JP2023142912A - laminate - Google Patents

Abstract

To provide a laminate in which the peeling resistance of a layer of a 4-methyl -1 pentene-based polymer is improved, which is easily peeled off from a molded body and is less likely to impair surface smoothness of the surface of the molded body, even when it is used for molding a resin with relatively high adhesion.SOLUTION: A laminate of the present invention has: a base material layer (I); a layer (II) formed from a composition (Y) containing a graft-modified 4-methyl -1 pentene type polymer (B) obtained by graft-modifying a 4-methyl -1 pentene type polymer (A) that satisfies the following requirements (a) - (c); and a layer (III) formed from a composition (X) containing the 4-methyl -1 pentene type polymer (A). (a) The melting point (Tm) measured by differential scanning calorimeter (DSC) is 170 to 220°C. (b) The endothermic end temperature (TmE) in the melting (endothermic) curve measured by DSC is 230°C or less. (c) The exothermic start temperature (TcS) in the crystallization (exothermic) curve measured by DSC is 210°C or less.SELECTED DRAWING: None

Description

The present invention relates to a laminate having a layer containing a 4-methyl-1-pentene polymer.

4-Methyl-1-pentene polymers have very low surface tension and therefore excellent mold releasability and excellent heat resistance, so they are used in a variety of applications. For example, a laminate in which a resin layer of 4-methyl-1-pentene polymer is laminated on a paper or plastic substrate can be used as a release film for industrial use or as a release film for producing synthetic leather members (for example, the surface layer of synthetic leather). It is often used as a pattern. When forming a layer containing a 4-methyl-1-pentene polymer, a composition containing the 4-methyl-1-pentene polymer and a solvent may be used.

For example, it contains 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and/or 3-methyl-1-pentene, and at least one selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms. A composition containing a copolymer containing 1 to 20 mol % of structural units derived from one type of olefin and a solvent has been proposed (for example, Patent Document 1). Further, it contains 50 to 95 mol% of a structural unit derived from 4-methyl-1-pentene and/or 3-methyl-1-pentene, and at least one selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms. A composition containing a copolymer containing 5 to 50 mol% of structural units derived from one type of olefin and a solvent has also been proposed (for example, Patent Document 2).

JP2013-227421A JP2015-34258A

The compositions described in Patent Documents 1 and 2 have the advantage that a laminate having a thin copolymer layer can be produced by applying the composition to a film or the like. However, depending on the application, the copolymer layers described in Patent Documents 1 and 2 have insufficient toughness and tend to crack, and the cracks cause the copolymer layer to peel off from the laminate. It may become easier. In order to prevent the 4-methyl-1-pentene polymer layer from peeling off, it is possible to improve the adhesion between the 4-methyl-1-pentene polymer layer and the substrate. However, if the adhesion of the 4-methyl-1-pentene polymer layer that becomes the mold release layer to the base material is increased, the resin used as the molding material will more easily adhere to the mold release layer, resulting in a laminate. There is a tendency for the mold releasability to be easily impaired. When resin is molded using a laminate with such reduced mold release properties as a release film, it becomes difficult to peel the laminate from the resulting molded product, and the smoothness of the surface of the molded product may be impaired. It becomes easier. This problem tends to occur when molding resins such as epoxy resins that have high polarity and strong adhesive properties.

The present invention provides a laminate in which the peeling resistance of a 4-methyl-1-pentene polymer layer is improved. It is an object of the present invention to provide a laminate that is easy to clean and that does not easily impair the surface smoothness of the molded product.

As a result of studies conducted by the present inventors, a layer (II) formed from a composition containing a base material layer (I) and a graft-modified 4-methyl-1-pentene polymer (B) that satisfies specific requirements. It has been found that the above problems can be solved by a laminate having a layer (III) formed from a composition containing a 4-methyl-1-pentene polymer (A) that satisfies specific requirements. , we have completed the present invention.

That is, the present invention has, for example, the following matters [1] to [7].

[1] Graft-modified 4-methyl-1-pentene obtained by graft-modifying the base layer (I) and a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (a) to (c). A layer (II) formed from a composition (Y) containing a system polymer (B),
a layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A);
A laminate having.
(a) The melting point (Tm) measured by differential scanning calorimeter (DSC) is 170 to 220°C.
(b) The endothermic end temperature (TmE) in the melting (endothermic) curve measured by DSC is 230°C or less.
(c) The exotherm onset temperature (TcS) in the crystallization (exotherm) curve measured by DSC is 210°C or less.

[2] In [1], 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 5.0 dl/g. The described laminate.

[3] The amount (U1) of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) is 80 to 100 mol%, and the 4-methyl-1-pentene polymer (A) has ethylene or 3 carbon atoms. The total amount (U2) of structural units derived from ~20 α-olefins (excluding 4-methyl-1-pentene) is 20 to 0 mol% (however, the sum of the above U1 and the above U2 is assumed to be 100 mol%). The laminate according to [1] or [2], which is ).

[4] Any one of [1] to [3], wherein the resin constituting the base layer (I) is a resin containing as a main component at least one selected from the group consisting of polyamide and polyester. The described laminate.

[5] The laminate according to any one of [1] to [4], wherein the composition (Y) further contains an isocyanate compound (C).

[6] The laminate according to any one of [1] to [5], which is a release film.

[7] The step of arranging the release film according to [6] between the mold used for molding the epoxy resin and the epoxy resin, and between the epoxy resin and the pressure plate (1 )and,
a step (2) of molding an epoxy resin located between the mold and the pressure plate by heating and pressurizing it;
a step (3) of peeling off the release film from the surface of the epoxy resin molded body obtained in the step (2);
A method for producing a molded object, including:

According to the present invention, the laminate has improved peeling resistance of the 4-methyl-1-pentene polymer layer, and even when used for molding a resin with relatively strong adhesive properties, the molded product can be easily removed from the molded product. Provided is a laminate that is easy to peel and does not easily impair the surface smoothness of the molded product.

≪Laminated body≫
The laminate of the present invention has a base layer (I) and a layer (II) formed from a composition (Y) containing a graft-modified 4-methyl-1-pentene polymer (B) that satisfies predetermined requirements. and a layer (III) formed from a composition (X) containing a 4-methyl-1-pentene polymer (A) that satisfies predetermined requirements.

<Layer (III)>
Layer (III) is formed from a composition (X) containing a 4-methyl-1-pentene polymer (A) that meets predetermined requirements.

[4-Methyl-1-pentene polymer (A)]
The 4-methyl-1-pentene polymer (A) satisfies the following requirements (a) to (c). In the following description, the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) may be referred to as "constituent unit (i)." Similarly, in the 4-methyl-1-pentene polymer (A), the constituent units derived from ethylene or α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are defined as "constituent units". It may be written as "unit (ii)".

[Requirement (a)]
The melting point (Tm) measured with a differential scanning calorimeter (DSC) by the method described in the Examples below is 170 to 220°C, preferably 180 to 217°C, more preferably 190 to 215°C. When the melting point (Tm) measured by a differential scanning calorimeter (DSC) is within the above range, the layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A) Good heat resistance.
The value of the melting point (Tm) depends 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). tends to be rate dependent. Therefore, the melting point (Tm) can be adjusted by using the olefin polymerization catalyst described later and by controlling the content of the structural unit (ii).

[Requirement (b)]
The endothermic end temperature (TmE) in the melting (endothermic) curve measured with a differential scanning calorimeter (DSC) is 230°C or less, preferably less than 230°C, more preferably 228°C by the method described in the Examples below. ℃ or less, more preferably less than 228°C. Here, the endothermic end temperature means the temperature at which melting ends. The endothermic end temperature and the exothermic start temperature, which will be described later, are indicators different from the onset and offset, which are generally the intersection points of the baseline and the tangent to the steady line.
The endothermic end temperature can be determined by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (A), controlling the content of the structural unit (ii), etc. can be set to a desired value.

