Coated film laminate

Abstract

To provide a coated film laminate film which has sufficient adhesion strength between a film base material and a coated film, and is less likely to cause coated film peeling.SOLUTION: A coated film laminate film has (B) a coated film on at least one surface of (A) a stretch film, in which (A) the stretch film is laminated directly on (B) the coated film; (B) the coated film is formed using a coating material containing (b1) an active energy ray-curable resin; a thickness of (B) the coated film is 11 μm or less; when arithmetic average roughness (Ra) of a formation surface of (B) the coated film of (A) the stretch film is represented by a (unit is μm) and thickness of (B) the coated film is represented by b (unit is μm), the following expression (1): b≤3a+5.5 is satisfied; and the arithmetic average roughness (Ra) is a value measured according to JIS B 0601:2013 under the condition that a cut-off value λc is 0.80 mm and an evaluation length L is 4.0 mm.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a coated film laminate. More specifically, it relates to a coated film laminate having stretchability.

Background Art

[0002] Conventionally, when producing or transporting an article, or when using an article, in order to protect the surface of the article from scratches, damage, and adhesion of contaminants, a protective film is often laminated on the surface of the article. From the viewpoint of workability when laminating the protective film on the surface of the article, stretchability or flexibility is often required. Further, when using an article, the protective film laminated on the surface thereof is often required to have not only scratch resistance but also some functions such as water repellency, antibacterial property, antiviral property, antireflection property, and infrared shielding property. When attempting to impart these functions, it is convenient to form a coating film containing a functionalizing agent such as a water repellent, an antibacterial agent, an antiviral agent, low refractive index fine particles, and heat ray shielding fine particles on the surface of a film substrate having stretchability or flexibility. And, as the binder of the coating film, an active energy ray curable resin is desired because it has good scratch resistance, a short curing time required, and high productivity. Further, as a film substrate having stretchability or flexibility, a polyolefin resin film is generally used, and it is desired to use this. However, since the adhesion strength between the polyolefin resin film and the coating film formed using a paint having an active energy ray curable resin as a binder is low, there is a disadvantage that the coating film is easily peeled off.

[0003] Further, since the surface of an article often has a three-dimensional shape / three-dimensional shape, the protective film is often required to be able to follow the surface shape of the article. However, there is also a disadvantage that a coating film formed using a paint having an active energy ray curable resin as a binder often easily cracks when the protective film is stretched following the surface shape of the article.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a coated film laminated film that has sufficient adhesion strength between the film substrate and the coated film even when the coated film forming surface of the film substrate contains a polyolefin resin, and is less likely to cause peeling of the coated film.

Means for Solving the Problems

[0006] As a result of intensive research, the present inventor has found that the above problems can be achieved by a specific coated film laminated film.

[0007] That is, aspects of the present invention are as follows. [1]. A coated film laminated film having (B) a coated film on at least one surface of (A) a stretch film; The (A) stretch film and the (B) coated film are directly laminated; The (B) coated film is formed using a (b) paint containing a (b1) active energy ray curable resin; The thickness of the (B) coated film is 16 μm or less; When the arithmetic mean roughness (Ra) of the (B) coated film forming surface of the (A) stretch film is a (unit: μm) and the thickness of the (B) coated film is b (unit: μm), the following formula (1) is satisfied: b ≦ 3a + 5.5 ··· (1) Here, the arithmetic mean roughness (Ra) is measured in accordance with JIS B0601:2013 under the conditions that the cut-off value λc is 0.80 mm and the evaluation length L is 4.0 mm. The above-mentioned coated film laminated film. [2]. The coated film laminated film according to item [1], wherein the resin forming the (B) coated film forming surface of the (A) stretch film contains a polyolefin resin. [3]. The coated film laminated film according to item [1] or [2], wherein the resin forming the (B) coated film forming surface of the (A) stretch film contains an ethylene resin. [4]. The coated film laminated film according to any one of items [1] to [3], wherein the resin forming the (B) coated film forming surface of the (A) stretch film contains an ethylene-vinyl acetate copolymer. [5]. The coated film laminated film according to any one of items [1] to [4], wherein the arithmetic mean roughness (Ra) of the (B) coated film forming surface of the (A) stretch film is 0.1 μm or more. [6]. The thickness of the (B) coated film is 0.5 to 9.5 μm; When the arithmetic mean roughness (Ra) of the (B) coated film forming surface of the (A) stretch film is a (unit: μm) and the thickness of the (B) coated film is b (unit: μm), the following formula (2) is satisfied: b ≦ 3a + 4 ···(2) The coated film laminated film according to any one of items [1] to [5]. [7]. The coated film laminated film according to any one of items [1] to [6], wherein the (b) paint contains 100 parts by mass of the (b1) active energy ray curable resin, 0.1 to 20 parts by mass of the (b2) photopolymerization initiator, and 1 to 100 parts by mass of an inorganic compound functioning as an antibacterial agent or an antiviral agent. [8]. The coated film laminated film according to any one of items [1] to [7], which is for protecting the surface of an article. [9]. A method of using the coated film laminate according to any one of items [1] to [8] for protecting the surface of an article.

Advantages of the Invention

[0008] Even when the coating film forming surface of the film substrate of the coated film laminate of the present invention contains a polyolefin resin, the film substrate and the coating film have sufficient adhesion strength, and coating film peeling hardly occurs. In the preferred coated film laminate of the present invention, even when the coating film forming surface of the film substrate contains a polyolefin resin, the film substrate and the coating film have sufficient adhesion strength, coating film peeling hardly occurs, and cracking of the coating film hardly occurs even when stretched following the surface shape of the article. Therefore, the coated film laminate of the present invention can be suitably used for protecting the surface of an article having a three-dimensional shape / three-dimensional surface.

Embodiments for Carrying Out the Invention

[0009] In this specification, the term "resin" is used as a term that includes a resin mixture containing two or more resins and a resin composition containing components other than the resin. In this specification, the term "film" is used interchangeably or equivalently with the term "sheet". In this specification, the terms "film" and "sheet" are used for those that can be industrially wound into a roll. The term "plate" is used for those that cannot be industrially wound into a roll. Also, in this specification, laminating one layer on top of another layer in order includes both directly laminating those layers and laminating with one or more other layers such as an anchor coat intervening between those layers.

[0010] In this specification, the term "above" related to a numerical range is used to mean a certain numerical value or more than a certain numerical value. For example, "above 20%" means 20% or more than 20%. The term "below" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, "below 20%" means 20% or less than 20%. Also, the symbol "~" related to a numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, the other certain numerical value is a numerical value larger than the certain numerical value. For example, "10~90%" means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper limit and the lower limit of the numerical range can be arbitrarily combined, and the arbitrarily combined embodiments should be construed as being read. For example, from the description such as "usually above 10%, preferably above 20%. On the other hand, usually below 40%, preferably below 30%." or "usually 10~40%, preferably 20~30%." related to the numerical range of a certain characteristic, it should be construed that the numerical range of that certain characteristic is 10~40%, 20~30%, 10~30%, or 20~40% in one embodiment.

[0011] Except in examples or unless otherwise specified, all numerical values used in this specification and the claims should be understood to be modified by the term "about". Without intending to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of significant figures and by applying ordinary rounding methods.

[0012] 1. Coated film laminate The coated film laminated film of the present invention has (B) a coating film on at least one surface of (A) a stretch film, usually on one surface. In one embodiment, the coated film laminated film of the present invention may have, in order from the surface layer side, the above (B) coating film, the above (A) stretch film, and (C) an adhesive layer. The above (A) stretch film and the above (B) coating film are directly laminated. The above (B) coating film is formed using a paint containing (b1) an active energy ray curable resin. The thickness of the above (B) coating film is 16 μm or less. The coated film laminated film of the present invention satisfies the following formula (1) when the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above (A) stretch film is a (unit: μm) and the thickness of the above (B) coating film is b (unit: μm). b≦3a+5.5 ···(1)

[0013] Here, the arithmetic mean roughness (Ra) is a value measured in accordance with JIS B0601:2013 under the conditions that the cut-off value λc is 0.80 mm and the evaluation length L is 4.0 mm. Hereinafter, each layer will be described.

[0014] As a method for controlling the thickness of the above (B) coating film to the designed thickness, the following method is preferable. First, a preliminary experiment is performed in advance. Typically, a coating film is formed on the surface of a film substrate with a smooth surface, for example, a biaxially stretched polyethylene terephthalate resin film, using the coating material for forming the above (B) coating film to obtain a relational expression between the coating conditions of the coating material and the thickness (thickness after curing) of the coating film. Next, when producing the coated film laminated film of the present invention, the thickness of the above (B) coating film is controlled to the designed thickness based on the relational expression.

[0015] 1-1. (A) Stretch film The above-mentioned (A) stretch film is a film substrate for directly forming the above-mentioned (B) coating film on its surface. The above-mentioned (A) stretch film functions to impart mechanical strength to the coating film laminate of the present invention. Here, the stretch film means a film having stretchability or flexibility that can follow the surface shape of an article. Typically, the 5% strain tensile stress of the above-mentioned (A) stretch film may usually be 12 MPa or less, preferably 9 MPa or less, more preferably 6 MPa or less, and still more preferably 1 to 4 MPa from the viewpoint of stretchability or flexibility that can follow the surface shape of the article.

[0016] The 10% strain tensile stress of the above-mentioned (A) stretch film may usually be 18 MPa or less, preferably 14 MPa or less, more preferably 9 MPa or less, and still more preferably 1.5 to 6 MPa from the viewpoint of stretchability or flexibility that can follow the surface shape of the article.

[0017] The 25% strain tensile stress of the above-mentioned (A) stretch film may usually be 25 MPa or less, preferably 18 MPa or less, more preferably 12 MPa or less, and still more preferably 2 to 8 MPa from the viewpoint of stretchability or flexibility that can follow the surface shape of the article.

