JP2019001139A - Multilayer biaxially oriented film and transfer film - Google Patents

Abstract

To provide a film in which delamination (ply separation) hardly occurs, and which is particularly excellent in surface smoothness, and is excellent in mold releasability and heat resistance.SOLUTION: A multilayer biaxially oriented film is provided in which a layer A and a layer B are laminated. The layer A is composed of a resin composition including a 4-methyl-1-pentene polymer (A1) and a 4-methyl-1-pentene copolymer (A2). In the layer A, a content of (A1) is 5-50 mass% of the layer A, a content of (A2) is 50-95 mass%, (A1) contains 90-100 mol% of a constitutional unit derived from 4-methyl-1-pentene and has a melting point (Tm) of 200-250°C, (A2) has a content of a constitutional unit derived from the 4-methyl-1-pentene of 65 or more and less than 96 mol%, has a content of a constitutional unit (BQ) derived from α-olefin (excluding 4-methyl-1-pentene) having 2 to 20 carbon atoms of more than 4 and 35 or less mol%, and has a melting point (Tm) that is not observed or 100-199°C. The layer B is composed of a resin composition including polypropylene (B1).SELECTED DRAWING: None

Description

  The present invention relates to a multilayer biaxially stretched film excellent in releasability. In particular, the present invention relates to a multilayer biaxially stretched film that is excellent in releasability by containing a 4-methyl-1-pentene polymer in the release layer and hardly causes delamination during biaxial stretching. More specifically, the present invention relates to a multilayer biaxially stretched film useful for a release film, a release liner, a separator film, a transfer film and the like.

  In general, resin materials, metal products, glass products, and the like for building materials and optical materials are attached with a surface protective film on the surface to prevent surface scratches and foreign matter from being transported, stored or processed. In addition to properties such as flexibility and mechanical properties, the surface protective film is required to have various properties according to the object to be protected, the purpose of protection, the use environment, and the like. For this reason, the development of surface protective films has been promoted from various viewpoints. For example, a surface protective film (Patent Document 1) mainly composed of a polyethylene component and a surface protective film of a resin composition comprising an oligomer of 4-methyl-1-pentene and 1-decene mainly composed of a polypropylene component have been studied. (Patent Document 2).

  Biaxially stretched polypropylene films are widely used as packaging and industrial material films because they are excellent in light weight, thermal stability and mechanical properties. In recent years, it has been widely used as a non-silicone release material as a film for manufacturing electronic components, electronic substrates, and thermosetting materials such as fiber reinforced plastics, but further improvements have been demanded. . As a method for improving releasability, for example, it has been proposed that the peeling force can be further increased by blending a polymethylpentene polymer with polypropylene (Patent Documents 3 and 4). However, it is known that biaxial stretchability deteriorates by increasing the content of polymethylpentene, and delamination (delamination) occurs in the case of a multilayer film. Furthermore, the α-olefin copolymer is compatible. Improvements such as compounding have been proposed (Patent Document 5).

The present inventors have already disclosed a release film comprising a poly-4-methyl-1-pentene copolymer, which is excellent in releasability and has a relatively low moldable temperature. It has been confirmed that when the moldable temperature is lowered, there is no problem in practical use, but the transparency of the film tends to deteriorate (Patent Document 6).
As described above, in recent years, development of a film having excellent workability such as biaxial stretching, excellent appearance, and good releasability has been demanded.

JP 2006-116769 A JP 2010-275340 A JP 2008-189795 A JP-A-7-070384 JP2015-120331A JP 2014-12596 A

  In order to improve the gloss of a transfer product obtained when the above-mentioned known multilayer film containing a 4-methyl-1-pentene-based polymer is used as a transfer film, the present inventors provide a release layer. It was thought that the surface smoothness could not be improved. And it aimed at development of the multilayer biaxially stretched film which has the outstanding surface smoothness, maintaining the outstanding mold release property and heat resistance of the conventional film. That is, an object of the present invention is to provide a film that is difficult to delaminate (delaminate), is particularly excellent in surface smoothness, and is excellent in releasability and heat resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed a layer formed from a composition containing a specific 4-methyl-1-pentene polymer and a 4-methyl-1-pentene copolymer. The present inventors have found that a multilayer biaxially stretched film having the above can solve the above problems, and have completed the present invention.