The 4-methyl-1-pentene polymer (A) having an endothermic end temperature within the above range has excellent heat resistance. Therefore, the layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A) having an endothermic end temperature within the above range also tends to have excellent heat resistance. Furthermore, the 4-methyl-1-pentene polymer (A) whose endothermic end temperature is within the above range is more effective in coating agents than the 4-methyl-1-pentene polymer whose endothermic end temperature is not within the above range. Easily soluble in solvents available during preparation. Therefore, the properties of coating agents etc. prepared using the 4-methyl-1-pentene polymer (A) having an endothermic end temperature within the above range tend to be uniform.

[Requirement (c)]
The exotherm onset temperature (TcS) in the crystallization (exotherm) curve measured with a differential scanning calorimeter (DSC) is 210°C or less, preferably less than 210°C, more preferably less than 210°C, by the method described in the Examples below. The temperature is 205°C or lower, more preferably 203°C or lower.
The exothermic start temperature can be determined by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (A), controlling the content of the structural unit (ii), etc. can be set to a desired value.

The 4-methyl-1-pentene polymer (A) having an exothermic onset temperature within the above range has excellent heat resistance. Therefore, the layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A) having an exotherm onset temperature within the above range also tends to have excellent heat resistance. Furthermore, the 4-methyl-1-pentene polymer (A) whose exotherm onset temperature is within the above range is more effective in coating agents than the 4-methyl-1-pentene polymer whose exotherm onset temperature is not within the above range. Easily soluble in solvents available during preparation. For this reason, the properties of coating agents etc. prepared using the 4-methyl-1-pentene polymer (A) having an exothermic onset temperature within the above range tend to be uniform.

Since the 4-methyl-1-pentene polymer (A) used in the laminate of the present invention satisfies requirements (a) to (c), it has excellent solubility in solvents while maintaining heat resistance. Furthermore, the 4-methyl-1-pentene polymer (A) that satisfies requirements (a) to (c) has excellent solubility in a solvent, and thus easily remains dissolved in the solvent. Therefore, a 4-methyl-1-pentene polymer (A) that satisfies requirements (a) to (c) is a 4-methyl-1-pentene polymer that does not satisfy any one or more of requirements (a) to (c). - Compared to pentene-based polymers, it also has better storage stability when dissolved in a solvent. That is, by dissolving the composition (X) containing the 4-methyl-1-pentene polymer (A) that satisfies requirements (a) to (c), a composition having uniform properties and good storage stability can be obtained. Coating agents can be manufactured. As a result, the properties of layer (III) formed using the coating agent become uniform. Furthermore, the coating agent obtained by dissolving the composition (X) containing the 4-methyl-1-pentene polymer (A) can be easily coated on the layer to be coated, and the resulting layer (III ) and the layer in contact with the layer (III) in the laminate of the present invention becomes better.

The 4-methyl-1-pentene polymer (A) may further satisfy one or more of the following requirements (d) to (g), preferably all of the following requirements (d) to (g). Fulfill.

[Requirement (d)]
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A) measured in decalin at 135° C. by the method described in the Examples below is preferably 0.5 to 5.0 dl/g, More preferably 0.65 to 4.6 dl/g, still more preferably 0.8 to 4.4 dl/g.
The 4-methyl-1-pentene polymer (A) having an intrinsic viscosity [η] value within the above range has good heat resistance. Furthermore, a coating agent obtained by dissolving a composition (X) containing a 4-methyl-1-pentene polymer (A) having an intrinsic viscosity [η] value within the above range has good coating properties. Yes, suitable for forming coating layers. Coating agents containing polymers with an intrinsic viscosity [η] higher than 5.0 dl/g may cause lumps when applied, the coated surface may become uneven, or the coating may not be applied smoothly over a wide area. Coating properties may deteriorate due to
The intrinsic viscosity [η] can be adjusted, for example, by adjusting the amount of hydrogen added in the polymerization step when producing the 4-methyl-1-pentene polymer (A).

[Requirement (e)]
In the 4-methyl-1-pentene polymer (A), the structural unit derived from 4-methyl-1-pentene is referred to as "constituent unit (i)", and ethylene or an α-olefin having 3 to 20 carbon atoms (however, 4-methyl-1-pentene (excluding 4-methyl-1-pentene) is defined as "constituent unit (ii)", the 4-methyl-1-pentene polymer (A) preferably contains the following (e1) and (e2). ) is satisfied.
(e1) The amount (U1) of the structural unit (i) in the 4-methyl-1-pentene polymer (A) is preferably 80 to 100 mol%, more preferably 85 to 99.0 mol%, even more preferably is 90 to 98.5 mol% (provided that the total of structural unit (i) and structural unit (ii) is 100 mol%).
(e2) The amount (U2) of the structural unit (ii) in the 4-methyl-1-pentene polymer (A) is preferably 0 to 20 mol%, more preferably 1.0 to 15 mol%, and It is preferably 1.5 to 10 mol% (provided that the total of structural unit (i) and structural unit (ii) is 100 mol%).
Note that U1 and U2 are determined by the method described in the Examples. The 4-methyl-1-pentene polymer (A) in which U1 and U2 are within the above ranges has excellent heat resistance. Therefore, the layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A) in which U1 and U2 are within the above range also tends to have excellent heat resistance.

The α-olefin leading to the structural unit (ii) can be a linear α-olefin. Examples of the α-olefin leading to the structural unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- Examples include tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene, and the like.
Among these, linear α-olefins having 6 to 18 carbon atoms are preferred from the viewpoint of heat resistance. Specifically, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, etc. are preferred, and among them, 1-decene, 1-hexadecene, Particularly preferred is 1-octadecene.
The structural unit (ii) may be derived from only one selected from the group consisting of ethylene or α-olefins having 3 to 20 carbon atoms, or ethylene or α-olefins having 3 to 20 carbon atoms. - It may be derived from two or more selected from the group consisting of olefins.

Here, the 4-methyl-1-pentene polymer (A) includes a copolymer consisting only of the structural unit (i) and the structural unit (ii). In this case, the total amount of structural unit (i) and structural unit (ii) is 100 mol%.

The 4-methyl-1-pentene polymer (A) is a small amount that does not impair the purpose of the present invention, specifically, all the constituent units that constitute the 4-methyl-1-pentene polymer (A). If the total number of moles of is 100 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, other than structural unit (i) and structural unit (ii) It may further contain structural units derived from monomers other than 4-methyl-1-pentene, ethylene, and α-olefins having 3 to 20 carbon atoms.
The number of structural units derived from other monomers contained in the 4-methyl-1-pentene polymer (A) may be one or two or more.

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

Here, when the 4-methyl-1-pentene polymer (A) contains structural units derived from other monomers, the total content of structural units (ii) and structural units derived from other monomers is , the content of the structural unit (ii) preferably satisfies the following ranges. In this case, the total of structural unit (i), structural unit (ii), and structural units derived from other monomers is 100 mol%.

[Requirement (f)]
The 4-methyl-1-pentene polymer (A) is preferably an unmodified polymer that has not been modified with a functional group. When the 4-methyl-1-pentene polymer (A) is an unmodified polymer, the layer formed from the composition (X) containing the 4-methyl-1-pentene polymer (A) (III ) has better mold releasability. In addition, when the 4-methyl-1-pentene polymer (A) is an unmodified polymer, the layer (III) can be released even from a resin with relatively strong adhesiveness such as an epoxy resin. Good properties. Therefore, when the 4-methyl-1-pentene polymer (A) is an unmodified polymer, when a laminate having the layer (III) on the surface is used for molding an epoxy resin, the laminate is It can be easily peeled off from the body, and the surface smoothness of the molded body after peeling off the laminate tends to be good.

[Requirement (g)]
The crystallization temperature (Tc) determined by a differential scanning calorimeter (DSC) by the method described in the Examples below is preferably 110 to 220°C, more preferably 120 to 210°C, and even more preferably 130 to 200°C. It is. The crystallization temperature can be determined by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (A), controlling the content of the structural unit (ii), etc. It can be any desired value.
The 4-methyl-1-pentene polymer (A) having a crystallization temperature within the above range is preferable from the viewpoint of heat resistance. Furthermore, coating agents etc. obtained from compositions containing the 4-methyl-1-pentene polymer (A) having a crystallization temperature within the above range tend to have good properties and storage stability. As a result, the properties of layer (III) formed using the coating agent become uniform.