[0018] The tensile fracture stress of the above-mentioned (A) stretch film may usually be 5 MPa or more, preferably 8 MPa or more, and more preferably 10 MPa or more from the viewpoint of mechanical strength. The tensile fracture strain of the above-mentioned (A) stretch film may usually be 100% or more, preferably 200% or more, and more preferably 300% or more from the viewpoint of mechanical strength.

[0019] Here, the 5% elongation tensile stress, 10% elongation tensile stress, 25% elongation tensile stress, tensile fracture stress, and tensile fracture strain of the stretch film are measured by conducting a tensile test under the conditions of a temperature of 23 ± 2°C, a relative humidity of 50 ± 10%, a gauge length of 50 mm, a chuck distance of 50 mm, and a tensile speed of 200 mm / min in accordance with JIS K7161-2:2014, except that a strip-shaped test piece with a width of 15 mm and a length of 150 mm is used such that the machine direction of the stretch film is the tensile direction.

[0020] The above-mentioned (A) stretch film may be a single-layer film or a multilayer film. When the above-mentioned (A) stretch film is a single-layer film, the resin forming the above-mentioned (A) stretch film (in other words, the resin forming the above-mentioned (B) coating film forming surface of the above-mentioned (A) stretch film) may be appropriately selected from the viewpoint of imparting stretchability or flexibility that can follow the surface shape of the article. When the above-mentioned (A) stretch film is a single-layer film, the resin forming the above-mentioned (A) stretch film preferably may contain a polyolefin-based resin, and more preferably may mainly contain a polyolefin-based resin.

[0021] When the above-mentioned (A) stretch film is a multilayer film, the resins forming each layer of the multilayer film are appropriately selected from the viewpoints of imparting stretchability or flexibility that can follow the surface shape of the article and preventing peeling between the layers of the multilayer film when the protective film is stretched following the surface shape of the article. When the above-mentioned (A) stretch film is a multilayer film, the resin forming the above-mentioned (B) coating film forming surface of the multilayer film (the resin forming the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed) preferably may contain a polyolefin-based resin, and more preferably may mainly contain a polyolefin-based resin.

[0022] The phrase "mainly containing a polyolefin resin" means that, taking the total of the resin forming the above-mentioned (A) stretch film or the resin forming the above-mentioned (B) coating film forming surface of the above-mentioned multilayer film as 100% by mass, the polyolefin resin is usually contained in an amount of 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and typically 90 - 100% by mass.

[0023] The above-mentioned polyolefin resin is a resin mainly containing α-olefins (such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene, etc.). The content of the structural unit derived from α-olefin in the above-mentioned polyolefin resin, taking the total of all structural units as 100% by mass, may usually be 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and typically 70 - 100% by mass. Examples of the above-mentioned polyolefin resin include ethylene resins, propylene resins, 1-butene resins, and 4-methyl-1-pentene resins, etc.

[0024] The above-mentioned ethylene resin is a resin mainly containing a structural unit derived from ethylene. The content of the structural unit derived from ethylene in the above-mentioned ethylene resin, taking the total of all structural units as 100% by mass, may usually be 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and typically 70 - 100% by mass.

[0025] Examples of the above ethylene-based resins include polyethylene such as ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and ethylene-α-olefin copolymers such as ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer; ethylene-(meth)acrylic acid alkyl ester copolymers such as ethylene-ethyl acrylate copolymer and ethylene-methyl methacrylate copolymer; ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer; ionomer resins obtained by crosslinking between molecules of the ethylene-unsaturated carboxylic acid copolymers with metal ions; and ethylene-vinyl acetate copolymer, etc.

[0026] Examples of the above metal ions used in the above ionomer resins include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, zinc ion, magnesium ion, and manganese ion, etc.

[0027] The above propylene-based resin is a resin mainly containing structural units derived from propylene. The content of the structural units derived from propylene in the above propylene-based resin is usually 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, typically 70 to 100% by mass, with the total sum of all structural units being 100% by mass.

[0028] Examples of the above propylene-based resins include polypropylene such as propylene homopolymer and copolymers of propylene and one or more of α-olefins (such as ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene, etc.) (including block copolymers and random copolymers).

[0029] The above-mentioned 1-butene-based resin is a resin mainly containing structural units derived from 1-butene. The content of the structural units derived from 1-butene in the above-mentioned 1-butene-based resin is usually 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and typically 70 to 100% by mass, with the total of all structural units being 100% by mass.

[0030] Examples of the above-mentioned 1-butene-based resin include poly-1-butene such as a 1-butene homopolymer and a copolymer (including a block copolymer and a random copolymer) of 1-butene and one or more of α-olefins (for example, ethylene, propylene, 1-hexene, 1-octene, and 4-methyl-1-pentene).

[0031] The above-mentioned 4-methyl-1-pentene-based resin is a resin mainly containing structural units derived from 4-methyl-1-pentene. The content of the structural units derived from 4-methyl-1-pentene in the above-mentioned 4-methyl-1-pentene-based resin is usually 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and typically 70 to 100% by mass, with the total of all structural units being 100% by mass.

[0032] Examples of the above-mentioned 4-methyl-1-pentene resin include poly-4-methyl-1-pentene such as a 4-methyl-1-pentene homopolymer and a copolymer (including a block copolymer and a random copolymer) of 4-methyl-1-pentene and one or more of α-olefins (for example, ethylene, propylene, 1-butene, 1-hexene, and 1-octene).

[0033] From the viewpoint of film formability, the melt mass flow rate of the above-mentioned polyolefin-based resin measured according to JIS K7210-1:2014 under the conditions of a temperature of 190°C and a load of 21.18 N is preferably 0.1 to 20 g / 10 min, more preferably 0.5 to 10 g / 10 min, and still more preferably 1 to 6 g / 10 min.

[0034] The melt mass flow rate measured under the conditions of a temperature of 230°C and a load of 21.18 N in accordance with JIS K7210-1:2014 of the above polyolefin resin may preferably be 0.1 to 30 g / 10 min, more preferably 0.5 to 15 g / 10 min, and still more preferably 1 to 10 g / 10 min from the viewpoint of film-forming properties.

[0035] When the above (A) stretch film is a single-layer film, the polyolefin resin used for forming the above (A) stretch film may be appropriately selected from the viewpoint of imparting stretchability or flexibility that can follow the surface shape of the article. When the above (A) stretch film is a single-layer film, the polyolefin resin used for forming the above (A) stretch film may preferably contain an ethylene-based resin, and more preferably may contain an ethylene-vinyl acetate copolymer.

[0036] When the above-mentioned (A) stretch film is a multilayer film, the polyolefin resin used for forming the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed is appropriately selected from the viewpoints of imparting stretchability or flexibility capable of following the surface shape of the article, and preventing peeling between the layers of the multilayer film when the protective film is stretched following the surface shape of the article. When the above-mentioned (A) stretch film is a multilayer film, the polyolefin resin used for forming the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed may preferably mainly contain an ethylene-based resin, and more preferably mainly contain an ethylene-vinyl acetate copolymer. When the above-mentioned (A) stretch film is a multilayer film, the resin for forming the layers other than the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed is appropriately selected from the viewpoints of imparting stretchability or flexibility capable of following the surface shape of the article, and preventing peeling between the layers of the multilayer film when the protective film is stretched following the surface shape of the article. When the above-mentioned (A) stretch film is a multilayer film, the resin for forming the layers other than the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed may preferably contain a polyolefin resin. The polyolefin resin may preferably contain an ethylene-based resin, and more preferably may contain an ethylene-vinyl acetate copolymer.

[0037] When the above-mentioned (A) stretch film is a single-layer film and an ethylene-based resin-containing material is used for forming the above-mentioned (A) stretch film, or when the above-mentioned (A) stretch film is a multilayer film and an ethylene-based resin-containing material is used for forming the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed, the content of the structural unit derived from ethylene in the ethylene-based resin-containing material (resin mixture containing an ethylene-based resin), with the total of all structural units being 100% by mass, may usually be 100% by mass or less, preferably 98% by mass or less, more preferably 96% by mass or less, and still more preferably 94% by mass or more from the viewpoint of the stretchability or flexibility of the above-mentioned (A) stretch film. On the other hand, from the viewpoint of the blocking resistance of the above-mentioned (A) stretch film, it may usually be 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

[0038] The melting point of the ethylene-based resin-containing material (resin mixture containing an ethylene-based resin) may usually be 80°C or higher, preferably 90°C or higher, and more preferably 100°C or higher from the viewpoint of the heat resistance of the protective film.

[0039] Here, the melting point is measured according to JIS K7121:2012 using a differential scanning calorimeter. It is held at 190°C for 5 minutes, cooled to -10°C at 10°C / min, held at -10°C for 5 minutes, and then heated to 190°C at 10°C / min. Among the peaks appearing in the second melting curve (the melting curve measured in the final heating process), it is the peak top temperature of the peak that appears on the highest temperature side. As the above-mentioned differential scanning calorimeter, for example, the Diamond DSC type differential scanning calorimeter of PerkinElmer Japan Co., Ltd. can be used.

[0040] When the above-mentioned (A) stretch film is a single-layer film and a resin mixture containing an ethylene-vinyl acetate copolymer is used for forming the above-mentioned (A) stretch film, or when the above-mentioned (A) stretch film is a multilayer film and a resin mixture containing an ethylene-vinyl acetate copolymer is used for forming the surface layer on the side where the above-mentioned (B) coating film of the multilayer film is formed, the content of the structural unit derived from vinyl acetate in the resin mixture containing the ethylene-vinyl acetate copolymer (resin mixture containing an ethylene-vinyl acetate copolymer) may usually be 2% by mass or more, preferably 4% by mass or more, more preferably 6% by mass or more, from the viewpoints of the stretchability or flexibility of the above-mentioned (A) stretch film and the stretchability of the above-mentioned (B) coating film, with the total of all structural units being 100% by mass. On the other hand, from the viewpoint of the blocking resistance of the above-mentioned (A) stretch film, it may usually be 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

[0041] As the above-mentioned polyolefin resin, one or a mixture of two or more of these can be used.

