WO2021193223A1 - Film stratifié et rouleau de film - Google Patents

Film stratifié et rouleau de film Download PDF

Info

Publication number
WO2021193223A1
WO2021193223A1 PCT/JP2021/010534 JP2021010534W WO2021193223A1 WO 2021193223 A1 WO2021193223 A1 WO 2021193223A1 JP 2021010534 W JP2021010534 W JP 2021010534W WO 2021193223 A1 WO2021193223 A1 WO 2021193223A1
Authority
WO
WIPO (PCT)
Prior art keywords
laminated film
resin layer
less
olefin
mass
Prior art date
Application number
PCT/JP2021/010534
Other languages
English (en)
Japanese (ja)
Inventor
田邨奈穂子
山中康平
大倉正寿
安岡哲
中道夏樹
長榮克和
井上則英
Original Assignee
東レフィルム加工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レフィルム加工株式会社 filed Critical 東レフィルム加工株式会社
Priority to JP2021515238A priority Critical patent/JP6966025B1/ja
Publication of WO2021193223A1 publication Critical patent/WO2021193223A1/fr

Links

Images

Classifications

    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/10—Copolymers of styrene with conjugated dienes
    • 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]

Definitions

  • the present invention relates to a laminated film and a film roll having sufficient followability to an adherend having a curved surface shape.
  • Products made of various materials such as synthetic resin, metal, and glass may be handled by attaching a surface protection sheet or film to prevent scratches and stains that occur during the processing / transportation process and storage.
  • a surface protective film or the like in which an adhesive layer is formed on a supporting base material made of a thermoplastic resin or paper is used, and the adhesive layer surface is attached to an adherend and used.
  • the characteristics required for such a surface protective film include sticking to adherends having various surface shapes as well as smooth surfaces, environmental changes such as temperature and humidity, and the degree to which a small stress is applied. Then, it does not peel off from the adherend, no adhesive component remains on the adherend when peeled from the adherend, and can be easily peeled off from the adherend after processing or use.
  • Products that require a surface protective film include, for example, display members, automobile members, building material members, optical instruments, and lenses for eyeglasses.
  • lenses for optical instruments and eyeglasses have a curved surface shape, so strong adhesive strength is required to protect the surface along that shape, but strong adhesive strength and peelability after use It was very difficult to achieve both non-contamination on the adherend.
  • Patent Documents 1 and 2 disclose a surface protective film for a spectacle lens that does not require a release film.
  • Patent Documents 1 and 2 satisfy the followability of a lens having a curved surface shape.
  • an object of the present invention is to provide a laminated film and a film roll having sufficient followability to an adherend having a curved surface shape.
  • a preferred embodiment of the laminated film and film roll of the present invention is as follows.
  • the tensile elastic modulus at 23 ° C. and 300 mm / min is 60 MPa or more and 300 MPa or less.
  • the laminated film according to any one of (1) to (3) which has a peeling force of 7.0 N / 25 mm or less.
  • the styrene-based elastomer has a shear storage elastic modulus at 25 ° C. and 1 Hz of 0.1 MPa or more and 0.8 MPa or less, and a tan ⁇ peak temperature at 1 Hz of ⁇ 40 ° C. or higher, according to (5).
  • Laminated film is a shear storage elastic modulus at 25 ° C. and 1 Hz of 0.1 MPa or more and 0.8 MPa or less, and a tan ⁇ peak temperature at 1 Hz of ⁇ 40 ° C. or higher, according to (5).
  • the layer including the surface of the laminated film on the side opposite to the surface having the resin layer A is selected from the group consisting of an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, and an ionomer.
  • the layer including the surface of the laminated film on the side opposite to the surface having the resin layer A contains an olefin resin containing 4-methyl-1-pentene units (1) to (17). ).
  • the schematic diagram which shows the measuring method in the adhesion evaluation with a low melting point alloy.
  • the present invention is preferably a laminated film having a base material and a resin layer A and satisfying the following (a) and (b).
  • the tensile elastic modulus at 23 ° C. and 300 mm / min is 60 MPa or more and 300 MPa or less.
  • the resin layer A is a layer containing at least a resin, and preferably has adhesiveness at 23 ° C. A preferred embodiment of the resin contained in the resin layer A will be described later.
  • the laminated film of the present invention has an indentation residual displacement rate (hereinafter, indentation residual displacement) when a load unloading test by nanoindentation is performed from the surface of the laminated film on the side having the resin layer A at 26 ° C. and a maximum load of 1 mN. It is important that the rate) is 40% or more.
  • the surface of the laminated film on the side having the resin layer A is the surface when the laminated film is viewed in the order of air, resin layer A, and base material when the laminated film is placed in air. To say.
  • the indentation residual displacement rate can be measured by the method described in Examples.
  • the indentation residual displacement rate is 40% or more, when the laminated film of the present invention is attached to an adherend having a curved surface shape, it is possible to prevent the laminated film from floating from the adherend because it cannot follow the curved surface. However, the adherend can be sufficiently protected. From the same viewpoint, the indentation residual displacement rate is preferably 50% or more, more preferably 60% or more.
  • the indentation residual displacement rate can be controlled by adjusting the material and thickness constituting the resin layer A and the base material. For example, by using a material that is easily plastically deformed in the resin layer A and the base material, the indentation residual displacement rate is increased. can do. Specifically, for example, when the entire resin layer A is 100% by mass, the styrene-based elastomer is contained in an amount of 50% by mass or more and 80% by mass or less, and the tackifier is contained in an amount of 15% by mass or more and less than 30% by mass.
  • the shear storage elastic modulus G'(25) of the styrene-based elastomer at 25 ° C. and 1 Hz is more preferably 1.0 MPa or less, further preferably 0.8 MPa or less, and particularly preferably 0.5 MPa or less.
  • the tackifier an aliphatic copolymer, an aliphatic / aromatic copolymer, a terpene resin, a terpene phenol resin, or a hydrogenated product thereof is preferably used.
  • the laminated film of the present invention has a tensile elastic modulus of 60 MPa or more and 300 MPa or less at 23 ° C. and 300 mm / min.
  • the tensile elastic modulus can be calculated by performing a tensile test in the mechanical direction (MD direction) and the width direction (TD direction) of the laminated film by the method described in the examples. If the MD direction and TD direction of the laminated film are unknown, the tensile elastic modulus can be calculated by the following method. First, a total of four tensile tests are performed at intervals of 45 ° starting from an arbitrary direction in the film surface, five times each.
  • the arithmetic mean value in each direction is obtained, and the arithmetic mean value (average for a total of 10 times) in the direction having the highest tensile elastic modulus and the direction of 90 ° with respect to this direction is the tensile elasticity of the laminated film of the present invention. Let it be a rate.
  • the rigidity of the laminated film can be made appropriate, and when the laminated film of the present invention is bonded to an adherend having a curved surface shape, it cannot follow the curved surface and is laminated. Since it is possible to prevent the film from floating from the adherend, the adherend can be sufficiently protected.
  • the tensile elastic modulus at 23 ° C. and 300 mm / min is more preferably 200 MPa or less.
  • the tensile elastic modulus is 60 MPa or more, it is possible to secure the handleability at the time of manufacturing or use.
  • the tensile elasticity can be adjusted by adjusting the material and thickness of the base material and the resin layer A, which will be described later. However, if the tensile elasticity is controlled to 60 MPa or more and 300 MPa or less, and productivity and recyclability are taken into consideration.
  • the resin used for the base material is mainly composed of low-density polyethylene having a density of about 910 kg / m 3 to 940 kg / m 3 or a polyethylene-based resin such as medium-density polyethylene or linear low-density polyethylene, and the resin layer A. It can be preferably mentioned that the thickness ratio of the above is 25% or less of the entire laminated film.
  • the main component described here means the one having the highest mass% (the one having a large content) among all the components constituting the base material.
  • the laminated film of the present invention has a tensile residual stress ratio (hereinafter referred to as a tensile residual stress ratio) of 70% or less after 10 seconds when a tensile stress relaxation test is performed at 23 ° C., 300 mm / min, and a strain of 40%. Is preferable.
  • the tensile residual stress ratio can be calculated by measuring the laminated film in the mechanical direction (MD direction) and the width direction (TD direction) by the method described in the examples. When the MD direction and TD direction of the laminated film are unknown, the tensile residual stress ratio can be calculated by the following method.
  • the tensile residual stress ratios in a total of four directions are evaluated five times at intervals of 45 ° starting from an arbitrary direction in the film surface. After that, the arithmetic mean value in each direction is obtained, and the arithmetic mean value (average for a total of 10 times) in the direction having the highest tensile residual stress ratio and the direction of 90 ° with respect to this direction is the tension of the laminated film of the present invention. Let it be the residual stress ratio.