[Method for producing 4-methyl-1-pentene polymer (A)]
The 4-methyl-1-pentene polymer (A) is produced by combining 4-methyl-1-pentene, the specific olefin that leads to the above-mentioned structural unit (ii), and, if necessary, the 4-methyl-1-pentene polymer (A) in the presence of an olefin polymerization catalyst. It can be obtained by polymerizing the other monomers using a known method.

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 WO 01/53369, WO 01/27124, JP 3-193796, JP 02-41303, WO 06/025540, or WO 06/025540. The metallocene catalyst described in No. 2014/123212 can be mentioned.

The 4-methyl-1-pentene polymer (A) is produced by heat-treating the 4-methyl-1-pentene polymer produced using the above catalyst in an extruder, mixer, etc. to meet the requirements (a). ) to (c) may be a 4-methyl-1-pentene polymer (A) prepared to satisfy the following conditions. In addition, the 4-methyl-1-pentene polymer (A) can be prepared using a commercially available 4-methyl-1-pentene polymer (for example, TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.) using an extruder or mixer. It may also be a 4-methyl-1-pentene polymer (A) prepared to satisfy requirements (a) to (c) by heat treatment in a method such as the following.

[Composition (X)]
Composition (X) contains the 4-methyl-1-pentene polymer (A), and optionally further contains other components (excluding the isocyanate compound (C) described below). The number of 4-methyl-1-pentene polymers (A) contained in the composition (X) may be one, or two or more.

The content of the 4-methyl-1-pentene polymer (A) in the composition (X) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. It is. When the content of the 4-methyl-1-pentene polymer (A) in the composition (X) is within the above range, the releasability and mechanical strength of the layer (III) formed from the composition (X) are improved. is excellent.

[Other components contained in composition (X)]
Composition (X) may further contain an antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, a leveling agent, a reinforcing agent, and an anti-blocking agent, as necessary, within a range that does not impair the purpose of the present invention. It may contain agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, and the like. Note that layer (III) formed from composition (X) may also contain other components contained in composition (X).
When the composition (X) contains other components, the amount of the other components can be any amount that does not impair the purpose of the present invention, but the total amount of the other components is the same as that of the composition. The amount is usually about 0.005 to 5 parts by weight, preferably about 0.01 to 3 parts by weight, per 100 parts by weight of (X).

As the antioxidant, known antioxidants can be used. Specifically, hindered phenol compounds, sulfur-based antioxidants, lactone-based antioxidants, organic phosphite compounds, organic phosphonite compounds, or a combination of several types of these can be used.

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, and these can be used alone or in combination of two or more. can. The amount of such a lubricant to be blended is usually about 0.01 to 3 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of composition (X).

As the slip agent, it is preferable to use 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. Among these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the 4-methyl-1-pentene polymer (A).

Examples of anti-blocking agents include finely powdered silica, finely powdered aluminum oxide, finely powdered clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely powdered crosslinked resin, such as crosslinked acrylic and methacrylic resin powder. be able to. Among these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

Further, when layer (III) is formed using a coating agent in which composition (X) is dissolved as described later, it is also a preferred embodiment to add a leveling agent to composition (X). As a leveling agent for reducing the surface roughness of the layer (III) formed using a coating agent, a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent, etc. can be used. It is preferable to use one that has good compatibility with the 4-methyl-1-pentene polymer (A) in the composition (X).

As the reinforcing agent, oxides of metals such as silicon, titanium, aluminum, and zirconium, polyfunctional alkoxy compounds or oligomers thereof, and clay minerals are used in the 4-methyl-1-pentene polymer (A) in the composition (X). For example, 5 to 50 parts by mass can be added to 100 parts by mass, and the hardness and elastic modulus of the layer (III) formed from the composition (X) can be increased. If the amount added is less than 5 parts by mass, the effect will be too low, and if it exceeds 50 parts by mass, the transparency or mechanical strength of layer (III) may be impaired.

[Method for producing composition (X)]
Composition (X) can be produced by mixing the 4-methyl-1-pentene polymer (A) and other components (excluding the isocyanate compound (C)). Alternatively, without producing the composition (X) itself, a coating agent in which the composition (X) is dissolved is produced by dissolving all the components contained in the composition (X) in a solvent. Composition (X) may be produced as a result by drying.

[Thickness of layer (III)]
The thickness of layer (III) included in the laminate of the present invention is preferably 25 μm or less, more preferably 0.01 to 20 μm, and even more preferably 0.03 to 10 μm.
The thickness of layer (III) can be adjusted, for example, by the concentration of the 4-methyl-1-pentene polymer (A) in the coating agent used to form layer (III). The lower the concentration of the 4-methyl-1-pentene polymer (A) contained in the coating agent, the thinner the resulting layer (III) tends to be.

<Layer (II)>
Layer (II) is formed from a composition (Y) containing a graft-modified 4-methyl-1-pentene polymer (B) obtained by graft-modifying a 4-methyl-1-pentene polymer (A). be done.

[Graft modified 4-methyl-1-pentene polymer (B)]
The 4-methyl-1-pentene polymer (A) that is the material for the graft-modified 4-methyl-1-pentene polymer (B) is not particularly limited as long as it satisfies requirements (a) to (c). The 4-methyl-1-pentene polymer (A), which is the material for the graft-modified 4-methyl-1-pentene polymer (B), is ethylene or an α-olefin having 3 to 20 carbon atoms (however, 4-methyl -1-pentene)), the content of the structural unit (ii) and the preferable α-olefin that leads to the structural unit (ii) are as follows: This is the same as the 4-methyl-1-pentene polymer (A) contained in III). In addition, the 4-methyl-1-pentene polymer (A), which is a material for the graft-modified 4-methyl-1-pentene polymer (B), is the 4-methyl-1-pentene contained in the layer (III). It may be the same as or different from the system polymer (A).

When modifying the 4-methyl-1-pentene polymer (A) to produce the graft-modified 4-methyl-1-pentene polymer (B), an ethylenically unsaturated monomer having a functional group is used. It will be done. The ethylenically unsaturated monomers used for modification are preferably unsaturated carboxylic acids and/or derivatives thereof. Examples of unsaturated carboxylic acids and/or derivatives thereof include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups and alkyl alcohols, unsaturated compounds having one or more carboxylic anhydride groups, etc. be able to.

Examples of the unsaturated group contained in the unsaturated compound include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group, and the like. Unsaturated carboxylic acids and/or derivatives thereof can be used alone or in combination of two or more. Among these ethylenically unsaturated monomers, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

The method for producing the graft-modified 4-methyl-1-pentene polymer (B) by graft-modifying the 4-methyl-1-pentene polymer (A) with an ethylenically unsaturated monomer is not particularly limited, Conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be employed. For example, 4-methyl-1-pentene polymer (A) is melted and an ethylenically unsaturated monomer is added to graft-modify it, or 4-methyl-1-pentene polymer (A) is added to a solvent. There is a method of dissolving it to form a solution, and adding an ethylenically unsaturated monomer thereto for graft modification.

The amount of graft modification of the graft modified 4-methyl-1-pentene polymer (B) is preferably 0 when the mass of the 4-methyl-1-pentene polymer (A) before modification is 100% by mass. .1 to 5.0% by weight, more preferably 0.4 to 3.0% by weight, even more preferably 0.8 to 2.0% by weight. When the amount of graft modification of the graft modified 4-methyl-1-pentene polymer (B) is within the above range, the adhesion between the base layer (I) and the layer (II) is excellent, and furthermore, the layer (II) It also tends to have excellent adhesion between layer (III) and layer (III).

[Composition (Y)]
The composition (Y) contains a graft-modified 4-methyl-1-pentene polymer (B), and optionally further contains other components such as an isocyanate compound (C). The other components contained in the composition (Y) other than the isocyanate compound (C) are the same as the other components contained in the composition (X). In addition, the content of other components other than the isocyanate compound (C) contained in the composition (Y) is based on the content based on the graft-modified 4-methyl-1-pentene polymer (A). It is the same as composition (X) except that the 1-pentene polymer (B) is used. Layer (III) formed from composition (Y) may contain other components such as the isocyanate compound (C) contained in composition (Y). The composition (Y) may contain one type of graft-modified 4-methyl-1-pentene polymer (B), or may contain two or more types.

