CN113613890B - Laminated film - Google Patents

Laminated film Download PDF

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Publication number
CN113613890B
CN113613890B CN202080024223.5A CN202080024223A CN113613890B CN 113613890 B CN113613890 B CN 113613890B CN 202080024223 A CN202080024223 A CN 202080024223A CN 113613890 B CN113613890 B CN 113613890B
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Prior art keywords
resin layer
laminated film
mass
resin
styrene
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CN113613890A (en
Inventor
马场祐辅
町田哲也
井上则英
田邨奈穗子
大仓正寿
辰喜利海
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Toray Advanced Film Co Ltd
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Toray Advanced Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Abstract

The present invention relates to a laminated film having excellent dependence on an adherend, which exhibits uniform adhesion to adherends having different surface shapes and can be widely used. The laminated film has a base material and a resin layer A on at least one surface side of the base material, and satisfies the following (a), (b) and (c). (a) The maximum value F of the probe tack at 23℃on the side of the resin layer A was 0.2g/mm 2 Above and 2.5g/mm 2 The following is given. (b) The ratio (hp/hm) of the residual displacement hp (unit μm) to the maximum displacement hm (unit μm) of the resin layer A side when the nanoindentation-based load/unload test is performed at 26 ℃ under a maximum load of 1mN is 0.50 to 0.90. (c) the resin layer A has a melting point Tm at 50 ℃ or higher.

Description

Laminated film
Technical Field
The present invention relates to a laminated film which exhibits a constant adhesive force to various adherends having different surface shapes, irrespective of the shape of the adherend, and is excellent in dependence of the adherend.
Background
In some products made of various materials such as synthetic resins, metals, and glasses, a protective sheet or film may be attached to the surface of the products to prevent scratches and stains generated during processing, transportation, and storage. In general, a surface protective film or the like having an adhesive layer formed thereon is used on a support base material comprising a thermoplastic resin or paper, and the adhesive layer is attached to an adherend.
In particular, in recent years, the popularity of liquid crystal displays and touch panel devices has been advancing, which are composed of a plurality of optical sheets, optical films, and the like, which contain synthetic resins. In the above-mentioned optical member, it is necessary to minimize defects such as optical distortion, and therefore, in order to prevent flaws or stains which may cause defects, a surface protective film is often used.
As characteristics of such a surface protective film, the following characteristics are required: the adhesive is not easy to be peeled off from an adherend under the conditions of environmental changes such as temperature and humidity or the degree of small stress; when the adhesive is peeled from the adherend, the adhesive and the adhesive component do not remain on the adherend; after processing and use, the adhesive can be easily peeled off; etc.
In the optical member, products having various surface shapes have been developed on the market for adherends having a surface with a concave-convex shape such as a diffusion plate and a prism sheet, and development of a surface protective film that exhibits uniform adhesion to adherends having different surface shapes and can be widely used, that is, a surface protective film having little dependence on adherends has been demanded.
As the surface protective film used for an adherend having a concave-convex shape on the surface, the techniques described in patent documents 1 and 2 are cited.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-253435
Patent document 2: japanese patent laid-open publication No. 2013-117019
Disclosure of Invention
Problems to be solved by the invention
However, the techniques described in patent documents 1 and 2 as the surface protective film used for an adherend having a concave-convex shape on the surface do not improve the adhesion force difference due to the difference in concave-convex shape of the adherend, that is, the so-called dependence of the adherend.
Accordingly, the present invention aims to solve the above problems. That is, a laminated film having excellent dependence on adherends, which exhibits uniform adhesion to adherends having different surface shapes and can be widely used, is provided.
Means for solving the problems
The above problems can be solved by the following means.
A laminated film having a base material and a resin layer A on at least one surface side of the base material, wherein the laminated film satisfies the following (a), (b) and (c),
(a) The maximum value F of the probe tack at 23℃on the side of the resin layer A was 0.2g/mm 2 Above and 2.5g/mm 2 In the following the procedure is described,
(b) The ratio (hp/hm) of the residual displacement hp (unit μm) to the maximum displacement hm (unit μm) of the resin layer A side when the nanoindentation-based load/unload test is performed at 26 ℃ under a maximum load of 1mN is 0.50 to 0.90,
(c) The resin layer A has a melting point Tm at 50 ℃ or higher.
ADVANTAGEOUS EFFECTS OF INVENTION
In view of the above problems, the present invention can provide a laminated film having excellent dependence on an adherend and exhibiting good adhesive properties to various adherends having different surface shapes.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described below.
The laminated film has a base material and a resin layer a on at least one surface side of the base material. Here, the resin layer a is a layer containing at least a resin, which is provided on at least one surface side of the base material, and satisfies the following (a), (b), and (c). The resin layer a may contain a resin, and the type of the resin is not particularly limited, but the resin in the resin layer a is preferably selected so that the laminated film satisfies the following (a), (b), and (c). The preferred embodiment of the resin contained in the resin layer a is described below.
(a) The maximum value F of the probe tack at 23℃on the side of the resin layer A was 0.2g/mm 2 Above and 2.5g/mm 2 The following is given.
(b) The ratio (hp/hm) of the residual displacement hp (unit μm) to the maximum displacement hm (unit μm) of the resin layer A side when the nanoindentation-based load/unload test is performed at 26 ℃ under a maximum load of 1mN is 0.50 to 0.90.
(c) The resin layer A has a melting point Tm at 50 ℃ or higher.
As for the laminate film of the present invention, the maximum value F of the probe tack at 23℃on the side of the resin layer A was 0.2g/mm 2 Above and 2.5g/mm 2 The following is given. The probe tack maximum F is more preferably 0.3g/mm 2 The above is more preferably 0.4g/mm 2 The above. Further, the probe viscosity maximum F is more preferably 2.0g/mm 2 Hereinafter, it is more preferably 1.5g/mm 2 The following is given.
The maximum value F of probe tackiness on the side of the resin layer A is less than 0.2g/mm 2 In the case where the laminate film of the present invention is used as a surface protective film, sufficient adhesive force may not be obtained. In addition, the probe tackiness maximum F on the side of the resin layer A is more than 2.5g/mm 2 In some cases, the adhesion force becomes excessive, and in particular, the adhesion force to an adherend having small surface roughness becomes excessive, and thus the adherend dependence becomes excessive.
The probe tack maximum value F can be controlled by adjusting the material constituting the resin layer a, the flexibility, thickness, surface roughness, and the like of the resin layer a, which will be described later, and can be reduced by, for example, hardening the resin layer aMethod of increasing surface roughness of resin layer A to reduce probe tackiness maximum value F by controlling the thickness of layer A to 0.2g/mm 2 Above and 2.5g/mm 2 The following is given.