[0042] Examples of resins other than the above-mentioned polyolefin resin that can be included in the resin mixture containing the above-mentioned polyolefin resin (resin mixture containing a polyolefin resin) include, for example, a random copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product of the random copolymer, a block copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product of the block copolymer, a polyvinyl chloride resin, and a polyvinyl acetate resin.

[0043] Examples of the random copolymer of an aromatic vinyl compound and a conjugated diene compound include, for example, styrene-butadiene random copolymer (SBR). Examples of the hydrogenated product of the random copolymer of an aromatic vinyl compound and a conjugated diene compound include, for example, the hydrogenated product of styrene-butadiene random copolymer (HSBR).

[0044] Examples of the block copolymer of the aromatic vinyl compound and the conjugated diene compound include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), etc. Examples of the hydrogenated product of the block copolymer of the aromatic vinyl compound and the conjugated diene compound include styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated product of styrene-butadiene-styrene copolymer: SBBS), partially hydrogenated product of styrene-isoprene-styrene copolymer, and partially hydrogenated product of styrene-isoprene-butadiene-styrene copolymer, etc.

[0045] Examples of the above polyvinyl chloride resin include polyvinyl chloride (vinyl chloride homopolymer), vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-(meth)methyl acrylate copolymer, vinyl chloride-(meth)ethyl acrylate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, and vinyl chloride-based copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride such as various vinyl ether copolymers; and modified (chlorinated, etc.) products of polyvinyl chloride and vinyl chloride-based copolymers such as post-chlorinated vinyl copolymers, etc.

[0046] Examples of the polyvinyl acetate resin include polyvinyl acetate (vinyl acetate homopolymer), vinyl acetate-ethylene copolymer (copolymer having a content of structural units derived from vinyl acetate of 50% by mass or more based on the total of all structural units being 100% by mass), and vinyl acetate-vinyl chloride copolymer.

[0047] As the resin used for forming the above-mentioned (A) stretch film, one or a mixture of two or more of these can be used.

[0048] The resin used for forming the above-mentioned (A) stretch film may further contain optional components to the extent not contrary to the object of the present invention. Examples of the optional components include antioxidants, weathering stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, slip agents, antiblocking agents, inorganic particles, organic particles, pigments, and dyes. The blending amount of the optional components may usually be about 10 parts by mass or less, about 5 parts by mass or less, about 0.01 to 10 parts by mass, or about 0.1 to 5 parts by mass.

[0049] The method for forming the above-mentioned (A) stretch film is not particularly limited, and known film forming methods can be used. Examples of the film forming methods include a method of forming a film using a calender roll rolling film forming apparatus equipped with a calender roll rolling machine and a winding device; a method of forming a film using a T-die film forming apparatus equipped with an extruder, a T-die, and a winding device; and a method of forming a film using an inflation film forming apparatus equipped with an extruder, a circular die, an inflation device, and a winding device having a nip mechanism.

[0050] Examples of the calender roll rolling machine include vertical three-roll, vertical four-roll, L-type four-roll, reverse L-type four-roll, and Z-type rolls. Examples of the extruder include single-screw extruder, co-rotating twin-screw extruder, and counter-rotating twin-screw extruder. Examples of the T-die include manifold die, fish-tail die, and coat-hanger die.

[0051] As a method for forming the above-mentioned (A) stretch film, a method of forming a film using a T-die film forming apparatus including an extruder, a T-die, and a rewinding apparatus having a mechanism for nipping the molten film extruded from the T-die between a cooling roll and a receiving roll is preferable. As the above-mentioned cooling roll, by using a roll whose surface is embossed to an appropriate roughness, typically a satin-finished metal roll (satin metal roll), the arithmetic mean roughness (Ra) of the surface of the above-mentioned (A) stretch film on the side pressed by the cooling roll can be controlled. As the above-mentioned receiving roll, by using a roll whose surface is embossed to an appropriate roughness, typically a satin-finished rubber roll (satin rubber roll), the arithmetic mean roughness (Ra) of the surface of the above-mentioned (A) stretch film on the side pressed by the receiving roll can be controlled.

[0052] From the viewpoint of the adhesion between the above-mentioned (A) stretch film and the above-mentioned (B) coating film, the arithmetic mean roughness (Ra) of the above-mentioned (B) coating film forming surface of the above-mentioned (A) stretch film is preferably 0.1 μm or more, more preferably 0.2 μm or more. From the viewpoint of developing stretchability in the above-mentioned (B) coating film, it may be further preferably 0.8 μm or more, still more preferably 1 μm or more, even more preferably 2 μm or more, and most preferably 3 μm or more. On the other hand, from the viewpoint of smoothing the surface of the above-mentioned (B) coating film, it is usually 10 μm or less, preferably 7 μm or less, and more preferably 5 μm or less.

[0053] Here, the arithmetic mean roughness (Ra) is a value measured in accordance with JIS B0601:2013 under the conditions that the cut-off value λc is 0.80 mm and the evaluation length L is 4.0 mm.

[0054] The thickness of the above-mentioned (A) stretch film is not particularly limited and is appropriately selected in consideration of the use of the protective film. From the perspective of the handleability of the protective film, the thickness of the above-mentioned (A) stretch film may usually be 20 μm or more, preferably 30 μm or more, more preferably 50 μm or more. On the other hand, from the perspective of workability when stretching and laminating the protective film to follow the surface shape of the article, it may usually be 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less.

[0055] 1-2. (B) Coated film The above-mentioned (B) coating film is usually formed on at least one surface of the above-mentioned (A) stretch film, preferably on one surface. The above-mentioned (B) coating film is formed using a paint containing the above-mentioned component (b1) active energy ray curable resin. Therefore, the coating film laminated film of the present invention has high productivity during production. The above-mentioned (B) coating film functions to impart functions such as scratch resistance, water repellency, antibacterial property, antiviral property, antireflection property, and infrared ray shielding property to the coating film laminated film of the present invention.

[0056] In one embodiment, the above-mentioned (B) coating film may be formed using a paint containing the above-mentioned component (b1) active energy ray curable resin and (b2) a photopolymerization initiator. In one preferred embodiment, the above-mentioned (B) coating film may be formed using a paint containing the above-mentioned component (b1) active energy ray curable resin, the above-mentioned component (b2) photopolymerization initiator, and (b3) a functionalizing agent. Hereinafter, each component will be described.

[0057] (b1) Active energy ray curable resin The above-mentioned component (b1) active energy ray curable resin functions to polymerize and cure by active energy rays such as ultraviolet rays and electron beams to form a coating film (cured coating film).

[0058] Examples of the component (a1) include (meth)acryloyl group-containing prepolymers or oligomers such as polyurethane (meth)acrylate, polyester (meth)acrylate, polyacrylic (meth)acrylate, epoxy (meth)acrylate, polyalkylene glycol poly(meth)acrylate, and polyether (meth)acrylate; (meth)acryloyl group-containing monofunctional reactive monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenyl cellosolve (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, and trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; (meth)acryloyl group-containing bifunctional reactive monomers such as diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane; (meth)acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate; (meth)acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra(meth)acrylate; and (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate. One or more selected from these, or a resin having one or more of the above as constituent monomers, can be mentioned.In this specification, "(meth)acrylate" means acrylate or methacrylate.

[0059] As the above component (b1), one or a mixture of two or more of these can be used.

[0060] (b2) Photoinitiator The above component (b2), the photoinitiator, is a compound that generates active species such as radicals upon irradiation with active energy rays. By generating active species such as radicals, the above component (b2) functions to polymerize and cure the above component (b1), the active energy ray-curable resin, and completely cure the coating film.

[0061] Examples of the above component (b2) photoinitiator include benzophenone compounds such as benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one, α-hydroxyalkylphenone compounds, and alkylphenone compounds such as acetophenone dimethyl acetal; anthraquinone compounds such as methyl anthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; acylphosphine oxide compounds; biimidazole compounds; titanocene compounds; oxime ester compounds; oxime phenylacetic acid ester compounds; hydroxyketone compounds; triazine compounds; and aminobenzoate compounds, etc.

[0062] From the viewpoint of ensuring complete curing of the coating film, a compound that generates radicals upon irradiation with active energy rays is preferable as the above component (b2).

[0063] As the above component (b2), one or a mixture of two or more of these can be used.

[0064] The blending amount of the above component (b2) is appropriately selected from the viewpoints of suppressing the pot life of the paint and the coloring of the coating film (cured coating film), and ensuring the complete curing of the coating film. From the viewpoint of ensuring the complete curing of the coating film, the blending amount of the above component (b2) is usually 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more, based on 100 parts by mass of the above component (b1). On the other hand, from the viewpoints of suppressing the pot life of the paint and the coloring of the coating film (cured coating film), it may be usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 6 parts by mass or less.

[0065] (a3) Functionalizing agent The above paint (B) for forming a coating film may further contain the above component (b3) functionalizing agent. The above component (b3) functionalizing agent functions to impart a function to the above (B) coating film.

[0066] Examples of the above component (b3) functionalizing agent include (b3-1) a functionalizing agent for an organic compound that exhibits a function by being present on the coating film surface, (b3-2) fine particles of an inorganic compound that functions as an antibacterial agent or an antiviral agent, (b3-3) low refractive index fine particles, (b3-4) high refractive index fine particles, and (b3-5) heat ray shielding fine particles.

[0067] Examples of the above component (b3-1) functionalizing agent for an organic compound that exhibits a function by being present on the coating film surface include a water repellent, an oil repellent, an antistatic agent, an anti-fouling agent, an anti-fogging agent, an anti-mold agent, and an insect repellent.