When the composition (Y) is 100% by mass, the content of the graft-modified 4-methyl-1-pentene polymer (B) in the composition (Y) is preferably 20 to 100% by mass, more preferably The amount is 50 to 100% by weight, more preferably 80 to 100% by weight. When the content of the graft-modified 4-methyl-1-pentene polymer (B) in the composition (Y) is within the above range, sufficient adhesion can be achieved between the layer (II) and the layer (III). You can have it. Further, when the composition (Y) contains the isocyanate compound (C), the content of the graft-modified 4-methyl-1-pentene polymer (B) in the composition (Y) is 20% by mass or more (however, When the composition (Y) is 100% by mass), the reaction between the graft-modified 4-methyl-1-pentene polymer (B) and the isocyanate compound (C) is effective, and the layer ( The adhesion between II) and layer (III) becomes even better.

[Isocyanate compound (C)]
It is preferable that the composition (Y) contains an isocyanate compound (C). The isocyanate compound (C) is not particularly limited as long as it is a compound having an isocyanate group, but it is suitable for adhesion between the layer (II) and the base layer (I), and for the adhesion between the layer (II) and the layer (III). A polyfunctional isocyanate compound having two or more isocyanate groups in one molecule is preferred from the viewpoint of improving the adhesion between the two.

Examples of bifunctional isocyanate compounds having two isocyanate groups in one molecule include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2 -dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, Aliphatic diisocyanates such as thiodihexyl diisocyanate;
m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toridine diisocyanate, 1,4-naphthalene diisocyanate, 1,5 - Aromatic diisocyanates such as naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate; and hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl Examples include alicyclic diisocyanates such as methane 4,4'-diisocyanate.

The isocyanate compound (C) may be a biuret form or an isocyanurate form which is a trimer of a bifunctional isocyanate compound, and may be an adduct (i.e., an adduct) of a polyol such as trimethylolpropane and a bifunctional isocyanate compound. It may be an adduct of an alcohol such as methanol and a bifunctional isocyanate compound (that is, an allophanate compound).

Among these, from the viewpoint of yellowing resistance, adhesion and heat resistance, the isocyanate compound (C) is preferably an aliphatic isocyanate compound, and an aliphatic isocyanate compound having two or more isocyanate groups in one molecule. More preferably, it is an aliphatic diisocyanate, an isocyanurate of an aliphatic diisocyanate, an allophanate of an aliphatic diisocyanate and an alcohol, or an adduct of an aliphatic diisocyanate and a polyol. Particularly preferred is an isocyanurate form of aliphatic diisocyanate.

The isocyanate compound (C) may be a commercially available product, such as Takenate (registered trademark) series (Mitsui Chemicals, Inc.) such as Takenate D103H, D204, D160N, D170N, D165N, D178NL, D110N, and D370N. and Coronate HX, HXR, HXL, HXLV, HK, HK-T, HL, and 2096 (manufactured by Nippon Polyurethane Industries, Ltd.).

When the composition (Y) contains the isocyanate compound (C), the content thereof is usually 0.001 to 2.0 parts by mass based on 100 parts by mass of the graft-modified 4-methyl-1-pentene polymer (B). 00 parts by mass, preferably 0.001 to 1.50 parts by mass.
The isocyanate compound (C) may be contained singly or in combination of two or more types in the composition (Y).

[Method for producing composition (Y)]
Composition (Y) can be produced by mixing the graft-modified 4-methyl-1-pentene polymer (B) and other components such as the isocyanate compound (C). Alternatively, without producing the composition (Y) itself, a coating agent in which the composition (Y) is dissolved is produced by dissolving all the components contained in the composition (Y) in a solvent. Composition (Y) may be produced as a result by drying.

[Thickness of layer (II)]
The thickness of layer (II) contained in the laminate of the present invention is preferably 25 μm or less, more preferably 0.01 to 20 μm, and even more preferably 0.03 to 10 μm.
The thickness of layer (II) can be adjusted, for example, by the concentration of the graft-modified 4-methyl-1-pentene polymer (B) in the coating agent used to form layer (II). The lower the concentration of the graft-modified 4-methyl-1-pentene polymer (B) contained in the coating agent, the thinner the resulting layer (II) tends to be.

<Base material layer (I)>
The base layer (I) included in the laminate of the present invention is preferably a base film. The material of the base film that can be used as the base layer (I) is not particularly limited, and it may be a single layer or a multilayer, and the thickness is not particularly limited, but the film can be easily formed. It is preferable that the thermoplastic resin contains a thermoplastic resin. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides such as nylon 6, nylon 66, and wholly aromatic polyamides, high density polyethylene, medium density polyethylene, low density polyethylene, and ethylene-α-olefin copolymer. Polyolefins such as linear low-density polyethylene, polypropylene, 4-methyl-1-pentene polymers (excluding those containing 4-methyl-1-pentene polymer (A)), polybutene, etc. Can be mentioned. The base layer (I) is more preferably a base film made of a resin containing as a main component at least one member selected from the group consisting of polyamide and polyester. In addition, the main component here means the component with the largest content ratio (mass) among the structural units contained in the resin.

Further, the method for forming the base film may be a general method such as extrusion, uniaxial or biaxial stretching, and is not particularly limited.
These base films also contain heat stabilizers, weather stabilizers, ultraviolet absorbers, lubricants, slip agents, nucleating agents, antiblocking agents, antistatic agents, antifogging agents, pigments, dyes, and inorganic or organic fillers. Additives such as the like may be added to the extent that the object of the present invention is not impaired. The thickness of these base films is usually 10 to 100 μm, but is not particularly limited.

<Laminated body>
The laminate of the present invention has the above-described base layer (I), layer (II), and layer (III).
Both layer (II) and layer (III) contained in the laminate of the present invention may be one layer or two or more layers. When the laminate of the present invention includes two or more layers (II), these layers (II) may be the same or different as long as the requirements for the layer (II) described above are satisfied. Similarly, when the laminate of the present invention includes two or more layers (III), these layers (III) may be the same or different as long as the requirements for the layer (III) described above are satisfied.
Further, the base layer (I) included in the laminate of the present invention may have another layer such as a primer layer provided on its surface. Furthermore, the laminate of the present invention may have layers other than the base layer (I), layer (II), and layer (III).
When the laminate of the present invention is used as a release film as described later, the laminate of the present invention has a layer (III) as the outermost layer of the laminate and a base layer (I). In one embodiment, it is preferable that the layer in direct contact with the layer is the layer (II), and it is more preferable that the base layer (I), the layer (II), and the layer (III) are laminated in this order. This is a preferred form.

≪Method for manufacturing laminate≫
The laminate of the present invention can be suitably manufactured, for example, by the following manufacturing method. That is,
A coating agent in which the composition (X) is dissolved by mixing the 4-methyl-1-pentene polymer (A), the solvent (D), and optionally other components contained in the composition (X). a step of preparing (S1);
By mixing the graft-modified 4-methyl-1-pentene polymer (B), the solvent (D), and optionally the isocyanate compound (C) with other components contained in the composition (Y), a composition can be prepared. A step (S2) of preparing a coating agent in which (Y) is dissolved;
By applying a coating agent in which the composition (X) is dissolved or a coating agent in which the composition (Y) is dissolved to a part or the entire surface of the base layer (I), and removing the solvent (D). Step (S3) of forming layer (II) or layer (III);
A coating agent in which composition (X) is dissolved or a coating agent in which composition (Y) is dissolved is applied to a part or the entire surface of layer (II) or layer (III), and solvent (D) is removed. a step (S4) of forming layer (II) or layer (III) by
The laminate of the present invention can be manufactured by a method including the following. Note that step (S4) may be performed one or more times, and one or more layers of layer (II) and layer (III) need to be manufactured.

