CN113613890A - Laminated film - Google Patents

Laminated film Download PDF

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Publication number
CN113613890A
CN113613890A CN202080024223.5A CN202080024223A CN113613890A CN 113613890 A CN113613890 A CN 113613890A CN 202080024223 A CN202080024223 A CN 202080024223A CN 113613890 A CN113613890 A CN 113613890A
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China
Prior art keywords
resin layer
resin
mass
styrene
less
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Granted
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CN202080024223.5A
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Chinese (zh)
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CN113613890B (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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Publication of CN113613890A publication Critical patent/CN113613890A/en
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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]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a laminated film which exhibits uniform adhesive force to adherends having different surface shapes and can be widely used, and which has excellent adherend dependency. The laminated film comprises a substrate and a resin layer A on at least one surface side of the substrate, and satisfies the following (a), (b) and (c). (a) The maximum value F of the probe tack at 23 ℃ on the A side of the resin layer was 0.2g/mm2Above and 2.5g/mm2The following. (b) The resin layer (A) has a ratio (hp/hm) of a residual displacement hp (unit [ mu ] m) to a maximum displacement hm (unit [ mu ] m) when a nanoindentation-based load-shedding test is performed at 26 ℃ under a maximum load of 1mN, which is 0.50 to 0.90. (c) The resin layer A has a melting point Tm of 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 regardless of the shape of the adherend and is excellent in adherend dependency.
Background
In some cases, a product made of various materials such as synthetic resin, metal, and glass is handled by attaching a sheet or film for protection to the surface thereof in order to prevent scratches and stains generated in the processing step, the transportation step, and the storage. In general, a surface protective film or the like having an adhesive layer formed thereon is used as a support base material made of a thermoplastic resin or paper, and the adhesive layer is used by attaching the surface of the adhesive layer to an adherend.
In particular, in recent years, liquid crystal displays and touch panel devices have been spreading and are composed of a plurality of members such as optical sheets and optical films made of synthetic resins. Since it is necessary to minimize defects such as optical distortion, a surface protective film is often used to prevent scratches and stains that may cause the defects.
As the properties of such a surface protective film, the following properties are required: is not easily peeled from an adherend under environmental changes such as temperature and humidity or under a small stress level; when peeled off from an adherend, the adhesive and the adhesive component do not remain on the adherend; can be easily peeled off after being processed and used; and so on.
In the above optical member, there are commercially available adherends having irregularities on the surface, such as a diffuser plate and a prism sheet, and there is a demand for a surface protective film that exhibits uniform adhesive force to such adherends having different surface shapes and can be widely used, that is, a surface protective film having low adherend dependency.
As a surface protective film used for an adherend having a surface with irregularities, techniques described in patent documents 1 and 2 can be cited.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2007 and 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, which are surface protective films used for the above-mentioned adherend having an uneven surface, do not improve the difference in adhesive strength due to the difference in uneven surface of the adherend, that is, do not improve so-called adherend dependency.
Accordingly, the present invention has an object to solve the above problems. That is, a laminated film which exhibits uniform adhesive force to adherends having different surface shapes and can be widely used and which is excellent in adherend dependency is provided.
Means for solving the problems
The above problems can be solved by the following means.
A laminated film comprising a substrate and a resin layer A on at least one surface side of the substrate, wherein the laminated film satisfies the following (a), (b) and (c),
(a) the maximum value F of the probe tack at 23 ℃ on the A side of the resin layer was 0.2g/mm2Above and 2.5g/mm2In the following, the following description is given,
(b) the resin layer A side has a ratio (hp/hm) of a residual displacement hp (unit μm) to a maximum displacement hm (unit μm) when a nanoindentation-based load-shedding test is performed at 26 ℃ under a maximum load of 1mN of 0.50 to 0.90,
(c) the resin layer A has a melting point Tm of 50 ℃ or higher.
ADVANTAGEOUS EFFECTS OF INVENTION
In view of the above problems, the present invention can provide a laminated film which is excellent in adherend dependency and exhibits good adhesion characteristics 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 is a laminated film having 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 which is disposed on at least one surface side of the substrate and contains at least a resin, and satisfies the following (a), (b), and (c). The resin layer a may contain any 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). Preferred embodiments of the resin contained in the resin layer a will be described below.
(a) The maximum value F of the probe tack at 23 ℃ on the A side of the resin layer was 0.2g/mm2Above and 2.5g/mm2The following.
(b) The resin layer (A) has a ratio (hp/hm) of a residual displacement hp (unit [ mu ] m) to a maximum displacement hm (unit [ mu ] m) when a nanoindentation-based load-shedding test is performed at 26 ℃ under a maximum load of 1mN, which is 0.50 to 0.90.
(c) The resin layer A has a melting point Tm of 50 ℃ or higher.
In the laminated film of the present invention, the maximum value F of the probe tack at 23 ℃ on the resin layer A side is 0.2g/mm2Above and 2.5g/mm2The following. The maximum value F of the viscosity of the probe is more preferably 0.3g/mm2Above, more preferably 0.4g/mm2The above. Further, the maximum value F of the probe viscosity is more preferably 2.0g/mm2Hereinafter, more preferably 1.5g/mm2The following.