In the laminate film of the present invention, the ratio of the residual displacement hp (in μm) to the maximum displacement hm (in μm) (hp/hm. or less, hp/hm) on the resin layer a side when the nanoindentation-based load/unload test is performed at 26 ℃ under a maximum load of 1mN is 0.50 or more and 0.90 or less. The hp/hm is more preferably 0.60 or more, and still more preferably 0.70 or more. Further, hp/hm is more preferably 0.80 or less.
When hp/hm is less than 0.50, the adhesive force of the resin layer a is too small, and particularly the adhesive force to an adherend having a large surface roughness is small, and the adherend dependence is too large in some cases when the resin layer a is adhered to the adherend. In the case where hp/hm is more than 0.90, the adhesion may become excessive. hp/hm can be controlled by the material constituting the resin layer a, etc., described later.
The resin layer a in the laminated film of the present invention has a melting point Tm at 50 ℃ or higher, and more preferably has a melting point Tm at 100 ℃ or higher. In the case where the resin layer a of the present invention has 2 or more melting points, the melting point at the high temperature side is defined as the melting point Tm of the resin layer a of the present invention. The upper limit of Tm is not particularly limited, but is preferably substantially 180℃or lower. When Tm is lower than 50 ℃ or when the resin layer a does not have a melting point, the laminated film of the present invention may be stored at a high temperature or may increase in contact area between the resin layer a and the adherend over time after being attached to the adherend, and the adhesive force may become excessive. When Tm is higher than 180 ℃, the viscosity may become too high and productivity may be deteriorated when the resin layer a is molded by melt extrusion.
As a method for providing the resin layer a with Tm at 50 ℃ or higher, there is a method of adding a crystalline resin having a melting point of 50 ℃ or higher to a material constituting the resin layer a. That is, there is a method according to an embodiment in which the resin layer a contains a crystalline resin having a melting point of 50 ℃ or higher. As a suitable crystalline resin contained in such a resin layer a, for example, a crystalline olefin-based resin is preferable from the viewpoints of compatibility with other components used in the resin layer a and productivity. Specific examples of the olefin-based resin are described below.
The probe tack maximum F, hp/hm obtained by nanoindentation measurement, and melting point Tm of the resin layer A can be measured by the methods described in examples.
The storage elastic modulus G' (A) of the resin layer A of the present invention under the conditions of 50℃and 1Hz is preferably 1.5MPa or more, more preferably 2.0MPa or more, and still more preferably 2.5MPa or more. The upper limit of the storage elastic modulus G' (a) is not particularly set, but is preferably 30MPa from the viewpoint of adhesion properties such as adhesion.
The storage elastic modulus G' (a) of the resin layer a is preferably 1.5MPa or more, from the viewpoint of suppressing an increase in the contact area between the resin layer a and the adherend and an increase in the adhesive force when the laminated film of the present invention is stored at high temperature or with time after being attached to the adherend. The storage elastic modulus G' (a) of the resin layer a can be measured by the method described in examples.
The storage elastic modulus G '(a) of the resin layer a can be controlled by the material constituting the resin layer a, and for example, as a method for increasing the storage elastic modulus G' (a), a method for further increasing the molecular weight of a styrene-based elastomer is given as an embodiment in which the resin layer a contains the styrene-based elastomer; a method in which a crystalline resin having a melting point of 50 ℃ or higher is used as the resin in the resin layer A; a method in which an unhydrogenated or partially hydrogenated aromatic copolymer and/or an aliphatic/aromatic copolymer is used as the resin in the resin layer a; etc.
The arithmetic average roughness Ra (a) of the resin layer a side of the present invention is preferably 0.20 μm or more, more preferably 0.30 μm or more, and particularly preferably 0.40 μm or more. The arithmetic average roughness Ra (a) is preferably 0.80 μm or less, more preferably 0.70 μm or less, and particularly preferably 0.60 μm or less. The arithmetic average roughness Ra (a) is preferably 0.20 μm or more, from the viewpoint of reducing the dependence of the adherend, and suppressing an increase in the contact area between the resin layer a and the adherend when stored at high temperature or with the lapse of time after the lamination film of the present invention is attached to the adherend, and suppressing an increase in the adhesive force. The arithmetic average roughness Ra (a) on the resin layer a side can be measured by the method described in the examples. The arithmetic average roughness Ra (a) on the resin layer a side can be controlled by the material constituting the resin layer a, the material constituting the base material, and the thickness of the resin layer a, which will be described later.
As described above, the laminated film of the present invention has a base material and a resin layer a on at least one surface side of the base material. Here, the resin layer a means a laminate having a limited thickness, and preferably has adhesiveness at normal temperature.
The term "adhesive property" as used herein means that the adhesive strength between the resin layer A and the SUS304 plate is 1g/25mm or more when the adhesive strength is measured after the resin layer A side of the laminate film is attached to the SUS304 plate having an arithmetic average roughness Ra of 0.2 μm and a ten-point average roughness Rz of 2.8 μm using a roll press (special press roll manufactured by Seikagaku An Tian refiner) at a bonding pressure of 0.35 MPa. The adhesiveness of the resin layer A is more preferably 2g/25mm or more, and still more preferably 5g/25mm or more. The upper limit of the adhesion of the resin layer a is not particularly limited as the adhesion is higher, but in the case of exceeding 1000g/25mm, the adhesion may be difficult to peel after the adhesion and the workability may be lowered, so that the upper limit is preferably about 1000g/25 mm.
The resin layer a is not particularly limited as long as it is disposed on at least one surface side of the base material, but is preferably disposed on at least one outermost layer of the laminated film of the present invention. By disposing the adhesive resin layer a on the outermost layer of the laminated film, the laminated film can be bonded to an adherend via the resin layer a. The resin layer a is not particularly limited as long as it is disposed on at least one surface side of the base material, and therefore, the base material and the resin layer a may be disposed in direct contact with each other, or another layer such as an easy-to-adhere layer may be provided between the base material and the resin layer a.
The resin layer a is not particularly limited insofar as the effect of the present invention is not impaired, and may include an elastomer such as an acrylic elastomer, a silicone elastomer, a natural rubber elastomer, or a synthetic rubber elastomer. Among these, thermoplastic synthetic rubber-based adhesives are preferably used from the viewpoint of recyclability, and among these, styrene-based elastomers are more preferable.