[Coating agent in which composition (X) is dissolved]
The coating agent in which the composition (X) is dissolved is one in which the composition (X) is dissolved in a solvent (D). Therefore, the coating agent contains the components contained in the composition (X) used for preparing the coating agent and a solvent (D). For example, when the composition (X) contains 100% by mass of the 4-methyl-1-pentene polymer (A), the coating agent may contain the 4-methyl-1-pentene polymer (A) in a solvent (D ). In addition, when the composition (X) used for preparing the coating agent contains other components in addition to the 4-methyl-1-pentene polymer (A), the resulting coating agent does not contain these substances. It will be done.

The content of the 4-methyl-1-pentene polymer (A) in the coating agent in which the composition (X) is dissolved is usually 0.01 to 50% by mass, preferably 0.05 to 30% by mass. , more preferably 0.07 to 25% by weight, still more preferably 0.1 to 20% by weight, particularly preferably 0.2 to 20% by weight, and most preferably 0.3 to 20% by weight. The content of the solvent (D) in the coating agent is usually 50 to 99.99% by mass, preferably 70 to 99.95% by mass, more preferably 75 to 99.93% by mass, and even more preferably 80% by mass. ~99.9% by weight, particularly preferably 80-99.8% by weight, most preferably 80-99.7% by weight.

Since the content of the 4-methyl-1-pentene polymer (A) and the solvent (D) in the coating agent is within the above range, the handling property and the solvent when forming the layer (III) from the coating agent are improved. This provides a good balance between ease of removal and ease of removal.

[Coating agent in which composition (Y) is dissolved]
The coating agent in which the composition (Y) is dissolved is one in which the composition (Y) is dissolved in a solvent (D). Therefore, the coating agent contains the components contained in the composition (Y) used for preparing the coating agent and a solvent (D).

The content of the graft-modified 4-methyl-1-pentene polymer (B) in the coating agent in which composition (Y) is dissolved is the 4-methyl-1-pentene polymer (B) in the coating agent in which composition (X) is dissolved. It is the same as the content of polymer (A).
The content of the graft-modified 4-methyl-1-pentene polymer (B) and the solvent (D) in the coating agent is within the above range, which improves handling property and when forming the layer (II) from the coating agent. This provides a good balance between the ease of removing the solvent and the ease of removing the solvent.

[Solvent (D)]
The solvent (D) is particularly limited as long as it can dissolve the 4-methyl-1-pentene polymer (A), the graft-modified 4-methyl-1-pentene polymer (B), and the isocyanate compound (C). However, organic solvents can be suitably used. Examples of the solvent (D) include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate. Examples include esters such as. Furthermore, a mixed solvent obtained by mixing two or more of these solvents may also be used as the solvent (D). Among these, toluene, cyclohexane, methylcyclohexane, a mixed solvent of these solvents and ethyl acetate, etc. can be suitably used. Note that the solvent (D) used in the production of the coating agent in which the composition (X) is dissolved may be the same as the solvent (D) used in the production of the coating agent in which the composition (Y) is dissolved. , may be different.

[Method for producing a coating agent in which composition (X) is dissolved]
The method for producing a coating agent in which composition (X) is dissolved is not particularly limited, and can be produced by a commonly used method. For example, the composition (X) is dissolved by adding the 4-methyl-1-pentene polymer (A) to the solvent (D) and stirring at a temperature below the boiling point of the solvent (D) for a predetermined period of time. It is possible to produce a coating agent that is In addition, after heat-treating a separately prepared 4-methyl-1-pentene polymer to prepare a 4-methyl-1-pentene polymer (A), the obtained 4-methyl-1-pentene polymer A coating agent in which composition (X) is dissolved can also be produced by adding coalescence (A) to solvent (D) and stirring for a predetermined period of time at a temperature below the boiling point of solvent (D). When the coating agent contains the other components other than the 4-methyl-1-pentene polymer (A), the timing at which the other components are added is based on the 4-methyl-1-pentene polymer (A). It may be before adding the 4-methyl-1-pentene polymer (A), or it may be at the same time as the addition of the 4-methyl-1-pentene polymer (A). There may be.

[Method for producing a coating agent in which composition (Y) is dissolved]
The method for producing a coating agent in which the composition (Y) is dissolved is also not particularly limited, and in the method for producing a coating agent in which the composition (Y) is dissolved, in place of the 4-methyl-1-pentene polymer (A). A graft-modified 4-methyl-1-pentene polymer (B) may be used.
In addition, when the composition (Y) contains an isocyanate compound (C), the isocyanate compound (C) may be added to the solvent (D) in which the graft-modified 4-methyl-1-pentene polymer (B) is dissolved. . Further, the isocyanate compound (C) may be added to the solvent (D) before dissolving the graft-modified 4-methyl-1-pentene polymer (B). In this case, the graft-modified 4-methyl-1-pentene polymer (B) may be added to the solvent (D) in which the isocyanate compound (C) is dissolved. Furthermore, the graft-modified 4-methyl-1-pentene polymer (B) and the isocyanate compound (C) may be added to the solvent (D) at the same time. Further, when the coating agent contains the other components other than the graft-modified 4-methyl-1-pentene polymer (B) and the isocyanate compound (C), the timing at which the other components are added is arbitrary.

[Step of forming layer (II) or layer (III)]
Hereinafter, an example of the process performed in the step (step (S3) or (S4)) of forming layer (II) or layer (III) will be described. In step (S3), specifically, the coating agent is attached to the surface of the base layer (I) and heated to a temperature close to the boiling point of the solvent (D) in the coating agent, thereby removing the solvent in the coating agent. (D) is removed to some extent. The method of applying the coating agent is not particularly limited, but may include application using a brush or brush, spraying, screen printing, flow coating, spin coating, dipping, bar coater, T die, T with bar. Examples include methods of coating on a roll or flat plate using a die, doctor knife, roll coating, die coating, etc.
In the step (S4), a coating agent is attached to the surface of the layer (II) or layer (III) obtained in the step (S3) or the most recently performed step (S4), and the solvent (D ) to remove some of the solvent (D) in the coating agent.

Note that the removal of the solvent in the present application does not mean only the complete removal of the solvent (D) from the coating agent, but also the removal of the 4-methyl-1-pentene polymer (D) contained in the coating agent. It also includes removing the solvent (D) to the extent that A) or the graft-modified 4-methyl-1-pentene polymer (B) can be formed as a layer. Specifically, the mass of layer (III) produced using a coating agent in which composition (X) is dissolved or layer (II) produced using a coating agent in which composition (Y) is dissolved is 100%. This includes removing the solvent until it becomes about 0.001 to 0.5% by mass. The method for removing the solvent is not particularly limited, and may be dried by leaving it to stand, but it is generally removed by heating and drying at 30 to 220°C. In addition, in order to prevent thermal deterioration and thermal decomposition of the 4-methyl-1-pentene polymer (A) or the graft-modified 4-methyl-1-pentene polymer (B), 4-methyl-1-pentene polymer It is preferable to remove the solvent (D) at a temperature below the melting point (Tm) of (A) or the graft-modified 4-methyl-1-pentene polymer (B). On the other hand, if the drying temperature is too low, the drying time becomes long and productivity deteriorates, and if the drying temperature is too high, problems such as foaming and deterioration occur. In order to dry in a short time while preventing foaming, drying may be performed while increasing the temperature in two or more steps or continuously. In addition, after the drying process, the 4-methyl-1-pentene polymer (A) and the graft-modified 4-methyl-1-pentene polymer (B) are dissolved in water, methanol, ethanol, acetone, methylene chloride, etc. The amount of solvent remaining in layer (II) or layer (III) can also be reduced by immersing the layer in a difficult solvent or exposing it to a vapor atmosphere of the solvent. The amount of solvent remaining in layer (II) or layer (III) 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.

≪Uses of laminates≫
Since the laminate of the present invention has excellent heat resistance as described above, it can be particularly suitably used as a protective film for various display devices, semiconductor devices, optical members, printed circuit boards, capacitors, and the like. Furthermore, even when the laminate of the present invention is used for molding a resin with relatively strong adhesive properties such as epoxy resin, it is easy to peel from the molded product and does not impair the surface smoothness of the molded product. Therefore, it is suitably used as a release film or a release layer of a release film.