The maximum value F of the tack of the probe on the A side of the resin layer is less than 0.2g/mm2In the case where the laminate film of the present invention is used as a surface protective film, sufficient adhesion may not be obtainedForce. Further, the maximum value F of the probe tack on the resin layer A side is more than 2.5g/mm2In the case of (3), the adhesive force becomes too large, and particularly the adhesive force to an adherend having small surface roughness becomes large, and the adherend dependency becomes too large in some cases.
The maximum value F of the viscosity of the probe can be controlled by adjusting the material constituting the resin layer a, the flexibility, thickness, surface roughness, etc. described later, and for example, the maximum value F of the viscosity of the probe can be controlled to 0.2g/mm by reducing the maximum value F of the viscosity of the probe by a method of hardening the resin layer a, a method of reducing the thickness of the resin layer a, or a method of increasing the surface roughness of the resin layer a2Above and 2.5g/mm2The following.
In the laminate film of the present invention, the ratio (hp/hm., hereinafter referred to as hp/hm) of the residual displacement hp (unit μm) to the maximum displacement hm (unit μm) when a load-unload test by nanoindentation is performed under the conditions of 26 ℃ and a maximum load of 1mN on the resin layer a side is 0.50 or more and 0.90 or less. 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, when the resin layer a side of the multilayer film of the present invention is attached to an adherend, the resin layer a is difficult to follow the uneven portion of the adherend, the adhesive strength becomes too small, and particularly the adhesive strength to the adherend having a large surface roughness becomes small, and the adherend dependency becomes too large in some cases. When hp/hm is larger than 0.90, the adhesive force sometimes becomes too large. hp/hm can be controlled by a material constituting the resin layer a described later, or the like.
The resin layer a in the laminate 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. When the resin layer a of the present invention has 2 or more melting points, the melting point on 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 it is preferably substantially 180 ℃ or lower. When Tm is less than 50 ℃ or when the resin layer a does not have a melting point, the contact area between the resin layer a and the adherend may increase and the adhesive force may become too large when the laminated film of the present invention is stored at high temperature or over time after being attached to the adherend. When Tm is higher than 180 ℃, viscosity may be too high to deteriorate productivity when resin layer a is melt-extruded and molded.
As a method for making the resin layer a have Tm at 50 ℃ or higher, a method of adding a crystalline resin having a melting point of 50 ℃ or higher to a material constituting the resin layer a can be mentioned. That is, an embodiment in which the resin layer a contains a crystalline resin having a melting point of 50 ℃ or higher is exemplified. As a suitable crystalline resin contained in the resin layer a, for example, a crystalline olefin-based resin is preferable from the viewpoint of compatibility with other components used in the resin layer a and productivity. Specific examples of the olefin-based resin are described below.
The maximum value of probe tack F, hp/hm obtained by nanoindentation measurement, and the 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 is preferably 1.5MPa or more, more preferably 2.0MPa or more, and still more preferably 2.5MPa or more at 50 ℃ and 1 Hz. The upper limit of the storage elastic modulus G' (a) is not particularly set, but is preferably 30MPa from the viewpoint of adhesive properties such as adhesiveness.
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 an adherend and an increase in the adhesive strength when the laminated film of the present invention is stored at high temperature or over time after being attached to an 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 as an embodiment in which the resin layer a contains the styrene-based elastomer; a method of using a crystalline resin having a melting point of 50 ℃ or higher as the resin in the resin layer a; a method of using an unhydrogenated product or a partially hydrogenated product of an aromatic copolymer and/or an aliphatic/aromatic copolymer as the resin in the resin layer a; and so on.
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 adherend dependency, suppressing an increase in the contact area between the resin layer a and the adherend and suppressing an increase in the adhesive force when the laminated film of the present invention is stored at high temperature or over time after being attached to the adherend. The arithmetic average roughness ra (a) on the resin layer a side can be measured by the method described in 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 includes the substrate and the resin layer a on at least one surface side of the substrate. Here, the resin layer a means a layer having a limited thickness, and preferably has adhesiveness at normal temperature.
The term "the resin layer A has adhesiveness" means that the adhesive strength is 1g/25mm or more when the adhesive strength between the resin layer A and the SUS304 sheet is measured after the resin layer A side of the laminated film is attached to the SUS304 sheet with an arithmetic average roughness Ra of 0.2 μm and a ten-point average roughness Rz of 2.8 μm under a bonding pressure of 0.35MPa using a roll press (a special pressure-bonding roll manufactured by Antaha Seisakusho K.K.). 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 is not particularly limited as the adhesiveness of the resin layer a is higher, but when it exceeds 1000g/25mm, peeling may become difficult after application and workability may be deteriorated, so that the upper limit is preferably about 1000g/25 mm.
The resin layer a is not particularly limited in position as long as it is disposed on at least one side of the substrate, but is preferably disposed on at least one outermost layer of the laminate film of the present invention. By disposing the adhesive resin layer a on the outermost layer of the laminate film, the laminate 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 substrate, and therefore, the substrate and the resin layer a may be disposed so as to be in direct contact with each other, or another layer such as an easy-adhesion layer may be provided between the substrate and the resin layer a.
The resin layer a is not particularly limited as long as the effects of the present invention are 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, from the viewpoint of recyclability, a thermoplastic synthetic rubber-based adhesive is preferably used, and among them, a styrene-based elastomer is more preferred.
