Composition, laminate, and packaging film

Abstract

To provide a laminate and a packaging film that exhibit both favorable heat sealability and favorable appearance, as well as a composition which yields the laminate.SOLUTION: A composition comprises a polymer (A) satisfying the following requirement (A-I), a polymer (B) satisfying the following requirement (B-I), and a solvent. (A-I): The polymer (A) contains 50.0 to 100 mol% of a structural unit derived from 4-methyl-1-pentene, and contains 0 to 50.0 mol% of a structural unit derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene). (B-I): The polymer (B) contains 50.0 to 95.0 mol% of a structural unit derived from 4-methyl-1-pentene, and contains 5.0 to 50.0 mol% of a structural unit derived from an α-olefin having 2 to 4 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compositions, laminates and packaging films. [Background technology]

[0002] Films formed from copolymers containing structural units derived from 4-methyl-1-pentene have been known to have excellent gas permeability, and therefore, such films are widely used as packaging materials for fresh foods, for example.

[0003] As such a film, for example, Patent Document 1 proposes a film obtained by cast molding a resin composition containing a thermoplastic resin (A) that is a copolymer containing structural units derived from 4-methyl-1-pentene and structural units derived from an α-olefin having from 2 to 20 carbon atoms, and a thermoplastic resin (B) that is an olefin copolymer and is other than the thermoplastic resin (A). In Patent Document 1, a polymer other than the polymer containing structural units derived from 4-methyl-1-pentene (specifically, the thermoplastic resin (B)) is blended in order to improve heat sealability.

[0004] Patent Document 2 proposes the following laminate with the aim of further improving the gas permeability of the film and laminated film described in Patent Document 1. A laminate comprising a substrate and a heat seal layer in this order toward one side in a thickness direction, the heat seal layer being a dried product of a coating composition, the coating composition containing a resin component, the resin component being a copolymer of 4-methyl-1-pentene and an α-olefin having from 2 to 20 carbon atoms (excluding 4-methyl-1-pentene), and / or a modified product of the copolymer, the copolymer having a content of the 4-methyl-1-pentene-derived structural units of from 50 mol % to 99 mol % relative to the total amount of the 4-methyl-1-pentene-derived structural units and the α-olefin-derived structural units, and the content of the α-olefin-derived structural units of the copolymer being from 1 mol % to 50 mol %, and the laminate having an oxygen permeability coefficient and a carbon dioxide permeability coefficient of from 1000 cm 3 mm / (m 2 ·24hr·atm) or higher. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2016-121322 [Patent Document 2] International Publication No. 2024 / 048470 Summary of the Invention [Problem to be solved by the invention]

[0006] The laminate described in Patent Document 2 has excellent heat-sealing properties, but there is room for improvement in terms of the appearance of the laminate, and there has been a demand for a composition that can provide a laminate and a packaging film that have both good heat-sealing properties and good appearance.

[0007] The present invention provides a laminate and a packaging film that are both excellent in heat sealability and appearance, as well as a composition that can provide the laminate. [Means for solving the problem]

[0008] The present invention relates to, for example, the following [1] to

[10] . [1] A polymer (A) that satisfies the following requirement (AI); A polymer (B) that satisfies the following requirement (BI); a solvent; A composition comprising: (AI): The polymer (A) contains 50.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 50.0 mol % of structural units derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene). (BI): Polymer (B) contains 50.0 to 95.0 mol % of structural units derived from 4-methyl-1-pentene and 5.0 to 50.0 mol % of structural units derived from an α-olefin having 2 to 4 carbon atoms.

[0009] [2] The composition according to [1], wherein the mass ratio (A / B) of the content of the polymer (A) to the content of the polymer (B) is 0.05 to 5.0.

[0010] [3] The composition according to [1] or [2], wherein the polymer (A) contains 88.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 12.0 mol % of structural units derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0011] [4] The composition according to any one of [1] to [3], wherein the polymer (B) contains 50.0 to 87.0 mol % of structural units derived from 4-methyl-1-pentene and 13.0 to 50.0 mol % of structural units derived from an α-olefin having 2 to 4 carbon atoms.

[0012] [5] The composition according to any one of [1] to [4], wherein the polymer (A) has a melting point of 150° C. or higher.

[0013] [6] The composition according to any one of [1] to [5], wherein the polymer (B) has a melting point of less than 150°C.

[0014] [7] the polymer (A) has an intrinsic viscosity in decalin at 135°C of 0.5 to 3.0 dl / g; The composition according to any one of [1] to [6], wherein the polymer (B) has an intrinsic viscosity in decalin at 135° C. of 0.5 to 3.0 dl / g.

[0015] [8] A laminate including a base material and a heat seal layer in this order toward one side in a thickness direction, The heat seal layer is a laminate that is a dried product of the composition according to any one of [1] to [7].

[0016] [9] The laminate according to [8], wherein the substrate contains a 4-methyl-1-pentene polymer.