  • the tensile residual stress ratio is more preferably 60% or less.
  • the lower limit of the tensile residual stress ratio is preferably 20% or more, more preferably 30% or more from the viewpoint of handleability during manufacturing or use.
  • the tensile residual stress rate can be controlled by adjusting the material and thickness of the resin layer A and the base material, which will be described later, but the tensile residual stress rate is increased by using a material that is easily plastically deformed as the base material. be able to. Specific examples thereof include a method using an olefin-based elastomer having a tan ⁇ (25) of 1.5 or more at 25 ° C. and 1 Hz, and among them, 4-methyl-methyl having a tan ⁇ (25) of 1.5 or more at 1 Hz.
  • a method in which 1-pentene / ⁇ -olefin copolymer is used in an amount of 5% by mass or more in 100% by mass of the base material can be preferably mentioned.
  • one surface of the laminated film and the other surface are bonded at 23 ° C. and 0.1 MPa, stored at 23 ° C. for 24 hours, and then stored in a room at 23 ° C. for 1 hour.
  • the 180 ° peeling force (hereinafter referred to as the peeling force after storage at 23 ° C.) is preferably 6.0 N / 25 mm or less, more preferably 4.0 N / 25 mm or less, and further preferably 3.0 N / 25 mm or less. , 2.0 N / 25 mm or less is particularly preferable. From the viewpoint of handleability, it is preferable that the peeling force is low, and a lower limit is not particularly provided.
  • the practical lower limit is 0.2N. It is about / 25 mm.
  • the laminated film of the present invention one surface of the laminated film and the other surface are bonded at 23 ° C. and 0.1 MPa, stored at 50 ° C. for 24 hours, and then further in a room at 23 ° C.
  • the 180 ° peeling force after storage for hours (hereinafter referred to as the peeling force after storage at 50 ° C.) is preferably 7.0 N / 25 mm or less, more preferably 5.0 N / 25 mm or less, 4 It is more preferably 0.0 N / 25 mm or less, and most preferably 3.0 N / 25 mm or less.
  • the peeling force after storage at 50 ° C. is within the above preferable range, the laminated film of the present invention can be easily used even when it is transported and stored for a long period of time after being wound into a roll without using a release film. It becomes possible to unwind to.
  • the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. can be measured by the method described in Examples.
  • the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. are the material of the resin layer A described later or the material of the layer including the surface opposite to the surface having the resin layer A.
  • the surface roughness it can be controlled within the above preferable range.
  • the ten-point average roughness Rz of the surface opposite to the surface having the resin layer A which will be described later, is set to 5 ⁇ m or more, and the peak of tan ⁇ at 1 Hz of the resin layer A is ⁇ 40 ° C.
  • the above styrene-based elastomer is contained, and in addition, the layer including the surface on the side opposite to the surface having the resin layer A is a 4-methyl-1-pentene / ⁇ -olefin copolymer.
  • a method including the above can be mentioned more preferably.
  • the laminated film of the present invention preferably has an arithmetic mean waviness Wa of 0.20 ⁇ m or less on the surface of the laminated film on the side having the resin layer A.
  • the arithmetic mean swell Wa to 0.20 ⁇ m or less, the contact area with the adherend when the laminated film of the present invention is attached to the adherend is improved, and good adhesion is exhibited. Can be done.
  • the laminated film around the lens may peel off and float.
  • the arithmetic mean waviness Wa to 0.20 ⁇ m or less, the adhesion immediately after bonding is excellent, and the peeling of the laminated film after bonding can be suppressed.
  • the arithmetic mean swell Wa is the transportability of the film during manufacturing and processing, and the blocking of the surface on the side having the resin layer A and the surface on the opposite side when the laminated films are stacked and stored in a single sheet or roll shape. From the viewpoint of suppressing the above, 0.05 ⁇ m or more is preferable.
  • the arithmetic mean waviness Wa can be controlled by adjusting the material used for the resin layer A, which will be described later, the peeling force of the surface on the side opposite to the surface having the resin layer A, and the manufacturing conditions of the laminated film. ..
  • a method of reducing the arithmetic mean waviness Wa a method of selecting a combination having good compatibility with the material used for the resin layer A, a method of using a styrene-based elastomer having a wide molecular weight distribution, and a method of adding a lubricant component. And so on.
  • the methods for producing the laminated film of the present invention there is a method of winding the laminated film in a roll shape in a state where the surface on the side opposite to the surface having the resin layer A is laminated at the time of production.
  • the surface on the side opposite to the surface having the resin layer A is peeled off, but by lowering the peeling force at this time, the resin layer at the time of peeling is peeled off. Deformation of the surface on the side having A can be suppressed, and the arithmetic mean waviness Wa can be lowered.
  • a method of adjusting the peeling force to control the arithmetic mean waviness Wa is preferable, and a method of increasing the cohesive force of the resin layer A or lowering the peeling force of the surface opposite to the surface having the resin layer A is lowered. The method of doing is more preferable.
  • the arithmetic mean swell Wa can be measured by the method described in the examples.
  • the surface of the laminated film on the side having the resin layer A has adhesiveness at 23 ° C.
  • the adhesive strength to the polycarbonate plate measured by the method described in the examples is preferably 2.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more, and 5.0 N / 25 mm or more. It is more preferably 25 mm or more.
  • the adhesive strength to the polycarbonate plate is preferably 20 N / 25 mm or less, more preferably 15 N / 25 mm or less, still more preferably 12 N / 25 mm or less, from the viewpoint of suppressing contamination of the adherend after peeling the laminated film.
  • the adhesiveness of the resin layer A and the adhesive strength to the polycarbonate plate can be adjusted depending on the material and thickness used for the resin layer A and the material used for the base material.
  • a preferred embodiment of the laminated film of the present invention has a base material and a resin layer A as described above.
  • the position of the resin layer A is not particularly limited, but it is preferably arranged on at least one outermost layer of the laminated film of the present invention.
  • the adhesive resin layer A By arranging the adhesive resin layer A on the outermost layer of the laminated film, the laminated film can be bonded to the adherend via the resin layer A.
  • the resin layer A is not particularly limited as long as it is arranged on the side of at least one surface of the base material. Therefore, the base material and the resin layer A may be arranged so as to be in direct contact with each other, or the base material and the resin layer A may be arranged. Another layer, such as an easy-adhesion layer, may be provided between them.
  • the resin layer A is not particularly limited as long as the effects of the present invention are not impaired, and may contain elastomers such as acrylic, silicone, natural rubber, and synthetic rubber. Among these, from the viewpoint of recyclability, the resin layer A preferably contains a thermoplastic synthetic rubber-based pressure-sensitive adhesive, and more preferably contains a styrene-based elastomer.
  • the styrene-based elastomer refers to a resin having a shear storage elastic modulus G'(25) at 25 ° C. and 1 Hz of 10 MPa or less and containing at least a styrene component as a monomer component.
  • examples of the styrene-based elastomer include styrene-butadiene copolymer (SBR) and the like.
  • Styrene-conjugated diene copolymers such as styrene / isoprene / styrene copolymer (SIS) and styrene / butadiene / styrene copolymer (SBS) and their hydrogenated products can be used.
  • SIS isoprene / styrene copolymer
  • SBS styrene / butadiene / styrene copolymer
  • HBR hydrogenated styrene / butadiene copolymer
  • SEBS st
  • a system copolymer can be preferably used.
  • styrene / isobutylene-based copolymer for example, a styrene / isobutylene / styrene triblock copolymer (SIBS), a styrene / isobutylene block copolymer (SIB), or a mixture thereof is preferably used.
  • SIBS styrene / isobutylene / styrene triblock copolymer
  • SIB styrene / isobutylene block copolymer
  • styrene-conjugated diene-based copolymers such as styrene-butadiene-styrene copolymer (SBS), their hydrogenated products, and styrene-isobutylene-based copolymers are more preferably used. be able to. Further, only one type of styrene-based elastomer may be used, or two or more types may be used in combination.
  • the indentation elastic modulus of the laminated film of the present invention is controlled to 40% or more to prevent the laminated film from floating from the adherend because it cannot follow the curved surface when it is attached to an adherend having a curved surface shape.
  • the shear storage elastic modulus G'(25) of the styrene-based elastomer at 25 ° C. and 1 Hz is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, further preferably 0.8 MPa or less, and 0. 5.5 MPa or less is particularly preferable.
  • the shear storage elastic modulus G'(25) of the styrene-based elastomer is preferably 0.05 MPa or more. , 0.1 MPa or more is more preferable. Further, from the viewpoint of controlling the indentation elastic modulus of the laminated film of the present invention to 40% or more, and further controlling the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. within the above-mentioned preferable range, the styrene-based film is used.