In the present invention, the styrene-based elastomer is 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. Examples of suitable styrene-based elastomers to be contained in the resin layer a include styrene/conjugated diene-based copolymers such as styrene/butadiene copolymer (SBR), styrene/isoprene/styrene copolymer (SIS), and styrene/butadiene/styrene copolymer (SBS), and hydrogenated products thereof (e.g., hydrogenated styrene/butadiene copolymer (HSBR), styrene/ethylene butylene/styrene triblock copolymer (SEBS), and styrene/ethylene butylene diblock copolymer (SEB)), and styrene/isobutylene-based copolymers (e.g., styrene/isobutylene/styrene triblock copolymer (SIBS), styrene/isobutylene diblock copolymer (SIB), or mixtures thereof). Among the above, styrene/conjugated diene copolymers such as styrene/butadiene/styrene copolymers (SBS) and hydrogenated products thereof, and styrene/isobutylene copolymers are preferably used. The styrene-based elastomer may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the styrene elastomer in the resin layer a, which is preferably contained in the resin layer a, is preferably 40 mass% or more, and more preferably 50 mass% or more, when the whole resin layer a is 100 mass%. The content of the styrene 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 content of the styrene elastomer in the resin layer a is within the above-described preferable range, good adhesive properties can be obtained when the laminate film of the present invention is used as an adhesive film.
The melt flow rate (MFR, measured at 230 ℃ C. and 2.16 kg) of the styrene 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 within the above range, the productivity is excellent, and when the laminated film of the present invention is used as a surface protective film, good adhesion characteristics are exhibited.
The styrene-based elastomer suitable for the resin layer a preferably contains a styrene component in an amount of 5 mass% or more, more preferably 8 mass% or more, based on 100 mass% of the entire styrene-based elastomer. The styrene-based elastomer preferably contains a styrene component in an amount of 55 mass% or less, more preferably 40 mass% or less. When the styrene component content in the styrene-based elastomer is within the above range, the laminated film of the present invention exhibits good adhesion when attached to an adherend, and exhibits good adhesive properties by suppressing adhesive residue and the like.
The resin layer A of the present invention preferably contains an olefin-based resin having a melt flow rate (MFR, measured at 230 ℃ C. and 2.16 kg) of 0.01g/10 min or more and 1.5g/10 min or less. By including the olefin resin having an MFR of 0.01g/10 min or more and 1.5g/10 min or less in the resin layer a, the elastomer which is the matrix component of the resin layer a is structured so as to have the olefin resin dispersed therein as a domain component (domain component), and the arithmetic average roughness ra (a) on the resin layer a side can be preferably suppressed, and the adherend dependency when the laminate film of the present invention is used as an adhesive film can be reduced. The MFR of the olefin resin in the resin layer A is more preferably 0.1g/10 min or more, and still more preferably 0.2g/10 min or more. The MFR of the olefin-based 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-based resin may aggregate to become FE. On the other hand, when the MFR exceeds 1.5g/10 min, the dispersibility of the domain component is improved, and it may be difficult to adjust the arithmetic average roughness ra (a) of the resin layer a to the range specified in the present application. Examples of the olefin-based resin suitably contained in the resin layer a include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultrahigh-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/ethyl (meth) acrylate polymer, ethylene/methyl (meth) acrylate copolymer, ethylene/n-butyl (meth) acrylate copolymer, ethylene/vinyl acetate copolymer, among which crystalline polypropylene, crystalline polyethylene, and crystalline polyethylene, Propylene-based resins such as low crystalline polypropylene, amorphous polypropylene, propylene/α -olefin copolymers, and propylene/ethylene/α -olefin copolymers. These olefin 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 olefin-based resin referred to herein may be a material that conforms to an olefin-based elastomer described later. On the other hand, the olefin-based resin referred to herein does not include the styrene-based elastomer.
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, assuming that the entire resin layer a is 100% by mass. 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 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 adjusted desirably while ensuring good productivity, whereby the adhesive properties are further improved such as reduced adherend dependency when the laminated film of the present invention is used as an adhesive film.
The resin layer a of the present invention preferably contains an olefin elastomer. The olefinic elastomer of the present invention means an olefinic resin having a storage elastic modulus G' (25) at 25 ℃ and 1Hz of 10MPa or less and/or an olefinic resin having a tan delta (25) at 25 ℃ and 1Hz of 0.5 or more. That is, since the olefin-based elastomer is an olefin-based resin having a specific storage elastic modulus G' (25) and a specific tan δ (25), the material conforming to the olefin-based elastomer also conforms to the olefin-based resin. As described above, since the olefin-based resin does not include the styrene-based elastomer, the olefin-based elastomer that is a part of the olefin-based resin does not include the styrene-based elastomer.
The resin layer a of the present invention preferably contains an olefinic elastomer, and among the olefinic elastomers, an olefinic elastomer having a tan δ (25), which is tan δ at 25 ℃ and 1Hz, of 0.5 or more is more preferred. The tan δ (25) of the olefinic elastomer is more preferably 1.0 or more, and particularly preferably 1.5 or more. By containing the olefin elastomer in the resin layer a of the present invention, the maximum value F of the probe tack and hp/bm obtained by nanoindentation on the resin layer a side can be controlled desirably.