[0068] Examples of the above component (b3-2) fine particles of an inorganic compound that functions as an antibacterial agent or an antiviral agent include fine particles of a copper compound, a silver compound, a tin compound, a molybdenum compound, and a zinc compound. Examples of the above copper compound include cuprous halides such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous compounds such as cuprous thiocyanate (CuSCN); cupric carbonate (CuCO 3) Copper(II) oxide (CuO), and copper(II) chloride (CuCl 2 ) and other copper(II) compounds can be mentioned. Examples of the silver compound include silver halide compounds such as silver(I) iodide (AgI). Examples of the tin compound include tin halide compounds such as tin(IV) iodide (SnI 4 ). Examples of the molybdenum compound include molybdenum oxide compounds such as molybdenum(VI) oxide (MoO 3 ), molybdenum-silver composite oxides, molybdenum-zinc composite oxides, and molybdenum-copper composite oxides. Examples of the zinc compound include zinc oxide compounds such as zinc oxide (ZnO).

[0069] Other examples of the fine particles of the inorganic compound that functions as the antibacterial agent or antiviral agent in the component (b3-2) include, for example, potassium aluminum sulfate, zirconium silver sodium hydrogen phosphate, silver magnesium aluminum phosphate glass (FCN registration number 433 of the U.S. Food and Drug Administration), silver magnesium calcium phosphate borate glass (FCN registration number 432 of the U.S. Food and Drug Administration), silver zinc magnesium aluminum calcium sodium borate phosphate glass (FCN registration number 476 of the U.S. Food and Drug Administration), silver magnesium sodium phosphate glass (FCN registration number 434 of the U.S. Food and Drug Administration), silver zinc magnesium aluminum calcium sodium borate phosphate glass (FCN registration number 1981 of the U.S. Food and Drug Administration), silver zeolite (CAS number 0130328-18-6), silver copper zeolite (CAS number 0130328-19-7), silver zinc zeolite (CAS number 0130328-20-0), and fine particles such as copper-tin alloy.

[0070] The average particle diameter of the fine particles of the inorganic compound that functions as the above component (b3-2), an antibacterial agent or an antiviral agent, is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less from the viewpoint of productivity when forming the above (B) coating film. When it is desired to impart a clear transparency to the above (A) coating film, the average particle diameter of the above component (b3-2) may usually be 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less. On the other hand, there is no particular lower limit for the average particle diameter of the above component (a3-2), but from the viewpoint of productivity when producing the fine particles of the inorganic compound that functions as the above antibacterial agent or antiviral agent, it may usually be 1 nm or more.

[0071] In this specification, the average particle diameter is the particle diameter at which the cumulative percentage from the smaller particles reaches 50% by mass in the particle size distribution curve measured by the laser diffraction / scattering method using a laser diffraction / scattering particle size analyzer. As the above laser diffraction / scattering particle size analyzer, for example, "MT3200II (trade name)" of Nikkiso Co., Ltd. can be used.

[0072] Examples of the above component (b3-3), low refractive index fine particles, include fine particles (solid fine particles) of low refractive index materials such as silica, magnesium fluoride, fluororesin, and silicone resin, and hollow fine particles.

[0073] The average particle diameter of the above component (b3-3), low refractive index fine particles, is appropriately determined in consideration of the thickness of the low refractive index layer and the productivity when producing the low refractive index fine particles. The average particle diameter of the above component (b3-3) may usually be 1 to 150 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and still more preferably 15 to 60 nm. The definition and measurement method of the average particle diameter are as described above.

[0074] Examples of the above component (b3-4), high refractive index fine particles, include metal oxides such as titanium oxide, zinc oxide, indium oxide, tin oxide, zirconium oxide, and aluminum oxide; and fine particles of composite oxides in which these metal oxides are doped with foreign elements such as antimony and tin.

[0075] The average particle diameter of the above component (b3-4) high refractive index fine particles is appropriately determined in consideration of the viewpoint of maintaining transparency and the productivity in manufacturing the high refractive index fine particles. The average particle diameter of the above component (b3-4) may usually be 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and still more preferably 15 to 100 nm. The definition and measurement method of the average particle diameter have been described above.

[0076] Examples of the above component (b3-5) heat ray shielding fine particles include fine particles such as tin-doped indium oxide, antimony-doped tin oxide, cesium-doped tungsten oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and niobium-doped titanium oxide.

[0077] The average particle diameter of the above component (b3-5) heat ray shielding fine particles is appropriately determined in consideration of the viewpoint of maintaining transparency and the productivity in manufacturing the heat ray shielding fine particles. The average particle diameter of the above component (b3-5) may usually be 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and still more preferably 15 to 100 nm. The definition and measurement method of the average particle diameter have been described above.

[0078] As the above component (b3) functionalizing agent, one or a mixture of two or more of these can be used.

[0079] The blending amount of the above component (b3) is appropriately selected in consideration of the type of the functionalizing agent, from the viewpoints of surely expressing the function and suppressing troubles caused by an excessive blending amount of the functionalizing agent.

[0080] When using, as the component (b3) functionalizing agent, a functionalizing agent of an organic compound that exhibits its function by being present on the surface of the component (b3-1) coating film, the blending amount of the component (b3-1) is usually 0.1 part by mass or more, preferably 0.5 part by mass or more, more preferably 1 part by mass or more, from the viewpoint of reliably exhibiting the function, based on 100 parts by mass of the component (b1). On the other hand, the blending amount of the component (b3-1) is usually 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less, from the viewpoint of suppressing bleed-out.

[0081] When using, as the component (b3) functionalizing agent, fine particles of an inorganic compound that functions as an antibacterial agent or an antiviral agent as the component (b3-2), the blending amount of the component (b3-2) is usually 1 part by mass or more, preferably 3 part by mass or more, more preferably 5 part by mass or more, from the viewpoint of reliably exhibiting antibacterial or antiviral properties, based on 100 parts by mass of the component (b1). On the other hand, the blending amount of the component (b3-2) is usually 100 parts by mass or less, preferably 60 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoints of the coating workability of the paint and maintaining the transparency of the coating film.

[0082] When using, as the component (b3) functionalizing agent, the component (b3-3) low refractive index fine particles and attempting to make the (B) coating film function as a low refractive index layer, the blending amount of the component (b3-3) is usually 10 to 200 parts by mass, preferably 20 to 100 parts by mass, more preferably 30 to 80 parts by mass, based on 100 parts by mass of the component (b1). Here, the refractive index of the low refractive index layer may usually be 1.2 to 1.5, preferably 1.25 to 1.45, more preferably 1.28 to 1.4.

[0083] In this specification, the refractive index of the above-mentioned (B) coating film is measured in accordance with Method A of JIS K7142:2008, using an Abbe refractometer, with a sodium D line (wavelength 589.3 nm), a contact liquid of 1-bromonaphthalene, the surface of the biaxially stretched polypropylene-based resin film side when preparing the sample being in contact with the prism, and the bar coater operation direction of the sample being in the length direction of the test piece. For the sample, the paint used for forming the above-mentioned (B) coating film is applied onto the surface of a biaxially stretched polypropylene-based resin film with a thickness of 20 μm using a bar coater so that the thickness after curing is 2 μm, and the obtained coating film after drying and curing is peeled off from the biaxially stretched polypropylene-based resin film and used.

[0084] When using the above-mentioned component (b3-4) high refractive index fine particles as the above-mentioned component (b3) functionalizing agent and attempting to make the above-mentioned (B) coating film function as a high refractive index layer, the blending amount of the above-mentioned component (b3-4) may be usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and still more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the above-mentioned component (b1). Here, the refractive index of the above-mentioned high refractive index layer may be usually 1.55 to 2.0, preferably 1.6 to 1.9, and more preferably 1.65 to 1.8. The definition and measurement method of the refractive index have been described above.

[0085] When using the above-mentioned component (b3-5) heat ray shielding fine particles as the above-mentioned component (b3) functionalizing agent and attempting to make the above-mentioned (B) coating film function as a heat ray shielding layer, the blending amount of the above-mentioned component (b3-5) may be usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and still more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the above-mentioned component (b1). Here, the shielding coefficient of the coating film laminated film having the above-mentioned heat ray shielding layer may be usually 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.

[0086] In this specification, the shading coefficient of the above-mentioned (B) coating film is calculated according to the calculation of the shading coefficient and solar heat gain factor in JIS A5759:2016. The solar transmittance and solar reflectance are measured under the condition that the surface on the heat ray shielding layer side of the test piece (a laminate of a specified glass plate and a coating film laminated film according to the above JIS standard) faces the light source. After measuring the normal emissivity with the glass surface of the test piece as the indoor side surface and the surface on the heat ray shielding layer side of the test piece as the outdoor side surface, calculating the corrected emissivity, it is calculated by the formula (4) of the above JIS standard.

[0087] The coating material for forming the above-mentioned (B) coating film may further contain optional components other than the above components (b1) to (b3) to the extent that it does not conflict with the object of the present invention. Examples of the optional components include silane coupling agents, defoaming agents, leveling agents, surfactants, thixotropic agents, printability improvers, dispersants (for example, amine-based dispersants such as phosphate esters of high molecular weight copolymers having a polyamine structure), antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, inorganic particles, organic particles, pigments, and dyes. As the optional components, one or a mixture of two or more of these can be used. The blending amount of the optional components may be usually 10 parts by mass or less, 5 parts by mass or less, 0.01 to 5 parts by mass, or about 0.01 to 10 parts by mass with respect to 100 parts by mass of the above component (a1).

[0088] The coating material for forming the above-mentioned (B) coating film may further contain a solvent from the viewpoint of productivity when forming a wet coating film. The solvent is not particularly limited as long as it does not react with the above components (b1) to (b3) and the above optional components or catalyze (promote) the self-reaction (including degradation reaction) of these components. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. As the solvent, one or a mixture of two or more of these can be used.

[0089] The coating material for forming the above-mentioned (B) coating film can be obtained by mixing and stirring these components.

[0090] The above-mentioned (B) coating film is formed by directly applying the coating material for forming the above-mentioned (B) coating film on at least one surface of the above-mentioned (A) stretch film, usually on one surface, to form a wet coating film, pre-drying it, and then irradiating it with active energy rays to cure it. That is, the above-mentioned (B) coating film is directly formed on the surface of the above-mentioned (A) stretch film.