  • the peak of tan ⁇ at 1 Hz of the elastomer is preferably ⁇ 40 ° C. or higher, more preferably ⁇ 30 ° C. or higher. Further, from the viewpoint of adhesion to the adherend and stability of physical properties at room temperature, the peak of tan ⁇ at 1 Hz of the styrene-based elastomer is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, and 5 ° C. The following is more preferable, and ⁇ 20 ° C. or lower is particularly preferable.
  • the shear storage elastic modulus and tan ⁇ can be measured by the method described in Examples.
  • the content of the styrene-based elastomer in the resin layer A is preferably 40% by mass or more, more preferably 50% by mass or more, when the entire resin layer A is 100% by mass.
  • the content of the styrene-based elastomer in the resin layer A is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
  • the melt flow rate (measured at MFR, 230 ° C., 2.16 kg) of the styrene-based elastomer preferably contained in the resin layer A is preferably 3 g / 10 minutes or more from the viewpoint of productivity during the production of the laminated film. , 7 g / 10 minutes or more is more preferable, and 10 g / 10 minutes or more is further preferable.
  • the MFR of the styrene-based elastomer enhances the cohesive force of the resin layer A, suppresses adhesive residue, and peels off the surface of the laminated film on the side opposite to the surface having the resin layer A. From the viewpoint of suppressing deformation of the surface on the side having the layer A, 60 g / 10 minutes or less is preferable, 30 g / 10 minutes or less is more preferable, and 15 g / 10 minutes or less is further preferable.
  • the content of the styrene component 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, assuming that the entire styrene-based elastomer is 100% by mass.
  • the content of the styrene component in the styrene-based elastomer is preferably 55% by mass or less, more preferably 40% by mass or less.
  • the resin layer A in the present invention preferably contains a tackifier from the viewpoint of enhancing the adhesiveness to the adherend.
  • a tackifier those known for this purpose can be used.
  • an aliphatic copolymer, an aromatic copolymer, an aliphatic / aromatic copolymer, or an alicyclic copolymer can be used.
  • Petroleum resins such as polymers, terpene-based resins, terpenephenol-based resins, rosin-based resins, alkylphenol-based resins, xylene-based resins, and hydrogenated products thereof, which are generally used in this application, can be used.
  • aliphatic copolymers aliphatic / aromatic copolymers, terpene resins, from the viewpoint of excellent compatibility with the styrene-based elastomer and increasing the indentation residual displacement rate of the laminated film, Terpenphenol-based resins and hydrogenated products thereof are preferably used.
  • the content of the tackifier is preferably 10% by mass or more, more preferably 15% by mass or more, assuming that the entire resin layer A is 100% by mass.
  • the content of the tackifier is preferably 40% by mass or less, more preferably less than 30% by mass, further preferably 25% by mass or less, and particularly preferably 20% or less, when the entire resin layer A is 100% by mass. preferable.
  • the content of the tackifier to 40% by mass or less, the cohesive force of the resin layer A is enhanced, the adhesive residue is suppressed, and the surface of the laminated film is opposite to the surface of the laminated film having the resin layer A.
  • the side surface is peeled off, the deformation of the side surface having the resin layer A can be suppressed.
  • the resin layer A in the present invention preferably contains an olefin-based elastomer.
  • the olefin-based elastomer referred to in the present invention is an olefin-based resin having a storage elastic modulus G'(25) at 25 ° C. and 1 Hz of 10 MPa or less, and / or tan ⁇ (25) at 25 ° C. and 1 Hz is 0. .
  • the olefin-based elastomer referred to in the present invention does not include the above-mentioned styrene-based elastomer.
  • the resin layer A in the present invention preferably contains an olefin-based elastomer, and among the above-mentioned olefin-based elastomers, an olefin-based elastomer having a tan ⁇ (25) of 0.5 or more at 25 ° C. and 1 Hz is used. It is more preferable to include it.
  • the tan ⁇ (25) of the olefin elastomer is more preferably 1.0 or more, and particularly preferably 1.5 or more.
  • the upper limit of tan ⁇ (25) of the olefin-based elastomer is not particularly set, but is substantially 3.0 or less.
  • olefin-based elastomer examples include amorphous polypropylene, low-crystalline polypropylene, amorphous polybutene, and olefin-based resins containing 4-methyl-1-pentene units, and examples thereof include amorphous resins.
  • Polypropylene and olefin resins containing 4-methyl-1-pentene units can be preferably used.
  • the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. are reduced to the preferable range, and the adherend has a curved surface shape.
  • the resin layer A in the present invention contains a 4-methyl-1-pentene / ⁇ -olefin copolymer.
  • the content of the olefin-based elastomer in the resin layer A in the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, when the resin layer A is 100% by mass.
  • the content of the olefin elastomer in the resin layer A is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the resin layer A in the present invention preferably contains an olefin resin other than the above-mentioned olefin elastomer from the viewpoint of controlling the viscoelasticity of the resin layer to adjust the adhesive force and obtaining good film forming property.
  • the olefin resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene / ⁇ -olefin copolymer, crystalline polypropylene, and low-crystalline resin.
  • the ⁇ -olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and for example, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, etc. And 1-heptene can be preferably mentioned.
  • low-density polyethylene linear low-density polyethylene, ethylene / ⁇ -olefin copolymer, propylene / ⁇ -olefin copolymer, polybutene, crystalline polypropylene, low crystalline polypropylene, and amorphous
  • sex polypropylene and 4-methyl-1-pentene / ⁇ -olefin copolymers are preferably used.
  • the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, when the resin layer A is 100% by mass. preferable.
  • the resin layer A in the present invention appropriately contains resin components other than the above-mentioned styrene-based elastomer, tackifier, and olefin-based elastomer, and other components such as particles, fillers, and additives as long as the object of the present invention is not impaired. It may be added.
  • additives for example, lubricants, crystal nucleating agents, antioxidants, heat-resistant imparting agents, weather-resistant agents, antistatic agents and the like can be preferably mentioned. These additives may be used alone or in combination, but the total content of these additives is preferably 3% by mass or less, preferably 2% by mass, assuming that the entire resin layer A is 100% by mass. % Or less is more preferable.
  • the thickness of the resin layer A in the present invention is preferably 2.0 ⁇ m or more, more preferably 5.0 ⁇ m or more, and further follows the adherend having a curved surface shape from the viewpoint of ensuring the adhesiveness to the adherend. From the viewpoint of enhancing the properties, 10 ⁇ m or more is particularly preferable, and 15 ⁇ m or more is most preferable. Further, the thickness of the resin layer A is from the viewpoint of productivity and cost, from the viewpoint of ensuring handleability during manufacturing and use without excessively reducing the tensile elastic modulus of the laminated film, and when peeling from the adherend. From the viewpoint of suppressing adhesive residue, it is preferably 35 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the thickness ratio of the resin layer A is 25% or less of the entire laminated film.
  • the thickness ratio is based on ⁇ m. According to this aspect, the tensile elastic modulus of the laminated film of the present invention can be adjusted within the above preferable range.
  • the laminated film of the present invention has a base material.
  • the base material refers to a sheet-like material having a finite thickness.
  • the material of the base material is not particularly limited, but for example, an olefin resin or an ester resin can be used. Among them, it is preferable to use an olefin resin as a main component from the viewpoint of productivity and processability, and a polyethylene resin is used. It is more preferable to use it as a main component.
  • the main component described here means the one having the highest mass% (the one having a large content) among all the components constituting the base material.
  • Examples of the olefin-based resin contained in the base material as the main component include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and low-crystalline or amorphous ethylene / ⁇ -olefins.
  • the main components should be low-density polymer with a density of about 910 kg / m 3 to 940 kg / m 3 , medium-density polyethylene, and linear low-density polyethylene. Is the most preferable.
  • the above-mentioned olefin-based resin may be used alone or in combination.
  • the ⁇ -olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and for example, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, etc. And 1-heptene can be preferably mentioned.
  • the olefin-based resin referred to here may correspond to the above-mentioned olefin-based elastomer.
  • the base material in the present invention preferably contains the olefin-based elastomer.
  • tan ⁇ 25
  • tan ⁇ 25
  • tan ⁇ 25
  • olefin-based elastomers are preferable, olefin-based elastomers having a tan ⁇ (25) of 1.0 or more are more preferable, and olefin-based elastomers having a tan ⁇ (25) of 1.5 or more are even more preferable.