Examples of the olefin 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.
The content of the olefinic elastomer in the resin layer a of the present invention is preferably 3 mass% or more, and more preferably 5 mass% or more, assuming that the resin layer a is 100 mass%. The content of the olefinic elastomer in the resin layer a is preferably 30% by mass or less, and more preferably 20% by mass. When the content of the olefin elastomer in the resin layer a exceeds 30 mass%, the adhesive force to the adherend may be too low.
The resin layer a of the present invention preferably contains an adhesion promoter in view of improving the adhesion to an adherend. As the tackifier, a material known in the present application can be used, and for example, a material generally used in the present application, such as a petroleum resin such as an aliphatic copolymer, an aromatic copolymer, an aliphatic/aromatic copolymer, and an alicyclic copolymer, a terpene resin, a terpene phenol resin, a rosin resin, an alkylphenol resin, a xylene resin, or a hydrogenated product thereof can be used. The content of the tackifier is preferably 5% by mass or more, and more preferably 10% by mass or more, when the entire resin layer a is 100% by mass. The content of the tackifier is preferably 40% by mass or less, and more preferably 30% by mass or less, when the entire resin layer a is 100% by mass.
The resin layer a of the present invention more preferably contains at least an aromatic copolymer or an aliphatic/aromatic copolymer in the tackifier. The aromatic copolymer or the aliphatic/aromatic copolymer is preferably an unhydrogenated or partially hydrogenated aromatic copolymer or an unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer. Here, the partial hydrogenation means that the hydrogenation rate is 1% by mass or more and less than 90% by mass; the term "non-hydrogenated" means that the hydrogenation rate is 0 mass% or more and less than 1 mass%. The hydrogenation ratio of the partially hydrogenated aromatic copolymer or the partially hydrogenated aliphatic/aromatic copolymer is more preferably less than 80% by mass, still more preferably less than 70% by mass, and particularly preferably less than 50% by mass. By including the non-hydrogenated or partially hydrogenated aromatic copolymer or the non-hydrogenated or partially hydrogenated aliphatic/aromatic copolymer in the resin layer a, the value of the probe tack maximum value F can be preferably controlled, and the adherend dependency can be reduced. In particular, a material having a softening point of 80 ℃ or higher can be preferably used as the unhydrogenated or partially hydrogenated aromatic copolymer or the unhydrogenated or partially hydrogenated aliphatic/aromatic copolymer. That is, the resin layer A of the laminate film of the present inventionThe copolymer 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 ℃ or higher. The hydrogenation rate can be determined by nuclear magnetic resonance spectroscopy (f)1H-NMR spectrum) was measured.
In addition to the above, other components such as a lubricant and other additives may be added to the resin layer a of the present invention as appropriate within a range not to impair the object of the present invention.
The lubricant used in the resin layer a of the present invention is a material that can be added to prevent the chips from sticking to each other and blocking (blocking) and adhering to the surfaces of the chips when the styrene-based elastomer chips (chips) are formed into chips, and the adhesion is adjusted by precipitating on the surface of the resin layer a, and can be used 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. 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, when the entire resin layer a is 100% by mass.
Examples of the other additives include a crystal nucleating agent, an antioxidant, a heat resistance imparting agent, a weather resistant agent, and an antistatic agent. These additives may be used alone or in combination, and the total content of these additives is preferably 3% by mass or less, more preferably 2% by mass or less, when the entire resin layer a is 100% by 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, and the like can be used, and when the particles are bonded to an adherend, the particles are preferably organic particles that have a low possibility of damaging the adherend. 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 copolymer resin particles of 2 or more monomers used for synthesis of the above resins, and these may be used alone or in combination.
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 0.1 μm or more, more preferably 1.0 μm or more, and further preferably 2.0 μm or more. 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, and more preferably 2.0 μm or more, from the viewpoint of securing adhesiveness to an adherend. The thickness of the resin layer a is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 3.0 μm or less, from the viewpoint of reducing the adherend dependency and suppressing the deterioration of adhesion with time or heating after the attachment to the adherend.
The laminated film of the present invention has a substrate. The substrate as used herein refers to a layer having a finite thickness. The material of the base material is not particularly limited, and for example, olefin-based resins and ester-based resins can be used, and among them, olefin-based resins are preferably used as the main component from the viewpoint of productivity and processability. The main component referred to herein is the component having the highest mass% (component having a large content) of all the components constituting the base material.
Examples of the olefin-based resin contained as a 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 among these, polypropylene is particularly preferably used. These may be used alone or in combination. The α -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 olefin-based resin referred to herein may be a material that conforms to the olefin-based elastomer described above. On the other hand, the olefin-based resin referred to herein does not include the styrene-based elastomer.
Among the olefin-based resins, the base material preferably has a structure in which the domain component is dispersed in the matrix resin as the main component, in order to control the arithmetic average roughness ra (a) of the resin layer a within a desired range. In order to form the above structure, for example, a method of using polypropylene as a main component constituting the base material and adding a polyolefin incompatible therewith; this is achieved using commercially available block polypropylene, so-called block copolymers or impact copolymers.