[0017]

[10] A packaging film comprising the laminate according to [8] or [9]. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a laminate and a packaging film that are excellent in both heat sealability and appearance, and a composition from which the laminate can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0019] In the present disclosure, the expressions "XX or more and YY or less" and "XX to YY" that represent a numerical range mean a numerical range that includes the lower and upper limits that are the endpoints, unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0020] [Polymer (A)] The composition of the present invention contains a polymer (A). By containing the polymer (A), the laminate and packaging film obtained by coating the composition have a good appearance. Polymer (A) satisfies the following requirement (AI). In the following description, a structural unit derived from 4-methyl-1-pentene may be referred to as a "structural unit (i)." Similarly, a structural unit derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene) may be referred to as a "structural unit (ii)."

[0021] [Requirements (AI)] The polymer (A) contains 50.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 50.0 mol % of structural units derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0022] The content (UA1) of the structural unit (i) in the polymer (A) is preferably 88.0 to 100 mol %, more preferably 90.0 to 99.0 mol %, and even more preferably 92.0 to 98.5 mol % (where the total of the content of the structural unit (i) and the content of the structural unit (ii) is taken to be 100 mol %). The content (UA2) of the structural unit (ii) in the polymer (A) is preferably 0 to 12.0 mol %, more preferably 1.0 to 10.0 mol %, and even more preferably 1.5 to 8.0 mol % (where the total of the content of the structural unit (i) and the content of the structural unit (ii) is 100 mol %). UA1 and UA2 are determined by the method described in the Examples. A polymer (A) having UA1 and UA2 in the above ranges has an excellent balance between heat resistance and solubility in solvents. Therefore, films obtained from compositions containing a polymer (A) having UA1 and UA2 in the above ranges also tend to have excellent heat resistance.

[0023] The α-olefin from which the structural unit (ii) is derived can be a linear α-olefin, such as 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 heat resistance, linear α-olefins having 6 to 18 carbon atoms are preferred. Specifically, the α-olefins from which structural unit (ii) is derived are preferably 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, and 1-octadecene, with 1-decene, 1-hexadecene, and 1-octadecene being particularly preferred.

[0024] The structural unit (ii) may be derived from only one type selected from the group consisting of α-olefins having 5 to 20 carbon atoms, or may be derived from two or more types selected from the group consisting of α-olefins having 5 to 20 carbon atoms.

[0025] A preferred embodiment of polymer (A) is a copolymer consisting of only structural units (i) and (ii), in which case the total content of structural units (i) and (ii) is 100 mol %.

[0026] Another preferred embodiment of polymer (A) is a copolymer that contains, in addition to the structural units (i) and (ii), structural units derived from polymerizable monomers other than 4-methyl-1-pentene and α-olefins having 5 to 20 carbon atoms in a small amount that does not impair the object of the present invention, specifically 10.0 mol % or less, preferably 5.0 mol % or less, and more preferably 3.0 mol % or less. The number of types of other polymerizable monomers may be one or two or more.

[0027] Specific preferred examples of 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. Examples of non-conjugated polyenes include olefins, 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.

[0028] When polymer (A) contains a structural unit derived from another polymerizable monomer, the total content of structural unit (ii) and the structural unit derived from the other polymerizable monomer preferably falls within the range for the content of structural unit (ii). In this case, the total content of structural unit (i), structural unit (ii), and the structural unit derived from the other polymerizable monomer is 100 mol %.

[0029] [Melting point of polymer (A)] The melting point (Tm) of the polymer (A) measured by a differential scanning calorimeter (DSC) according to the method described in the Examples below is preferably 150°C or higher. When the melting point (Tm) of the polymer (A) is within the above range, the heat resistance is good. The melting point (Tm) is more preferably 170°C or higher, and even more preferably 190°C or higher. The upper limit of the melting point (Tm) is not particularly limited, but is, for example, 500°C or lower. The melting point (Tm) value tends to depend on the stereoregularity of the polymer (A) and the content of the structural unit (ii) in the polymer (A). For this reason, the melting point (Tm) can be adjusted by using an olefin polymerization catalyst described below and further controlling the content of the structural unit (ii).

[0030] [Endothermic end temperature of polymer (A)] The endothermic end temperature (TmE) of the polymer (A) in the melting (endothermic) curve measured by a differential scanning calorimeter (DSC) according to the method described in the Examples below is preferably 230°C or lower, more preferably 220°C or lower, from the viewpoints of heat resistance, solubility in solvents, and the surface smoothness of films formed from coating agents and the like obtained from compositions containing the polymer (A). The lower limit of the endothermic end temperature is not particularly limited, but is usually 190°C or higher. Here, the endothermic end temperature refers to the temperature at which melting is completed. The endothermic end temperature and the exothermic onset temperature described below are indicators different from the onset and offset, which are generally the intersections between the baseline and the tangent to the steady-state line. The endothermic end temperature can be adjusted to a desired value, for example, by appropriately selecting an olefin polymerization catalyst when polymerizing the polymer (A) and by controlling the content of the structural unit (ii).

[0031] [Exothermic onset temperature of polymer (A)] The exotherm onset temperature (TcS) of polymer (A) in a crystallization (exotherm) curve measured with a differential scanning calorimeter (DSC) by the method described in the Examples below is preferably 200° C. or lower, more preferably 180° C. or lower, and even more preferably 160° C. or lower, from the viewpoints of heat resistance, solubility in solvents, and surface smoothness of films formed from coating agents and the like obtained from compositions containing polymer (A). The lower limit of the exotherm onset temperature is not particularly limited, but is usually 140° C. or higher. The exotherm initiation temperature can be adjusted to a desired value, for example, by appropriately selecting an olefin polymerization catalyst when polymerizing the polymer (A) and by controlling the content of the structural unit (ii).