That is, the present invention relates to the following [1] to [6].
[1] A multilayer biaxially stretched film in which an A layer and a B layer are laminated,
A layer is composed of a resin composition containing a 4-methyl-1-pentene polymer (A1) and a 4-methyl-1-pentene copolymer (A2),
In the A layer, the content of the 4-methyl-1-pentene polymer (A1) is 5% by mass to 50% by mass with respect to the total mass of the A layer. The content of the polymer (A2) is 50% by mass to 95% by mass with respect to the total mass of the A layer,
The 4-methyl-1-pentene polymer (A1) satisfies the following requirements (A1-I) to (A1-II), and the 4-methyl-1-pentene copolymer (A2) satisfies the following requirements ( A multilayer biaxially stretched film satisfying A2-I) to (A2-II).
(A1-I) Containing 90 to 100 mol% of a structural unit derived from 4-methyl-1-pentene.
(A1-II) The melting point (Tm) measured by DSC is in the range of 200 ° C to 250 ° C.
(A2-I) The content of the structural unit (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 96 mol%, and an α-olefin having 2 to 20 carbon atoms (4-methyl- The content of the structural unit (BQ) derived from 1-pentene is more than 4 mol% and 35 mol% or less.
(A2-II) The melting point (Tm) measured by DSC is not observed or is in the range of 100 ° C to 199 ° C.
[2] The multilayer biaxially stretched film according to [1], wherein the 4-methyl-1-pentene polymer (A1) further satisfies the following requirement (A1-III).
(A1-III) Intrinsic viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g.
[3] The multilayer biaxially stretched film according to [1] or [2], wherein the 4-methyl-1-pentene polymer (A2) further satisfies the following requirement (A2-III).
(A2-III) Intrinsic viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g.
[4] The multilayer biaxially stretched film according to any one of [1] to [3], wherein the B layer is formed from a resin composition containing polypropylene (B1).
[5] Three-layer structure in which the layer structure is A layer / B layer / A layer or A layer / B layer / C layer (where C layer is a layer different from both the A layer and the B layer) The multilayer biaxially stretched film according to any one of [1] to [4], wherein
[6] The multilayer biaxially stretched film according to any one of [1] to [5], wherein the multilayer biaxially stretched film is a transfer film.

  According to the present invention, there is provided a multilayer biaxially stretched film that hardly causes delamination or the like during biaxial stretching, is particularly excellent in surface smoothness, and is excellent in releasability and heat resistance.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to. In addition, in this specification, the numerical range represented using "to" means the range which includes the numerical value described before and behind "to" as a lower limit and an upper limit.

  In addition, in this specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the plurality present in the composition unless otherwise specified. Means the total amount of substances.

In the multilayer biaxially stretched film of the present invention, an A layer and a B layer are laminated, and the A layer is a 4-methyl-1-pentene polymer (A1) (hereinafter also simply referred to as a polymer (A1)). It comprises a resin composition containing 4-methyl-1-pentene copolymer (A2) (hereinafter also simply referred to as copolymer (A2)).
Hereinafter, the A layer and the B layer will be described in detail, and then the layer configuration and the film manufacturing method will be described.

≪A layer≫
The A layer contains a 4-methyl-1-pentene polymer (A1) and a 4-methyl-1-pentene copolymer (A2). In the A layer, the content of the 4-methyl-1-pentene polymer (A1) is 5% by mass or more and 50% by mass or less based on the total mass of the A layer, and the 4-methyl-1-pentene copolymer Content of union (A2) is 50 mass% or more and 95 mass% or less with respect to the total mass of A layer. Preferably, the content of the 4-methyl-1-pentene polymer (A1) is 10% by mass or more and 40% by mass or less based on the total mass of the A layer, and the 4-methyl-1-pentene copolymer The content of the combined (A2) is 60% by mass or more and 90% by mass or less with respect to the total mass of the A layer. When in the above range, the 4-methyl-1-pentene polymer (A1) can be finely dispersed in the A layer. Moreover, the heat resistance of A layer is excellent because content of 4-methyl- 1-pentene polymer (A1) is more than the said lower limit. When the content of the 4-methyl-1-pentene copolymer (A2) is not less than the above lower limit value, the interlayer strength is excellent and it is difficult to delaminate.

  Further, as will be described later, the polymer (A1) and the copolymer (A2) both contain a specific amount or more of a structural unit derived from 4-methyl-1-pentene, whereby the polymer (A1) and It is considered that the compatibility with the copolymer (A2) is excellent and the gloss of the resulting film is excellent.

[4-Methyl-1-pentene polymer (A1)]
Hereinafter, the 4-methyl-1-pentene polymer (A1) which is a component constituting the A layer will be described. The 4-methyl-1-pentene polymer (A1) satisfies the following requirements (A1-I) to (A1-II).

<Requirement (A1-I)>
The 4-methyl-1-pentene polymer (A1) contains 90 to 100 mol% of structural units derived from 4-methyl-1-pentene. Preferably, a structural unit derived from an olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is contained at a ratio of 0 mol% to 10 mol%. In addition, as a C2-C20 olefin, it is not limited to 1 type, You may combine 2 or more types.

Here, from the viewpoint of heat resistance, the structural unit derived from 4-methyl-1-pentene is preferably contained in an amount of 93 mol% or more.
On the other hand, the structural unit derived from an olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is contained in an amount of 10 mol% or less, preferably 7 mol% or less.

  Examples of the olefin having 2 to 20 carbon atoms that can be contained in the 4-methyl-1-pentene polymer (A1) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1- Preferred examples include butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene and the like. These olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more. From the viewpoint of imparting appropriate elastic modulus, flexibility and flexibility, olefins having 8 to 18 carbon atoms (for example, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-heptadecene) Octadecene) is preferred.