The melt flow rate (MFR, measured at 230 ℃ and 2.16 kg) of the resin used in the base material 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 viewpoints of productivity, stability when laminated with adjacent layers, and the like. From the same viewpoint 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 still more preferably 20g/10 min or less.
The substrate of the present invention preferably comprises a styrenic elastomer. That is, the substrate of the laminated film of the present invention particularly preferably contains an olefin-based resin and a styrene-based elastomer. When the base material contains a styrene elastomer and the styrene elastomer is used for the resin layer a, the affinity between the base material and the resin layer a is improved, and the interfacial adhesion between the base material 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, when the base material is 100 mass% as a whole. The content of the styrene-based elastomer in the base material is preferably 20 mass% or less, and more preferably 10 mass% or less. As the styrene-based elastomer used for the substrate of the present invention, known materials can be used, and for example, the same styrene-based elastomer as that suitable for the resin layer a can be used.
The method of incorporating a styrene-based elastomer into a substrate of the present invention includes, for example, a method of recovering and recycling the laminated film containing a styrene-based elastomer in the resin layer a, and adding the obtained recovered material to the laminated film and using the same for a substrate, and this method is preferably employed from the viewpoint of recycling of the resin and reduction in production cost.
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 added to the base material of the present invention as appropriate within a range that does not impair the characteristics of the laminate film of the present invention. The substrate of the present invention may further contain an easy-adhesion component for good lamination with the resin layer a of the present invention.
The thickness of the substrate constituting the laminated film of the present invention may be appropriately adjusted depending on 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 during production and use, and productivity. From the same viewpoint 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 still more preferably 80 μm or less.
The laminate film of the present invention preferably has a resin layer B 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 including at least a resin and 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, which means a layer having a limited thickness.
The resin layer B is not particularly limited as long as it is disposed on the opposite side of the substrate from the surface 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 provided between the substrate and the resin layer B.
Examples of the resin used for the resin layer B of the laminated film of the present invention include olefin resins and ester resins, and among them, olefin resins are preferably used as a main component from the viewpoint of productivity and processability. The main component herein refers to the component having the highest mass% (component having a large content) among the components constituting the resin layer B of the laminated film.
Examples of the olefin 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 (meth) 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 α -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 resins, a method of adding a polyolefin incompatible with polypropylene as a main component constituting the resin layer B is preferable from the viewpoint of imparting releasability by controlling the roughness of the resin layer B; commercially available block polypropylene, so-called block copolymers or impact copolymers are used. The olefin resin in the resin layer B may be used alone or in combination of 2 or more. The olefin-based resin referred to herein may be a material that conforms to the olefin-based elastomer described above. On the other hand, the olefin-based resin referred to herein does not include the styrene-based elastomer.
The melt flow rate (MFR, measured at 230 ℃ and 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 still more preferably 2g/10 min or more, from the viewpoint of productivity, stability when laminated with an adjacent layer, and the like. From the same viewpoint 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 still more preferably 20g/10 min or less.
The material constituting the resin layer B may further contain, as a release agent, a slipping 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 has the resin layer B, and therefore, when the laminated film is wound in a roll shape in the production process and the slitting process, the laminated film can be wound in a good winding posture, and the laminated film can be unwound satisfactorily without an excessive force when the film is unwound from a roll in slitting or use. As another method for imparting releasability to the surface of the laminate film of the present invention opposite to the resin layer a, there is a method of adding the above-mentioned slipping agent or the like to the substrate without providing the resin layer B, and the method of providing the resin layer B is more preferable from the viewpoints of productivity, cost, and mold release effect.
The arithmetic average roughness ra (B) of the resin layer B of the laminate film of the present invention is preferably 0.1 μm or more, and 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 the strength are lowered.
The laminate film of the present invention has a substrate and a resin layer a on at least one surface side of the substrate, but as described above, preferably has a resin layer B on the side opposite to the side having the resin layer a. The laminated film of the present invention may be provided with other layers than the substrate, the resin layer a, and the resin layer B within a range not impairing the effects of the present invention, but the resin layer a and the resin layer B are preferably located on the outermost surface of the laminated film. The thickness of the laminated film of the present invention is preferably 10 μm or more, and more preferably 25 μm or more, from the viewpoint 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 explained 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 laminated structure having a resin layer a, a substrate and a resin layer B in this order, there are included: the so-called coextrusion method in which the resin compositions constituting the respective layers are melt-extruded from separate extruders and laminated and integrated in a nozzle; or a method in which the resin layer a, the substrate, and the resin layer B are melt-extruded and then laminated by a lamination method, and the like, and from the viewpoint of productivity, the resin layer a, the substrate, and the resin layer B are preferably produced by a coextrusion method. The materials constituting the respective layers may be those obtained by mixing the respective components in a henschel mixer or the like, or those obtained by kneading all or a part of the materials of the respective layers in advance. As the coextrusion method, a known method such as an inflation method or a T-die method can be used, and a hot-melt coextrusion method using a T-die method is particularly preferable from the viewpoint of excellent thickness accuracy and control of the surface shape.
In the case of the production by the coextrusion method, the components constituting the resin layer a, the substrate, and the resin layer B 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) on the resin layer a side may not be controlled within a desired range. The lower limit is not particularly set, but when the resin temperature is lower than 180 ℃, the melt viscosity is too high, and thus the productivity may be lowered.