<Method for manufacturing molded body>
When the laminate of the present invention is used as a release film, the laminate of the present invention can be suitably used for manufacturing the following molded products. That is,
A step (1) of disposing the laminate according to the present invention as a release film between at least one of the mold used for molding the epoxy resin and the epoxy resin, and between the epoxy resin and the pressure plate;
a step (2) of molding an epoxy resin located between the mold and the pressure plate by heating and pressurizing it;
a step (3) of peeling off the release film from the surface of the epoxy resin molded body obtained in step (2);
The laminate of the present invention can be used in a method for manufacturing a molded article, etc. The epoxy resin used in the above manufacturing method is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, multifunctional epoxy resin, flexible epoxy resin, glycidyl ester epoxy resin, and biphenyl epoxy resin. may be used.
In addition, the manufacturing method described here is an example, and the resin serving as a raw material for the molded body may be a thermosetting resin other than an epoxy resin, or may be a thermoplastic resin.

Hereinafter, the present invention will be explained in more detail based on Examples. However, the present invention is not limited to these examples.

<Method for measuring physical properties of polymer>
[composition]
The amount of structural unit (i) in the 4-methyl-1-pentene polymer (A) (4-methyl-1-pentene content, U1) and the amount of structural unit (ii) (α-olefin content, U2) was calculated from the ¹³ C-NMR spectrum using the following equipment and conditions.

Using an ECP500 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., the solvent was an o-dichlorobenzene/heavybenzene (80/20% by volume) mixed solvent, the sample concentration was 55 mg/0.6 mL, the measurement temperature was 120°C, and the observation nucleus was ^13C (125MHz), the sequence is single-pulse proton decoupling, the pulse width is 4.7 μs (45° pulse), the repetition time is 5.5 seconds, the number of integrations is over 10,000 times, and the chemical shift is 27.50 ppm. It was measured as a reference value. The composition of 4-methyl-1-pentene and α-olefin was quantified from the obtained ¹³ C-NMR spectrum.
Note that the amounts of the structural units (i) and (ii) in the graft-modified 4-methyl-1-pentene polymer (B) are based on the amount of the 4-methyl-1-pentene polymer (B) used for graft modification. The amounts of structural unit (i) and structural unit (ii) in A) are the same.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] was measured at 135°C using a decalin solvent. That is, approximately 20 mg of the sample 4-methyl-1-pentene polymer (A) or graft-modified 4-methyl-1-pentene polymer (B) was weighed out, dissolved in 15 mL of decalin, and poured into oil at 135°C. The specific viscosity η _sp was measured in the bath. 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 determined as the intrinsic viscosity (see the formula below).
[η]=lim(η _sp /C) (C→0)

[Graft modification amount]
The amount of graft modification of the graft-modified 4-methyl-1-pentene polymer (B) (i.e., the amount of modification when the mass of the 4-methyl-1-pentene polymer (A) before modification is 100% by mass) The content of structural units derived from the ethylenically unsaturated monomer used in the above was determined by the following method. First, a sample of the graft-modified 4-methyl-1-pentene polymer (B) was processed at 250°C, preheated for 5 minutes, and pressed for 3 minutes to prepare a press film. IR measurement was performed using an infrared spectrophotometer (manufactured by JASCO Corporation, model FT-IR410) using a transmission method. In the following examples, since maleic anhydride was used for graft modification, the amount of graft modification was calculated from the peak intensities at 1860 cm ^-1 and 4321 cm ^-1 .

[Melting point (Tm), endothermic end temperature (TmE), exothermic start temperature (TcS), crystallization temperature (Tc)]
Both the 4-methyl-1-pentene polymer (A) and the graft-modified 4-methyl-1-pentene polymer (B) were measured using a DSC measurement device (DSC220C) manufactured by Seiko Instruments Inc. , exothermic and endothermic curves were determined in accordance with ASTM D3418, and the melting point (Tm), crystallization temperature (Tc), endothermic end temperature (TmE), and exothermic onset temperature (TcS) were determined as follows.

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

The temperature at which the endothermic end of the melting (endothermic) curve was defined as the endothermic end temperature (TmE). Further, the temperature at which heat generation started in the crystallization (heat generation) curve was defined as the heat generation start temperature (TcS).

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

<Preparation Example 1: (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydro Cyclopenta[a]indene)) Preparation of zirconium dichloride>
Using the method described in Preliminary Experiment 5 (paragraphs 0346 to 0348) of International Publication No. 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 SUS autoclave equipped with stirring blades and sufficiently 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 this 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, 0.039 mmol of liquid methylaluminoxane was added in terms of aluminum atom, and 0.039 mmol of liquid methylaluminoxane (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-) obtained in Preparation Example 1 was added. 8-Methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) 2 mL of a toluene solution containing 0.00013 mmol of zirconium dichloride was pressurized into an autoclave with nitrogen, and polymerization was carried out. started.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. Ten minutes after the start of the polymerization, 5 mL of methanol was pressurized into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. 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. Table 1 shows various physical properties of Polymer 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-neck flask equipped with a stirrer and fully purged with nitrogen, 30 mL of purified decane and a particulate solid having a D50 of 28 μm and an aluminum atom content of 43% by mass were placed under a nitrogen stream. Polymethylaluminoxane (synthesized using the method described in International Publication No. 2014/123212) was charged in an amount of 14.65 mmol in terms of aluminum atoms to form a suspension. The suspension obtained in Preparation Example 1 (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6 , 7,7a,8-octahydrocyclopenta[a]indene)) 50.0 mg (0.0586 mmol) of zirconium dichloride was added as a 4.58 mmol/L toluene solution with stirring. After 1 hour, stirring was stopped, and the resulting mixture was washed with 100 mL of decane by decantation, and then decane was added to form a 50 mL slurry liquid (zirconium atom carrying rate: 98%).

[Synthesis Example 2-2: Preparation of prepolymerized catalyst component]
1.0 mL of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol/mL in terms of aluminum atoms) was charged into the slurry liquid prepared in Synthesis Example 2-1 at 25° C. under a nitrogen stream. After cooling to 15° C., 10 mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start of charging of 4-methyl-1-pentene was defined 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 decane slurry (9.5 g/L, 0.56 mmol/L in terms of zirconium atoms).

[Production of polymer 2a]
At room temperature and under a nitrogen stream, 425 mL of purified decane was inserted into a 1 L internal volume 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 the reaction mixture of Synthesis Example 2-2 was charged. A decane slurry as a prepolymerization catalyst component was charged in an amount of 0.00175 mmol in terms of zirconium atoms. 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 (manufactured by Idemitsu Kosan, a mixture of 1-hexadecene and 1-octadecene) was polymerized over 2 hours. It was continuously charged into the vessel at a constant speed. The start of the polymerization was defined as the start of charging the mixed solution, and the temperature was maintained at 45° C. for 4.5 hours. 23.75 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours had passed from the start of polymerization, the temperature was lowered to room temperature, the pressure was removed, and the polymerization solution 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 Polymer 2a. Yield was 142g.
When the content of structural units in polymer 2a was determined, the content of structural units derived from 4-methyl-1-pentene was 96.5 mol%, and the content of structural units derived from α-olefin was 3. It was .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.

[Manufacture of polymer 2]
A phenolic stabilizer Irganox 1010 0.02 phr (manufactured by Ciba BASF) was blended with Polymer 2a as a heat-resistant stabilizer, and a resin temperature of 280°C and a screw rotation speed of 150 rpm were used using a Labo Plastomill mixer manufactured by Toyo Seiki Seisakusho. Polymer 2 was obtained by kneading with.
The amount of structural units in Polymer 2 is the same as in Polymer 2a. The melting point (Tm) of Polymer 2 was 201°C, and the limiting viscosity [η] (in decalin at 135°C) was 1.0 dl/g. Other physical properties of Polymer 2 are shown in Table 1.