[0091] Here, "the above-mentioned (B) coating film is directly formed on the surface of the above-mentioned (A) stretch film" means that no other layer such as an anchor coat is interposed between the above-mentioned (A) stretch film and the above-mentioned (B) coating film, and it is not intended to exclude corona discharge treatment or plasma treatment of the (B) coating film forming surface of the above-mentioned (A) stretch film.

[0092] The method of directly applying the coating material for forming the above-mentioned (B) coating film on the surface of the above-mentioned (A) stretch film to form a wet coating film is not particularly limited, and known coating methods can be used. From the perspective of applying the coating material with good productivity by the roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

[0093] The method of the above-mentioned pre-drying is not particularly limited, and known drying methods can be used. As the method of the above-mentioned pre-drying, for example, the web is passed through a drying furnace usually set at a temperature of about 23 to 150 °C, preferably at a temperature of 40 to 100 °C, more preferably 50 to 80 °C, at a line speed such that the time required to pass from the inlet to the outlet is about 0.5 to 10 minutes, preferably 1 to 5 minutes.

[0094] The irradiation dose of the active energy ray is appropriately determined in consideration of the properties of the paint from the viewpoint of being sufficient to completely cure the coating film. The irradiation dose of the active energy ray is usually 10 to 10,000 mJ / cm 2 or so, preferably 200 to 2,000 mJ / cm 2 , more preferably 300 to 700 mJ / cm 2 may be.

[0095] The thickness of the above-mentioned (B) coating film is appropriately determined from the viewpoints of adhesion to the above-mentioned (A) stretch film and scratch resistance. The thickness of the above-mentioned (B) coating film is usually 16 μm or less from the viewpoint of adhesion to the above-mentioned (A) stretch film. The thickness of the above-mentioned (B) coating film may preferably be 12 μm or less, more preferably 9.5 μm or less, and still more preferably 7 μm or less from the viewpoint of adhesion to the above-mentioned (A) stretch film. The thickness of the above-mentioned (B) coating film may be even more preferably 5.5 μm or less, and most preferably 4 μm or less from the viewpoint of developing stretchability in the above-mentioned (B) coating film. On the other hand, the thickness of the above-mentioned (B) coating film may be usually 0.5 μm or more, preferably 1 μm or more, and more preferably 1.5 μm or more from the viewpoint of scratch resistance.

[0096] As a method for controlling the thickness of the above-mentioned (B) coating film to the designed thickness, as described above, the following method is preferable. First, a preliminary experiment is carried out in advance. Typically, a coating film is formed on the surface of a film substrate with a smooth surface, for example, a biaxially stretched polyethylene terephthalate resin film, using the paint for forming the above-mentioned (B) coating film to obtain a relational expression between the coating conditions of the paint and the thickness (thickness after curing) of the coating film. Next, when producing the coating film laminated film of the present invention, the thickness of the above-mentioned (B) coating film is controlled to the designed thickness based on the relational expression.

[0097] The coating film laminated film of the present invention usually satisfies the following formula (1) when the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above-mentioned (A) stretch film is a (unit: μm) and the thickness of the above-mentioned (B) coating film is b (unit: μm). It may preferably satisfy the following formula (1-2), more preferably satisfy the following formula (1-3), and still more preferably satisfy the following formula (2). b ≤ 3a + 5.5 ···(1) b ≤ 3a + 5 ···(1-2) b ≤ 3a + 4.5 ···(1-3) b ≤ 3a + 4 ···(2)

[0098] Here, the arithmetic mean roughness (Ra) conforms to JIS B0601:2013 and is a value measured under the conditions that the cut-off value λc is 0.80 mm and the evaluation length L is 4.0 mm.

[0099] Although the coating film of the present invention is directly formed on the surface of the stretch film of (A) above, and further, even if the coating film forming surface of the stretch film of (A) is formed of a polyolefin resin, the stretch film of (A) and the coating film of (B) exhibit good adhesion. However, such a coating film laminated film usually has a thickness of the coating film of (B) of 16 μm or less and satisfies the above formula (1).

[0100] Although the coating film of the present invention is preferably formed using a paint containing an active energy ray curable resin, the coating film of (B) exhibits stretchability. Here, when the coating film has stretchability, except for using a strip-shaped test piece with a width of 10 mm and a length of 150 mm taken from the coating film laminated film so that the machine direction becomes the tensile direction, in accordance with JIS K7161-2:2014, at a temperature of 23 ± 2°C and a relative humidity of 50 ± 10%, when a tensile test of the coating film laminated film is performed under the conditions of a gauge length of 50 mm, a chuck distance of 50 mm, and a tensile speed of 50 mm / min, the tensile strain when the gloss / sheen on the surface of the coating film partially or entirely changes (technically presumed to be coating film cracking) is usually 5% or more, preferably 10% or more, more preferably 15% or more.

[0101] Although there is no intention to be restricted by theory, even though the above-mentioned (B) coating film is formed using a paint containing an active energy ray-curable resin, the reason for the expression of stretchability is considered as follows. By irradiation with active energy rays, double bonds are generated in the resin constituting the (B) coating film formation surface of the above-mentioned (A) stretch film. For example, when the resin constituting the (B) coating film formation surface of the above-mentioned (A) stretch film is an ethylene-vinyl acetate copolymer, acetic acid is eliminated from the structural unit derived from vinyl acetate, and double bonds are generated. Then, the double bonds crosslink with the polymerization sites (acryloyl group, methacryloyl group, etc.) of the active energy ray-curable resin. As a result, the above-mentioned (B) coating film is crosslinked and reinforced with the above-mentioned (A) stretch film by a large number of chemical bonds. Furthermore, the coating film laminated film of the present invention originally exhibits good adhesion between the above-mentioned (A) stretch film and the above-mentioned (B) coating film. Therefore, although the above-mentioned (B) coating film is a coating film formed using a paint containing an active energy ray-curable resin, it comes to exhibit stretchability.

[0102] In addition, since a large number of crosslinking points are formed between the above-mentioned (B) coating film and the above-mentioned (A) stretch film, when forming the above-mentioned (B) coating film on the surface of the above-mentioned (A) stretch film, it is not necessary to perform an easy adhesion treatment on the (B) coating film formation surface of the above-mentioned (A) stretch film.

[0103] 1-3. (C) Adhesive layer In one embodiment, the coating film laminated protective film of the present invention may have the above-mentioned (B) coating film, the above-mentioned (A) stretch film, and the above-mentioned (C) adhesive layer in this order. By providing the above-mentioned (C) adhesive layer, it becomes possible to bond regardless of the material and surface state (such as surface smoothness) of the surface (protective film bonding surface) of the article.

[0104] The pressure-sensitive adhesive used for forming the above-mentioned (C) pressure-sensitive adhesive layer is not particularly limited and is appropriately determined in consideration of the material of the surface of the article to which the protective film is to be laminated and the purpose of laminating the protective film. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and silicone pressure-sensitive adhesives. As the pressure-sensitive adhesive, one kind or a mixture of two or more kinds of these can be used.

[0105] The above-mentioned pressure-sensitive adhesive can further contain optional components other than the resin component of the pressure-sensitive adhesive, as desired, within the limit not contrary to the object of the present invention. Examples of the optional components include additives such as photopolymerization initiators, compounds having two or more isocyanate groups in one molecule, flame retardants, antistatic agents, surfactants, leveling agents, thixotropy-imparting agents, anti-pollution agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments, dyes, inorganic particles, and organic particles. The blending amount of the optional components may be usually 100 parts by mass or less, 50 parts by mass or less, 0.01 to 100 parts by mass, or about 0.01 to 50 parts by mass, with the resin component of the pressure-sensitive adhesive being 100 parts by mass.

[0106] The pressure-sensitive adhesive used for forming the above-mentioned (C) pressure-sensitive adhesive layer may further contain a solvent from the viewpoint of productivity when forming a wet coating film. The solvent is not particularly limited as long as it does not react with the resin component of the pressure-sensitive adhesive and the above-mentioned optional components or catalyze (accelerate) the self-reaction (including degradation reaction) of these components. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. As the solvent, one kind or a mixture of two or more kinds of these can be used.

[0107] The pressure-sensitive adhesive used for forming the above-mentioned (C) pressure-sensitive adhesive layer can be obtained by mixing and stirring these components.

[0108] The above-mentioned (C) adhesive layer is formed by applying an adhesive used for forming the (C) adhesive layer directly or via an anchor on the surface of the above-mentioned (A) stretch film opposite to the surface on which the above-mentioned (B) coating film is formed to form a wet coating film, and then drying it. Alternatively, after forming an adhesive layer by applying an adhesive used for forming the (C) adhesive layer on the surface of an arbitrary film substrate to form a wet coating film and drying it, this may be transferred onto the surface of the above-mentioned (A) stretch film opposite to the surface on which the above-mentioned (B) coating film is formed.

[0109] The method for forming a wet coating film of the adhesive used for forming the above-mentioned (C) adhesive layer is not particularly limited, and known coating methods can be used. From the viewpoint of applying the adhesive with good productivity by a roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

[0110] The method for the above-mentioned drying is not particularly limited, and known drying methods can be used. As the above-mentioned drying method, for example, the web is passed through a drying furnace usually set at a temperature of about 23 to 150 °C, preferably 40 to 100 °C, more preferably 50 to 80 °C, and the time required to pass from the inlet to the outlet is about 0.5 to 10 minutes, preferably 1 to 5 minutes, at a line speed such that this can be achieved.

[0111] The thickness of the above-mentioned (C) adhesive layer is not particularly limited, and it is appropriately selected in consideration of the material and surface state (such as surface smoothness) of the article to which the protective film is adhered, and the purpose of adhering the protective film. From the viewpoint of adhesive strength, the thickness of the above-mentioned (C) adhesive layer may usually be 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. On the other hand, from the viewpoint of productivity when forming the above-mentioned (C) adhesive layer, it may usually be 100 μm or less, preferably 60 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less.