[0032] [Crystallization temperature of polymer (A)] The crystallization temperature (Tc) of the polymer (A) determined by differential scanning calorimetry (DSC) using 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. The crystallization temperature can be adjusted to a desired value, for example, by appropriately selecting an olefin polymerization catalyst used when polymerizing the polymer (A) and by controlling the content of the structural unit (ii). A polymer (A) having a crystallization temperature within the above range is preferred from the viewpoints of heat resistance and moldability, and therefore coating agents and the like obtained from compositions containing the polymer (A) having a crystallization temperature within the above range tend to have good properties and storage stability.

[0033] [Intrinsic viscosity of polymer (A) in decalin at 135°C] The intrinsic viscosity [η] of the polymer (A) measured in decalin at 135° C. by the method described in the examples below is preferably 0.5 to 3.0 dl / g, more preferably 0.7 to 2.0 dl / g. The polymer (A) having an intrinsic viscosity [η] within the above range has good coatability when made into a composition. The intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the polymer (A).

[0034] [Polymer (B)] The composition of the present invention contains a polymer (B). By containing the polymer (B), the laminate and packaging film obtained from the composition have good heat sealability. Polymer (B) satisfies the following requirement (BI). In the following description, a structural unit derived from 4-methyl-1-pentene may be referred to as a "structural unit (i)." Similarly, a structural unit derived from an α-olefin having 2 to 4 carbon atoms may be referred to as a "structural unit (iii)."

[0035] Requirements The polymer (B) contains 50.0 to 95.0 mol % of structural units derived from 4-methyl-1-pentene and 5.0 to 50.0 mol % of structural units derived from an α-olefin having 2 to 4 carbon atoms.

[0036] The content (UB1) of the structural unit (i) in the polymer (B) is preferably 50.0 to 87.0 mol %, more preferably 60.0 to 87.0 mol %, and even more preferably 70.0 to 87.0 mol % (provided that the total of the content of the structural unit (i) and the content of the structural unit (iii) is 100 mol %). The content (UB3) of the structural unit (iii) in the polymer (B) is preferably 13.0 to 50.0 mol %, more preferably 13.0 to 40.0 mol %, and even more preferably 13.0 to 30.0 mol % (provided that the total of the content of the structural unit (i) and the content of the structural unit (iii) is 100 mol %). UB1 and UB3 are determined by the method described in the Examples. A polymer (B) having UB1 and UB3 within the above ranges has an excellent balance of heat resistance, rigidity, and solubility in solvents. Therefore, a film obtained from a composition containing a polymer (B) having UB1 and UB3 within the above ranges also tends to have an excellent balance of heat resistance and rigidity.

[0037] Examples of the α-olefin from which the structural unit (iii) is derived include ethylene, propylene and 1-butene, with propylene being preferred. The structural unit (iii) may be derived from only one type selected from the group consisting of α-olefins having 2 to 4 carbon atoms, or may be derived from two or more types selected from the group consisting of α-olefins having 2 to 4 carbon atoms.

[0038] A preferred embodiment of polymer (B) is a copolymer consisting only of structural units (i) and (iii), in which case the total content of structural units (i) and (iii) is 100 mol %.

[0039] Another preferred embodiment of polymer (B) is a copolymer that contains, in addition to the structural units (i) and (iii), structural units derived from polymerizable monomers other than 4-methyl-1-pentene and α-olefins having 2 to 4 carbon atoms in a small amount that does not impair the object of the present invention, specifically 10.0 mol % or less, preferably 5.0 mol % or less, and more preferably 3.0 mol % or less. The number of types of the other polymerizable monomers may be one or more.

[0040] Preferred specific examples of such other polymerizable monomers include the same monomers as the other polymerizable monomers contained in the polymer (A).

[0041] When polymer (B) contains a structural unit derived from another polymerizable monomer, the total content of structural unit (iii) and the structural unit derived from the other polymerizable monomer preferably falls within the range of the content of structural unit (iii). In this case, the total content of structural unit (i), structural unit (iii), and the structural unit derived from the other polymerizable monomer is 100 mol%.

[0042] [Melting point of polymer (B)] The melting point (Tm) of polymer (B) measured by a differential scanning calorimeter (DSC) according to the method described in the Examples below is preferably less than 150°C. When the melting point (Tm) of polymer (B) is within the above range, the polymer (B) has excellent heat resistance and, in turn, good resistance to harsh processes such as high-temperature, high-pressure sterilization. The melting point (Tm) is more preferably 149°C or lower, even more preferably 145°C or lower, and particularly preferably 140°C or lower. The lower limit of the melting point (Tm) is not particularly limited, but is, for example, 80°C or higher. The melting point (Tm) value tends to depend on the stereoregularity of the polymer (B) and the content of the structural unit (iii) in the polymer (B). For this reason, the melting point (Tm) can be adjusted by using an olefin polymerization catalyst described below and further controlling the content of the structural unit (iii).