  The 4-methyl-1-pentene polymer (A1) is a 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms (4-methyl-1-methylated ester) as long as the object of the present invention is not impaired. A structural unit derived from a polymerizable compound other than pentene (hereinafter also referred to as a polymerizable compound) may be included.

  Examples of the polymerizable compound include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, 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 and 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 norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyl Reden-2-norbol , 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Non-conjugated polyenes.

  In the 4-methyl-1-pentene polymer (A1) in the present invention, the units derived from the polymerizable compound are all polymerizable compound structures contained in the 4-methyl-1-pentene polymer (A1). 10 mol% or less may be contained with respect to the unit, and may be contained in an amount of 5 mol% or less and 3 mol% or less.

<Requirement (A1-II)>
The 4-methyl-1-pentene polymer (A1) in the present invention has a melting point (Tm) measured by DSC in the range of 200 to 250 ° C. Preferably it exists in the range of 200 to 245 degreeC, More preferably, it is in the range of 200 to 240 degreeC. The melting point (Tm) value is a value that changes depending on the stereoregularity of the polymer and the amount of α-olefin polymerized together, and is controlled and adjusted to a desired composition using an olefin polymerization catalyst described later. It is possible.

A polymer composition containing a 4-methyl-1-pentene polymer (A1) having a melting point (Tm) in the above range is preferable from the viewpoint of heat resistance.
The 4-methyl-1-pentene polymer (A1) preferably satisfies the following requirement (A1-III) in addition to the above requirements (A1-I) to (AI-II).

<Requirement (A1-III)>
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A1) measured in decalin at 135 ° C. is preferably 0.5 to 5.0 dL / g.

Here, the intrinsic viscosity [η] is more preferably in the range of 1.0 to 4.0 dL / g, and further preferably in the range of 1.2 to 3.5 dL / g.
The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added during the polymerization when the 4-methyl-1-pentene polymer (A1) is produced.

  The 4-methyl-1-pentene polymer (A1) having an intrinsic viscosity [η] in the above range exhibits good fluidity at the time of resin composition production and various moldings, and 4-methyl-1 -Good dispersibility in the pentene copolymer (A2), which is preferable in the appearance of the resulting multilayer biaxially stretched film.

[Method for producing 4-methyl-1-pentene polymer (A1)]
The 4-methyl-1-pentene polymer (A1) may be produced by polymerizing olefins, or may be produced by thermally decomposing a high molecular weight 4-methyl-1-pentene polymer. Good. Moreover, you may refine | purify by methods, such as the molecular distillation which fractionates with the difference in the solubility with respect to a solvent, or the fractionation according to the difference in boiling point.

When producing by a polymerization reaction, for example, by adjusting the amount of 4-methyl-1-pentene and α-olefin copolymerized as necessary, the type of polymerization catalyst, the polymerization temperature, the amount of hydrogenation during polymerization, etc. The melting point, stereoregularity, molecular weight and the like of the obtained 4-methyl-1-pentene polymer (A1) are controlled. The production method by the polymerization reaction may be a known method. For example, it can be produced by a method using a known catalyst such as a Ziegler Natta catalyst or a metallocene catalyst.
The polymer (A1) may be a commercially available polymer such as TPX manufactured by Mitsui Chemicals, Inc. in addition to the polymer produced as described above.

[4-Methyl-1-pentene copolymer (A2)]
The 4-methyl-1-pentene copolymer (A2) satisfies the following requirements (A2-I) to (A2-II).

<Requirement (A2-I)>
The 4-methyl-1-pentene copolymer (A2) contains a constituent unit (P) derived from 4-methyl-1-pentene in a proportion of 65 mol% or more and less than 96 mol%, and 4-methyl-1- It has a structural unit (BQ) derived from an α-olefin having 2 to 20 carbon atoms other than pentene in a proportion of more than 4 mol% and 35 mol% or less.

  The content of the structural unit (P) is 65 mol% or more and less than 96 mol%, preferably 68 mol% or more and less than 92 mol%, more preferably 68 mol% or more and less than 90 mol%, particularly preferably. Is 80 mol% or more and less than 88 mol%.

When the content of the structural unit (P) is 65 mol% or more, the heat resistance is excellent, and the gloss of the film that is excellent in compatibility with the polymer (A1) is excellent.
The content of the structural unit (BQ) (when the structural unit (BQ) is 2 or more, the total content of the 2 or more) is more than 4 mol% and 35 mol% or less, preferably 8 mol % To 32 mol% or less, more preferably more than 10 mol% to 32 mol% or less, and particularly preferably more than 12 mol% to 20 mol% or less.

  When the content of the structural unit (BQ) in the 4-methyl-1-pentene copolymer (A2) exceeds 4 mol%, the resulting laminated film has excellent interlayer strength and is difficult to delaminate. Examples of the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene forming the structural unit (BQ) include ethylene, propylene, 1-butene, 1-hexene, 1-octene and 1-decene. 1-hexadecene and 1-octadecene are preferable, α-olefins having 2 to 4 carbon atoms, that is, ethylene, propylene, and 1-butene are more preferable, and propylene is particularly preferable.