[0112] Figure 1 is a conceptual cross-sectional view showing an example of the coating film laminated film of the present invention. It has a coating film 1 (B), a layer 2 forming the (B) coating film 1 forming surface of the (A) stretch film, an intermediate layer 3 of the (A) stretch film, a layer 4 forming the (C) adhesive layer 5 forming surface of the (A) stretch film, and a (C) adhesive layer 5. The layer 2 forming the (B) coating film 1 forming surface of the (A) stretch film and the layer 4 forming the (C) adhesive layer 5 forming surface of the (A) stretch film are formed using a virgin material of ethylene-vinyl acetate copolymer. The intermediate layer 3 of the (A) stretch film is formed using a mixture of a virgin material of ethylene-vinyl acetate copolymer and a recycled material such as film ears (parts at both ends in the width direction where the thickness is outside the set range during film formation).

Example

[0113] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

[0114] Measurement method (a) Grid test 1 (adhesion of coating film): According to JIS K5600-5-6:1999, after making 25 grid cuts (1 grid = 2 mm × 2 mm) from the coating film side of the coating film laminated film, a tape for adhesion test was attached to the grid, rubbed with a finger, and then peeled off. The evaluation criteria followed Table 1 of the above JIS standard. The adhesion of the coating film of the coating film laminated film of the present invention may preferably be Classification 2, Classification 1, or Classification 0, more preferably Classification 1 or Classification 0, and still more preferably Classification 0. Classification 0: The edges of the cuts are completely smooth and there is no peeling in any of the grid cells. Classification 1: Small peeling of the coating film at the intersections of the cuts. The part affected by the cross-cut does not clearly exceed 5%. Classification 2: The coating film is peeled along the edges of the cuts and / or at the intersections. The part affected by the cross-cut clearly exceeds 5% but does not exceed 15%. Classification 3: The coating film has partially or completely peeled off along the edge of the cut, and / or various parts of the eyes have partially or completely peeled off. The cross-cut part is clearly affected by more than 15% but not more than 35%. Classification 4: The coating film has partially or completely peeled off along the edge of the cut, and / or several eyes have partially or completely peeled off. The cross-cut part is clearly affected by more than 35% but not more than 65%. Classification 5: When the degree of peeling exceeds that of Classification 4.

[0115] (b) Cross-cut test 2 (adhesion of the coating film after heat and humidity treatment): After treating the coating film laminated film in an environment of 60°C and 90% relative humidity for 50 hours, it was tested in the same manner as the above test (a) Cross-cut test 1.

[0116] (c) Elongation of the coating film: Except for using a strip-shaped test piece with a width of 10 mm and a length of 150 mm taken from the coating film laminated film so that the machine direction is the tensile direction, in an environment of 23 ± 2°C and 50 ± 10% relative humidity, when the tensile test of the coating film laminated film was conducted under the conditions of a gauge length of 50 mm, a chuck distance of 50 mm, and a tensile speed of 50 mm / min in accordance with JIS K7161-2:2014, the tensile strain (unit: %) when the gloss / sheen of the coating film surface changed partially or entirely (technically presumed to have coating film cracking) was measured as the elongation of the coating film. When the gloss / sheen of the coating film surface did not change up to a tensile strain of 50%, it was determined that the elongation of the coating film exceeded 50%, and it was described as ">50" in the table. When the gloss / sheen of the coating film surface changed at a tensile strain of less than 2%, it was described as "<2".

[0117] (d) Chemical resistance 1: 20 ml of acetone was mixed with 10 drops of Pilot Corporation's red ink "Pilot Ink Red" (trade name) to prepare a test solution. A test piece measuring 50 mm × 50 mm was cut from the coated film laminate. Using a dropper, 5 drops of the above test solution were dropped onto the coated film surface of the test piece, and then covered with a watch glass. After leaving it standing for 24 hours in an environment at a temperature of 23 ± 2°C and a relative humidity of 50 ± 10%, the test piece was wiped with a paper wiper soaked with water and then dried with a dry paper wiper to remove the test solution adhering to the surface of the test piece. Thereafter, the location where the test solution was dropped on the test piece and its surroundings were visually observed by a person with a corrected visual acuity of 1.0, either with the naked eye or using a magnifying glass (10×), and evaluated according to the following criteria. A: Even when using a magnifying glass, no cracks or deformations were observed. No difference in color tone was observed between the part of the coated film laminate that had come into contact with the test solution and the part that had not. B: Even when using a magnifying glass, no cracks or deformations were observed. However, there was a difference in color tone between the part of the coated film laminate that had come into contact with the test solution and the part that had not (the contact part was redder compared to the non-contact part). C: No cracks or deformations were observed with the naked eye. However, when using a magnifying glass, cracks and deformations were observed. D: Cracks and deformations were observed even with the naked eye.

[0118] (e) Chemical resistance 2: The test was conducted and evaluated in the same manner as in the above test (d) Chemical resistance 1, except that 2-propanol was used instead of acetone.

[0119] (f) Water contact angle (water repellency): Using a DSA20 (trade name) automatic contact angle meter manufactured by KRUSS, the water contact angle (unit: degree) of the coated film surface of the protective film was measured in accordance with JIS R3257:1999, 6. Static drop method (the method calculated from the width and height of the water drop), except that the volume of the water drop was 8 μL.

[0120] Raw materials used (a) Raw materials of the stretch film: (a-1) Ethylene vinyl acetate copolymer "Evaflex V5711 (trade name)" of Mitsui Dow Chemical Co., Ltd., content of structural units derived from vinyl acetate 10% by mass, melt flow rate (190 °C, 21.18 N) 3 g / 10 min, melting point 95 °C. (a-2) Ethylene-α-olefin copolymer "Kernel KF283 (trade name)" of Nippon Polyethylene Co., Ltd., density 921 Kg / m 3 , melt mass flow rate (190 °C, 21.18 N) 2.5 g / 10 min, melting point 124 °C (having three peaks of peak top temperatures of 107 °C, 118 °C, and 124 °C). (a-3) Ethylene methacrylic acid copolymer "Nuclel N0903HC (trade name)" of Mitsui Dow Chemical Co., Ltd., melt mass flow rate (190 °C, 21.18 N) 3 g / 10 min, content of structural units derived from methacrylic acid 9% by mass (content of structural units derived from ethylene 91% by mass), melting point 98 °C. (a-4) Ethylene ethyl acrylate copolymer "Lexparl A3100 (trade name)" of Nippon Polyethylene Co., Ltd., melt mass flow rate (190 °C, 21.18 N) 3 g / 10 min, content of structural units derived from ethyl acrylate 10% by mass (content of structural units derived from ethylene 90% by mass), melting point 100 °C. (a-5) Ethylene vinyl acetate copolymer "Ultra Sen 515 (trade name)" of Tosoh Corporation, melt mass flow rate 2.5 g / 10 min, content of structural units derived from vinyl acetate 6% by mass (content of structural units derived from ethylene 94% by mass), melting point 100 °C.

[0121] (A) Stretch film: (A-1) Using the above resin (a-1), a film-forming apparatus (a film-forming apparatus equipped with an extruder 6, a T-die 7, and a winding device having a mechanism that nips with a cooling roll 9 and a receiving roll 10) whose conceptual diagram is shown in FIG. 2 was used, and the above resin was continuously extruded from the T-die 7 as a molten film 8. At this time, as the cooling roll 9, a matte metal roll with an arithmetic mean roughness (Ra) of 3.8 μm on the roll surface was used, and as the receiving roll 10, a corrugated rubber roll with an arithmetic mean roughness (Ra) of 1.4 μm on the roll surface was used. The arithmetic mean roughness (Ra) of the roll surface is a value measured under the conditions of complying with JIS B0601:2013, a cut-off value λc of 0.80 mm, and an evaluation length L of 4.0 mm. Next, the extruded molten film 8 was fed and introduced between the rotating cooling roll 9 and the rotating receiving roll 10, and pressed by the cooling roll 9 and the receiving roll 10. Subsequently, the pressed molten film 8 was held by the cooling roll 9 and sent to the next rotating roll 11 to form a film 12 (stretch film (A-1)) with a thickness of 120 μm. At this time, the resin temperature at the T-die outlet was 210 °C, the surface temperature of the cooling roll 9 was 25 °C, the temperature of the cooling water flowing through the receiving roll 10 was 16 °C, and the winding speed was 15 m / min. The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-1) on the side pressed by the cooling roll 9 was 3.52 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.23 μm.

[0122] (A-2) A stretch film (A-2) with a thickness of 120 μm was formed in the same manner as the above stretch film (A-1), except that a matte metal roll with an arithmetic mean roughness (Ra) of 0.55 μm on the roll surface was used as the cooling roll 9 of the film-forming apparatus. The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-2) on the side pressed by the cooling roll 9 was 0.45 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.24 μm.

[0123] (A-3) As the cooling roll 9 of the film forming apparatus, an embossed metal roll with an arithmetic mean roughness (Ra) of the roll surface of 0.55 μm was used, and a stretch film (A-3) with a thickness of 120 μm was formed in the same manner as the stretch film (A-1) except that the resin (a-2) was used instead of the resin (a-1). The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-3) on the side pressed by the cooling roll 9 was 0.28 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.03 μm.

[0124] (A-4) As the cooling roll 9 of the film forming apparatus, an embossed metal roll with an arithmetic mean roughness (Ra) of the roll surface of 0.55 μm was used, and a stretch film (A-4) with a thickness of 120 μm was formed in the same manner as the stretch film (A-1) except that the resin (a-3) was used instead of the resin (a-1). The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-4) on the side pressed by the cooling roll 9 was 0.52 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.33 μm.