[0043] [Molecular weight of polymer (B)] The weight average molecular weight of the polymer (B), measured by gel permeation chromatography (GPC) and converted into standard polystyrene, is preferably 200,000 to 500,000, and more preferably 300,000 to 400,000. The weight average molecular weight / number average molecular weight (Mw / Mn) of the polymer (B) is preferably 1.0 to 4.0, more preferably 1.5 to 3.0. From the viewpoint of coatability and solubility in solvents, it is preferable that at least one of the weight average molecular weight and Mw / Mn of the polymer (B) is within the above range, and it is more preferable that both the weight average molecular weight and Mw / Mn are within the above range.

[0044] [Intrinsic viscosity of polymer (B) in decalin at 135°C] The intrinsic viscosity [η] of the polymer (B) measured in decalin at 135° C. by the method described in the examples below is preferably 0.5 to 3.0 dl / g, more preferably 0.7 to 2.0 dl / g. The polymer (B) having an intrinsic viscosity [η] within the above range has good coatability when made into a composition. The intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the polymer (B).

[0045] [Method for producing polymer (A)] The polymer (A) can be obtained by polymerizing a polymerizable monomer, such as 4-methyl-1-pentene, which will be a structural unit of the polymer (A), in the presence of an olefin polymerization catalyst, by a known method.

[0046] Examples of olefin polymerization catalysts that can be used in producing the polymer (A) include metallocene catalysts. Preferred metallocene catalysts include those described in WO 01 / 53369, WO 01 / 27124, JP-A 3-193796, JP-A 02-41303, WO 06 / 025540, and WO 2014 / 123212. Alternatively, polymer (A) can be obtained by polymerizing a polymerizable monomer such as 4-methyl-1-pentene, which serves as a structural unit of polymer (A), based on the method described in WO 2004 / 87775.

[0047] The polymer (A) may be a polymer (A) prepared so as to satisfy the requirement (AI) by heat-treating a polymer once produced using the catalyst, etc., in an extruder, a mixer, etc. Alternatively, the polymer (A) may be a polymer (A) prepared so as to satisfy the requirement (AI) by heat-treating a commercially available 4-methyl-1-pentene polymer (for example, TPX manufactured by Mitsui Chemicals, Inc.) in an extruder, a mixer, etc.

[0048] [Method for producing polymer (B)] The polymer (B) can be obtained by polymerizing a polymerizable monomer such as 4-methyl-1-pentene, which is a structural unit of the polymer (B), by the same method as the method for producing the polymer (A). Furthermore, the polymer (B) may be obtained by heat treating a polymer that has already been produced, similar to the polymer (A). The polymer (B) may be a commercially available 4-methyl-1-pentene polymer (for example, Absortomer manufactured by Mitsui Chemicals, Inc.).

[0049] The polymer (A) may be a modified product obtained by graft-modifying an unmodified polymer (A) with a graft component, and the same applies to the polymer (B). A method for graft-modifying the polymer (A) or polymer (B) with the graft component includes, for example, first dissolving the unmodified polymer (A) or polymer (B) in a known organic solvent (e.g., toluene), then adding the graft component and a radical polymerization initiator, mixing them, and heating (specifically, melt-mixing).

[0050] Examples of the graft component include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a vinyl ester compound, and a thiol group-containing ethylenically unsaturated compound. The graft component is preferably an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride. More preferably, the graft component is an unsaturated carboxylic acid anhydride. Further preferably, the graft component is maleic anhydride. The graft component may be used alone or in combination of two or more.

[0051] Examples of the radical polymerization initiator include organic peroxides and organic peresters. The radical polymerization initiators may be used alone or in combination of two or more.

[0052] [mass ratio (A / B) of the content of polymer (A) to the content of polymer (B)] The mass ratio (A / B) of the content of polymer (A) to the content of polymer (B) in the composition of the present invention is preferably 0.05 to 5.0, more preferably 0.2 to 0.7. When the mass ratio (A / B) is within the above range, the coatability of the composition is good, and the balance between the appearance and heat sealability of the laminate obtained from the composition is better.

[0053] [Solid content concentration] The solid content concentration of the composition of the present invention is preferably 5.0 to 10.0% by mass, more preferably 6.5 to 8.5% by mass. When the solid content concentration is within this range, the laminate obtained from the composition will have a better balance of transparency, appearance, and heat sealability. The solid content concentration of the composition refers to the ratio of the mass of all components excluding the solvent, which will be described later, to 100% by mass of the composition.

[0054] [solvent] Examples of solvents contained in the composition of the present invention include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ketones, alkyl esters, glycol ether esters, ethers, and polar aprotic solvents. Aliphatic hydrocarbons include, for example, n-hexane, n-heptane, and octane. Alicyclic hydrocarbons include, for example, cyclohexane and methylcyclohexane. Aromatic hydrocarbons include, for example, toluene and xylene.

[0055] Ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Alkyl esters include, for example, methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. Examples of glycol ether esters include methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate.

[0056] Ethers include, for example, diethyl ether, tetrahydrofuran, and dioxane. Polar aprotic solvents include, for example, N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, and hexamethylphosphonylamide.