  • the upper limit of tan ⁇ (25) of the olefin-based elastomer is not particularly set, but is substantially 3.0 or less.
  • the olefin-based elastomer having a tan ⁇ (25) of 0.5 or more the same olefin-based elastomer suitable for the resin layer A described above can be used, and for example, amorphous polypropylene, low crystalline polypropylene, and non-crystalline polypropylene can be used. Examples thereof include crystalline polypropylene and olefin resins containing 4-methyl-1-pentene units, and among them, olefin resins containing 4-methyl-1-pentene units are preferably used.
  • an olefin resin containing 4-methyl-1-pentene unit as the base material, not only the tensile residual stress ratio of the laminated film of the present invention can be controlled to 70% or less, but also 4-methyl-1 is applied to the resin layer A.
  • an olefin resin containing a penten unit is used, the interlayer adhesion between the base material and the resin layer A is enhanced, and when the laminated film of the present invention is attached to the adherend and then peeled off from the adherend, the resin is peeled off from the adherend. It is possible to suppress peeling between the base material and the resin layer A and suppress adhesive residue on the adherend.
  • the interlayer adhesion between the base material and the resin layer B is enhanced, and the laminated film of the present invention is attached to the adherend.
  • the peeling between the base material and the resin layer B can be suppressed, and the base material and the resin layer A can be suppressed from remaining on the adherend.
  • the olefin resin containing the 4-methyl-1-pentene unit described above has low compatibility with the tackifier suitable for the resin layer A, the tackifier of the resin layer A is transferred to the base material.
  • the most preferable olefin-based elastomer for the substrate of the present invention is an olefin-based resin containing 4-methyl-1-pentene units having a tan ⁇ (25) of 1.5 or more. Further, from the same viewpoint as described above, a 4-methyl-1-pentene / ⁇ -olefin copolymer is particularly preferably used as the olefin resin containing 4-methyl-1-pentene unit.
  • the content of the olefin-based elastomer in the base material is preferably 5% by mass or more, preferably 5% by mass or more, when the entire base material is 100% by mass, from the viewpoint of controlling the tensile residual stress ratio of the laminated film of the present invention to 70% or less. More preferably by mass% or more.
  • the content of the olefin elastomer in the base material is preferably 40% by mass or less, preferably 30% by mass or less, from the viewpoint of ensuring handleability during manufacturing and use without excessively lowering the tensile elastic modulus of the laminated film. Is more preferable.
  • the melt flow rate of the olefin resin suitable for the base material in the present invention is 0 from the viewpoints of productivity and stability during lamination with adjacent layers. .5 g / 10 minutes or more is preferable, 1 g / 10 minutes or more is more preferable, and 2 g / 10 minutes or more is further preferable.
  • the MFR of the olefin resin used as the base material is preferably 30 g / 10 minutes or less, more preferably 25 g / 10 minutes or less, and even more preferably 20 g / 10 minutes or less.
  • the base material in the present invention preferably contains a styrene-based elastomer. That is, the base material of the laminated film of the present invention preferably contains an olefin-based resin, more preferably contains an olefin-based resin and a styrene-based elastomer, and is an olefin-based resin excluding the olefin-based elastomer and the olefin-based elastomer. , And styrene-based elastomers are particularly preferable.
  • the styrene-based elastomer in the base material when the styrene-based elastomer is used in the resin layer A, the affinity between the base material and the resin layer A is improved, and the interfacial adhesive force between the base material and the resin layer A is enhanced. , It is possible to prevent the occurrence of adhesive residue when peeling from the adherend.
  • the content of the styrene-based elastomer in the base material is preferably 1% by mass or more, more preferably 2% by mass or more.
  • the content of the styrene-based elastomer in the base material is preferably 20% by mass or less, more preferably 10% by mass or less.
  • styrene-based elastomer used for the base material in the present invention known ones can be used, and for example, the same styrene-based elastomer suitable for the resin layer A described above can be used.
  • a method of incorporating the styrene-based elastomer in the base material in the present invention for example, a method of recovering the present laminated film containing the styrene-based elastomer in the resin layer A, adding a recycled raw material to be used as the base material, is used. It can be mentioned, and adopting this method is a preferable method from the viewpoint of resin recycling and reduction of production cost.
  • the base material of the present invention various additives such as a crystal nucleating agent, a lubricant, an antioxidant, a weathering agent, an antistatic agent, and a pigment are appropriately added as long as the characteristics of the laminated film of the present invention are not impaired. It may be added. Further, the base material in the present invention may further contain an easy-adhesion component for satisfactorily laminating with the resin layer A in 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 10 ⁇ m or more from the viewpoint of transportability and productivity during manufacturing and use. 20 ⁇ m or more is more preferable, and 40 ⁇ m or more is further preferable. Further, the thickness of the base material constituting the laminated film is preferably 200 ⁇ m or less from the same viewpoint as described above.
  • the laminated film of the present invention can be preferably used as a surface protective film for spectacle lenses because it has sufficient followability to an adherend having a curved surface shape.
  • the laminated film of the present invention can be used, for example, in the following process.
  • a plastic eyeglass lens is usually polished to a surface finish.
  • a low melting point alloy is cast in a block shape on the back surface of the lens polishing surface and integrated with the lens, and this block shape low melting point is obtained.
  • a method is used in which a rotating shaft is attached to an alloy and the polishing surface is rotated by the rotation of the rotating shaft for polishing.
  • a removable surface protective film is attached to the back surface in order to protect the lens surface and ensure the adhesion with the alloy.
  • the adhesive surface of the surface protective film adheres to the back surface of the lens during polishing and has the function of easily peeling off after polishing, and the surface opposite to the adhesive surface of the surface protective film is at a temperature equal to or higher than the melting point of the low melting point alloy. It has heat resistance that allows casting of low melting point alloys, and also has the function of adhering to the cooled and solidified low melting point alloys.
  • the laminated film of the present invention it is preferable to use an olefin resin having a polar group in the layer including the surface on the side opposite to the surface on the side having the resin layer A.
  • the base material contains an olefin resin having a polar group.
  • the laminated film of the present invention has the resin layer A, the base material, and the resin layer B described later in this order, at least the resin layer B contains an olefin resin having a polar group. Is preferable.
  • olefin-based resin having a polar group examples include a copolymer of ethylene and a monomer having a polar group, acid-modified polyethylene, and acid-modified polypropylene, and specifically, ethylene / ethyl (meth) acrylate common weight.
  • ethylene / methyl (meth) acrylate copolymer ethylene / (meth) acrylic acid ester copolymer such as ethylene / n-butyl (meth) acrylate copolymer, ethylene / acrylic acid copolymer, ethylene / methacryl
  • acid copolymers ionomers, maleic anhydride-modified polypropylene, and maleic anhydride-modified polyethylene.
  • ethylene / acrylic acid copolymer ethylene / methacrylic acid copolymer, ionomer, maleic anhydride-modified polypropylene, and maleic anhydride-modified polyethylene. It is preferable to use more than one species, more preferably one or more selected from an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, and an ionomer, and an ethylene / acrylic acid copolymer and / or ethylene. -It is more preferable to use a methacrylic acid copolymer.
  • the adhesion with the low melting point alloy is set to 30 N / 10 mm ⁇ or more to provide sufficient adhesion. Can be secured.
  • the content of the olefin-based resin having a polar group in 100% by mass of the layer including the surface on the side opposite to the surface having the resin layer A is 40% by mass from the viewpoint of enhancing the adhesion to the low melting point alloy.
  • the above is preferable, 60% by mass or more is more preferable, and 70% by mass or more is further preferable.
  • the content of the olefin-based resin having polar groups in the layer including the surface opposite to the surface on the side having the resin layer A is such that the amount of polar groups on the surface is saturated even if a certain amount or more is added.
  • 90% by mass or less is preferable. More preferably, it is 80% by mass or less.
  • the layer including the surface opposite to the surface having the resin layer A From the viewpoint of enhancing the adhesion to the low melting point alloy and suppressing blocking while satisfying the above (a) and (b), in the layer including the surface opposite to the surface having the resin layer A.
  • an ethylene / acrylic acid copolymer and / or an ethylene / methacrylic acid copolymer is used as the olefin resin having a polar group
