown in Table 1.

[Preparation of substrate layer (I) (substrate film)]
A cast film (substrate film I-1) having a thickness of 100 μm was obtained by forming polypropylene (Prime Polymer Co., Ltd., brand: F113G) into a film using a cast film forming machine with a T die at a cylinder temperature of 230° C. The obtained cast film was used as the substrate layer (I).
A cast film (substrate film I-2) having a thickness of 100 μm was obtained in the same manner as for the substrate film I-1, except that the polypropylene was changed to low-density polyethylene (manufactured by Prime Polymer Co., Ltd., brand: SP0540) and the film was molded at a cylinder temperature of 200° C. The obtained cast film was used as the substrate layer (I).

Example 1
[Preparation of composition (X1)]
To 10 g of polymer 1, 0.1 mass % of tri(2,4-di-t-butylphenyl)phosphate as an antioxidant and 0.1 mass % of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat stabilizer were added, and methylcyclohexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added so that the solid content concentration became 5 mass %, and the mixture was stirred at 90°C for 1 hour at 200 rpm to prepare a composition (X1) containing polymer 1.

[Preparation of Laminate]
The settings of an applicator were adjusted so that the resin layer (II) formed from the composition (X1) prepared above had a thickness of 0.3 μm after drying. The composition (X1) was applied to the base film I-1 prepared above at 25° C., uniformly spread with an applicator, and then dried at 100° C. for 20 seconds to obtain a laminate including the base film I-1 and the resin layer (II).

[Storage stability]
Methylcyclohexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to 10 g of polymer 1 so that the solid content concentration was 5% by mass, and the mixture was placed in a container equipped with a stirrer and stirred at 90° C. for 1 hour at 200 rpm to obtain a composition containing polymer 1, which was then stored at room temperature (23° C.) for 24 hours. Thereafter, the composition was visually observed under visible light, and the storage stability was evaluated according to the following evaluation criteria. Evaluations of AA and BB indicate excellent storage stability.
〔Evaluation criteria〕
AA: The composition was transparent.
BB: The composition appeared cloudy, but had fluidity.
CC: The composition appeared cloudy and had no fluidity.

[Surface free energy]
Distilled water, diiodomethane, and bromonaphthalene were selected as liquids with different surface tensions, and the surface free energy was determined using these liquids. These selected liquids were dropped onto the surface of the resin layer (II) of the laminate prepared above, and the wetting state of the laminate by each liquid was analyzed using a DropMaster 500 image processing type solid-liquid interface analysis system (manufactured by Kyowa Interface Science Co., Ltd.), to determine the surface free energy (mN/m) of the resin layer (II).

[Measurement of water contact angle]
Using a DropMaster 500 image processing type solid-liquid interface analysis system (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle value when a water droplet was dropped on the resin layer (II) side of the laminate (film) obtained in the examples and comparative examples was measured.
A larger contact angle value means a higher hydrophobicity, a higher releasability for highly polar materials, and superior water repellency.

[Contact angle measurement of hexadecane]
Using a DropMaster 500 image processing type solid-liquid interface analysis system (manufactured by Kyowa Interface Science Co., Ltd.), hexadecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dropped onto the resin layer (II) of the laminate (film) obtained in the examples and comparative examples, and the contact angle value was measured 10 seconds after the drop. A larger contact angle value means higher oil repellency.
In addition, when the wet spread measurement result immediately after dropping the test liquid was less than 5°, it was recorded as "<5" in the table.

Example 2
A composition (X2) was prepared, a laminate was produced, and the physical properties were evaluated in the same manner as in Example 1, except that polymer 2 was used instead of polymer 1. The obtained results are shown in Table 2.

Example 3
The composition (X3) was prepared, a laminate was produced, and the physical properties were evaluated in the same manner as in Example 1, except that the polymer 3 was used instead of the polymer 1. The obtained results are shown in Table 2.

Example 4
Preparation of composition (X4), production of a laminate, and evaluation of physical properties were performed in the same manner as in Example 1, except that polymer 4 was used instead of polymer 1. The obtained results are shown in Table 2.

Example 5
Except for adjusting the applicator settings so that the thickness of the resin layer (II) obtained after drying was 5.0 μm, the laminate was produced and its physical properties were evaluated in the same manner as in Example 2. The obtained results are shown in Table 2.