[0125] (A-5) As the cooling roll 9 of the film forming apparatus, an embossed metal roll with an arithmetic mean roughness (Ra) of the roll surface of 0.55 μm was used, and a stretch film (A-5) with a thickness of 120 μm was formed in the same manner as the stretch film (A-1) except that the resin (a-4) was used instead of the resin (a-1). The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-5) on the side pressed by the cooling roll 9 was 0.41 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.22 μm.

[0126] (A-6) As the cooling roll 9 of the film forming apparatus, an embossed metal roll with an arithmetic mean roughness (Ra) of the roll surface of 0.55 μm was used, and a stretch film (A-6) with a thickness of 120 μm was formed in the same manner as the stretch film (A-1) except that the resin (a-5) was used instead of the resin (a-1). The arithmetic mean roughness (Ra) of the surface of the obtained stretch film (A-6) on the side pressed by the cooling roll 9 was 0.39 μm, and the arithmetic mean roughness (Ra) of the surface on the side pressed by the receiving roll 10 was 1.21 μm.

[0127] Regarding the above stretch films (A-1) to (A-6), in accordance with JIS K7161-2:2014 except using strip-shaped test pieces with a width of 15 mm and a length of 150 mm taken so that the machine direction of the stretch film is the stretching direction, in an environment of a temperature of 23 ± 2°C and a relative humidity of 50 ± 10%, a tensile test was conducted under the conditions of a gauge length of 50 mm, a chuck distance of 50 mm, and a tensile speed of 200 mm / min, and the 5% strain tensile stress, 10% strain tensile stress, 25% strain tensile stress, tensile fracture stress, and tensile fracture strain were measured. The results are shown in Table 1. In Table 1, "Cooling roll side (Ra)" means the arithmetic mean roughness (Ra) of the surface of the stretch film on the side pressed by the cooling roll 9. "Receiving roll side (Ra)" means the arithmetic mean roughness (Ra) of the surface of the stretch film on the side pressed by the receiving roll 10.

[0128]

Table 1

[0129] (b) Raw materials used in the coating material for forming the coating film: (b1) Active energy ray curable resin: (b1-1) A solvent diluted solution of epoxy acrylate-based polyfunctional (meth) acrylate "Beam Set 371 (trade name)" of Arakawa Chemical Industries, Ltd., the number of (meth) acryloyl groups in one molecule is 6, the acid value is 0.32 KOHmg / g, the epoxy equivalent is 65 Kg / eq, and the solid content (content of the above epoxy acrylate-based polyfunctional (meth) acrylate) is 65% by mass. (b1-2) Dipentaerythritol hexaacrylate of Nippon Kayaku Co., Ltd. (b1-3) A solvent-diluted solution of a copolymer having a so-called dendrimer structure of "SIRIUS-501 (trade name)" of Osaka Organic Chemical Industry Co., Ltd., which is a copolymer of dipentaerythritol hexaacrylate and a tetrafunctional thiol, with a sulfur content of 2.2% by mass. The number average molecular weight in terms of polystyrene, mass average molecular weight, and Z average molecular weight were determined from the differential molecular weight distribution curve measured using gel permeation chromatography with tetrahydrofuran as the mobile phase, which were 940, 12000, and 73000 respectively, and the solid content (content of the above copolymer) was 50% by mass. (b1-4) A solvent-diluted solution of a polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd., "Art Resin UN-953 (trade name)", with a functional group number of 20. The number average molecular weight in terms of polystyrene, mass average molecular weight, and Z average molecular weight were determined from the differential molecular weight distribution curve measured using gel permeation chromatography with tetrahydrofuran as the mobile phase, which were 2000, 26000, and 110000 respectively, and the solid content (content of the above polyfunctional urethane (meth) acrylate) was 40% by mass.

[0130] (b2) Photoinitiator: (b2-1) An acetophenone-based photoinitiator (1-hydroxycyclohexyl-phenyl ketone) "Omnirad 184 (trade name)" of IGM Resins. (b2-2) An acetophenone-based photoinitiator (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one) "Omnirad 127 (trade name)" of IGM Resins.

[0131] (b3) Functionalizing agent: (b3-1) A solvent-diluted solution of an acryloyl group-containing fluoropolyether-based water repellent of Shin-Etsu Chemical Co., Ltd., "KY-1203 (trade name)", with a solid content (content of the above water repellent) of 20% by mass. (a3-2) Antiviral agent of NBC Mesh Tech Co., Ltd. (ethanol suspension of cuprous iodide fine particles), average particle diameter of cuprous iodide fine particles (particle diameter at which the cumulative value from the smaller particles becomes 50 mass% in the particle size distribution curve measured by laser diffraction / scattering method) 120 nm, solid content (content of the above cuprous iodide fine particles) 11 mass%.

[0132] (b4) Others: (b4-1) Amine-based dispersant "DISPER BYK-145 (trade name)" of Big Chem Japan Co., Ltd.

[0133] (b5) Solvent: (b5-1) Methyl isobutyl ketone. (b5-2) 2-Methoxyethanol. (b5-3) 1-Methoxy-2-propanol. (b5-4) Propylene glycol monomethyl ether acetate. (b5-5) Ethyl acetate.

[0134] (B) Paint for film formation (B-1) 154 parts by mass (100 parts by mass in terms of solid content) of the above component (b1-1), 3 parts by mass of the above component (b2-1), 1 part by mass of the above component (b2-2), 1 part by mass (0.2 part by mass in terms of solid content) of the above component (b3-1), 180 parts by mass of the above component (b5-1), and 80 parts by mass of the above component (b5-2) were mixed and stirred to obtain a paint for film formation (B-1).

[0135] (B-2) to (B-5): Paints (B-2) to (B-5) were obtained in the same manner as the above paint (B-1) except that the formulation was changed as shown in Table 2.

[0136] In addition, the values in terms of solid content of the components other than the solvent (the above components (b5-1) to (b5-5)) are described in Table 2.

[0137]

Table 2

[0138] Example 1 On the surface of the stretch film (A-1) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 3.52 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 3.

[0139] Examples 2 - 15 A coated film laminated film was obtained in the same manner as in Example 1, except that the paint shown in Table 3 was appropriately used instead of the above paint (B-1) as the paint for forming the above (B) coating film, and the coating amount was appropriately changed so that the film thickness after curing was the thickness shown in Table 3. The above tests (a) to (f) were conducted. The results are shown in Table 3.

[0140] Example 16 On the surface of the stretch film (A-2) pressed by the receiving roll 10 (the arithmetic mean roughness (Ra) is 1.24 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 3.

[0141] Examples 17 - 29 A coated film laminated film was obtained in the same manner as in Example 16, except that the paint shown in Table 3 or Table 4 was appropriately used instead of the above paint (B-1) as the paint for forming the above (B) coating film, and the coating amount was appropriately changed so that the film thickness after curing was the thickness shown in Table 3 or Table 4. The above tests (a) to (f) were conducted. The results are shown in Table 3 or Table 4.

[0142] Example 30 On the surface of the stretch film (A-2) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 0.45 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing would be 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 4.

[0143] Examples 31 - 43 As the paint for forming the above (B) coating film, except that the paint shown in Table 4 was appropriately used instead of the above paint (B-1), and the coating amount was appropriately changed so that the film thickness after curing would be the thickness shown in Table 4, a coated film laminated film was obtained in the same manner as in Example 30. The above tests (a) to (f) were conducted. The results are shown in Table 4.

[0144] Example 44 On the surface of the stretch film (A-3) pressed by the receiving roll 10 (the arithmetic mean roughness (Ra) is 1.03 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing would be 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 4.

[0145] Examples 44 - 57 As the paint for forming the above (B) coating film, except that the paint shown in Table 4 or Table 5 was appropriately used instead of the above paint (B-1), and the coating amount was appropriately changed so that the film thickness after curing would be the thickness shown in Table 4 or Table 5, a coated film laminated film was obtained in the same manner as in Example 44. The above tests (a) to (f) were conducted. The results are shown in Table 4 or Table 5.

[0146] Example 58 On the surface of the stretch film (A-3) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 0.28 μm), a film Mayer bar coating apparatus (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 5.

[0147] Examples 59 - 71 Except that the paint shown in Table 5 was appropriately used instead of the above paint (B-1) as the paint for forming the above (B) coating film, and the coating amount was appropriately changed so that the film thickness after curing was the thickness shown in Table 5, a coated film laminated film was obtained in the same manner as in Example 58. The above tests (a) to (f) were conducted. The results are shown in Table 5.

[0148] Example 72 On the surface of the stretch film (A-4) pressed by the receiving roll 10 (the arithmetic mean roughness (Ra) is 1.33 μm), a film Mayer bar coating apparatus (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 5.

[0149] Examples 73 - 85 Except that the paint shown in Table 6 was appropriately used instead of the above paint (B-1) as the paint for forming the above (B) coating film, and the coating amount was appropriately changed so that the film thickness after curing was the thickness shown in Table 6, a coated film laminated film was obtained in the same manner as in Example 72. The above tests (a) to (f) were conducted. The results are shown in Table 6.

[0150] Example 86 On the surface of the stretch film (A-4) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 0.52 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 6.

[0151] Examples 87 - 99 Except that the paints shown in Table 6 or Table 7 were appropriately used instead of the above paint (B-1) as the paint for forming the above (B) coating film, and the coating amount was appropriately changed so that the film thickness after curing was the thickness shown in Table 6 or Table 7, a coated film laminated film was obtained in the same manner as in Example 86. The above tests (a) to (f) were conducted. The results are shown in Table 6 or Table 7.