  • ethylene having an acid content of 6 to 15% by mass determined by FT-IR measurement is used.
  • -It is preferable to contain 90% by mass or less of the acrylic acid copolymer and / or the ethylene / methacrylic acid copolymer, and more preferably 80% by mass or less.
  • the laminated film of the present invention includes an olefin resin containing 4-methyl-1-pentene units in a layer including a surface opposite to the surface having the resin layer A, a silicone resin, and a fluorine resin. , Fatty acid metal salts, fatty acid amides, inorganic particles, organic particles, and other components for enhancing releasability and slipperiness may be further added.
  • the layer including the surface on the side opposite to the surface having the resin layer A mentioned here is the same as the above.
  • the laminated film of the present invention has a two-layer structure of a base material and a resin layer A. It refers to a base material, and as another example, when the laminated film of the present invention has a resin layer A, a base material, and a resin layer B described later in this order, it means at least a resin layer B.
  • both adhesion to a low melting point alloy, releasability and slipperiness are compatible, and further contamination in the processing process.
  • olefin resins containing 4-methyl-1-pentene units, silicone resins, fluororesins, and organic particles are more preferable.
  • the layer including the surface opposite to the surface having the resin layer A contains an olefin resin containing 4-methyl-1-pentene units. It is particularly preferable to contain an olefin resin containing a -methyl-1-pentene unit and organic particles.
  • the content of the olefin-based resin containing the 4-methyl-1-pentene unit described above is the surface on the side having the resin layer A from the viewpoint of reducing the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. It is preferably contained in an amount of 2% by mass or more in 100% by mass of the layer including the surface on the opposite side, more preferably 5% by mass or more, still more preferably 10% by mass or more.
  • the content of the olefin resin containing 4-methyl-1-pentene unit is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of ensuring adhesion to the low melting point alloy.
  • the content of the organic particles described above controls the ten-point average roughness Rz of the surface of the laminated film on the side opposite to the surface having the resin layer A to be high, and enhances the transportability during manufacturing and use.
  • 0.5% by mass in 100% by mass of the layer including the surface on the side opposite to the surface on the side having the resin layer A 0.5% by mass in 100% by mass of the layer including the surface on the side opposite to the surface on the side having the resin layer A. It is preferably contained in an amount of 1.0% by mass or more, and more preferably 1.0% by mass or more. Further, from the viewpoint of ensuring cost and adhesion to the low melting point alloy, it is preferably contained in an amount of 5% by mass or less, and more preferably 3% by mass or less.
  • the ten-point average roughness Rz of the surface of the laminated film of the present invention on the side opposite to the surface having the resin layer A is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more.
  • the upper limit of the ten-point average roughness Rz is not particularly set, but if it is 15 ⁇ m or more, deterioration of thickness accuracy and strength may become a problem.
  • the ten-point average roughness Rz of the surface of the laminated film on the side opposite to the surface having the resin layer A is the above-mentioned inorganic particles or organic particles on the surface opposite to the surface on the side having the resin layer A. Can be controlled by adding.
  • the ten-point average roughness Rz can be calculated by the method described in Examples, but if the mechanical direction (MD direction) and width direction (TD direction) of the laminated film are unknown, any arbitrary in the film surface can be obtained. Evaluation was performed three times in each of the four directions at 90 ° intervals starting from the direction, and the arithmetic mean value (average for a total of 12 times) was used as the surface of the laminated film of the present invention on the side having the resin layer A. Let it be the ten-point average roughness Rz of the surface on the opposite side.
  • the laminated film of the present invention preferably has the resin layer A, the base material, and the resin layer B in this order.
  • the resin layer B is a layer containing at least a resin, and is a layer different from the resin layer A.
  • the resin layer B refers to a layered film having a finite thickness, and preferably has a mold releasability with respect to the surface of the laminated film on the side having the resin layer A, and further, the laminated film of the present invention has a mold releasability.
  • it When used as a surface protective film for spectacle lenses, it preferably has adhesion to a low melting point alloy.
  • the resin layer B has the resin layer A, the base material, and the resin layer B in this order, the positions thereof are not particularly limited. Therefore, the base material and the resin layer B may be arranged so as to be in direct contact with each other. Another layer may be provided between the base material and the resin layer B. It is preferable that the laminated film of the present invention has the resin layer A, the base material, and the resin layer B in this order from the viewpoint of recyclability and cost, and the tensile elastic modulus of the laminated film of the present invention and the above-mentioned low melting point It is also preferable from the viewpoint of achieving both adhesion with the alloy.
  • Examples of the resin used for the resin layer B of the laminated film of the present invention include an olefin resin and an ester resin, and among them, it is preferable to use an olefin resin as a main component from the viewpoint of productivity and processability.
  • the main component described here refers to a component having the highest mass% (high content) among the components constituting the resin layer B of the laminated film.
  • olefin-based resin suitable as the main component of the resin layer B examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and low-crystalline or amorphous ethylene / ⁇ -olefins.
  • Polymer polypropylene, propylene / ⁇ -olefin copolymer, propylene / ethylene / ⁇ -olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene / n -Ethylene- (meth) acrylic acid ester copolymers such as butyl (meth) acrylate copolymers, ethylene-methyl methacrylate copolymers, ionomers, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, and ethylene / acetic acid.
  • Vinyl copolymers can be mentioned.
  • an ethylene / ethyl (meth) acrylate copolymer and an ethylene / methyl (meth) acrylate copolymer Ethylene-n-butyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid ester copolymer such as ethylene-methyl methacrylate copolymer, ionomer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, etc.
  • a preferable resin as a resin containing a carboxylic acid group or a carboxylic acid base in the resin layer B and a preferable content thereof are carboxylic acid groups contained in a layer including a surface on the side opposite to the surface having the resin layer A.
  • it is the same as the resin containing a metal carboxylate base and its content.
  • the ⁇ -olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and for example, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, etc. And 1-heptene can be preferably mentioned.
  • the olefin-based resin referred to here may correspond to the above-mentioned olefin-based elastomer.
  • the melt flow rate of the olefin resin suitable for the resin layer B in the present invention is determined from the viewpoints of productivity and stability during lamination with an adjacent layer. 0.5 g / 10 minutes or more is preferable, 1 g / 10 minutes or more is more preferable, and 2 g / 10 minutes or more is further preferable. Further, the MFR of the resin used for the resin layer B is preferably 30 g / 10 minutes or less, more preferably 25 g / 10 minutes or less, and further preferably 20 g / 10 minutes or less from the same viewpoint as described above.
  • the material constituting the resin layer B is for further enhancing the releasability and slipperiness of 4-methyl-1-pentene / ⁇ -olefin copolymer, fatty acid metal salt, fatty acid amide, inorganic particles, organic particles and the like. Ingredients may be added.
  • 4-methyl-1-pentene / ⁇ -olefin copolymer, silicone from the viewpoint of achieving both adhesion to low melting point alloys, releasability and slipperiness, and suppressing contamination in the processing process.
  • One or more selected from based resins, fluororesins, and organic particles are preferable.
  • the resin layer B contains a 4-methyl-1-pentene / ⁇ -olefin copolymer, and both 4-methyl-1-pentene / ⁇ -olefin are contained. It is more preferable to contain a polymer and organic particles.
  • the content of the 4-methyl-1-pentene / ⁇ -olefin copolymer described above is 2 in 100% by mass of the resin layer B from the viewpoint of reducing the peeling force after storage at 23 ° C. and the peeling force after storage at 50 ° C. It is preferably contained in an amount of 10% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the content of the 4-methyl-1-pentene / ⁇ -olefin copolymer is preferably 30% by mass or less, preferably 20% by mass or less, from the viewpoint of ensuring adhesion to the low melting point alloy. Is more preferable.
  • the content of the organic particles described above is 0. It is preferably contained in an amount of 5% by mass or more, and more preferably 1.0% by mass or more. Further, from the viewpoint of ensuring cost and adhesion to the low melting point alloy, it is preferably contained in an amount of 5% by mass or less, and more preferably 3% by mass or less.