[0057] The solvent is preferably an alicyclic hydrocarbon and / or an alkyl ester, more preferably methylcyclohexane and / or ethyl acetate, and even more preferably a combination of methylcyclohexane and ethyl acetate. The solvent may be used alone or in combination of two or more kinds.

[0058] [Additives] The composition of the present invention may contain additives as needed, provided that the effects of the present invention are not impaired.

[0059] Examples of additives include leveling agents, antifoaming agents, antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, surfactants, pigments, thixotropic agents, thickeners, tackifiers, surface conditioners, antisettling agents, weathering agents, pigment dispersants, antistatic agents, fillers, antifungal agents, and silane coupling agents. The additives may be used alone or in combination of two or more.

[0060] [Method of producing the composition] The composition containing the polymer (A), the polymer (B), and the solvent may be produced, for example, by adding the polymer (A) and the polymer (B) to a solvent and mixing them, or by mixing a composition (X1) produced by mixing the polymer (A) and the solvent with a composition (X2) produced by mixing the polymer (B) and the solvent.

[0061] The solvent in composition (X2) may be the same as or different from the solvent in composition (X1). If the solvent in composition (X2) and the solvent in composition (X1) are the same or have similar boiling points, the solvent can be easily removed when the composition is applied to a substrate and dried.

[0062] [Laminate] The laminate of the present invention is a laminate comprising a substrate and a heat seal layer in this order toward one side in the thickness direction, and the heat seal layer is a dried product of the composition. The thickness of the heat seal layer after drying is preferably 1 to 15 μm, more preferably 3 to 10 μm. When the thickness of the heat seal layer is in the above range, the gas permeability of the laminate is preferably increased.

[0063] [Base material] The substrate is not particularly limited and may be made of any known material, such as polyolefin resins such as ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and polyolefin thermoplastic elastomers, as well as porous substrates such as paper, fabrics, knitted fabrics, and nonwoven fabrics. From the viewpoint of the balance between heat resistance and transparency, the substrate preferably contains a 4-methyl-1-pentene polymer. When the substrate contains a 4-methyl-1-pentene polymer, the content of the 4-methyl-1-pentene polymer is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass (i.e., when the substrate is a 4-methyl-1-pentene polymer), relative to 100% by mass of the substrate.

[0064] When the base material contains a 4-methyl-1-pentene polymer, the 4-methyl-1-pentene polymer preferably contains 50.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 50.0 mol % of structural units derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).The 4-methyl-1-pentene polymer more preferably contains 90.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 10.0 mol % of structural units derived from a linear α-olefin having 10 to 20 carbon atoms.

[0065] When the base material contains a 4-methyl-1-pentene polymer, the thermal properties of the 4-methyl-1-pentene polymer measured with a differential scanning calorimeter (DSC) by the method described in the examples below are preferably as follows: The melting point (Tm) is preferably 180 to 260°C, more preferably 200 to 240°C. The endothermic end temperature (TmE) is preferably 200 to 300°C, more preferably 220 to 260°C. The exothermic onset temperature (TcS) is preferably 170 to 250°C, more preferably 190 to 230°C. The crystallization temperature (Tc) is preferably 160 to 240°C, more preferably 180 to 220°C. These thermal properties can be adjusted to desired values ​​by appropriately selecting an olefin polymerization catalyst when polymerizing the base 4-methyl-1-pentene polymer, and by controlling the content of structural units derived from ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0066] When the base material contains a 4-methyl-1-pentene polymer, the 4-methyl-1-pentene polymer has an intrinsic viscosity [η] of preferably 1.0 to 5.0 dL / g, more preferably 1.5 to 3.0 dL / g, as measured in decalin at 135°C by the method described in the Examples below. The intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added in the polymerization step when producing the 4-methyl-1-pentene polymer used as the base material.

[0067] When the substrate contains a 4-methyl-1-pentene polymer, a commercially available 4-methyl-1-pentene polymer may be used as the 4-methyl-1-pentene polymer.

[0068] [Method of manufacturing the substrate] The method for producing the substrate is not particularly limited, and any known molding method can be used, such as extrusion molding methods such as the T-die method and the extrusion tubular method (inflation method), solution casting, and calender molding.

[0069] The thickness of the substrate is preferably 10 to 500 μm, more preferably 20 to 300 μm, and even more preferably 30 to 200 μm. The substrate may contain additives such as leveling agents, antifoaming agents, antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, surfactants, pigments, thixotropic agents, thickeners, tackifiers, surface conditioners, antisettling agents, weathering agents, pigment dispersants, antistatic agents, fillers, antifungal agents, and silane coupling agents. The additives may be used alone or in combination of two or more.

[0070] [Method of manufacturing laminate] The laminate can be produced by applying the composition to one surface of a substrate in the thickness direction and drying it. Before applying the composition, the substrate may be subjected to a surface treatment, such as corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, or saponification treatment.

[0071] The composition can be applied by a conventionally known method, and known means such as application using an applicator, application using a brush or paintbrush, spraying, screen printing, flow coating, spin coating, dipping, a bar coater, a T-die, a T-die with a bar, a doctor knife, roll coating, and die coating can be used.