In the present invention, the styrene-based elastomer means a resin having a storage elastic modulus G' (25) of 10MPa or less at 25 ℃ and 1Hz and containing at least a styrene component as a monomer component. As suitable styrene-based elastomers contained in the resin layer a, for example, styrene/conjugated diene-based copolymers such as styrene/butadiene copolymer (SBR), styrene/isoprene/styrene copolymer (SIS), styrene/butadiene/styrene copolymer (SBS), and hydrogenated products thereof (for example, hydrogenated styrene/butadiene copolymer (HSBR), styrene/ethylene butylene/styrene triblock copolymer (SEBS), styrene/ethylene butylene diblock copolymer (SEB)), styrene/isobutylene-based copolymers (for example, styrene/isobutylene/styrene triblock copolymer (SIBS), styrene/isobutylene diblock copolymer (SIB), or mixtures thereof can be used. Among the above, styrene/conjugated diene copolymers such as styrene/butadiene/styrene copolymers (SBS) and hydrogenated products thereof, styrene/isobutylene copolymers are preferably used. The styrene-based elastomer may be used in an amount of 1 or 2 or more.
When the total resin layer a is 100% by mass, the content of the styrene-based elastomer suitably contained in the resin layer a is preferably 40% by mass or more, more preferably 50% by mass or more. The content of the styrene-based elastomer in the resin layer a is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 75% by mass or less. When the laminate film of the present invention is used as an adhesive film, good adhesive properties can be obtained by setting the content of the styrene-based elastomer in the resin layer a within the above-described preferable range.
The melt flow rate (MFR, measured at 230 ℃ C., 2.16 kg) of the styrene-based elastomer suitably contained in the resin layer A is preferably 3g/10 min or more, more preferably 7g/10 min or more, and still more preferably 10g/10 min or more. The MFR of the styrene-based elastomer is preferably 50g/10 min or less, more preferably 30g/10 min or less, and still more preferably 20g/10 min or less. When the MFR of the styrene-based elastomer suitable for the resin layer a is in the above range, the productivity is excellent, and the laminate film of the present invention exhibits good adhesive properties when used as a surface protective film.
When the total styrene-based elastomer is 100% by mass, the styrene component content in the styrene-based elastomer suitable for the resin layer a is preferably 5% by mass or more, more preferably 8% by mass or more. The content of the styrene component in the styrene-based elastomer is preferably 55 mass% or less, more preferably 40 mass% or less. When the content of the styrene component in the styrene-based elastomer is within the above range, the laminate film of the present application exhibits good adhesion and excellent adhesion properties by suppressing residual glue when the laminate film is adhered to an adherend.
The resin layer A of the present application preferably contains an olefin resin having a melt flow rate (MFR, measured at 230 ℃ C. And under 2.16 kg) of 0.01g/10 min or more and 1.5g/10 min or less. By including the olefin-based resin having an MFR of 0.01g/10 min or more and 1.5g/10 min or less in the resin layer a, the structure in which the olefin-based resin is dispersed as a domain component (domain component) is formed in the elastomer as the base component of the resin layer a, and therefore the arithmetic average roughness Ra (a) on the resin layer a side can be preferably suppressed, and the dependence of the adherend when the laminated film of the present application is used as an adhesive film can be reduced. The MFR of the olefin-based resin in the resin layer A is more preferably 0.1g/10 min or more, still more preferably 0.2g/10 min or more. The MFR of the olefin resin is more preferably 1.3g/10 min or less, and still more preferably 1.0g/10 min or less. When the MFR is less than 0.01g/10 min, the dispersion of the domain components is poor, and the olefin resin may be aggregated to become FE. On the other hand, when the MFR exceeds 1.5g/10 min, the dispersibility of the regional components is improved, and it may be difficult to adjust the arithmetic average roughness Ra (A) of the resin layer A to the range defined in the present application. Examples of the olefin-based resin that is suitably contained in the resin layer a include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, low-crystalline or amorphous ethylene/α -olefin copolymer, crystalline polypropylene, low-crystalline polypropylene, amorphous polypropylene, propylene/α -olefin copolymer, propylene/ethylene/α -olefin copolymer, polybutene, 4-methyl-1-pentene/α -olefin copolymer, ethylene/(meth) acrylic acid ethyl ester polymer, ethylene/methyl (meth) acrylic acid methyl ester copolymer, ethylene/(meth) acrylic acid n-butyl ester copolymer, ethylene/vinyl acetate copolymer, and among these, propylene-based resins such as crystalline polypropylene, low-crystalline polypropylene, amorphous polypropylene, propylene/α -olefin copolymer, and propylene/ethylene/α -olefin copolymer are preferably used. These olefinic resins may be used alone or in combination. The α -olefin is not particularly limited as long as it can be copolymerized with ethylene, propylene, and 4-methyl-1-pentene, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, and 1-heptene. Among these, crystalline polypropylene is particularly preferable as the olefin resin in the resin layer a. The olefinic resin may be a material that conforms to an olefinic elastomer described later. On the other hand, the olefinic resin herein does not include the styrene-based elastomer.
When the total resin layer a is 100% by mass, the content of the olefin-based resin in the resin layer a is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more. The content of the olefin-based resin in the resin layer a is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When the content of the olefin-based resin in the resin layer a is within the above range, the arithmetic average roughness Ra (a) on the resin layer a side can be desirably adjusted while ensuring good productivity, and thus, when the laminated film of the present invention is used as an adhesive film, the dependence of an adherend becomes small, and the adhesive property is further improved.
The resin layer a of the present invention preferably contains an olefin elastomer. The olefinic elastomer of the present invention is an olefinic resin having a storage elastic modulus G' (25) of 10MPa or less at 25 ℃ and 1Hz and/or an olefinic resin having a tan δ (25) of 0.5 or more at 25 ℃ and 1 Hz. That is, since the olefin elastomer is an olefin resin having a specific storage elastic modulus G' (25) and a specific tan δ (25), the material conforming to the olefin elastomer also conforms to the olefin resin. Further, since the olefinic resin does not include the styrene-based elastomer as described above, the olefinic elastomer as a part of the olefinic resin does not include the above-described styrene-based elastomer.
The resin layer a of the present invention preferably contains an olefin elastomer, and more preferably contains an olefin elastomer having tan δ (25) of 0.5 or more under conditions of 25 ℃ and 1 Hz. The tan δ (25) of the olefin elastomer is more preferably 1.0 or more, particularly preferably 1.5 or more. By incorporating the olefin-based elastomer in the resin layer a of the present invention, the probe tack maximum F and hp/bm obtained by nanoindentation on the resin layer a side can be desirably controlled.