  • the laminated film of the present invention can be wound in a good winding shape when the laminated film is wound into a roll in a manufacturing process or a slit process, or can be wound from a roll at the time of slitting or use.
  • the force when unwinding the film does not become too large, and the film can be unwound satisfactorily.
  • the above-mentioned lubricant or the like is used without providing the resin layer B.
  • a method of adding the resin layer to the base material can be mentioned, but a method of providing the resin layer B is more preferable from the viewpoint of productivity, cost, and mold release effect.
  • the preferable range of the ten-point average roughness Rz of the resin layer B surface of the laminated film of the present invention is the ten-point average roughness Rz of the surface of the laminated film on the side opposite to the surface having the resin layer A. Similar to the preferred range.
  • the laminated film of the present invention preferably has a base material and a resin layer A, but as described above, it is more preferable to have the resin layer A, the base material, and the resin layer B in this order. Further, the laminated film of the present invention may be provided with another layer other than the base material, the resin layer A and the resin layer B as long as the effects of the present invention are not impaired, but the resin layer A and the resin layer B may be provided. It is preferable that each is located on the outermost surface of the laminated film.
  • the thickness of the laminated film of the present invention is preferably 15 ⁇ m or more, more preferably 30 ⁇ m or more, from the viewpoint of transportability and productivity during production and use.
  • the thickness of the laminated film is preferably 250 ⁇ m or less from the same viewpoint as described above.
  • the film roll of the present invention is preferably a film roll in which the laminated film is in contact with the surface on the side having the resin layer A and the surface on the opposite side.
  • the method for producing the laminated film of the present invention is not particularly limited.
  • the resin compositions constituting each of them are individually extruded.
  • the so-called coextrusion method in which the resin layer A, the base material, and the resin layer B are individually melt-extruded and then laminated by the laminating method can be mentioned. From the viewpoint of properties, it is preferably produced by a coextrusion method.
  • a material mixed with 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.
  • the coextrusion method known methods such as an inflation method and a T-die method are used, but the heat-melt coextrusion method by the T-die method is particularly preferable from the viewpoint of excellent thickness accuracy and surface shape control.
  • the constituent components of the resin layer A, the base material, and the resin layer B are each extruded from a melt extruder, laminated and integrated inside the T die, and coextruded. Then, the laminated film can be obtained by cooling and solidifying with a metal cooling roll, forming the film into a film, and winding the film into a roll.
  • the form of winding in a roll shape is not particularly limited, and only the laminated film may be wound, or the release film may be separately attached to the resin layer A side of the laminated film and then wound in a roll shape.
  • the laminated film of the present invention is wound into a roll in a state where the surface on the side having the resin layer A and the surface on the opposite side, in this case, the resin layer B surface are in contact with each other.
  • the method is more preferred.
  • the laminated film of the present invention can be used as a surface protective film for preventing scratches and stains during manufacturing, processing, and transportation of synthetic resin plates, metal plates, glass plates, etc., and is particularly used for optical equipment and eyeglasses. It can be preferably used as a surface protective film for use by adhering it to an adherend having a curved surface shape such as a lens of the above, and among them, it can be most preferably used as a surface protective film for a spectacle lens.
  • the molded product has the laminated film of the present invention from the viewpoint of preventing scratches and stains during manufacturing, processing, and transportation.
  • the molded product include a synthetic resin plate, a metal plate, and a glass plate.
  • the manufacturing process of the molded body includes a step of attaching the laminated film of the present invention, a step of processing the molded body, and a step of peeling the laminated film in this order.
  • processing examples include cutting, punching, bending, polishing, surface modification, laminating, and laminating.
  • the ten-point average roughness Rz of the surface opposite to the surface having the resin layer A is based on JIS B0601-1994 using a high-precision fine shape measuring instrument (SURFCORDER ET4000A) manufactured by Kosaka Laboratory. The measurement was performed under the following measurement conditions. The measurement was performed three times for each type of laminated film, and the arithmetic mean value was used. Measurement range: Machine direction (MD direction) 0.2 mm, width direction (TD direction) 2 mm Measurement pitch: Machine direction (MD direction) 10 ⁇ m, width direction (TD direction) 0.2 ⁇ m Touch needle: Diamond needle with tip radius of 2.0 ⁇ m Load: 100 ⁇ N Cutoff: 0.8 mm.
  • MFR Melt flow rate
  • Dynamic shear deformation was performed at 1 Hz and a strain of 0.01%, and the peak temperature of tan ⁇ in the heating process, the shear storage elastic modulus G'(25) at 25 ° C., and tan ⁇ (25) at 25 ° C. were evaluated.
  • Indentation residual displacement rate H (unit%) (Residual displacement hp (unit: ⁇ m) / maximum displacement hm (unit: ⁇ m)) ⁇ 100 ... Equation (1) Temperature: 26 ° C Maximum load: 1mN Load speed / unloading speed: 0.1 mN / s Load-Load at the start of the unloading test: 0 mN Holding time at maximum load: 1 second Surface detection method: Tilt method Surface detection threshold coefficient: 1.5 Spring correction: Real-time spring correction.
  • Arithmetic mean swell Wa The measurement is performed using a scanning white interference microscope "VS1540" (manufactured by Hitachi High-Tech Science, the measurement conditions and device configuration will be described later), and the shooting screen is complemented (completely complemented) by the attached analysis software. After surface correction by approximation, the surface shape was determined by processing with a median filter (3 ⁇ 3 pixels). The obtained surface shape was treated with a Gaussian filter (cutoff value of 50 ⁇ m) to output a waviness image from which short wavelength components were removed. From the obtained swell image, the arithmetic mean swell Wa was calculated according to the following formula.
  • ⁇ Arithmetic mean swell Wa formula> The height of the point (x, y) of the swell image is Zw (x, y), the measurement range in the x direction is lp, the measurement range in the y direction is ly, and the average value of the heights of the swell image is Ave (Zw). Then,
  • the measurement is performed on the surface of the laminated film on the side having the resin layer A, starting from the diagonal intersection of the laminated film cut into a square of 5 cm ⁇ 5 cm, and a total of 9 measurement positions are measured according to the following procedure.
  • a total of 9 measurement positions are measured according to the following procedure.
  • was determined measurement was performed at each measurement position, Wa at each measurement position was obtained according to the above procedure, and the arithmetic average value was adopted as Wa.
  • Measurement 1 Position measurement of the start point 2: Position measurement 3.0 mm to the right of the start point 3: Position measurement 6.0 mm to the right of the start point 4: Position measurement 3.0 mm below the start point 5: 3 from the start point 0.0 mm below, 3.0 mm right position measurement 6: 3.0 mm below the start point, 6.0 mm right position measurement 7: Position measurement 6.0 mm below the start point 8: 6.0 mm below the start point, 3.0 mm right position measurement 9: 6.0 mm below the start point, 6.0 mm right position ⁇ Measurement conditions and device configuration> Objective lens: 10x Lens barrel: 1x Zoom lens: 1x Wavelength filter: 530nm white Measurement mode: Wave Measurement software: VS-Measure 10.0.4.0 Analysis software: VS-Viewer 10.0.3.0 Measurement area: 1009.7 ⁇ m ⁇ 1010.5 ⁇ m Number of pixels: 1842 x 1844.
  • the diameter of the laminated film is such that the surface on the side opposite to the surface on the side having the resin layer A is on the bottom. It was placed on a SUS jig having an opening of 80 mm, and both end surfaces in the TD direction were fixed with the jig. Then, a polycarbonate lens having a diameter of 80 mm and a curvature of 19 m -1 is pressed from above the opening at 5 kgf from the surface (upper side) of the laminated film on the side having the resin layer A to bond the laminated film and the lens, and then the lens.
  • the lower chuck portion of the tensile tester (Orientec universal tester "Tensilon” (registered trademark)) grips the lower part of the bonded sample, and is further 1 mm away from the resin layer B surface in the vertical direction.
  • the melting point metal alloy portion was gripped by the loop portion of the metal wire having the loop portion.
  • the metal wire was pulled upward in parallel with the surface on the side opposite to the surface having the resin layer A at a tensile speed of 50 mm / min to peel off the low melting point alloy, and the maximum value of the peeling force was obtained.
  • the above test was performed 5 times on one type of laminated film, and the arithmetic mean value was calculated.
  • Example 1 The constituent resins of each layer were prepared as follows.
  • Substrate MFR is (measured at 190 °C) 10.5g / 10 min, 80 wt% of commercially available low density polyethylene (LDPE) having a density of 918 kg / m 3, an olefin elastomer (made by Mitsui Chemicals, "Abusotoma” (Registered 20% by mass of EP-1001, MFR of 10 g / 10 min (measured at 230 ° C.), tan ⁇ peak temperature of 29 ° C., G'(25) 33 MPa, tan ⁇ (25) 1.9) was used.