The structural unit (BQ) may be the same as or different from the structural unit (AQ) when the polymer (A) includes the structural unit (AQ).
The 4-methyl-1-pentene copolymer (A2) is a component other than the structural unit (P) derived from 4-methyl-1-pentene and 4-methyl-1-pentene as long as the effects of the present invention are not impaired. Other structural units other than the structural unit (BQ) derived from an α-olefin having 2 to 20 carbon atoms may be included. The content rate of another structural unit is 0-10 mol%, for example.

  Examples of the monomer that forms other structural units include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins, and the like.

  As the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin, and halogenated olefin, for example, the compounds described in paragraphs 0034 to 0041 of JP2013-169585A are used. be able to.

As the monomer forming the other structural unit, vinylcyclohexane and styrene are particularly preferable.
When the other structural unit is contained in the 4-methyl-1-pentene copolymer (A2), the other structural unit may be contained only in one kind, or in two or more kinds. May be.

The value of the content (mol%) of each structural unit in the 4-methyl-1-pentene copolymer (A2) is measured by a measurement method by ¹³ C-NMR, and the specific measurement method is described in the section of Examples. As described in.

<Requirement (A2-II)>
The melting point (Tm) of the 4-methyl-1-pentene copolymer (A2) is not observed or is in the range of 100 ° C. to 199 ° C., more preferably not observed, or is in the range of 110 ° C. to 180 ° C. More preferably, it exists in the range of 110 to 160 degreeC, Most preferably, it exists in the range of 125 to 150 degreeC.

The melting point (Tm) of the 4-methyl-1-pentene copolymer (A2) is a value measured by the same method as the melting point (Tm) of the polymer (A).
The 4-methyl-1-pentene copolymer (A2) preferably satisfies one or more of the following requirements in addition to the above requirements (A2-I) to (A2-II).

<Requirement (A2-III)>
The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A2) measured at 135 ° C. in a decalin solvent is 0.5 to 4.0 dl / g, preferably 0.5 dl / g to 3.5 dl / g, more preferably 1.0 dl / g to 3.5 dl / g. When the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A2) is within the above range, it is preferable from the viewpoint of moldability.
The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A2) is a value measured by the same method as the intrinsic viscosity [η] of the polymer (A).

<Requirement (A2-IV)>
The molecular weight distribution (Mw / Mn) of the 4-methyl-1-pentene copolymer (A2) is preferably 1.0 to 3.5, and preferably 1.1 to 3.0.
The weight average molecular weight (Mw) of the 4-methyl-1-pentene copolymer (A2) is preferably 1 × 10 ⁴ to 2 × 10 ⁶ and more preferably from the viewpoint of moldability of the layer made of the composition. Is 1 × 10 ⁴ to 1 × 10 ⁶ .
In addition, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the 4-methyl-1-pentene copolymer (A2) are values calculated by the method described in the examples.

<Requirement (A2-V)>
The melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A2) measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238 is the fluidity during molding of the composition. From this viewpoint, it is preferably 0.1 g / 10 min to 100 g / 10 min, more preferably 0.5 g / 10 min to 50 g / 10 min, and further preferably 0.5 g / 10 min to 30 g / 10. Minutes.

[Method for producing 4-methyl-1-pentene copolymer (A2)]
The 4-methyl-1-pentene copolymer (A2) can be produced by, for example, International Publication No. 2005/121192, International Publication No. 2011/055803, International Publication No. 2014/050817, etc. by a conventionally known metallocene catalyst system. It can be synthesized by the method described in 1.

[Other resins]
In the resin composition constituting the A layer of the multilayer biaxially stretched film of the present invention, the above-mentioned 4-methyl-1-pentene polymer (A1) and 4-methyl are within the range not impairing the object of the present invention. Other resins other than the -1-pentene copolymer (A2) may be contained. Examples of other resins that can be added include polyolefin polymers such as polyethylene, polypropylene, poly 1-butene, styrene resins, and ethylene / α-olefin copolymers. The content of other resins is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to the total mass of the A layer.

〔Additive〕
The resin composition constituting the A layer of the multilayer biaxially stretched film of the present invention comprises a specific amount of 4-methyl-1-pentene polymer (A1) and a specific amount of 4-methyl-1-pentene copolymer ( A2), and further within the range not impairing the object of the present invention, for example, a weather resistance stabilizer, heat resistance stabilizer, antioxidant, ultraviolet absorber, antistatic agent, anti-slip agent, anti-blocking agent, Antifogging agent, nucleating agent, lubricant, pigment, dye, anti-aging agent, hydrochloric acid absorbent, inorganic or organic filler, organic or inorganic foaming agent, cross-linking agent, cross-linking aid, adhesive, softener, You may contain various additives, such as a flame retardant.

  The resin composition constituting the A layer in the present invention may contain a nucleating agent that is a specific optional component in order to further improve its moldability, that is, to increase the crystallization temperature and increase the crystallization speed. Good. In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di- -T-butylphenyl) sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, and the like, although the amount is not particularly limited, but is 0.1% relative to 100 parts by mass of the resin composition. It is preferable that there is about 1-1 mass part. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.