[0072] After the composition is applied, it may be dried by leaving it at room temperature or by heating. The heating temperature is, for example, 50°C or higher, preferably 80°C or higher, and preferably 250°C or lower. In order to prevent thermal deterioration and thermal decomposition of the polymer (B), it is preferable to remove the solvent at a temperature lower than the melting point (Tm) of the polymer (B). The heating time is, for example, 10 to 600 seconds.

[0073] Removal of the solvent does not only mean complete removal of the solvent from the composition, but also includes removal of the solvent to an extent that a heat seal layer can be formed. The amount of solvent remaining in the heat seal layer after drying is preferably 0.5% by mass or less in total, more preferably 0.05% by mass or less in total, and even more preferably 0.01% by mass or less in total, relative to 100% by mass of the heat seal layer.

[0074] [Application (packaging film)] The laminate of the present invention has good heat-sealing properties and good appearance, and therefore its use is not particularly limited and can be used in a wide range of applications. The laminate is particularly suitable for use as a packaging film. Such a packaging film includes the laminate of the present invention. Therefore, the packaging film has good heat-sealing properties and good appearance. [Example]

[0075] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0076] <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.

[0077] <Production Example 1: Production of Polymer A1> [Synthesis Example 1-1: Production of olefin polymerization catalyst] A 200 mL three-necked flask equipped with a stirrer and thoroughly purged with nitrogen was charged with 30 mL of purified decane and 14.65 mmol (in terms of aluminum atoms) of particulate solid polymethylaluminoxane (synthesized using the method described in International Publication No. WO 2014 / 123212) with a D50 of 28 μm and an aluminum atom content of 43% by mass at 30°C under a nitrogen stream to form 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 with stirring as a 4.58 mmol / L toluene solution. 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 make 50 mL of a slurry (zirconium atom loading rate: 98%).

[0078] [Synthesis Example 1-2: Preparation of prepolymerization catalyst component] To the slurry prepared in Synthesis Example 1-1, 1.0 mL of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atom) was added under a nitrogen stream at 25°C. After cooling to 15°C, 10 mL of 4-methyl-1-pentene was added to the reactor over 60 minutes. The start of the 4-methyl-1-pentene addition marked the start of prepolymerization. 2.0 hours after the start of prepolymerization, stirring was stopped, 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).

[0079] [Production of Polymer A1a] At room temperature under a nitrogen stream, 425 mL of purified decane was placed in a 1 L stainless steel polymerization vessel equipped with a stirrer and heated 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 added, followed by 0.00175 mmol in terms of zirconium atoms of the decane slurry of the prepolymerized catalyst component from Synthesis Example 1-2. 23.75 NmL of hydrogen was added, followed by a mixture of 230 mL of 4-methyl-1-pentene and 22.4 mL of Linearene 168 (Idemitsu Kosan, a mixture of 1-hexadecene and 1-octadecene) being continuously added to the polymerization vessel at a constant rate over 2 hours.

[0080] The polymerization initiation was determined as the start of the addition of the mixed solution, 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 added. After 4.5 hours had elapsed since the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization solution containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80°C for 8 hours to obtain Polymer A1a. The yield was 142 g. The content of each structural unit in Polymer A1a was determined to be 96.5 mol% for structural units derived from 4-methyl-1-pentene, and 3.5 mol% for structural units derived from α-olefins (1-hexadecene and 1-octadecene). The melting point (Tm) of Polymer A1a was 201°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 4.2 dL / g.

[0081] [Production of Polymer A1] Polymer A1a was blended with 0.02 phr of the phenolic stabilizer Irganox 1010 (manufactured by BASF Chiba) as a heat stabilizer, and the mixture was kneaded using a Laboplastomill mixer manufactured by Toyo Seiki Seisaku-sho, Ltd., at a resin temperature of 280°C and a screw rotation speed of 150 rpm to obtain polymer A1. Various physical properties of the obtained polymer A1 are shown in Table 1. The content of structural units derived from 4-methyl-1-pentene and the content of structural units derived from α-olefins (1-hexadecene and 1-octadecene) in polymer A1 were the same as those in polymer A1a.

[0082] <Production Example 2: Production of Polymer B1> 300 mL of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 mL of 4-methyl-1-pentene were mixed at 23°C into a thoroughly nitrogen-purged stainless steel autoclave equipped with a stirring blade. Next, 0.75 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) was mixed into the autoclave and stirred.

[0083] The autoclave was then heated to an internal temperature of 60°C and pressurized with propylene to a total pressure (gauge pressure) of 0.19 MPa. Next, 0.34 mL of a previously prepared toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride was introduced into the autoclave under pressure with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C. Sixty minutes after the start of polymerization, 5 mL of methanol was introduced into the autoclave under pressure with nitrogen to terminate the polymerization reaction, after which the autoclave was depressurized to atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring. This yielded a reaction solution containing a copolymer of 4-methyl-1-pentene and propylene.