  • LDPE low density polyethylene
  • olefin elastomer made by Mitsui Chemicals, "Abusotoma” (Registered 20% by mass of EP-1001, MFR of 10 g / 10 min (measured at 230 ° C.), tan ⁇ peak temperature of 29 ° C., G'(25) 33 MPa, tan ⁇ (25)
  • Resin layer A Styrene-based elastomer (SIBS manufactured by Kaneka, "Shibster” (registered trademark) 062H, MFR 50 g / 10 minutes (measured at 230 ° C.), tan ⁇ peak temperature -38 ° C., G'(25) 0. 80% by mass of 3MPa, 0.32) of tan ⁇ (25), and 20% by mass of a tackifier (Terpenphenol YS Polystar TH130 manufactured by Yasuhara Chemical Co., Ltd.), kneaded and chipped in advance with a twin-screw extruder. bottom.
  • SIBS Styrene-based elastomer manufactured by Kaneka, "Shibster” (registered trademark) 062H
  • MFR 50 g / 10 minutes measured at 230 ° C.
  • tan ⁇ peak temperature -38 ° C. G'(25) 0. 80% by mass of 3MPa, 0.32) of
  • Resin layer B 50% by mass of commercially available block polypropylene (BPP) having an MFR of 8.5 g / 10 minutes (measured at 230 ° C.), 20% by mass of the same commercially available LDPE used for the base material, and 20% by mass of the base material.
  • BPP block polypropylene
  • each extruder of the T-die composite film forming machine having three extruders so that the resin layer A is 25 ⁇ m, the base material is 90 ⁇ m, and the resin layer B is 5 ⁇ m.
  • the discharge amount of each extruder is adjusted, laminated in this order, extruded from a composite T-die at an extrusion temperature of 200 ° C, cast on a roll whose surface temperature is controlled to 40 ° C, and molded into a film. It was turned to obtain a laminated film.
  • Example 2 A laminated film was obtained in the same manner as in Example 1 except that the compositions constituting the resin layer A were as shown in Table 1.
  • Example 5 The composition constituting the resin layer A is as shown in Table 1, and 50% by mass of a styrene-based elastomer (SIBS manufactured by Kaneka Corporation, "Shibster” (registered trademark) 062H) and a tackifier (manufactured by Arakawa Chemicals Co., Ltd., "" Implemented except that 20% by mass of "Arcon” (registered trademark) M135) and 30% by mass of the same olefin elastomer (“Absortmer” (registered trademark) EP-1001 manufactured by Mitsui Chemicals, Inc.) used as the base material were used.
  • a laminated film was obtained in the same manner as in Example 1.
  • Example 6 A laminated film was obtained in the same manner as in Example 1 except that the compositions constituting the resin layer A were as shown in Table 1.
  • the composition constituting the resin layer A was composed of a styrene-based elastomer (Asahi Kasei SEBS, “SOE” (registered trademark) S1613, MFR of 14 g / 10 minutes (measured at 230 ° C.), and tan ⁇ peak temperature of -17.
  • G'(25) was 0.7 MPa
  • tan ⁇ (25) was 0.11) in 70% by mass
  • a tackifier terpene phenol YS Polyster TH130 manufactured by Yasuhara Chemicals
  • a laminated film was obtained in the same manner as in Example 1 except that 10% by mass of the same olefin elastomer (“Absorter” (registered trademark) EP-1001 manufactured by Mitsui Chemicals) was used.
  • Example 8 A laminated film was obtained in the same manner as in Example 1 except that the compositions constituting the resin layer A were as shown in Table 1.
  • Example 9 The composition constituting the base material was carried out except that a commercially available low-density polyethylene (LDPE) having an MFR of 10.5 g / 10 minutes (measured at 190 ° C.) and a density of 918 kg / m 3 was used as 100% by mass. A laminated film was obtained in the same manner as in Example 1.
  • LDPE low-density polyethylene
  • Example 10 The composition constituting the base material, MFR is (measured at 190 °C) 10.5g / 10 min, commercially available low density polyethylene having a density of 918 kg / m 3 a (LDPE) 50 wt%, MFR is 7.5 g / 10 min (measured at 190 ° C.), a commercially available high density polyethylene having a density of 961kg / m 3 and (HDPE) 30% by weight, an olefin-based elastomer (made by Mitsui Chemicals, "Abusotoma" (TM) EP-1001) 20 mass A laminated film was obtained in the same manner as in Example 3 except that% was used.
  • LDPE low density polyethylene having a density of 918 kg / m 3 a
  • HDPE high density polyethylene having a density of 961kg / m 3 and (HDPE) 30% by weight
  • TM olefin-based elastomer
  • Example 11 The composition constituting the base material, MFR is (measured at 190 °C) 10.5g / 10 min, commercially available low density polyethylene having a density of 918 kg / m 3 a (LDPE) 30 wt%, MFR is 7.5 g / 10 min (measured at 190 ° C.), a commercially available high density polyethylene having a density of 961kg / m 3 and (HDPE) 50% by weight, an olefin-based elastomer (made by Mitsui Chemicals, "Abusotoma" (TM) EP-1001) 20 mass A laminated film was obtained in the same manner as in Example 3 except that% was used.
  • LDPE low density polyethylene having a density of 918 kg / m 3 a
  • HDPE high density polyethylene having a density of 961kg / m 3 and (HDPE) 50% by weight
  • TM olefin-based elastomer
  • Example 12 An output of 50 W using a corona surface modification evaluation device TEC-4AX (electrode specifications: ceramic cylindrical electrode, diameter 10 mm, discharge width 230 mm) manufactured by Kasuga Electric Co., Ltd. on the resin layer B surface side of the laminated film according to Example 1. , Corona discharge treatment was performed at a transport speed of 4 m / min.
  • TEC-4AX electrode specifications: ceramic cylindrical electrode, diameter 10 mm, discharge width 230 mm
  • the composition constituting the resin layer B is an ethylene / methacrylic acid copolymer (EMAA) "Nucrel” (registered trademark) AN42012C (FT-IR method calculated by the FT-IR method) manufactured by Mitsui Dow Polychemical, and the acid content is 9% by mass.
  • EAA ethylene / methacrylic acid copolymer
  • AN42012C FT-IR method calculated by the FT-IR method
  • Example 14 A laminated film was obtained in the same manner as in Example 7 except that the composition constituting the resin layer B was the same as in Example 13.
  • Example 15 A laminated film was obtained in the same manner as in Example 7 except that the composition constituting the resin layer B was 100% by mass of "Nucrel” (registered trademark) AN42012C manufactured by Mitsui Dow Polychemical.
  • Example 16 The composition constituting the resin layer B was 75% by mass of "Nucrel” (registered trademark) AN42012C manufactured by Mitsui Chemicals, and 15% by mass of the same PE particle masterbatch used for the resin layer B in Example 1. , 4-Methyl-1-pentene / ⁇ -olefin copolymer (Mitsui Chemicals "Absortmer” (registered trademark) EP-1013 (MFR 10 g / 10 minutes (measured at 230 ° C.)) was set to 10% by mass. A laminated film was obtained in the same manner as in Example 7 except for the above.
  • Example 17 A laminated film was obtained in the same manner as in Example 1 except that the compositions constituting the base material, the resin layer A, and the resin layer B were as shown in Table 3.
  • the composition constituting the resin layer A is a styrene elastomer (Asahi Kasei SEBS, "Tough Tech” (registered trademark) H1052, MFR 13 g / 10 minutes (measured at 230 ° C.), tan ⁇ peak temperature -46 ° C., G'. Except for the fact that (25) was 1.8 MPa, tan ⁇ (25) was 0.07) in 70% by mass, and the tackifier (Arakawa Chemical Industry Co., Ltd., "Alcon” (registered trademark) M135) was used in 30% by mass. A laminated film was obtained in the same manner as in Example 1.
  • Comparative Example 2 A laminated film was obtained in the same manner as in Example 1 except that the composition constituting the base material was 100% by mass of the same commercially available block polypropylene (BPP) as that used in the resin layer B.
  • BPP block polypropylene
  • composition constituting the base material commercially available low-density polyethylene (LDPE) having an MFR of 10.5 g / 10 minutes (measured at 190 ° C.) and a density of 918 kg / m 3 was used in the resin layer B at 48% by mass.
  • LDPE low-density polyethylene
  • BPP block polypropylene
  • the composition constituting the resin layer A is a styrene-based elastomer (SEBS manufactured by Clayton, "Clayton” (registered trademark) G1657, MFR of 9 g / 10 minutes (measured at 230 ° C.), tan ⁇ peak temperature of -50 ° C., G'.
  • SEBS styrene-based elastomer
  • MFR 9 g / 10 minutes (measured at 230 ° C.), tan ⁇ peak temperature of -50 ° C., G'.
  • (25) was 1.0 MPa
  • tan ⁇ (25) was 0.07) was 80% by mass
  • the tackifier terpene phenol YS polystar TH130 manufactured by Yasuhara Chemical Co., Ltd.
  • Comparative Example 5 The composition constituting the resin layer A was the same as in Comparative Example 4, the composition constituting the base material was 80% by mass of "Nucrel” (registered trademark) AN42012C manufactured by Mitsui Dow Polychemical, and the resin layer in Example 1. The same PE particle masterbatch as that used for B was set to 20% by mass. Further, it is charged into each extruder of a T-die composite film forming machine having two extruders, and the discharge amount of each extruder is adjusted so that the resin layer A is 25 ⁇ m and the base material is 95 ⁇ m, and the discharge amount of each extruder is adjusted in this order. It was laminated and extruded from a composite T-die at an extrusion temperature of 200 ° C., cast onto a roll whose surface temperature was controlled to 40 ° C., and wound into a film to obtain a laminated film.
  • "Nucrel” registered trademark
  • AN42012C manufactured by Mitsui Dow Polychemical
  • Example 6 A laminated film was obtained in the same manner as in Example 1 except that the compositions constituting the base material, the resin layer A, and the resin layer B were as shown in Table 3.
  • the laminated film and film roll of the present invention have sufficient adhesiveness and followability to an adherend, they are preferably used as surface protective films for products made of various materials such as synthetic resins, metals, and glass. Can be done.