<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 SUS autoclave equipped with stirring blades and sufficiently purged with nitrogen. This autoclave was successively charged with 15 mL of 1-decene and 0.3 mL of a 1.0 mmol/mL toluene solution of triisobutylaluminum (TIBAL), and stirring was started. Next, 140 mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60°C.
Thereafter, 0.06 mmol of liquid methylaluminoxane prepared in advance in terms of aluminum atoms was added, and further, 0.06 mmol of liquid methylaluminoxane (8-octamethylfluoren-12'-yl-(2-(adamantane)) obtained in Preparation Example 1 was added. -1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) 2 mL of a toluene solution containing 0.0002 mmol of zirconium dichloride was heated with nitrogen. The mixture was pressurized into an autoclave and polymerization was started.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. Thirty minutes after the start of the polymerization, 5 mL of methanol was pressurized with nitrogen into the autoclave to stop 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. Table 1 shows various physical properties of the obtained polymer 3.

<Production Example 4: Production of Polymer 4>
[Production of polymer 4a]
750 ml of 4-methyl-1-pentene was charged at 23° C. into a 1.5 liter SUS autoclave equipped with stirring blades and sufficiently purged with nitrogen. This autoclave was charged with 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was turned on.
Next, the autoclave was heated to an internal temperature of 60° C. and pressurized with propylene so that the total pressure was 0.15 MPa (gauge pressure). Next, 1 mmol of liquid methylaluminoxane was added in terms of aluminum atom, and diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium was added. 0.34 ml of a toluene solution containing 0.003 mmol of dichloride was pressurized into the autoclave with nitrogen to initiate polymerization.
During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. Five minutes after the start of the polymerization, 5 ml of methanol was pressurized with nitrogen into the autoclave to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring to precipitate the polymer 4a. The obtained powdery polymer 4a was dried at 130° C. under reduced pressure for 12 hours.
When the content of structural units in polymer 4a was determined, the content of structural units derived from 4-methyl-1-pentene was 92.0 mol%, and the content of structural units derived from α-olefin was 8 mol%. It was .0 mol%.

[Manufacture of polymer 4]
100 parts by weight of the obtained polymer 4a, 2 parts by weight of maleic anhydride, and 0.02 parts by weight of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 as an organic peroxide. Polymer 4 was obtained by kneading the mixture at a resin temperature of 280° C. and a screw rotation speed of 150 rpm using a Labo Plastomill mixer manufactured by Toyo Seiki Seisakusho Co., Ltd. The amount of structural units in polymer 4 is the same as in polymer 4a. Table 1 shows various physical properties of the obtained polymer 4.

<Production Example 5: Production of Polymer 5>
Polymer 5 was obtained in the same manner as for producing Polymer 4, except that Polymer 2 was used instead of Polymer 4a. The amount of structural units in Polymer 5 is the same as in Polymer 2. Table 1 shows various physical properties of the obtained polymer 5.

<Production Example 6: Production of Polymer 6>
Polymer 6 was obtained in the same manner as for producing Polymer 4, except that Polymer 3 was used instead of Polymer 4a. The amount of structural units in Polymer 6 is the same as in Polymer 3. Table 1 shows various physical properties of the obtained polymer 6.

<Raw materials>
The raw materials used in Preparation Examples 1 to 7 below are as follows.
・“4-Methyl-1-pentene polymer (A)”: Polymers 1 to 3 produced according to Production Examples 1 to 3 above
・"Graft modified 4-methyl-1-pentene polymer (B)": Polymers 4 to 6 produced according to Production Examples 4 to 6 above
・"Isocyanate compound (C)": Takenate D170N (manufactured by Mitsui Chemicals, Inc., trimer of hexamethylene diisocyanate (isocyanurate modified product of HDI), isocyanate group content 20.7% by mass)
・"Solvent (D)": Methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.)

<Preparation of coating agent in which composition (X) is dissolved>
[Preparation Example 1: Preparation of coating agent in which composition (X1) is dissolved]
0.1% by mass of tri(2,4-di-t-butylphenyl) phosphate as an antioxidant, based on 10 g of polymer 1 (that is, assuming the mass of polymer 1 as 100% by mass); Add 0.1% by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer so that the solid concentration becomes 5% by mass. To this, methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a solvent (D), and the coating agent was stirred at 200 rpm for 3 hours at 90°C to dissolve the composition (X1) containing polymer 1. Manufactured.

[Preparation Example 2: Preparation of coating agent in which composition (X2) is dissolved]
A coating agent in which composition (X2) was dissolved was produced in the same manner as in the preparation of a coating agent in which composition (X1) was dissolved, except that polymer 2 was used instead of polymer 1.

[Preparation Example 3: Preparation of coating agent in which composition (X3) is dissolved]
A coating agent in which composition (X3) was dissolved was produced in the same manner as in the preparation of a coating agent in which composition (X1) was dissolved, except that polymer 3 was used instead of polymer 1.

<Preparation of coating agent in which composition (Y) is dissolved>
[Preparation Example 4: Preparation of coating agent in which composition (Y1) is dissolved]
[Preparation of coating agent by dissolving composition (Y1a)]
0.1% by mass of tri(2,4-di-t-butylphenyl) phosphate as an antioxidant, based on 10 g of polymer 4 (that is, assuming the mass of polymer 4 as 100% by mass); 0.1% by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat stabilizer was added to bring the solid content concentration to 6.25% by mass. Methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) was added as the solvent (D), and the mixture was stirred at 90° C. and 200 rpm for 3 hours. Thereafter, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the solid content concentration was 5% by mass, and the mixture was stirred at 60°C for 15 minutes at 200 pm to form a composition containing polymer 4 (Y1a). A coating agent was prepared by dissolving .

[Preparation of coating agent by dissolving composition (Y1)]
After cooling the coating agent in which the composition (Y1a) was dissolved to 23 ° C., 0.01% by mass of Takenate D170N (manufactured by Mitsui Chemicals, Inc.) was added (however, the mass of polymer 4 was taken as 100% by mass). The mixture was stirred at 200 rpm for 5 minutes to prepare a coating agent in which the composition (Y1) containing the polymer 4 and the isocyanate compound (C) was dissolved.

[Preparation Example 5: Preparation of coating agent in which composition (Y2) is dissolved]
[Preparation of coating agent by dissolving composition (Y2a)]
A coating agent in which composition (Y2a) was dissolved was prepared in the same manner as in the preparation of a coating agent in which composition (Y1a) was dissolved, except that polymer 5 was used instead of polymer 4.

[Preparation of coating agent by dissolving composition (Y2)]
The composition (Y1) was prepared in the same manner as the preparation of the coating agent in which the composition (Y1) was dissolved, except that a coating agent in which the composition (Y2a) was dissolved was used instead of a coating agent in which the composition (Y1a) was dissolved. A coating agent was prepared by dissolving Y2).

[Preparation Example 6: Preparation of coating agent in which composition (Y3) is dissolved]
[Preparation of coating agent by dissolving composition (Y3a)]
A coating agent in which composition (Y3a) was dissolved was prepared in the same manner as in the preparation of a coating agent in which composition (Y1a) was dissolved, except that polymer 6 was used instead of polymer 4.

[Preparation of coating agent by dissolving composition (Y3)]
The composition (Y1) was prepared in the same manner as the preparation of the coating agent in which the composition (Y1) was dissolved, except that a coating agent in which the composition (Y3a) was dissolved was used instead of a coating agent in which the composition (Y1a) was dissolved. A coating agent was prepared by dissolving Y3).

<Example 1>
[Preparation of laminate]
The settings of the applicator were adjusted so that the thickness of the layer of the composition obtained after drying the applied composition was 0.1 μm. A coating agent in which composition (Y1) was dissolved was applied to a polyester film (Lumirror (registered trademark) S10 manufactured by Toray Industries, Inc., described as "PET" in Tables 2 and 3) at 25°C and uniformly coated with an applicator. After stretching, it was dried at 100° C. for 20 seconds to produce layer (II).
Thereafter, a coating agent in which composition (X1) was dissolved was applied onto layer (II), spread uniformly with an applicator, and then dried at 100° C. for 20 seconds to produce layer (III). It was further dried at 80° C. for 20 hours to obtain a laminate.