Examples of the olefin-based elastomer shown in the resin layer a include amorphous polypropylene, low crystalline polypropylene, amorphous polybutene, and 4-methyl-1-pentene/α -olefin copolymer, and amorphous polypropylene and 4-methyl-1-pentene/α -olefin copolymer are preferably used.
When the resin layer a is set to 100 mass%, the content of the olefin-based elastomer in the resin layer a of the present invention is preferably 3 mass% or more, more preferably 5 mass% or more. The content of the olefin-based elastomer in the resin layer a is preferably 30 mass% or less, more preferably 20 mass%. When the content of the olefin-based elastomer in the resin layer a exceeds 30 mass%, the adhesion to the adherend may be too low.
From the viewpoint of improving the adhesion to an adherend, the resin layer a of the present invention preferably contains an adhesion promoter. As the tackifier, materials known in the present application can be used, and for example, materials commonly used in the present application, such as petroleum resins, terpene phenol resins, rosin resins, alkylphenol resins, xylene resins, and hydrides thereof, such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, and alicyclic copolymers, can be used. When the total resin layer a is 100 mass%, the content of the tackifier is preferably 5 mass% or more, and more preferably 10 mass% or more. When the total resin layer a is 100% by mass, the content of the tackifier is preferably 40% by mass or less, more preferably 30% by mass or less.
In the resin layer a of the present invention, the tackifier preferably contains at least an aromatic copolymer or an aliphatic/aromatic copolymer. The aromatic copolymer or aliphatic/aromatic copolymer is preferably an unhydrogenated or partially hydrogenated aromatic copolymer or an unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer. Here, the term "partially hydrogenated" means that the hydrogenation ratio is 1 mass% or more and less than 90 mass%; the term unhydrogenated means that the hydrogenation ratio is 0% by mass or more and less than 1% by mass. The hydrogenation ratio of the partially hydrogenated aromatic copolymer or the partially hydrogenated aliphatic/aromatic copolymer is more preferably less than 80 mass%, still more preferably less than 70 mass%, particularly preferably less than 50 mass%. By including the unhydrogenated or partially hydrogenated aromatic copolymer or the unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer in the resin layer a, the value of the probe tack maximum F can be preferably controlled, and thus the dependence on the adherend can be reduced. In particular, an unhydrogenated or partially hydrogenated aromatic copolymer or an unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer can be preferably used, and a material having a softening point of 80℃or higher can be used. That is, the resin layer a of the laminated film of the present invention particularly preferably contains an unhydrogenated or partially hydrogenated aromatic copolymer and/or an unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer having a softening point of 80 ℃. The hydrogenation rate can be determined by nuclear magnetic resonance spectroscopy 1 H-NMR spectrum) measurement.
In addition to the above, other components such as lubricants and other additives may be added to the resin layer a of the present invention as appropriate within a range that does not impair the object of the present invention.
The lubricant used in the resin layer a of the present invention is a material which can be used to prevent adhesion and blocking (blocking) of the chips to each other and to adhere to the chip surface when the chips (chips) of the styrene-based elastomer are formed, and which is added to the resin layer a by precipitating the chips on the surface thereof to adjust the adhesive force and to obtain good extrudability when the resin layer a is melt-extruded, and examples thereof include fatty acid metal salts such as calcium stearate and magnesium behenate, fatty acid amides such as ethylene bisstearamide and hexamethylene bisstearamide, and waxes such as polyethylene wax, polypropylene wax and paraffin wax. When the total resin layer a is 100% by mass, the content of the lubricant is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
Examples of the other additives include a crystal nucleating agent, an antioxidant, a heat resistance imparting agent, a weather resistance agent, an antistatic agent, and the like. These additives may be used alone or in combination, and the total content of these additives is preferably 3 mass% or less, more preferably 2 mass% or less, when the total mass of the resin layer a is 100 mass%.
The resin layer a of the present invention may contain particles for the purpose of controlling the arithmetic average roughness Ra (a) of the resin layer a. As the particles in the resin layer a, for example, inorganic particles, organic particles, or the like can be used, and when the particles are bonded to an adherend, the organic particles having a low possibility of damaging the adherend are preferable. Examples of the organic particles include acrylic resin particles, styrene resin particles, polyolefin resin particles, polyester resin particles, polyurethane resin particles, polycarbonate resin particles, polyamide resin particles, silicone resin particles, fluorine resin particles, and copolymerized resin particles of 2 or more monomers used for synthesizing the above resins, which may be used alone or in combination.
The average particle diameter of the particles in the resin layer a is preferably 0.1 μm or more, more preferably 1.0 μm or more, and even more preferably 2.0 μm or more, from the viewpoint of preferably controlling the arithmetic average roughness Ra (a) and the adhesive property of the resin layer a. The average particle diameter of the particles in the resin layer a is preferably 20.0 μm or less, more preferably 15.0 μm or less, and particularly preferably 10.0 μm or less.
The thickness of the resin layer a of the present invention is preferably 1.0 μm or more, more preferably 2.0 μm or more, from the viewpoint of securing adhesion to an adherend. In addition, from the viewpoint of reducing the dependence of the adherend and suppressing deterioration of adhesion with time or by heating after the adherend is attached, the thickness of the resin layer a is preferably 6.0 μm or less, more preferably 5.0 μm or less, and still more preferably 3.0 μm or less.
The laminated film of the present invention has a base material. The substrate referred to herein is a laminate having a finite thickness. The material of the base material is not particularly limited, and for example, an olefin resin or an ester resin can be used, and among them, an olefin resin is preferable as a main component from the viewpoints of productivity and processability. The main component as referred to herein means the component (component having a large content) having the highest mass% of all the components constituting the base material.
Examples of the olefin-based resin contained as the main component in the base material include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene/α -olefin copolymer, polypropylene, propylene/α -olefin copolymer, propylene/ethylene/α -olefin copolymer, ethylene/ethyl (meth) acrylate copolymer, ethylene/methyl (meth) acrylate copolymer, ethylene/n-butyl (meth) acrylate copolymer, and ethylene/vinyl acetate copolymer, and polypropylene is particularly preferably used. These may be used alone or in combination. The alpha-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, and 1-heptene. The olefinic resin may be a material that conforms to the olefinic elastomer. On the other hand, the olefinic resin herein does not include the styrene-based elastomer.