[0152] Example 100 On the surface of the stretch film (A-5) pressed by the receiving roll 10 (the arithmetic mean roughness (Ra) is 1.22 μm), a film Mayer bar coating device (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0153] Example 101 A coated film laminated film was obtained in the same manner as in Example 100 except that the coating amount was changed so that the film thickness after curing was 5 μm. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0154] Example 102 On the surface of the stretch film (A-5) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 0.41 μm), a film Mayer bar coater (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0155] Example 103 A coated film laminated film was obtained in the same manner as in Example 102, except that the coating amount was changed so that the film thickness after curing was 5 μm. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0156] Example 104 On the surface of the stretch film (A-6) pressed by the receiving roll 10 (the arithmetic mean roughness (Ra) is 1.21 μm), a film Mayer bar coater (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing was 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film to obtain a coated film laminated film. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0157] Example 105 A coated film laminated film was obtained in the same manner as in Example 104, except that the coating amount was changed so that the film thickness after curing was 5 μm. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0158] Example 106 On the surface of the stretch film (A-6) pressed by the cooling roll 9 (the arithmetic mean roughness (Ra) is 0.39 μm), a coating device of the film Mayer bar method (rod coating using a Mayer bar as a rod) was used, and the above paint (B-1) was applied so that the film thickness after curing would be 2.5 μm. After drying in a drying oven, ultraviolet rays were irradiated to form a cured coating film, and a coated film laminated film was obtained. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0159] Example 107 A coated film laminated film was obtained in the same manner as in Example 106 except that the coating amount was changed so that the film thickness after curing would be 5 μm. The above tests (a) to (f) were conducted. The results are shown in Table 7.

[0160]

Table 3

[0161]

Table 4

[0162]

Table 5

[0163]

Table 6

[0164]

Table 7

[0165] Although the coating film of the coating film laminated film of the present invention is directly formed on the surface of a stretch film made of a polyolefin resin as a film base material, it has been found that the adhesion between the coating film and the film base material is excellent. Therefore, it is considered that in the coating film laminated film of the present invention, even if the (B) coating film is directly formed on the surface of the (A) stretch film, and further even if the (B) coating film forming surface of the (A) stretch film is formed of a polyolefin resin, the (A) stretch film and the (B) coating film exhibit good adhesion. Also, it has been found that the coating film of the preferred coating film laminated film of the present invention exhibits stretchability. Therefore, it is considered that in the preferred coating film laminated film of the present invention, cracks in the coating film are less likely to occur even when stretched following the surface shape of an article. Furthermore, it has been found that the coating film laminated film of the present invention can impart chemical resistance and water repellency in one of the embodiments.

[0166] (C) Adhesive: (C-1) 270 parts by mass (100 parts by mass in terms of solid content) of the acrylic adhesive "Olivine BPS5296 (trade name)" of Toyochem Co., Ltd., 2.7 parts by mass (1.0 part by mass in terms of solid content) of the isocyanate curing agent "Olivine BXX4773 (trade name)" of Toyochem Co., Ltd., 1.5 parts by mass of the benzophenone-based ultraviolet absorber (2,2',4,4'-tetrahydroxybenzophenone) "SEESOR B106 (trade name)" of Shipro Kasei Co., Ltd., and 80 parts by mass of ethyl acetate were mixed and stirred to obtain a paint (C-1) for forming an adhesive layer.

[0167] Example 108 On the surface of the stretch film (A-1) of the coating film laminated film obtained in Example 12, on the side opposite to the (B) coating film forming surface, using a roll coater, the coating material (C-1) for forming the adhesive layer was applied so that the thickness after drying would be 20 μm, and then dried in a drying oven to form an adhesive layer, thereby obtaining a coating film laminated film with an adhesive layer. Next, the obtained coating film laminated film with an adhesive layer was adhered to the Braille of the train ticket vending machine using the adhesive layer. Subsequently, when it was confirmed whether the Braille of the train ticket vending machine could be read (or discriminated by touch), it was found that the Braille could be read without any problem. Also, it was confirmed that there was no change in the gloss / sheen of the coating film visually, that is, it was presumed that there were no cracks in the coating film.

[0168] Therefore, it was considered that the preferred coating film laminated film of the present invention can also be suitably used for protecting the surface of an article having a three-dimensional shape / solid shape.

[0169] Even if the coating film of the coating film laminated film of the present invention is directly formed on the surface of a stretch film made of a polyolefin resin as the film substrate, or particularly even if the coating film is directly formed on the surface of a stretch film made of linear low-density polyethylene, since the adhesion between the coating film and the film substrate is excellent, those skilled in the art will easily understand that even if a stretch film other than one in which the resin forming the coating film forming surface as the stretch film contains a polyolefin resin is used, the adhesion between the coating film and the film substrate will be excellent.

[0170] Aspects of the present invention may further be as follows. [1]. A coating film laminated film, (A) having a (B) coating film on at least one surface of a stretch film; the above (A) stretch film and the above (B) coating film are directly laminated; the resin forming the (B) coating film forming surface of the above (A) stretch film contains a polyolefin resin; The above-mentioned (B) coating film is formed using a paint (b) containing a (b1) radiation curable resin; When the crosshatch test is carried out in accordance with JIS K5600-5-6:1999 by making crosshatch cuts of 25 squares (1 square = 2 mm × 2 mm) from the coating film surface side of the coating film laminated film, it is classified as Class 2, Class 1, or Class 0; The above-mentioned coating film laminated film. [2]. The coating film laminated film according to item [1], wherein the resin forming the (B) coating film forming surface of the above-mentioned (A) stretch film contains an ethylene-based resin. [3]. The coating film laminated film according to item [1] or [2], wherein the resin forming the (B) coating film forming surface of the above-mentioned (A) stretch film contains an ethylene-vinyl acetate copolymer. [4]. The coating film laminated film according to any one of items [1] to [3], wherein the thickness of the above-mentioned (B) coating film is 16 μm or less. [5]. The coating film laminated film according to any one of items [1] to [4], wherein the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above-mentioned (A) stretch film is 0.1 μm or more. [6]. The thickness of the above-mentioned (B) coating film is 0.5 to 9.5 μm; When the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above-mentioned (A) stretch film is a (unit: μm) and the thickness of the above-mentioned (B) coating film is b (unit: μm), the following formula (2) is satisfied: b ≦ 3a + 4 ··· (2) The coating film laminated film according to any one of items [1] to [5]. [7]. The coating film laminated film according to any one of items [1] to [6], wherein the above-mentioned paint (b) contains 100 parts by mass of the above-mentioned (b1) radiation curable resin, 0.1 to 20 parts by mass of a (b2) photoinitiator, and 1 to 100 parts by mass of an inorganic compound functioning as an antibacterial agent or an antiviral agent. [8]. The coating film laminated film according to any one of items [1] to [7], which is for protecting the surface of an article. [9]. A method of using the coating film laminated film according to any one of [1] to [8] for protecting the surface of an article.

Brief Description of the Drawings

[0171]

Figure 1

Figure 2

Figure 3

Explanation of Reference Numerals

[0172] 1: (B) coating film 2: Layer constituting the (B) coating film 1 formation surface of the (A) stretch film 3: Intermediate layer of the (A) stretch film 4: Layer constituting the (C) adhesive layer 5 formation surface of the (A) stretch film 5: (C) adhesive layer 6: Extruder 7: T-die 8: Melted film 9: Cooling roll 10: Receiving roll 11: Rotating roll 12: Film

Claims

1. A coated film laminate, having (B) a coating film on at least one surface of (A) a stretch film; the 5% elongation tensile stress of the above (A) stretch film is 12 MPa or less; the above (A) stretch film and the above (B) coating film are directly laminated; the above (B) coating film is formed using a (b) paint containing an active energy ray curable resin having an acryloyl group or a methacryloyl group; the thickness of the above (B) coating film is 16 μm or less; the resin forming the (B) coating film forming surface of the above (A) stretch film is composed of an ethylene resin, when the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above (A) stretch film is a (unit: μm) and the thickness of the above (B) coating film is b (unit: μm), the following formula (1) is satisfied: b ≦ 3a + 5.5... (1) wherein the above arithmetic mean roughness (Ra) conforms to JIS B0601:2013 and is a value measured under the conditions of a cut-off value λc of 0.80 mm and an evaluation length L of 4.0 mm, the above coated film laminate.

2. The coated film laminate according to Claim 1, wherein the arithmetic mean roughness (Ra) of the (B) coating film forming surface of the above (A) stretch film is 1 μm or more and 10 μm or less.

3. The ethylene resin forming the (B) coating film forming surface of the above (A) stretch film is composed of one or more selected from the group consisting of polyethylene, ethylene / (meth)acrylic acid alkyl ester copolymer, ethylene / unsaturated carboxylic acid copolymer, ionomer resin obtained by crosslinking between molecules of ethylene / unsaturated carboxylic acid copolymer with metal ions, and ethylene / vinyl acetate copolymer, the coated film laminate according to Claim 1 or 2.

4. The ethylene resin forming the (B) coating film forming surface of the above (A) stretch film contains one or more selected from the group consisting of ethylene / vinyl acetate copolymer, ethylene / α-olefin copolymer, ethylene / methacrylic acid copolymer, and ethylene / ethyl acrylate copolymer, the coated film laminate according to any one of Claims 1 to 3.

5. The coated film laminate according to any one of Claims 1 to 4, wherein the ethylene resin forming the (B) coating film forming surface of the above (A) stretch film contains an ethylene / vinyl acetate copolymer.

6. the thickness of the above (B) coating film is 0.5 to 9.5 μm; When the arithmetic mean roughness (Ra) of the surface of the above-mentioned (B) coating film on the above-mentioned (A) stretch film is a (unit: μm) and the thickness of the above-mentioned (B) coating film is b (unit: μm), the following formula (2) is satisfied: b ≤ 3a + 4... (2) The coated film laminated film according to any one of claims 1 to 5.

7. The coated film laminated film according to any one of claims 1 to 6, wherein the above-mentioned (b) paint contains 100 parts by mass of an active energy ray curable resin having the above-mentioned (b1) acryloyl group or methacryloyl group, 0.1 to 20 parts by mass of a photopolymerization initiator, and 1 to 100 parts by mass of an inorganic compound functioning as an antibacterial agent or an antiviral agent.

8. The coated film laminated film according to any one of claims 1 to 7, which is for protecting the surface of an article.

9. A method of using the coated film laminated film according to any one of claims 1 to 8 for protecting the surface of an article.

Images