  In the resin composition, as long as it does not impair the purpose of the present invention, a secondary antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antifogging agent, a lubricant, Dyes, pigments, natural oils, synthetic oils, waxes, fillers, hydrochloric acid absorbents, other olefin polymers, and the like can be blended. The blending amount is not particularly limited, but is usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, and 0 to 1 part by weight with respect to 100 parts by weight of the resin composition. Is particularly preferred.

  A known antioxidant can be used as the antioxidant. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of these can be used.

  Examples of the lubricant include saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid, and sodium, calcium and magnesium salts thereof. These may be used alone or in combination of two or more. Can do. Moreover, 0.1-3 mass parts is preferable normally with respect to 100 mass parts of this resin composition, and, as for the compounding quantity of this lubricant, 0.1-2 mass parts is more preferable.

  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. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended in the range of usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin composition according to the present invention.

  When the A layer according to the present invention contains the optional component other than the component (A1) and the component (A2), the mass obtained by subtracting the optional component from the total mass of the A layer is defined as 100% by mass. (A1) Content definition (5-95 mass%) and component (A2) content (5-95 mass%) definition are applied.

≪B layer≫
The B layer in the multilayer biaxially stretched film of the present invention is a layer provided for imparting excellent mechanical properties to the multilayer biaxially stretched film of the present invention. The B layer is preferably formed from a resin composition containing polypropylene (B1). The polypropylene (B1) is a known polymer mainly composed of propylene. Examples thereof include a propylene homopolymer, a propylene / α-olefin copolymer of propylene and an α-olefin other than propylene (propylene). A random copolymer such as an ethylene copolymer, a propylene / 1-butene copolymer, a propylene / ethylene / 1-butene copolymer, a block copolymer, or a mixture thereof). As the polypropylene, isotactic polypropylene and syndiotactic polypropylene are preferably used, and the isotactic meso pendant fraction (mmmm) or the syndiotactic meso pendant fraction (rrrr) exhibiting stereoregularity is 90% or more. Preferably, it is 92% or more, and more preferably 93% or more. When the stereoregularity is high, the crystallinity of the resin is improved, and high thermal stability and mechanical properties can be imparted.

  The copolymerization ratio of α-olefin in the propylene / α-olefin copolymer is preferably 5% by mass or less. The propylene / α-olefin copolymer may be a random copolymer or a block copolymer, and may contain a nucleating agent (crystallization nucleating agent). The nucleating agent is not particularly limited, and various inorganic compounds, various carboxylic acids or metal salts thereof, dibenzylidene sorbitol compounds, aryl phosphate compounds, cyclic polyvalent metal aryl phosphate compounds, and aliphatic monocarboxylic acid alkalis Examples thereof include a metal salt or a mixture of basic aluminum, lithium, hydroxy, carbonate, hydrate, and α crystal nucleating agent such as various polymer compounds. These crystallization nucleating agents can be used alone or in combination of two or more materials.

  The MFR of the polypropylene (B1) can be measured according to JIS K7210. Specifically, it is preferably 0.5 to 25 g / 10 minutes, more preferably 1 to 15 g / 10 minutes, and more preferably 2 to 10 g / min under measurement conditions of a temperature of 230 ° C. and a load of 2.16 kg. More preferably, it is 10 minutes. When the MFR of polypropylene (A2) is in the above range, it is suitable for extrusion molding.

  The amount of ash resulting from the polymerization catalyst residue contained in the polypropylene (B1) is preferably as small as possible and is preferably 50 ppm or less in order to reduce fine foreign matter (fish eyes). More preferably, it is 40 ppm or less.

  In addition, the same heat stabilizer, antioxidant, slip agent, chlorine scavenger, antistatic agent, and the like as those added to the resin composition forming the A layer are added to the resin composition forming the B layer. It may be.

≪Multilayer biaxially stretched film≫
As the layer structure of the multilayer biaxially stretched film of the present invention, a two-layer structure in which an A layer and a B layer are laminated, a three-layer structure in which A layer / B layer / A layer are laminated in this order, an A layer and a B layer C layer (for example, ethylene-modified isotactic polypropylene resin (random copolymer or block copolymer), composition containing atactic polypropylene, syndiotactic polypropyne, etc., olefin polymer, styrene polymer, acrylic And a three-layer structure in which a layer formed from an adhesive material expressing adhesiveness obtained from a polymer or the like is laminated in the order of A layer / B layer / C layer. From the viewpoint of moldability at the time of lamination, a two-layer structure of A layer / B layer or a three-layer structure of A layer / B layer / A layer is preferable.

  Although there is no restriction | limiting in particular about the method of obtaining such a multilayer film, Usually, first, the raw material film (it is also called a raw material sheet) by which A layer, B layer, and another layer are laminated | stacked as needed. And then biaxially stretching the original film. The raw film can be formed by, for example, laminating a plurality of films independently on a surface layer film obtained in advance by T-die molding or inflation molding by a known laminating method such as extrusion lamination or extrusion coating. Examples of the method include laminating each film by dry lamination, and the like, but from the viewpoint of productivity, co-extrusion molding in which a plurality of components are subjected to a multilayer extruder is preferred.