In the above-mentioned olefin-based resin, in order to control the arithmetic average roughness Ra (a) of the resin layer a within a desired range, it is also preferable for the base material to have a structure in which the domain component is dispersed with respect to the matrix resin as the main component. In order to form the above structure, for example, a method of using polypropylene as a main component constituting a base material and adding a polyolefin incompatible therewith; this is achieved using the methods commercially available for block polypropylene, so-called block copolymers or impact copolymers.
From the viewpoints of productivity, stability when laminated with an adjacent layer, and the like, the melt flow rate (MFR, measured at 230 ℃ and under 2.16 kg) of the resin used in the substrate of the present invention is preferably 0.5g/10 min or more, more preferably 1g/10 min or more, and still more preferably 2g/10 min or more. From the same viewpoints as described above, the MFR of the resin used for the base material is preferably 30g/10 min or less, more preferably 25g/10 min or less, and even more preferably 20g/10 min or less.
The substrate of the present invention preferably comprises a styrenic elastomer. That is, the base material of the laminated film of the present invention particularly preferably contains an olefin resin and a styrene elastomer. When the styrene-based elastomer is used in the resin layer a, the substrate and the resin layer a have improved affinity, and thus the interfacial adhesion between the substrate and the resin layer a can be improved. The content of the styrene-based elastomer in the base material is preferably 1 mass% or more, and more preferably 2 mass% or more, based on 100 mass% of the entire base material. The content of the styrene-based elastomer in the base material is preferably 20 mass% or less, more preferably 10 mass% or less. The styrene-based elastomer used in the base material of the present invention may be any known material, and for example, the same materials as those described above for the styrene-based elastomer used for the resin layer a may be used.
Examples of the method for incorporating the styrene-based elastomer into the substrate of the present invention include a method for recovering and re-starting the laminate film containing the styrene-based elastomer in the resin layer a, and a method for adding the recovered material to the substrate, and using the method is preferable from the viewpoints of resin recyclability and production cost reduction.
Further, various additives such as a crystal nucleating agent, a lubricant, an antioxidant, a weather resistant agent, an antistatic agent, and a pigment may be appropriately added to the substrate of the present invention within a range that does not impair the characteristics of the laminated film of the present invention. The substrate of the present invention may further contain an easily adhesive component for good lamination with the resin layer a of the present invention.
The thickness of the base material constituting the laminated film of the present invention can be appropriately adjusted according to the required characteristics of the laminated film, but is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more from the viewpoints of transportability and productivity at the time of production and use. From the same viewpoints as described above, the thickness of the base material constituting the laminated film is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less.
In the laminated film of the present invention, the resin layer B is preferably provided on the side of the substrate opposite to the side having the resin layer a. Here, the resin layer B is a layer disposed on the opposite side of the substrate from the side having the resin layer a, and is a layer containing at least a resin and being different from the resin layer a. That is, the resin layer B is a layer that does not satisfy at least 1 of the above (a), (B), and (c). The resin layer B preferably has releasability, and means a laminate having a limited thickness.
The resin layer B is not particularly limited as long as it is disposed on the side of the substrate opposite to the side having the resin layer a, and therefore, the substrate and the resin layer B may be disposed in direct contact with each other, or another layer may be disposed between the substrate and the resin layer B.
Examples of the resin used in the resin layer B of the laminated film of the present invention include an olefin resin and an ester resin, and among them, an olefin resin is preferable as a main component from the viewpoints of productivity and processability. The main component herein means the component (component having a large content) having the highest mass% among the components constituting the resin layer B of the laminated film.
Examples of the olefin-based resin suitable for the resin layer B include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene/α -olefin copolymer, polypropylene, propylene/α -olefin copolymer, propylene/ethylene/α -olefin copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl (meth) acrylate copolymer, ethylene/n-butyl (meth) acrylate copolymer, and ethylene/vinyl acetate copolymer. These may be used alone or in combination. The alpha-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, and 1-heptene. Among the polyolefin-based resins, a method in which polypropylene is the main component constituting the resin layer B and a polyolefin incompatible therewith is added is preferable from the viewpoint of imparting releasability by controlling the roughness of the resin layer B; commercially available block polypropylenes, so-called block copolymers or impact copolymers are used. As the olefin-based resin in the resin layer B, only 1 kind may be used, or 2 or more kinds may be used in combination. The olefinic resin may be a material that conforms to the olefinic elastomer. On the other hand, the olefinic resin herein does not include the styrene-based elastomer.
The melt flow rate (MFR, measured at 230 ℃ C., 2.16 kg) of the resin used in the resin layer B of the present invention is preferably 0.5g/10 min or more, more preferably 1g/10 min or more, and even more preferably 2g/10 min or more, from the viewpoints of productivity, stability at the time of lamination with an adjacent layer, and the like. From the same viewpoints as described above, the MFR of the resin used in the resin layer B is preferably 30g/10 min or less, more preferably 25g/10 min or less, and even more preferably 20g/10 min or less.
The material constituting the resin layer B may further contain a release agent such as a fluorine-based resin, a silicone-based resin, a fatty acid metal salt, a fatty acid amide, inorganic particles, or organic particles.
The laminated film of the present invention, which has the resin layer B, can be wound in a good winding posture when the laminated film is wound in a roll shape in the production step and the slitting step, and can be unwound well without the force when unwinding the film from the roll during slitting and during use becoming excessive. As another method for imparting releasability to the surface of the laminated film of the present invention on the opposite side from the resin layer a, there may be mentioned a method in which the above-mentioned slip agent or the like is added to the base material without providing the resin layer B, and a method in which the resin layer B is provided is more preferable from the viewpoints of productivity, cost and release effect.
The resin layer B of the laminated film of the present invention preferably has an arithmetic average roughness Ra (B) of 0.1 μm or more, more preferably 0.2 μm or more. The upper limit of the arithmetic average roughness Ra (B) of the resin layer B is not particularly set, but when it is 2 μm or more, there is a problem that the thickness accuracy and strength may be lowered.
The laminated film of the present invention has a base material and a resin layer a on at least one surface side of the base material, but as described above, it is preferable to have a resin layer B on the opposite surface side to the side having the resin layer a. The laminate film of the present invention may be provided with layers other than the base material, the resin layer a, and the resin layer B, within a range that does not impair the effects of the present invention, but it is preferable that the resin layer a and the resin layer B are located on the outermost surfaces of the laminate film. The thickness of the laminated film of the present invention is preferably 10 μm or more, more preferably 25 μm or more, from the viewpoints of transportability and productivity at the time of production and use. From the same viewpoint as described above, the thickness of the laminated film is preferably 250 μm or less, and more preferably 100 μm or less.