Example 6
Except for adjusting the applicator settings so that the thickness of the resin layer (II) obtained after drying was 0.1 μm, the laminate was produced and its physical properties were evaluated in the same manner as in Example 2. The obtained results are shown in Table 2.

<Examples 7 to 12>
Except for changing the type of the substrate layer to substrate film I-2, the laminates of Examples 7 to 12 were produced and their physical properties were evaluated in the same manner as in Example 1. The obtained results are shown in Table 3.

<Comparative Example 1>
The substrate film I-1 was used as it was to measure the water contact angle and the surface free energy. The results are shown in Table 4.

<Comparative Example 2>
The water contact angle and surface free energy of the substrate film I-2 were measured as they were, and the results are shown in Table 4.

<Comparative Example 3>
Polymer 5 was used instead of polymer 1, and the mixture was stirred at 90° C. for 1 hour at 200 rpm in the same manner as in Example 1, but most of polymer 5 did not dissolve and remained undissolved. Thus, a composition in which polymer 5 was dissolved at a concentration sufficient to produce a coating film could not be obtained, and a laminate could not be produced with the composition of Comparative Example 3. Therefore, the evaluation results column in Table 4 is shown as "N/D."

As shown in Tables 2 to 4, it can be seen that the laminates according to the present invention in Examples 1 to 12 have superior water repellency compared to the laminates in Comparative Examples 1 and 2. It can be seen that the 4-methyl-1-pentene polymer contained in the resin layer of the laminates according to the present invention in Examples 1 to 12 has superior storage stability compared to the 4-methyl-1-pentene polymer contained in the resin layer of the laminate in Comparative Example 3. It can also be seen that the laminates according to the present invention in Examples 1 to 12 have superior oil repellency compared to the laminates in Comparative Examples 1 to 3.

Claims (12)

A substrate layer (I);
a resin layer (II) containing a 4-methyl-1-pentene polymer (A) satisfying the following requirements (a) to (c);
A laminate comprising:
(a) a melting point (Tm) measured by differential scanning calorimetry (DSC) of more than 180°C and not more than 220°C;
(b) the endothermic end temperature (TmE) in the melting (endothermic) curve measured by differential scanning calorimetry (DSC) is 230° C. or lower;
(c) The heat generation onset temperature (TcS) in the crystallization (heat generation) curve measured by a differential scanning calorimeter (DSC) is 210° C. or lower. The laminate according to claim 1, wherein the substrate layer (I) contains a polyolefin having a melting point of 200°C or less as measured by differential scanning calorimetry (DSC). The laminate according to claim 2, wherein the polyolefin having a melting point of 200°C or less is at least one resin selected from the group consisting of polypropylene, low-density polyethylene, and high-density polyethylene. The laminate according to claim 1 or 2, wherein the surface free energy of the resin layer (II) is 32 mN/m or less. The laminate according to claim 1 or 2, wherein the resin layer (II) has a water contact angle of 97° or more. The laminate according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer (A) has an intrinsic viscosity [η] in the range of 0.5 to 4.5 dl/g measured in decalin at 135°C. In the 4-methyl-1-pentene polymer (A), the amount of structural units (U1) derived from 4-methyl-1-pentene is 84 to 100 mol %,
3. The laminate according to claim 1, wherein the amount (U2) of structural units derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 16 mol % (wherein the sum of U1 and U2 is 100 mol %). The laminate according to claim 7, wherein the α-olefin is an α-olefin having 6 to 18 carbon atoms (excluding 4-methyl-1-pentene). The laminate according to claim 1 or 2, wherein the thickness of the resin layer (II) is 25 μm or less. The laminate according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer (A) is an unmodified polymer. A method for producing the laminate according to claim 1 or 2, comprising the steps of:
A step (1) of preparing a composition (X) containing the 4-methyl-1-pentene polymer (A) and an organic solvent (B);
(2) applying the composition (X) to at least one surface of the base layer (I) to form a resin layer (II) containing the 4-methyl-1-pentene polymer (A);
A method for producing a laminate, comprising: The method for producing a laminate according to claim 11, wherein the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A) measured in decalin at 135°C is in the range of 0.5 to 4.5 dl/g.