  Although the thickness of the film before extending | stretching which concerns on this invention, ie, a raw film, is not specifically limited, Usually, it is 100 micrometers-1000 micrometers, 150-800 micrometers is preferable, More preferably, it is 200-500 micrometers.

  The total thickness of the multilayer biaxially stretched film of the present invention is preferably 3 to 60 μm, more preferably 10 to 50 μm, and still more preferably 20 to 50 μm. When the total thickness of the film is 3 to 60 μm, a film having excellent mechanical properties and stretchability can be obtained.

  In the multilayer biaxially stretched film of the present invention, the thickness of one A layer is preferably 2 to 250%, more preferably 25 to 200%, relative to the thickness of one B layer. When the multilayer biaxially stretched film of the present invention contains two or more A layers, the thickness of each A layer may be the same or different from each other.

  The tape peeling force of the multilayer biaxially stretched film of the present invention at a peeling speed of 300 mm / min is preferably 7 N / 50 mm or less. More preferably, it is 1 to 6.5 N / 50 mm. The said tape peeling force can be adjusted with melting | fusing point and compounding quantity of 4-methylpentene-1 type | system | group copolymer (A). The tape peeling force is measured according to the pressure-sensitive adhesive sheet test method (JIS Z0237-2000). As a specific example of the measurement method, an acrylic adhesive material (product name: Nitto Tape 31B, manufactured by Nitto Denko Corporation) is used as an adhesive material, and a test film and an adhesive tape cut to a length of 50 mm × 100 mm are subjected to a temperature of 23 ° C. The adhesive film is allowed to stand for 1 hour in an environment with a relative humidity of 50%, and then the adhesive film is passed through the reciprocating passage while applying pressure with a rubber roll of about 2 kg and attached to the test plate. After pasting, it is placed in a constant environment at a temperature of 23 ° C or 50 ° C and a relative humidity of 50% for one day, and then peeled off in a 180 ° direction at a speed of 300 mm / min in an environment of a temperature of 23 ° C and a relative humidity of 50%. It can be evaluated by measuring the peeling force at the time.

  The 45 ° gloss of the multilayer biaxially stretched film of the present invention is preferably 70% or more. More preferably, it is 80% or more. The upper limit is not particularly limited, but is usually 130% or less. The measurement method of 45 ° gloss is as described in the Example section in detail.

≪Method for producing multilayer biaxially stretched film≫
About the method of mixing each component and preparing the resin composition pellet for A layer or B layer, various well-known methods, for example, a multistage polymerization method, a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler A method of mixing with a blender, kneader ruder or the like, or after mixing, a method of melt-kneading, for example, at 180 to 300 ° C. and granulating or pulverizing with a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. can do. By this method, high-quality resin composition pellets in which each component and additive are uniformly dispersed and mixed can be obtained.

The raw fabric sheet for a multilayer biaxially stretched film of the present invention can be obtained by melt-extruding the above resin composition pellets at a cylinder temperature of usually 180 to 300 ° C.
In order to produce a multilayer biaxially stretched film from the raw sheet, batch biaxial stretching, sequential biaxial stretching immediately after cast molding, or simultaneous biaxial stretching can be performed. In sequential biaxial stretching, the cast original fabric sheet is kept at 100 to 165 ° C., passed between rolls provided with a speed difference, stretched 2 to 5 times in the flow direction, and immediately cooled to room temperature. Next, the film is guided to a tenter and stretched 5 to 10 times in the width direction at a temperature of 150 ° C. or higher, and then relaxed and heat-set to obtain the film.

≪Usage≫
Specific examples of the multilayer biaxially stretched film of the present invention include the following general film applications.
Packaging film; for example, food packaging film, stretch film, wrap film, shrink film, easy peel film, aluminum vapor deposition film, PVDC coat film, and the like. Breathable film; for example, disposable diapers, sanitary products, surgical clothing, surgical gloves, surgical down, house wrap (breathable waterproof sheet), disposable warmers, household dehumidifiers, desiccants, oxygen absorbers, freshness-keeping agents, compost Sheet, simple jumper, etc. Rust prevention film; for example, automotive parts, knockdown parts, machinery / machine parts, iron / chrome products, steel pipes, wire rods, bolts / nuts, bearings, dies, tools, blades, cutting tools, building tools, etc. Examples include storage packaging and export packaging. Antifogging film; for example, a film for fruits and vegetables, a film for processed foods, etc.

  Directional films: confectionery twist packaging, agricultural materials, laminate substrates, coin packaging, wire bundling materials, fruit and vegetable packaging, cardboard cut tape, detergent refill containers, rice ball packaging, pillow packaging, stick packaging, boil and retort packaging, Examples include marine food packaging and infusion bags.