The resin layer A, the substrate and the resin layer B were laminated and integrated inside a T-die, and then co-extruded. Then, the film was cooled and solidified by a metal cooling roll, formed into a film shape, and wound into a roll shape, thereby obtaining a laminated film.
The laminate film of the present invention can be used as a surface protective film for producing and processing a synthetic resin plate, a metal plate, a glass plate, or the like, and preventing scratches and adhesion of dirt during transportation, and is preferably used as a surface protective film for optical use having irregularities on the surface, such as a diffuser plate and a prism sheet. In addition, the resin composition can be preferably used as a surface protective film for use in attaching to an adherend having a surface with an arithmetic average roughness Ra of 0.1 μm or more and 2 μm or less on a surface in contact with the resin layer a.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The measurement and evaluation of various physical properties were carried out 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) of the resin layer B, the arithmetic average roughness ra (X) of the adherend X, the ten point average roughness rz (X) of the adherend X, the arithmetic average roughness ra (Y) of the adherend Y, and the ten point average roughness rz (Y) of the adherend Y were measured 21 times at intervals of 10 μm in the longitudinal direction with respect to the range of 2mm in the width direction and 0.2mm in the length direction of the laminated film and the adherend in accordance with JIS B0601-1994 using a high-precision fine shape measuring instrument (surf core ET4000A) manufactured by shinkawa research. The measurement force was 100 μ N and the cutoff value was 0.8mm using a diamond needle having a tip radius of 2.0 μm.
(2) Maximum value of probe viscosity
Using a tack tester TAC1000 made of RHESCA, an SUS probe having a diameter of 5mm was contacted from the resin layer a side of the laminated film under the following conditions, and then the maximum load at the time of peeling was read and divided by the area of the probe to calculate the load per unit area. The test was conducted 5 times for each 1 laminated film, and the average value thereof was defined as the maximum value F of the probe tack on the resin layer a side of the laminated film.
Temperature: 23 deg.C
Retention time after sample set-up: 5 minutes
Contact speed, peeling speed: 2 mm/sec
Contact time: for 2 seconds.
(3) Ratio hp/hm of residual displacement hp to maximum displacement hm determined by nanoindentation
Using a nanoindenter test ENT-2100 manufactured by ELIONIX, 10 indentation tests by a load-unload test were performed from the resin layer a side of the laminated film under the following conditions using a Berkovich indenter (tip triangular pyramid) for each 1 laminated film. The hp/hm was determined from the obtained maximum displacement hm (unit μm) and residual displacement hp (unit μm), and the average of the hp/hm obtained by 10 measurements was defined as the hp/hm value on the resin layer a side of the laminate film.
Temperature: 26 deg.C
Maximum load: 1mN
Load speed-unload speed: 0.1mN/s
Load-load at the start of the unloading test: 0mN
Hold time at maximum load: 1 second
Surface detection mode: inclined mode
Surface detection threshold coefficient: 1.5
And (3) spring correction: and (5) real-time spring correction.
(4) Melting Point
Only the resin layer a was scraped from the laminated films shown in examples and comparative examples using a spatula made of stainless steel, and 5mg of the scraped resin was weighed as a measurement sample. Then, the sample was sampled on an aluminum pan, and the temperature was raised from room temperature to 250 ℃ at 20 ℃ per minute in a nitrogen atmosphere by using a differential scanning calorimeter (RDC 220 manufactured by Seiko electronics industries, Ltd.), and the temperature was lowered to 20 ℃ at 20 ℃ per minute after being held at 250 ℃ for 5 minutes. Then, the temperature was again raised to 250 ℃ at 40 ℃/min, and the temperature of the endothermic peak obtained at this time was defined as the melting point Tm of the resin layer a.
(5) Storage modulus of elasticity
Only the resin layer a was scraped out of the laminated films shown in examples and comparative examples using a stainless steel spatula, and the resin layer a was melt-molded to a thickness of 1mm to prepare samples. The measurement was carried out by using a rheometer AR2000ex manufactured by TA Instruments, cooling the resin from 200 ℃ to-20 ℃ at a rate of 20 ℃/min, then heating the resin from-20 ℃ to 100 ℃ at a rate of 10 ℃/min, and dynamically shear-deforming the resin at a frequency of 1Hz and a strain of 0.01%, and using a storage elastic modulus G 'at 50 ℃ during the heating as a storage elastic modulus G' (A) of the resin layer A.
Further, pellets of an olefin-based resin or a styrene-based elastomer were melt-molded into a thickness of 1mm, and the storage elastic modulus G 'at 25 ℃ in the course of temperature rise obtained by the measurement was defined as G' (25).