The method for producing the laminated film of the present invention will be described below.
The method for producing the laminated film of the present invention is not particularly limited, and for example, in the case of a 3-layer laminate structure having a resin layer a, a base material, and a resin layer B in this order, there can be mentioned: in the coextrusion method, the resin compositions constituting the respective layers are melt-extruded from respective extruders to integrate the layers in a nozzle; or a method in which the resin layer a, the base material, and the resin layer B are each melt-extruded and then laminated by a lamination method, and the like, and is preferably produced by a coextrusion method from the viewpoint of productivity. As the material constituting each layer, a material obtained by mixing the components by a henschel mixer or the like may be used, or a material obtained by kneading all or a part of the materials of each layer in advance may be used. As the coextrusion method, a known method such as a inflation method and a T-die method can be used, and a hot melt coextrusion method using a T-die method is particularly preferable from the viewpoints of excellent thickness accuracy and control of surface shape.
When the resin layer a, the base material, and the resin layer B are produced by the coextrusion method, the components are extruded by a melt extruder. In this case, the extrusion temperature of the resin layer a is preferably 250 ℃ or lower, more preferably 230 ℃ or lower, and further preferably 220 ℃ or lower. When the extrusion temperature of the resin layer a exceeds 250 ℃, the arithmetic average roughness Ra (a) of the resin layer a side may not be controlled within a desired range. The lower limit is not particularly set, but at a resin temperature lower than 180 ℃, the melt viscosity is too high, and thus productivity may be lowered.
The resin layer a, the base material and the resin layer B were laminated and integrated in a T die, and were co-extruded. Then, the film is cooled and solidified by a metal cooling roll, formed into a film shape, and wound into a roll shape, whereby a laminated film can be obtained.
The laminated film of the present invention can be used as a surface protective film for preventing scratches and dirt adhesion during transportation, for example, a surface protective film for optical use having irregularities on the surface, such as a diffusion plate and a prism sheet, in the production and processing of synthetic resin plates, metal plates, glass plates, and the like. Further, it can be preferably used as a surface protective film for adhering to an adherend having a surface in contact with the resin layer a and having an arithmetic average roughness Ra of 0.1 μm or more and 2 μm or less.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The measurement and evaluation of various physical properties were performed by the following methods.
(1) Surface roughness
The arithmetic average roughness Ra (a) on the resin layer a side, the arithmetic average roughness Ra (B) on the resin layer B, the arithmetic average roughness Ra (X) on the adherend X, the ten-point average roughness Rz (X) on the adherend X, the arithmetic average roughness Ra (Y) on the adherend Y, and the ten-point average roughness Rz (Y) on the adherend Y were measured 21 times at intervals along the length direction using a high-precision microform measurer (surfcorer ET 4000A) by the small-ban institute of co. The measurement was performed using a diamond needle having a tip radius of 2.0 μm, with a measurement force of 100. Mu.N and a cutoff value of 0.8 mm.
(2) Maximum value of probe viscosity
The maximum load at peeling was read from a SUS probe having a contact diameter of 5mm on the resin layer a side of the laminated film using an rhesa tack tester TAC1000 under the following conditions, and the load per unit area was calculated by dividing the area of the probe. The test was performed 5 times for each of the 1 laminated films, and the average value thereof was used as the probe tack maximum value F on the resin layer a side of the laminated film.
Temperature: 23 DEG C
Retention time after sample set up: for 5 minutes
Contact speed, peeling speed: 2 mm/s
Contact time: 2 seconds.
(3) Ratio hp/hm of residual displacement hp to maximum displacement hm determined by nanoindentation
Using a nanoindentation tester ENT-2100 manufactured by ELIONIX, indentation tests based on a load-unload test were performed 10 times for each 1 laminated film from the resin layer a side of the laminated film under the following conditions using a Berkovich indenter (front triangular pyramid). The hp/hm was obtained from the maximum displacement hm (unit μm) and the residual displacement hp (unit μm), and the average value of hp/hm obtained by 10 measurements was used as the value of hp/hm on the resin layer A side of the laminated film.
Temperature: 26 DEG C
Maximum load: 1mN
Load speed/unload speed: 0.1mN/s
Load at the beginning of the load-unload test: 0mN
Hold time at maximum load: 1 second
Surface detection mode: tilting mode
Surface detection threshold coefficient: 1.5
Spring correction: and correcting the spring in real time.
(4) Melting point
Using a stainless steel spatula, only the resin layer A was peeled from the laminated films shown in examples and comparative examples, and 5mg was weighed as a measurement sample. The sample was then sampled to an aluminum plate, and the temperature was raised from room temperature to 250℃at 20℃per minute under a nitrogen atmosphere using a differential scanning calorimeter (RDC 220 manufactured by the Seiko electronic industry), and the sample was kept at 250℃for 5 minutes, and then cooled to 20℃at 20℃per minute. Then, the temperature was again raised to 250℃at 40℃per minute, and the temperature of the endothermic peak obtained at this time was set as the melting point Tm of the resin layer A.
(5) Storage elastic modulus
Using a stainless steel spatula, only the resin layer A was peeled from the laminated films shown in examples and comparative examples, and the resultant film was melt-molded to a thickness of 1mm to prepare a sample. The measurement was performed by using a rheometer AR2000ex manufactured by TA Instruments, inc., cooling from 200℃to-20℃at a rate of 20℃per minute, then raising the temperature from-20℃to 100℃at a rate of 10℃per minute, and simultaneously subjecting the resultant sheet to dynamic shear deformation at a frequency of 1Hz and a strain of 0.01%, and using the storage elastic modulus G 'at 50℃during the temperature raising as the storage elastic modulus G' (A) of the resin layer A.
The pellets of the olefin resin and the styrene elastomer were melt-molded to a thickness of 1mm, and the storage elastic modulus G 'at 25℃during the temperature rise obtained by the measurement was defined as G' (25) in the same manner as described above.
(6) Thickness of (L)
An ultrathin slice having a cross section of 5mm in the width direction and thickness direction of the laminated film was produced by a slicing method, and platinum plating was performed on the cross section to produce an observation sample. Then, the cross section of the laminated film was observed with a field emission scanning electron microscope (S-4800) manufactured by Hitachi, and the thicknesses of the base material, the resin layer A and the resin layer B and the total thickness of the laminated film were measured from any place of the observed image at an acceleration voltage of 2.5 kV. Regarding the observation magnification, the thickness of the resin layer A, B was 5,000 times, and the thickness of the base material and the laminated film was 1,000 times. Further, the same measurement was performed 10 times in total, and the average value thereof was used as the thickness of each of the base material and the resin layer A, B, and the total thickness of the laminated film.