Self-cleaning film; for example, road signs, general signs, signboards, window glass, road materials, side mirrors and the like.
Separators; for example, battery separators, lithium ion battery separators, fuel cell electrolyte membranes, adhesive / adhesive separators.
Stretched film; for example, film for film capacitor, capacitor film, capacitor film for fuel cell.
Semiconductor process film; for example, dicing tape, back grind tape, die bonding film, polarizing plate film, surface protective film; for example, polarizing plate protective film, liquid crystal panel protective film, optical component protective film, lens protective film Protective films for electrical parts and appliances, protective films for mobile phones, protective films for personal computers, masking films, protective films for touch panels.

Film for electronic member; for example, diffusion film, reflection film, radiation resistant film, gamma ray resistant film, porous film.
Building material films; for example, building material window films, laminated glass films, bulletproof materials, bulletproof glass films, heat shield sheets, and heat shield films.
Transfer films; for example, transfer films for automobiles and industries, transfer films for packaging.
Release film; for example, release film for flexible printed circuit board (FPC), release film for ACM board, release film for rigid flexible board, release film for advanced composite material, release film for curing carbon fiber composite material, Release film for curing glass fiber composite, Release film for curing aramid fiber composite, Release film for curing nanocomposite, Release film for curing filler filler, Release film for semiconductor sealing, Release film for polarizing plate Mold film, diffusion sheet release film, prism sheet release film, reflection sheet release film, release film cushion film, fuel cell release film, various rubber sheet release films, urethane curing release Mold film, epoxy curing release film (manufacturing process members such as metal bats and golf clubs), etc. And the like.

  Particularly preferable examples include a release film, a release liner or a separator film, a transfer film, and a carrier used for producing a composite material used for a surface protective film and an adhesive tape. Particularly preferably, it is used as a transfer film.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.
〔composition〕
The contents (mol%) of 4-methyl-1-pentene and α-olefin in the polymer were measured by ¹³ C-NMR. The measurement conditions are as follows.
Measurement device: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
-Observation nucleus: ¹³ C (125 MHz)
・ Sequence: Single pulse proton decoupling ・ Pulse width: 4.7 μsec (45 ° pulse)
・ Repetition time: 5.5 seconds ・ Number of integration: 10,000 times or more ・ Solvent: orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent ・ Sample concentration: 55 mg / 0.6 mL
・ Measurement temperature: 120 ℃
-Standard value of chemical shift: 27.50ppm

[Melting point (Tm)]
The melting point (Tm) of the polymer was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device.
About 5 mg of the polymer was sealed in an aluminum pan for measurement and heated from room temperature to 280 ° C. at 10 ° C./min. In order to completely melt the copolymer, it was kept at 280 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating was performed to 280 ° C. at 10 ° C./min. The peak temperature (° C.) at the second heating was defined as the melting point (Tm) of the polymer.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the polymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device. Specifically, about 20 mg of the powdery copolymer was dissolved in 25 ml of decalin, and then the specific viscosity η _sp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner as described above. 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 [η] (unit: dl / g) (see Equation 1 below) .
[Η] = lim (η _sp / C) (C → 0) Equation 1

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the polymer is JIS
Based on K7210, the copolymer A2 (A2-1, A2-1) and polypropylene were measured at 230 ° C. under a load of 2.16 kg. The unit is g / 10 minutes. In addition, about polymer A1 (A1-1), it measured on 260 degreeC and the load conditions of 5.0 kg.
〔density〕
The density of the polymer was measured according to JIS K7112 (density gradient tube method).

[Production Example 1] Production of 4-methyl-1-pentene polymer (A1-1)
By changing the ratio of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene and hydrogen in accordance with the polymerization method described in Comparative Example 7 and Comparative Example 9 of International Publication No. 2006/054613, Table 1 4-methyl-1-pentene polymer A1-1 having the physical properties shown below was obtained.

[Production Example 2] Production of 4-methyl-1-pentene copolymer (A2-1)
Into a SUS autoclave with a stirring blade with a capacity of 1.5 L that has been sufficiently purged with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were added. After charging at 23 ° C., 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged and the stirrer was turned.

Next, the autoclave was heated until the internal temperature reached 60 ° C., and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance were converted into Al. 0.34 ml of a toluene solution containing (butyl-fluorenyl) zirconium dichloride was pressed into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

  Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent. Subsequently, the polymerization reaction product containing the obtained solvent was dried at 130 ° C. under reduced pressure for 12 hours to obtain 44.0 g of a powdery polymer A2-1 as a copolymer (B). Table 1 shows the measurement results of various physical properties.

[Production Example 3] Production of 4-methyl-1-pentene copolymer (A2-2)
Into a SUS autoclave with a stirring blade with a capacity of 1.5 L that has been sufficiently purged with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were added. Charged at 23 ° C. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance were converted into Al. 0.34 ml of a toluene solution containing (butyl-fluorenyl) zirconium dichloride was pressed into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

Sixty minutes after the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to the atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.
Subsequently, the polymerization reaction product containing the obtained solvent was dried at 100 ° C. under reduced pressure for 12 hours to obtain 36.9 g of a powdery copolymer A2-2. Table 1 shows the measurement results of various physical properties.