Landscapes

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

Abstract

La présente invention aborde le problème de la fourniture d'un film stratifié et d'un rouleau de film ayant une aptitude au suivi substantielle à une partie adhérée ayant une forme incurvée. Le film stratifié a un matériau de base et une couche de résine A et satisfait les conditions (a) et (b) suivantes. (a) Lorsqu'un essai d'élimination de charge par nanoindentation est réalisé à partir d'une surface sur le côté de la couche de résine A du film stratifié à 26 °C et une charge maximale de 1 mN, le film stratifié a une surface ayant un taux de déplacement résiduel de pressage de 40 % ou plus. (b) Le film stratifié a un module d'élasticité en traction de 60 Mpa ou plus et 300 Mpa ou moins à 23 °C et 300 mm/min.　
PCT/JP2021/010534 2020-03-25 2021-03-16 Film stratifié et rouleau de film WO2021193223A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021515238A JP6966025B1 (ja) 2020-03-25 2021-03-16 積層フィルム及びフィルムロール

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020-053884 2020-03-25
JP2020053884 2020-03-25
JP2021031360 2021-03-01
JP2021-031360 2021-03-01

Publications (1)

Publication Number Publication Date
WO2021193223A1 true WO2021193223A1 (fr) 2021-09-30

Family

ID=77890300

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/010534 WO2021193223A1 (fr) 2020-03-25 2021-03-16 Film stratifié et rouleau de film

Country Status (3)

Country Link
JP (1) JP6966025B1 (fr)
TW (1) TW202204148A (fr)
WO (1) WO2021193223A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024116704A1 (fr) * 2022-12-01 2024-06-06 東レフィルム加工株式会社 Film de protection de surface et son procédé de production

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010006927A (ja) * 2008-06-26 2010-01-14 Sekisui Chem Co Ltd 表面保護フィルム
WO2010084832A1 (fr) * 2009-01-21 2010-07-29 Dic株式会社 Film protecteur de surface
KR20140115704A (ko) * 2013-03-22 2014-10-01 일신화학공업 주식회사 성능이 향상된 자기점착성 보호필름
JP2016098237A (ja) * 2014-11-18 2016-05-30 株式会社サンエー化研 表面保護フィルムの製造方法
JP2016098238A (ja) * 2014-11-18 2016-05-30 株式会社サンエー化研 表面保護フィルムの製造方法
JP2017132995A (ja) * 2016-01-22 2017-08-03 東レ株式会社 積層体

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066395A (ja) * 2015-09-30 2017-04-06 東レ株式会社 積層体
WO2018110361A1 (fr) * 2016-12-16 2018-06-21 東レフィルム加工株式会社 Film détachable et film protecteur
WO2019087992A1 (fr) * 2017-10-31 2019-05-09 東レフィルム加工株式会社 Film stratifié

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010006927A (ja) * 2008-06-26 2010-01-14 Sekisui Chem Co Ltd 表面保護フィルム
WO2010084832A1 (fr) * 2009-01-21 2010-07-29 Dic株式会社 Film protecteur de surface
KR20140115704A (ko) * 2013-03-22 2014-10-01 일신화학공업 주식회사 성능이 향상된 자기점착성 보호필름
JP2016098237A (ja) * 2014-11-18 2016-05-30 株式会社サンエー化研 表面保護フィルムの製造方法
JP2016098238A (ja) * 2014-11-18 2016-05-30 株式会社サンエー化研 表面保護フィルムの製造方法
JP2017132995A (ja) * 2016-01-22 2017-08-03 東レ株式会社 積層体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024116704A1 (fr) * 2022-12-01 2024-06-06 東レフィルム加工株式会社 Film de protection de surface et son procédé de production

Also Published As

Publication number Publication date
JPWO2021193223A1 (fr) 2021-09-30
TW202204148A (zh) 2022-02-01
JP6966025B1 (ja) 2021-11-10

Similar Documents

Publication Publication Date Title
JP4941908B2 (ja) 表面保護フィルム
JP6206749B1 (ja) 積層フィルム
KR102509299B1 (ko) 적층 필름
JP6628101B2 (ja) 積層フィルム
JP2013227434A (ja) 粘着テープ
JP2011042779A (ja) 粘着テープ
WO2011096350A1 (fr) Film de protection de surface
JP6901665B2 (ja) 積層体
US20120321885A1 (en) Pressure-sensitive adhesive sheet
JP6966025B1 (ja) 積層フィルム及びフィルムロール
JP7150255B1 (ja) 積層フィルム及びフィルムロール
JP2011089012A (ja) 粘着フィルムロール
JP2018119138A (ja) 積層フィルム
JP7287863B2 (ja) 積層フィルム
CN113613890B (zh) 层叠膜
JP5116706B2 (ja) 表面保護シート
WO2024116704A1 (fr) Film de protection de surface et son procédé de production
JP2023134934A (ja) 表面保護フィルム
JP2023140482A (ja) 積層フィルム
JPWO2019203003A1 (ja) 積層フィルム

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021515238

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21774418

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21774418

Country of ref document: EP

Kind code of ref document: A1