[0084] The reaction solution containing the copolymer of 4-methyl-1-pentene and propylene was then dried under reduced pressure at 100°C for 12 hours to obtain polymer B1. The yield was 44.0 g. The content of each structural unit in polymer B1 was determined to be 85.0 mol% for structural units derived from 4-methyl-1-pentene and 15.0 mol% for structural units derived from α-olefin (propylene). The melting point (Tm) of polymer B1 was 132°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 1.5 dl / g. The physical properties of the obtained polymer B1 are shown in Table 2.

[0085] <Production Example 3: Production of Polymer C> Polymer C was obtained by varying the ratio of 4-methyl-1-pentene, other α-olefins (an equal mass mixture of 1-hexadecene and 1-octadecene), and hydrogen according to the polymerization method described in Comparative Example 9 of WO 2006 / 054613. The physical properties of the obtained polymer C are shown in Table 1.

[0086] <Method for measuring polymer properties> [composition] The content of the structural unit (i), the content of the structural unit (ii), and the content of the structural unit (iii) in each of the polymers synthesized in the above Production Examples were determined using the following apparatus and conditions. 13 The C-NMR spectrum was measured and calculated. The reference value for chemical shift was 27.50 ppm. The results are shown in Tables 1 and 2. Here, the structural unit (i) is a structural unit derived from 4-methyl-1-pentene, and the structural units (ii) and (iii) are structural units derived from copolymerizable monomers copolymerized with 4-methyl-1-pentene.

[0087] Apparatus: JEOL ECP500 nuclear magnetic resonance spectrometer Solvent: o-dichlorobenzene / heavy benzene (80% by volume / 20% by volume) mixed solvent Sample concentration: 55 mg / 0.6 mL Measurement temperature: 120℃ Observation kernel: 13 C(125MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45° pulse) Repeat time: 5.5 seconds Accumulation count: 10,000 times or more

[0088] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of each polymer synthesized in the above Production Examples was measured at 135° C. using decalin as a solvent. Specifically, approximately 20 mg of each polymer synthesized in the above Production Examples was weighed out and dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. This decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity ηsp was measured in the same manner. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was calculated as the limiting viscosity (see the formula below). The results are shown in Tables 1 and 2. [η]=lim(ηsp / C) (C→0)

[0089] [Melting point (Tm), endothermic end temperature (TmE), exothermic start temperature (TcS), crystallization temperature (Tc)] For the polymer A1 and polymer C synthesized in the above Production Examples, the exothermic and endothermic curves were measured using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the melting point (Tm) and crystallization temperature (Tc) were determined as follows. Approximately 5 mg of polymer was placed in a measurement aluminum pan and heated from 20°C to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 20°C at a cooling rate of 10°C / min and held at 20°C for 5 minutes. The temperature was then raised again from 20°C to 280°C at a heating rate of 10°C / min and again lowered to 50°C at a cooling rate of 50°C / min. The crystallization peak that appeared during the first temperature drop was taken as the crystallization temperature (Tc), and the melting point (Tm) was calculated based on the melting peak that appeared during the second temperature increase. When multiple melting peaks were present, the higher peak temperature was taken as the melting point (Tm).

[0090] The temperature at which endotherm in the melting (endotherm) curve ended was defined as the endotherm end temperature (TmE), and the temperature at which exotherm initiation in the crystallization (exotherm) curve began was defined as the exotherm onset temperature (TcS). The start and end points are the points at which it can be confirmed that the curve deviates from the baseline where the amount of heat becomes constant at the start or end of endothermic or exothermic reaction, and that a difference in the amount of heat begins to appear. The results are shown in Table 1.

[0091] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The weight average molecular weight (Mw) and weight average molecular weight / number average molecular weight (Mw / Mn) of the polymer B1 synthesized in the above Production Example were measured using gel permeation chromatography (GPC) under the following measurement conditions, and calculated using the standard polystyrene conversion method. The results are shown in Table 2. Measurement equipment: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated, manufactured by Waters) Column: Two GMH6-HT (Tosoh Corporation) and two GMH6-HTL (Tosoh Corporation) columns connected in series Eluent: o-dichlorobenzene Column temperature: 140℃ Flow rate: 1.0mL / min

[0092] [Table 1]

[0093] [Table 2]

[0094] <Preparation of Composition (X1-1)> Methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1.0 g of polymer A1 so that the solid content concentration was 5% by mass, and the mixture was stirred at 90°C and 600 rpm for 3 hours to produce a composition (X1-1) containing polymer A1.

[0095] <Preparation of Composition (X2-1)> [1st step] A flask (volume 5 L) that had been thoroughly purged with nitrogen was charged with 650 parts by mass of polymer B1, 1040 parts by mass of ethyl acetate (manufactured by Hiroshima Wako Co., Ltd.), and 1560 parts by mass of methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated to 70°C and then dissolved for 3 hours. The mixture was then cooled to 60°C or below to produce a composition containing polymer B1. The solids concentration of the composition containing polymer B1 was 20% by mass. [Second process] To 1.0 g of the composition containing polymer B1 prepared in the first step, a mixed solvent having a mass ratio of methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.):ethyl acetate (manufactured by Hiroshima Wako Co., Ltd.) of 6:4 was added so that the solid content concentration was 8 mass %, thereby producing a composition (X2-1) containing polymer B1.