[Example 1]
A three-layer biaxially stretched film laminated in the order of A layer / B layer / A layer was molded. First, as a resin composition for forming the A layer, the polymer A1-1: 20 parts by mass and the copolymer A2-1: 80 parts by mass are supplied to a twin-screw extruder and kneaded at 270 ° C. The resin composition was prepared and used as the raw material for the A layer. The resin forming the B layer is polypropylene (Prime Polypro (registered trademark) F113G (Propylene homopolymer, density: 910 kg / m ³ , MFR (230 ° C.): 3.0 g / 10 min, manufactured by Prime Polymer Co., Ltd.) )) Was used.

  Using the obtained resin composition and resin, a three-layer three-layer T-die sheet molding machine in which a T-die having a lip width of 330 mm is installed, three hopper inlets and a 30 mmφ screw are installed, 270 ° C., B layer cylinder temperature is set to 230 ° C., die temperature is set to 270 ° C., the melt-kneaded material is extruded from the T die at a thickness of 300 μm (A layer 50 μm / B layer 200 μm / A layer 50 μm) and cast-molded. Thus, a raw film of Example 1 was obtained. The thickness of each layer was calculated from the amount of extrusion.

Subsequently, using a batch type biaxial stretching machine KARO IV manufactured by Bruckner Co., a preheating temperature of 162 ° C., a preheating time of 2 minutes, a stretching temperature of 162 ° C., a stretching rate of 100% / second, a heat setting condition of 162 ° C., 30 seconds. The film obtained was stretched 3 times in the flow direction (MD) and 5 times in the width direction (TD) to obtain a multilayer biaxially stretched film having a total film thickness of 20 μm.
The evaluation results of the obtained multilayer biaxially stretched film are shown in Table 2. The specific test method is as follows.

[Delami during stretching]
After the multilayer biaxial stretching, the peeling between the layers of the A layer and the B layer of the multilayer biaxially stretched film was visually confirmed, and the presence or absence of delamination was confirmed.

[Uniformity after stretching]
The multilayer biaxially stretched film after biaxial stretching was visually confirmed, and when the surface was smooth and uniform, it was marked as ◯, and when there was a nonuniform portion such as wrinkles, it was marked as x.

(Gloss (Glossiness))
The multilayer biaxially stretched film after being biaxially stretched was based on JIS Z8741 and the average value of 5 points of data measured under conditions of an incident angle of 45 ° and a light receiving angle of 45 ° was defined as glossiness.

[Example 2, Comparative Examples 1 to 4]
The resin composition forming the A layer was prepared by mixing (dry blending) at the ratio shown in Table 2. Moreover, the multilayer biaxially stretched film was obtained by the method similar to Example 1 except having changed the thickness of each layer as shown in Table 2. The evaluation results of the obtained multilayer biaxially stretched film are shown in Table 2.

[Comparative Example 5]
With the composition described in Table 2, a biaxially stretched film was prepared using the polymer A1-1 alone for the A layer.

Claims (6)

A multilayer biaxially stretched film in which an A layer and a B layer are laminated,
A layer is composed of a resin composition containing a 4-methyl-1-pentene polymer (A1) and a 4-methyl-1-pentene copolymer (A2),
In the A layer, the content of the 4-methyl-1-pentene polymer (A1) is 5% by mass to 50% by mass with respect to the total mass of the A layer. The content of the polymer (A2) is 50% by mass to 95% by mass with respect to the total mass of the A layer,
The 4-methyl-1-pentene polymer (A1) satisfies the following requirements (A1-I) to (A1-II), and the 4-methyl-1-pentene copolymer (A2) satisfies the following requirements ( A multilayer biaxially stretched film satisfying A2-I) to (A2-II).
(A1-I) Containing 90 to 100 mol% of a structural unit derived from 4-methyl-1-pentene.
(A1-II) The melting point (Tm) measured by DSC is in the range of 200 ° C to 250 ° C.
(A2-I) The content of the structural unit (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 96 mol%, and an α-olefin having 2 to 20 carbon atoms (4-methyl- The content of the structural unit (BQ) derived from (excluding 1-pentene) exceeds 4 mol% and is 35 mol% or less.
(A2-II) The melting point (Tm) measured by DSC is not observed or is in the range of 100 ° C to 199 ° C. The multilayer biaxially stretched film according to claim 1, wherein the 4-methyl-1-pentene polymer (A1) further satisfies the following requirement (A1-III).
(A1-III) Intrinsic viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g. The multilayer biaxially stretched film according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer (A2) further satisfies the following requirement (A2-III).
(A2-III) Intrinsic viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g.   The multilayer biaxially stretched film according to any one of claims 1 to 3, wherein the B layer is formed from a resin composition containing polypropylene (B1).   The layer structure is a three-layer structure of A layer / B layer / A layer or A layer / B layer / C layer (where C layer is a layer different from both A layer and B layer). The multilayer biaxially stretched film according to any one of claims 1 to 4.   The multilayer biaxially stretched film according to any one of claims 1 to 5, wherein the multilayer biaxially stretched film is a transfer film.