(7)tanδ(25)
After the pellets of the olefin-based resin were melt-molded to a thickness of 1mm, the temperature was lowered from 200℃to-20℃at a rate of 20℃per minute using a rheometer AR2000ex manufactured by TA Instruments, and then the pellets were dynamically shear-deformed at a frequency of 1Hz and a strain of 0.01% while being raised from-20℃to 40℃at a rate of 10℃per minute, whereby tan delta at 25℃during the temperature raising was defined as tan delta (25).
(8) Softening point of
For softening point, based on JIS K-2207: the measurement was performed by the global method specified in 2006.
(9) Melt Flow Rate (MFR)
The melt index apparatus manufactured by Toyo Seisakusho Co., ltd was used, and the temperature was 230℃and the load was 2.16kg/cm in accordance with JIS K7210-1997 2 Is measured under the condition of (2). The units are g/10 min.
(10) Lamination of laminated film and adherend
The resin layer A side and the adherend of the laminate films of examples and comparative examples were subjected to storage and adjustment for 24 hours at a temperature of 23℃and a relative humidity of 50% under a bonding pressure of 0.35MPa using a roll press (special pressure-bonding roll manufactured by Seikagaku An Tian refiner). As the adherend, 2 kinds of adherends having matte surfaces (adherend X, adherend Y) formed on the opposite surfaces of a prism sheet made of an acrylic resin were used. The arithmetic average roughness Ra (X) of the adherend X was 0.2 μm, the ten-point average roughness Rz (X) was 2.2 μm, the arithmetic average roughness Ra (Y) of the adherend Y was 0.4 μm, and the ten-point average roughness Rz (Y) was 3.2 μm.
(11) Adhesive force
After the bonded sample obtained in the above (10) was stored in a room at 23℃for 24 hours, the adhesive force was measured at a tensile speed of 300 mm/min and a peeling angle of 180℃using a tensile tester (ORIENTEC "TENSILON" Universal tester, co., ltd.). For one type of laminated film, the adhesive force of each of the adherends X and Y was measured. The adhesive force ratio of the adherend X and the adherend Y was calculated according to the following formula (P1).
Adhesive force ratio = adhesive force to adherend X/adhesive force to adherend Y. Formula (P1)
The adhesion force of the adherend X and the adherend Y was evaluated on the basis of the following 3 stages.
And (3) the following materials: 5g/25mm or more and less than 15g/25mm
O: 3g/25mm or more and less than 5g/25mm, or 15g/25mm or more and less than 25g/25mm
X: less than 3g/25mm, or more than 25g/25mm
The adhesion ratio of the adherend X and the adherend Y calculated based on the formula (P1) was expressed as a laminated film having more excellent dependence on the adherend as approaching 1, and was evaluated in the following 3 steps.
And (3) the following materials: 0.5 or more and less than 2.0
O: 0.3 or more and less than 0.5, or 2.0 or more and less than 4.0
X: less than 0.3, or 4.0 or more.
(12) Adhesion after heat preservation
Among the bonded samples obtained in the above (10), the sample bonded to the adherend X was stored in a hot air dryer at 50 ℃ for 100 hours, then stored at 23 ℃ under a relative humidity of 50% for 1 hour, and then the adhesive force was measured at a tensile speed of 300 mm/min and a peeling angle of 180 ° using a tensile tester (ORIENTEC "TENSILON" universal tester, inc.). The adhesive force after heat-preservation at 50℃and the adhesive force ratio after preservation at 23℃with respect to the adherend X calculated in the above (11) were calculated as the adhesive deterioration ratio according to the following formula (P2).
Adhesive deterioration ratio=adhesive force after storage at 50 ℃ per adhesive force after storage at 23 ℃ formula (P2)
The laminate film having a higher adhesive deterioration rate calculated based on the formula (P2) as compared with 1 and showing a higher stability after heat storage was evaluated in the following 3 stages.
And (3) the following materials: 0.5 or more and less than 1.6
O: 0.3 or more and less than 0.5, or 1.6 or more and less than 2.5
X: less than 0.3, or more than 2.5.
Example 1
The constituent resins of the respective layers were prepared as follows.
A base material: 97 mass% of a commercially available block polypropylene having an MFR of 8.5G/10 min and 3 mass% of a styrene-based elastomer (SEBS, manufactured by Asahi chemical Co., ltd., "TAFTEC" H1052, an MFR of 13G/10 min, and G' (25). Ltoreq.10 MPa) were used.
Resin layer a: a styrene-based elastomer (SEBS, manufactured by Asahi chemical Co., ltd., "TAFTEC" H1052, MFR13G/10 min, G '(25). Ltoreq.10 MPa), a high melt tension polypropylene (WAYMAX MFX8, manufactured by Japanese polypropylene Co., ltd., MFR 1G/10 min, G' (25) > 10MPa, tan delta (25) < 0.5) in an amount of 70% by mass, and a tackifier (an aromatic copolymer, softening point 115 ℃ C., hydrogenation rate < 90%) in an amount of 15% by mass were used, and the resultant was kneaded and flaked by a biaxial extruder in advance.
Resin layer B: 95 mass% of the same material as the commercially available block polypropylene for the substrate and 5 mass% of a commercially available silicone-based surface modifier as a release agent were used.
Next, the constituent resins of the respective layers were fed into respective extruders of a T-die composite film forming machine having 3 extruders, the discharge amounts of the respective extruders were adjusted so that the resin layer a became 3.5 μm, the base material became 30 μm, and the resin layer B became 5 μm, and the layers were laminated in this order, extruded from the composite T-die at an extrusion temperature of 200 ℃, cast on a roll with a surface temperature controlled at 40 ℃, molded into a film shape, and wound to obtain a laminated film.
Then, the obtained laminated film was evaluated by the above method. The thickness of the base material was 30. Mu.m, the thickness of the resin layer B was 5. Mu.m, and the arithmetic average roughness Ra (B) of the resin layer B was 0.20. Mu.m.
Example 2
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 70% by mass of a styrene-based elastomer ("TAFTEC" H1052), 15% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), 5% by mass of an adhesion promoter "Archon" M115, and 10% by mass of an adhesion promoter "FTR"8100 (aromatic copolymer, three-well chemical system, softening point 100 ℃ c., hydrogenation rate < 90%).