(6) Thickness of
An ultrathin section having a cross section of 5mm in the width direction-thickness direction of the laminated film was produced by the slicing method, and platinum was plated on the cross section to prepare an observation sample. Next, the cross section of the laminated film was observed at an accelerating voltage of 2.5kV using a field emission scanning electron microscope (S-4800) manufactured by hitachi, and the thickness of the substrate, the resin layer a, and the resin layer B, and the total thickness of the laminated film were measured from any place of the observation image. The observation magnification was 5,000 times when the thickness of the resin layer A, B was measured, and 1,000 times when the thicknesses of the substrate and the laminated film were measured. Further, the same measurement was performed 10 times in total, and the average value thereof was used as the thickness of each of the substrate, 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 reduced from 200 ℃ to-20 ℃ at a rate of 20 ℃/min using a rheometer AR2000ex manufactured by TA Instruments, and then the temperature was increased from-20 ℃ to 40 ℃ at a rate of 10 ℃/min, and the dynamic shear deformation was performed at a frequency of 1Hz and a strain of 0.01%, and tan δ at 25 ℃ during the temperature increase was defined as tan δ (25).
(8) Softening point
For the softening point, based on JIS K-2207: the measurement was performed by the ring and ball method defined in 2006.
(9) Melt Flow Rate (MFR)
The melt index instrument manufactured by Toyo Seiki Seisaku-Sho K.K. was used according to JIS K7210-1997 at a temperature of 230 ℃ and a load of 2.16kg/cm2Under the conditions of (1). The units are g/10 min.
(10) Lamination of laminated film to adherend
The resin layer a side of the laminate film of examples and comparative examples and the adherend were adhered to each other using a roll press (special pressure-bonding roll manufactured by anguan seiko, manufactured by kayaku) at an adhesion pressure of 0.35Mpa, and the laminate film was stored at a temperature of 23 ℃ and a relative humidity of 50% and adjusted for 24 hours. As the adherend, 2 kinds of adherends having matte surfaces (adherend X, adherend Y) formed on the opposite surface of the prism sheet made of acrylic resin were used. The adherend X had an arithmetic average roughness Ra (X) of 0.2. mu.m, a ten-point average roughness rz (X) of 2.2. mu.m, and the adherend Y had an arithmetic average roughness Ra (Y) of 0.4. mu.m, a ten-point average roughness rz (Y) of 3.2. mu.m.
(11) Adhesive force
The bonded sample obtained in (10) above was stored in a room at 23 ℃ for 24 hours, and then an adhesive force was measured at a tensile speed of 300 mm/min and a peel angle of 180 ° using a tensile tester (ORIENTEC "TENSILON" Universal tester). The adhesive strength of each of the adherend X and the adherend Y was measured for one of the laminated films. The adhesion 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 adhesive strength of the adherend X and the adherend Y was evaluated on the basis of the following 3 stages.
Very good: 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 closer the adhesive force ratio of the adherend X and the adherend Y calculated based on the formula (P1) is to 1, the more excellent the adherend dependency is, and the evaluation is performed in the following 3 stages.
Very good: 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 more than 4.0.
(12) Adhesion after heat preservation
Of the bonded samples obtained in (10), a 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 subjected to a tensile testing machine (ORIENTEC "TENSILON" Universal testing machine) at a tensile speed of 300 mm/min and a peel angle of 180 ℃ to measure an adhesive force. The adhesive force after heat storage at 50 ℃ and the adhesive force ratio after storage at 23 ℃ to the adherend X calculated in (11) above were calculated as the adhesive force deterioration ratio in accordance with the following formula (P2).
Adhesive deterioration ratio-adhesive force after storage at 50 ℃ C./adhesive force after storage at 23 ℃ C. -. formula (P2)
The closer to 1 the adhesion degradation ratio calculated based on the formula (P2), the more excellent the stability after heat preservation, and the evaluation was made in the following 3 stages.
Very good: 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.
Base material: 97% by mass of a commercially available block polypropylene having an MFR of 8.5G/10 min and 3% by mass of a styrene-based elastomer (SEBS, "TAFTEC" H1052 manufactured by Asahi Kasei corporation, MFR13G/10 min, G' (25) ≦ 10MPa) were used.
Resin layer A: a styrene-based elastomer (SEBS manufactured by Asahi Kasei Co., Ltd., "TAFTEC" H1052, MFR13G/10 min, G '(25) ≦ 10MPa), 15 mass% high melt tension polypropylene (WAYMAX MFX8 manufactured by Japan Polypropylene corporation, MFR 1G/10 min, G' (25) > 10MPa, tan delta (25) < 0.5), and 15 mass% tackifier (Archon M115 manufactured by Kawakawa chemical industry, aromatic copolymer, softening point 115 ℃, hydrogenation rate < 90%) were used in an amount of 70 mass%, and the resulting mixture was kneaded and fragmented in advance by a twin-screw extruder.
Resin layer B: 95 mass% of the same material as that of the commercially available block polypropylene used 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-making machine having 3 extruders, and 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 a composite T-die at an extrusion temperature of 200 ℃, cast on a roll whose surface temperature was controlled at 40 ℃, formed into a film, and wound to obtain a laminated film.
Then, the obtained laminated film was evaluated by the above-described method. The thickness of the substrate was 30 μm, the thickness of the resin layer B was 5 μm, 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 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), 5 mass% of an adhesion promoter "Archon" M115, and 10 mass% of an adhesion promoter "FTR" 8100 (manufactured by mitsui chemical corporation, aromatic copolymer, softening point 100 ℃, hydrogenation ratio < 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 60 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), 5 mass% of a tackifier "Archon" M115, 10 mass% of a tackifier "FTR" 8100, and 10 mass% of an olefin-based elastomer ("absotromer" EP-1001 manufactured by mitsui chemical corporation, MFR 10G/10 min, G' (25)33MPa, and 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 changed to 80 mass% of a styrene-based elastomer ("TAFTEC" H1052), 10 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), and 10 mass% of a tackifier "Archon" M115.