[0096] <Production of substrate> The polymer C obtained in Production Example 3 was formed into a 100 μm film using a film-forming machine FS-50 (manufactured by Ikegai Corporation) under the conditions of a cylinder temperature of 280°C, a chiller temperature of 80°C, and a screw rotation speed of 20 rpm, thereby producing a substrate.

[0097] Example 1 [Preparation of Composition 1] After preparing the base material, composition (X1-1) and composition (X2-1) were mixed so that the contents of polymer A1 and polymer B1 were as shown in Table 1, thereby preparing composition 1. [Laminate manufacturing] The composition 1 was applied to one surface of the substrate in the thickness direction and dried at 100°C for 1 minute. As a result, a heat seal layer was disposed on one surface of the substrate in the thickness direction. The thickness of the heat seal layer after drying was 6µm. In this way, a laminate was produced.

[0098] <Examples 2 to 6> Compositions 2 to 6 were produced and laminates were manufactured according to the same procedure as in Example 1. However, the solid content ratio of composition (X1) and composition (X2) contained in compositions 2 to 6 was changed according to the description in Table 2. The thickness of the heat seal layer after drying was 6 μm in all cases.

[0099] <Comparative Example 1> A laminate was produced according to the same procedure as in Example 1, except that only composition (X1-1) was used instead of composition 1. The thickness of the heat seal layer after drying was 6 μm.

[0100] <Comparative Example 2> A laminate was produced according to the same procedure as in Example 1, except that only composition (X2-1) was used instead of composition 1. The thickness of the heat seal layer after drying was 6 μm.

[0101] <Physical property evaluation> [Haze measurement] The total haze and total light transmittance were determined by measuring the proportion of transmitted light that deviated from the incident light by 2.5° or more due to forward scattering, among the transmitted light that passed through the composition, using a turbidity meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136. The results are shown in Tables 3 and 4.

[0102] [Appearance evaluation] The obtained laminate was visually observed under visible light and evaluated according to the following evaluation criteria. The results are shown in Tables 3 and 4. (Evaluation criteria) ◯: Compared to Comparative Example 2, streaky coating marks on the laminate are less noticeable ×: Compared to Comparative Example 2, streaky coating marks are noticeable on the laminate In Comparative Example 2, streaky coating marks were noticeable on the laminate.

[0103] [Heat sealability] The resulting laminate was cut into strips of 160 mm wide x 15 mm long to prepare laminate strips. The strips were folded in half so that the heat-sealable layers were in contact, and heat-sealed using a heat-sealing tester (thermal gradient heat-sealing tester TP-701-B, manufactured by Tester Sangyo Co., Ltd.) under the following conditions: seal width: 20 mm, seal temperatures: 200°C and 220°C, seal pressure: 0.3 MPa, seal time: 1 second, to produce a film. Peel strength was evaluated by manually peeling the heat-sealed surface of the film.

[0104] When heat sealing was performed at a heat sealing temperature of 220°C, the effect of the present invention was judged to be obtained when the evaluation was ◯. When heat sealing was performed at a heat sealing temperature of 200°C, the effect of the present invention was judged to be even better when the evaluation was ◯. The results obtained are shown in Tables 3 and 4. (Evaluation criteria) ○: The material breaks or does not move at all even when force is applied. ×: Weak adhesion and interface failure.

[0105] [Table 3]

[0106] [Table 4]

Claims

1. A polymer (A) that satisfies the following requirement (AI); A polymer (B) that satisfies the following requirement (BI): a solvent; A composition comprising: (AI): Polymer (A) contains 50.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 50.0 mol % of structural units derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene). (BI): Polymer (B) contains 50.0 to 95.0 mol % of structural units derived from 4-methyl-1-pentene and 5.0 to 50.0 mol % of structural units derived from an α-olefin having 2 to 4 carbon atoms.

2. 2. The composition according to claim 1, wherein the mass ratio (A / B) of the content of the polymer (A) to the content of the polymer (B) is 0.05 to 5.

0.

3. The composition according to claim 1 or 2, wherein the polymer (A) contains 88.0 to 100 mol % of structural units derived from 4-methyl-1-pentene and 0 to 12.0 mol % of structural units derived from an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene).

4. The composition according to claim 1 or 2, wherein the polymer (B) contains 50.0 to 87.0 mol % of structural units derived from 4-methyl-1-pentene and 13.0 to 50.0 mol % of structural units derived from an α-olefin having 2 to 4 carbon atoms.

5. The composition according to claim 1 or 2, wherein the polymer (A) has a melting point of 150°C or higher.

6. The composition according to claim 1 or 2, wherein the polymer (B) has a melting point of less than 150°C.

7. The polymer (A) has an intrinsic viscosity of 0.5 to 3.0 dl / g in decalin at 135°C, 3. The composition according to claim 1, wherein the polymer (B) has an intrinsic viscosity in decalin at 135° C. of 0.5 to 3.0 dl / g.

8. A laminate including a base material and a heat seal layer in this order toward one side in a thickness direction, A laminate, wherein the heat seal layer is a dried product of the composition according to claim 1 or 2.

9. The laminate according to claim 8, wherein the substrate comprises a 4-methyl-1-pentene polymer.

10. A packaging film comprising the laminate of claim 8.

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