Example 3
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 60% by mass of a styrene-based elastomer ("TAFTEC" H1052), 15% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), 5% by mass of an adhesion promoter "Archon" M115, 10% by mass of an adhesion promoter "FTR"8100, and 10% by mass of an olefin-based elastomer (three well chemical system "absortome" EP-1001, mfr 10G/10 min, G' (25) 33mpa, tan δ (25) 1.9).
Example 4
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was 80% by mass of a styrene-based elastomer ("TAFTEC" H1052), 10% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), and 10% by mass of an adhesion promoter "Archon" M115.
Example 5
A laminate film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 70% by mass of a styrene-based elastomer ("TAFTEC" H1052), 10% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), 10% by mass of an adhesion promoter "Archon" M115, and 10% by mass of an olefin-based elastomer ("absortome" EP-1001).
Example 6
A laminate film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was 79.5 mass% of a styrene-based elastomer ("TAFTEC" H1052), 10 mass% of a high melt tension polypropylene ("WAYMAX" MFX 8), 10 mass% of an adhesion promoter "Archon" M115, and 0.5 mass% of a commercially available Ethylene Bis Stearamide (EBSA).
Example 7
Constitution ofThe resin layer A was composed of high-density polyethylene (Nipolon Hard 7300A, manufactured by Tosoh corporation, density 952 kg/m) 3 A laminate film was obtained in the same manner as in example 1, except that MFR 2G/10 min, G' (25) > 10MPa, and tan8 (25) < 0.5) were used in place of the high melt tension polypropylene ("WAYAX" MFX 8).
Example 8
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 70% by mass of a styrene-based elastomer ("TAFTEC" H1052), 15% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), and 15% by mass of an adhesion promoter "Archon" P125 (aromatic copolymer, softening point 125 ℃ and hydrogenation rate 90% or more, manufactured by the waste chemical industry).
Example 9
A laminated film was obtained in the same manner as in example 1, except that the thickness of the resin layer a was set to 2.8 μm.
Example 10
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 70% by mass of a styrene-based elastomer ("TAFTEC" H1052), 15% by mass of a high melt tension polypropylene ("WAYMAX" EX8000, MFR 1.5G/10 min, G' (25) > 10mpa, tan δ (25) < 0.5), 5% by mass of an adhesion promoter "Archon" M115, and 5% by mass of an adhesion promoter "FTR"8100 (three-well chemical, aromatic copolymer, softening point 100 ℃, hydrogenation rate < 90%).
Comparative example 1
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 90 mass% of a styrene-based elastomer ("TAFTEC" H1052) and 10 mass% of an adhesion promoter "Archon" M115.
Comparative example 2
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was 94% by mass of a styrene-based elastomer ("TAFTEC" H1052), 5% by mass of a high melt tension polypropylene ("WAYMAX" MFX 8), and 1% by mass of commercially available Ethylene Bis Stearamide (EBSA).
Comparative example 3
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 69 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" MFX 8), 15 mass% of an adhesion promoter ("Archon" M115), and 1 mass% of commercially available Ethylene Bis Stearamide (EBSA), and the thickness of the resin layer a was set to 2.5 μm.
Comparative example 4
A laminated film was obtained in the same manner as in example 1, except that the composition constituting the base material was 97% by mass of a homo-polypropylene (manufactured by sumitomo chemical corporation, "Nobrene" FLX80E4, MFR 8g/10 min), 3% by mass of a styrene-based elastomer ("TAFTEC" H1052), and the composition constituting the resin layer a was 20% by mass of a styrene-based elastomer ("TAFTEC" H1052) and 80% by mass of an olefin-based elastomer ("absortome" EP-1001).
Comparative example 5
A laminate film was obtained in the same manner as in example 1, except that the composition constituting the resin layer a was changed to 70 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" MFX3, MFR 9G/10 min, G' (25) > 10MPa, tan δ (25) < 0.5), and 15 mass% of an adhesion promoter "Archon" M115.
TABLE 1
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TABLE 2
Examples 1 to 9 satisfying the requirements of the present invention were laminated films having good adhesion to any adherend, low dependence on the adherend, and excellent in the inhibition of adhesive deterioration. On the other hand, in comparative examples 1 and 2, the laminated film had high adhesion to the adherend X, poor dependence on the adherend, and was a laminated film that was prone to adhesive deterioration. In comparative example 3, the adhesiveness to the adherend Y was insufficient. In comparative example 4, the adhesiveness of the laminated film to the adherend Y was insufficient, and also adhesive deterioration was liable to occur.
Industrial applicability
The laminated film of the present invention is excellent in adhesion properties such as adhesion dependence, and therefore can be preferably used for a surface protective film for products having various surface shapes and formed from various materials such as synthetic resins, metals, and glasses.

Claims (6)

1. A laminated film having a base material and a resin layer A on at least one surface side of the base material, wherein the laminated film satisfies the following (a), (b) and (c),
(a) The maximum value F of the probe tack at 23℃on the side of the resin layer A was 0.2g/mm 2 Above and 2.5g/mm 2 The following are set forth;
(b) The ratio (hp/hm) of the residual displacement hp (unit μm) to the maximum displacement hm (unit μm) of the resin layer A side when the nanoindentation-based load-unload test is performed at 26 ℃ under a maximum load of 1mN is 0.50 to 0.90;
(c) The resin layer A has a melting point Tm at 50 ℃ or higher,
wherein the resin layer A has a storage elastic modulus G' (A) of 1.5MPa or more at 50 ℃ and 1Hz,
the resin layer A contains 60 to 80 mass% of a styrene-based elastomer having a melt flow rate of 3g/10 min or more and 50g/10 min or less at 230 ℃ and 2.16kg, and the resin layer A contains 5 to 25 mass% of an olefin-based resin having a melt flow rate of 0.01g/10 min or more and 1.5g/10 min or less at 230 ℃ and 2.16 kg.
2. The laminated film according to claim 1, wherein an arithmetic average roughness Ra (a) of the resin layer a side is 0.20 μm or more and 0.80 μm or less.
3. The laminated film according to claim 1 or 2, wherein the resin layer a contains an olefin elastomer having a tan δ (25) of 0.5 or more under conditions of 25 ℃ and 1 Hz.
4. The laminated film according to claim 1 or 2, wherein the resin layer a contains an unhydrogenated or partially hydrogenated aromatic copolymer and/or an unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer having a softening point of 80 ℃ or higher.
5. The laminated film according to claim 1 or 2, wherein the base material comprises an olefin-based resin and a styrene-based elastomer.
6. The laminated film according to claim 1 or 2, wherein the substrate has a resin layer B on a side opposite to the side having the resin layer a.
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