(example 5)
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 mass% of a styrene-based elastomer ("TAFTEC" H1052), 10 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), 10 mass% of a tackifier "Archon" M115, and 10 mass% of an olefin-based elastomer ("absottomer" EP-1001).
(example 6)
A laminated 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" MFX8), 10 mass% of an adhesion promoter "Archon" M115, and 0.5 mass% of a commercially available Ethylene Bis Stearamide (EBSA).
(example 7)
In the composition constituting the resin layer A, high density polyethylene (Nipolon Hard 7300A, manufactured by Tosoh, density 952 kg/m) was used3A laminated 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 ("WAYMAX" 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 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), and 15 mass% of a tackifier "Archon" P125 (aromatic copolymer, manufactured by seikagawa chemical industry, having a softening point of 125 ℃ and a hydrogenation ratio of 90% or more).
(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 changed 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 mass% of a styrene-based elastomer ("TAFTEC" H1052), 15 mass% of a high melt tension polypropylene ("WAYMAX" EX8000, MFR 1.5G/10 min, G' (25) > 10MPa, tan. delta. (25) < 0.5), 5 mass% of an adhesion promoter "Archon" M115, and 5 mass% of an adhesion promoter "FTR" 8100 (manufactured by Mitsui chemical Co., Ltd., aromatic copolymer, softening point 100 ℃ and hydrogenation ratio < 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 a tackifier "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 mass% of a styrene-based elastomer ("TAFTEC" H1052), 5 mass% of a high melt tension polypropylene ("WAYMAX" MFX8), and 1 mass% of a 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" MFX8), 15 mass% of a tackifier ("Archon" M115), and 1 mass% of a commercially available Ethylene Bis Stearamide (EBSA), and the thickness of the resin layer a was changed to 2.5 μ M.
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 mass% of homopolypropylene ("Nobrene" FLX80E4, manufactured by sumitomo chemical corporation, MFR 8g/10 min) and 3 mass% of a styrene-based elastomer ("TAFTEC" H1052), and the composition constituting the resin layer a was 20 mass% of a styrene-based elastomer ("TAFTEC" H1052) and 80 mass% of an olefin-based elastomer ("absottomer" EP-1001).
Comparative example 5
A laminated film was obtained in the same manner as in example 1 except that the composition constituting the resin layer a was 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 a tackifier "Archon" M115.
[ Table 1]
Figure BDA0003277538510000241
[ Table 2]
Figure BDA0003277538510000251
Examples 1 to 9 satisfying the requirements of the present invention were laminated films having good adhesion to any adherend, small adherend dependency, and excellent adhesion deterioration suppression. On the other hand, in comparative examples 1 and 2, the laminated film had high adhesion to the adherend X, poor adherend dependency, and was likely to suffer adhesion deterioration. In comparative example 3, the adhesiveness to the adherend Y was not sufficient. In comparative example 4, the adhesiveness of the laminate film to the adherend Y was insufficient, and the adhesive deterioration was also likely to occur.
Industrial applicability of the invention
The laminate film of the present invention is excellent in adhesion characteristics such as adherend dependency, and therefore can be suitably used as a surface protective film for products having various surface shapes and made of various materials such as synthetic resins, metals, and glasses.

Claims (9)

1. A laminated film comprising a substrate and a resin layer A on at least one surface side of the substrate, wherein the laminated film satisfies the following (a), (b) and (c),
(a) the maximum value F of the probe tack at 23 ℃ on the A side of the resin layer was 0.2g/mm2Above and 2.5g/mm2The following;
(b) a ratio (hp/hm) of a residual displacement hp (unit μm) to a maximum displacement hm (unit μm) when a nanoindentation-based load-unload test is performed at 26 ℃ under a maximum load of 1mN on the resin layer A side is 0.50 or more and 0.90 or less;
(c) the resin layer A has a melting point Tm of 50 ℃ or higher.
2. The laminate film according to claim 1, wherein the resin layer A has a storage elastic modulus G' (A) of 1.5MPa or more at 50 ℃ and 1 Hz.
3. The laminate film according to claim 1 or 2, 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.
4. The laminate film according to any one of claims 1 to 3, wherein the resin layer A contains a styrene-based elastomer having a melt flow rate of 3g/10 minutes or more and 50g/10 minutes or less at 230 ℃ and 2.16 kg.
5. The laminate film according to any one of claims 1 to 4, wherein the resin layer A comprises 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 ℃ under 2.16 kg.
6. The laminate film according to any one of claims 1 to 5, wherein the resin layer A comprises an olefinic elastomer having a tan δ (25) of 0.5 or more at 25 ℃ and 1 Hz.
7. The laminate film according to any one of claims 1 to 6, 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.
8. The laminate film according to any one of claims 1 to 7, wherein the substrate comprises an olefin-based resin and a styrene-based elastomer.
9. The laminate film according to any one of claims 1 to 8, wherein the substrate has a resin layer B on a side opposite to a side having the resin layer A.
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