[Checkerboard test]
A test piece was prepared by marking a grid on the surface of layer (III) of the obtained laminate according to the grid test method described in JIS K5400. After pasting an adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) on the grid of the test piece, it was immediately pulled in a 90 degree direction to peel it off, and only one of the 100 grid marks was peeled off. The number of squares that were not filled was counted and used as an index of peeling resistance of the outermost layer of the laminate. In other words, the larger the number of unpeeled layers, the more difficult it is for the outermost layer of the laminate to peel off. In the laminate of Example 1, all 100 pieces of the grid remained without being peeled off. The test results obtained are shown in Table 2.

[Evaluation during epoxy resin molding]
Using the laminates after the grid test evaluation, epoxy resin was molded by the following molding method, and the ease of peeling the laminates from the molded products and the smoothness of the surface of the molded products were evaluated.

[Epoxy resin molding method]
A metal frame, a release film (TPX MX004, manufactured by Mitsui Chemicals, Ltd.), and an epoxy resin (Sumicon G730C, manufactured by Sumitomo Bakelite Co., Ltd.) were placed in this order on a metal plate for press molding. Furthermore, the laminate after the checkerboard test evaluation was placed on the epoxy resin in the direction in which the layer (III) was in contact with the epoxy resin. Thereafter, a metal plate was placed on the laminate, and the epoxy resin was heat-cured at a temperature of 180° C. for 2 minutes while applying a pressure of 5 MPa using a press molding machine manufactured by Toyo Seiki Seisakusho Co., Ltd. The molded body with the laminate attached thereto was taken out from the press.

[Peelability of epoxy resin from molded body]
The laminate was manually peeled off from the molded body to which the laminate was attached, and the peelability of the laminate from the epoxy resin molded body was evaluated based on the following criteria. The evaluation results are shown in Table 2.
○: The laminate is easily peeled off when pulled by hand.
×: The laminate adheres to the epoxy resin and cannot be removed by hand.

[Surface condition of epoxy resin molded object]
After evaluating the peelability of the epoxy resin from the molded body, the surface condition of the molded body from which the laminate was peeled off was observed and evaluated based on the following criteria. The evaluation results are shown in Table 2.
○: No wrinkles are visually observed on the surface of the molded product, and no irregularities are visually observed.
×: At least one wrinkle or unevenness was visually observed on the surface of the molded article.

<Example 2>
A laminate was obtained in the same manner as in Example 1, except that a coating agent in which composition (X2) was dissolved was used instead of a coating agent in which composition (X1) was dissolved. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 3>
A laminate was obtained in the same manner as in Example 1, except that a coating agent in which composition (X3) was dissolved was used instead of a coating agent in which composition (X1) was dissolved. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 4>
A laminate was obtained in the same manner as in Example 1, except that a coating agent in which composition (Y2) was dissolved was used instead of a coating agent in which composition (Y1) was dissolved. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 5>
A coating agent in which composition (X2) is dissolved is used instead of a coating agent in which composition (X1) is dissolved, and a coating agent in which composition (Y2) is dissolved is used in place of a coating agent in which composition (Y1) is dissolved. A laminate was obtained in the same manner as in Example 1, except for using the following. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 6>
A coating agent in which composition (X3) is dissolved is used instead of a coating agent in which composition (X1) is dissolved, and a coating agent in which composition (Y2) is dissolved is used in place of a coating agent in which composition (Y1) is dissolved. A laminate was obtained in the same manner as in Example 1, except for using the following. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 7>
A laminate was obtained in the same manner as in Example 1, except that a coating agent in which composition (Y3) was dissolved was used instead of a coating agent in which composition (Y1) was dissolved. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 2.

<Example 8>
A coating agent in which composition (X2) is dissolved is used instead of a coating agent in which composition (X1) is dissolved, and a coating agent in which composition (Y3) is dissolved is used in place of a coating agent in which composition (Y1) is dissolved. A laminate was obtained in the same manner as in Example 1, except for using the following. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 3.

<Example 9>
A coating agent in which composition (X3) is dissolved is used instead of a coating agent in which composition (X1) is dissolved, and a coating agent in which composition (Y3) is dissolved is used in place of a coating agent in which composition (Y1) is dissolved. A laminate was obtained in the same manner as in Example 1, except for using the following. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 3.

<Comparative example 1>
The settings of the applicator were adjusted so that the thickness of the layer of the composition obtained after drying the applied composition was 0.1 μm. A coating agent in which composition (X2) was dissolved was applied to a polyester film (Lumirror S10 manufactured by Toray Industries, Inc.) at 25°C, spread uniformly with an applicator, and then dried at 100°C for 20 seconds to form layer (III). Created. It was further dried at 80° C. for 20 hours to obtain a laminate. Thereafter, when the obtained laminate was subjected to a grid test in the same manner as in Example 1, the entire surface of the laminate was peeled off. For this reason, epoxy resin molding using the laminate after the grid test and evaluation at the time of epoxy resin molding were not performed. The results obtained are shown in Table 3.

<Comparative example 2>
Comparative Example 1 except that instead of producing layer (III) using a coating agent in which composition (X2) was dissolved, layer (II) was produced using a coating agent in which composition (Y2a) was dissolved. A laminate was obtained in the same manner. Thereafter, when the obtained laminate was subjected to a grid test in the same manner as in Example 1, the entire surface of the laminate was peeled off. For this reason, epoxy resin molding using the laminate after the grid test and evaluation at the time of epoxy resin molding were not performed. The results obtained are shown in Table 3.

<Comparative example 3>
Comparative Example 1 except that instead of producing layer (III) using a coating agent in which composition (X2) was dissolved, layer (II) was produced using a coating agent in which composition (Y2) was dissolved. A laminate was obtained in the same manner. Thereafter, the obtained laminate was subjected to a grid test in the same manner as in Example 1, and the laminate after the grid test was used to mold an epoxy resin. When the peelability of the epoxy resin molded article was checked, it was found that the laminate could not be peeled off from the epoxy resin molded article by hand. For this reason, the smoothness of the surface of the epoxy resin molded article was not observed. The results obtained are shown in Table 3.

<Comparative example 4>
Comparative Example 1 except that instead of producing layer (III) using a coating agent in which composition (X2) was dissolved, layer (II) was produced using a coating agent in which composition (Y1) was dissolved. A laminate was obtained in the same manner. Thereafter, in the same manner as in Example 1, the resulting laminate was subjected to a grid test and an evaluation during epoxy resin molding. The results obtained are shown in Table 3.

Claims (7)

A graft-modified 4-methyl-1-pentene polymer obtained by graft-modifying the base layer (I) and a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (a) to (c). A layer (II) formed from a composition (Y) containing (B);
a layer (III) formed from the composition (X) containing the 4-methyl-1-pentene polymer (A);
A laminate having.
(a) The melting point (Tm) measured by differential scanning calorimeter (DSC) is 170 to 220°C.
(b) The endothermic end temperature (TmE) in the melting (endothermic) curve measured by DSC is 230°C or less.
(c) The exotherm onset temperature (TcS) in the crystallization (exotherm) curve measured by DSC is 210°C or less. The laminate according to claim 1, 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 5.0 dl/g. body. The amount (U1) of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (A) is 80 to 100 mol%, and The total amount (U2) of structural units derived from α-olefin (excluding 4-methyl-1-pentene) is 20 to 0 mol% (however, the sum of U1 and U2 is 100 mol%). The laminate according to claim 1 or 2. The laminate according to any one of claims 1 to 3, wherein the resin constituting the base layer (I) is a resin containing as a main component at least one selected from the group consisting of polyamide and polyester. The laminate according to any one of claims 1 to 4, wherein the composition (Y) further contains an isocyanate compound (C). The laminate according to any one of claims 1 to 5, which is a release film. A step (1) of arranging the release film according to claim 6 between at least one of the mold used for molding the epoxy resin and the epoxy resin, and between the epoxy resin and the pressure plate;
a step (2) of molding an epoxy resin located between the mold and the pressure plate by heating and pressurizing it;
a step (3) of peeling off the release film from the surface of the epoxy resin molded body obtained in the step (2);
A method for producing a molded object, including: