Protective sheet and protective sheet with adhesive layer

Abstract

The present invention provides protective sheets and adhesive-coated protective sheets that are easy to apply to curved surfaces, offer excellent workability, and also have superior scratch recovery properties. [Solution] A protective sheet 1 comprising a base material 11 and a coating layer 12, wherein when the protective sheet 1 is stretched in an environment of 23°C and 50%RH with a width of 15 mm, a measuring length of 50 mm, and a tensile speed of 200 mm / min, the tensile elongation at which the base material 11 does not break and the coating layer 12 cracks is 60% or more, and the indentation stress when the surface of the coating layer 12 side of the protective sheet 1 or a laminate of protective sheets 1 with a thickness of 110 to 1000 μm is pressed to a depth of 100 μm at a speed of 0.01 mm / second over an area of ​​5 mmφ is 1 N or more and 8.8 N or less.

Description

[Technical Field]

[0001] The present invention relates to a protective sheet and a protective sheet with an adhesive layer that can be used to protect coatings and the like. [Background technology]

[0002] The exterior surfaces of automobile bodies are coated with paint to enhance their aesthetic appeal and rust resistance. These coatings are frequently damaged by scratches during driving, damage from sand, dust, and flying stones, scratches from fingernails, and scratches from luggage. Therefore, protective films are sometimes applied to the entire automobile body to protect the coatings, and for this purpose, it is desirable that these protective films be scratch-resistant.

[0003] Furthermore, protective coatings need to be applied to the body of an automobile, which has numerous curved surfaces. Therefore, protective coatings require workability that allows them to conform to highly curved areas.

[0004] Patent Document 1 discloses a coating protective film with high conformability to curved surfaces, and Patent Document 2 discloses an adhesive film that has excellent scratch resistance even after stretching. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 5989291 [Patent Document 2] Japanese Patent Publication No. 2020-125400 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, until now, no protective sheet possessing both the ease of installation and scratch resistance mentioned above was known. On the other hand, regarding scratch resistance, even if scratches occur, the ability to quickly make the scratches disappear and the surface of the protective sheet return to its original state, in other words, scratch recovery, can also be described as scratch recovery.

[0007] This invention has been made in view of the above circumstances, and aims to provide a protective sheet and a protective sheet with an adhesive layer that are easy to conform to curved surfaces, have excellent workability, and also have excellent scratch recovery properties. [Means for solving the problem]

[0008] To achieve the above objective, firstly, the present invention provides a protective sheet comprising a base material and a coating layer, wherein when the protective sheet is stretched in an environment of 23°C and 50%RH with a width of 15 mm, a measuring length of 50 mm, and a tensile speed of 200 mm / min, the tensile elongation at which the base material does not break and the coating layer cracks is 60% or more, and the indentation stress when the surface of the coating layer side of the protective sheet or a laminate of the protective sheet, with a thickness of 110 to 1000 μm, is pressed to a depth of 100 μm at a speed of 0.01 mm / second over an area of ​​5 mmφ is 1 N or more and 8.8 N or less (Invention 1).

[0009] The protective sheet according to the above invention (Invention 1) exhibits high flexibility and extensibility, particularly due to the above-mentioned elongation of the coating crack, making it easy to conform to curved surfaces and providing excellent workability. Furthermore, the protective sheet, particularly due to the above-mentioned indentation stress, makes scratches on the coating layer less visible in a short time (for example, 0.1 to 10 minutes), and the surface of the protective sheet easily returns to its original state, resulting in excellent scratch recovery.

[0010] In the above invention (Invention 1), it is preferable that the ratio of the amount of indentation (μm) when a 10N load is applied to the surface of the protective sheet on the coated layer side at a speed of 0.01 mm / min over an area of ​​5 mmφ to the thickness (μm) of the protective sheet is 72% or more and 99.9% or less (Invention 2).

[0011] In the above inventions (Inventions 1 and 2), it is preferable that the coating layer contains a silicone component (Invention 3).

[0012] In the above inventions (Inventions 1 to 3), it is preferable that the coating layer contains a fluorine-based polymer and a silicone component (Invention 4).

[0013] In the above inventions (Inventions 3 and 4), it is preferable that the silicone component is obtained by active energy ray curing (Invention 5).

[0014] In the above inventions (Inventions 1 to 5), it is preferable that the coating layer is cured by active energy rays (Invention 6).

[0015] In the above inventions (Inventions 1 to 6), it is preferable that the water contact angle of the surface on the coating layer side of the protective sheet is 100° or more (Invention 7).

[0016] In the above inventions (Inventions 1 to 7), it is preferable that the oleic acid contact angle of the surface on the coating layer side of the protective sheet is 52° or more (Invention 8).

[0017] In the above inventions (Inventions 1 to 8), it is preferable that the base material is made of a material containing 10% by mass or more of polyurethane (Invention 9).

[0018] In the above inventions (Inventions 1 to 9), it is preferable that the thickness of the substrate is 10 μm or more and 300 μm or less (Invention 10).

[0019] In the above inventions (Inventions 1 to 10), it is preferable that the thickness of the coat layer is 1 μm or more and 50 μm or less (Invention 11).

[0020] Secondly, the present invention provides a protective sheet with an adhesive layer, which includes the above protective sheet (Inventions 1 to 11) and an adhesive layer laminated on the surface of the protective sheet on the base material side. (Invention 12).

Advantages of the Invention

[0021] The protective sheet and the protective sheet with an adhesive layer according to the present invention are easy to follow the curved surface, excellent in workability, and also excellent in scratch recovery property.

Brief Description of the Drawings

[0022] [Figure 1] It is a cross-sectional view of a protective sheet according to an embodiment of the present invention. [Figure 2] It is a cross-sectional view of a protective sheet with an adhesive layer according to an embodiment of the present invention.

Embodiments for Carrying Out the Invention

[0023] Hereinafter, embodiments of the present invention will be described. 〔Protective Sheet〕 The protective sheet according to an embodiment of the present invention includes a base material and a coat layer. When the protective sheet according to this embodiment is stretched at 23°C and 50% RH with a width of 15 mm, a measurement length of 50 mm, and a tensile speed of 200 mm / min, the tensile elongation at which the base material does not break and the coat layer cracks (hereinafter sometimes referred to as "coat crack elongation") is preferably 60% or more. The detailed measurement method of the coat crack elongation in this specification is as shown in the test example described later.

[0024] Furthermore, the indentation stress when the surface of the protective sheet on the coated layer side according to this embodiment is pressed to a depth of 100 μm at a speed of 0.01 mm / second over an area of ​​5 mmφ is preferably 1 to 8.8 N. Here, the thickness of the protective sheet to be measured is in the range of 110 to 1000 μm, and if one protective sheet is insufficient to reach this thickness, multiple protective sheets are laminated to bring the total thickness within this range. The detailed method for measuring the indentation stress in this specification is as shown in the test examples described later.

[0025] The protective sheet according to this embodiment exhibits high flexibility and extensibility, particularly due to the above-mentioned elongation of the coating crack, making it easy to conform to curved surfaces and resulting in excellent workability. Furthermore, the protective sheet according to this embodiment, particularly due to the above-mentioned indentation stress, makes scratches on the coating layer less visible in a short time (for example, 0.1 to 10 minutes), and the surface of the protective sheet easily returns to its original state, resulting in excellent scratch recovery.

[0026] From the viewpoint of workability as described above, the elongation of the coating crack is more preferably 65% ​​or more, particularly preferably 70% or more, even more preferably 75% or more, and most preferably 80% or more. There is no particular upper limit to the elongation of the coating crack, but it is usually preferably 150% or less, more preferably 140% or less, and particularly preferably 130% or less.

[0027] Furthermore, from the viewpoint of scratch recovery, the indentation stress is more preferably 3 to 8.7 N, particularly preferably 5 to 8.6 N, even more preferably 7 to 8.5 N, and most preferably 8.1 to 8.4 N.

[0028] In the protective sheet according to this embodiment, the ratio (%) of the amount of indentation (μm) when a 10N load is applied to the surface of the coating layer side at a speed of 0.01 mm / min over an area of ​​5 mmφ to the thickness (μm) of the protective sheet is preferably 72 to 99.9%, more preferably 72.5 to 99%, particularly preferably 73 to 90%, even more preferably 73.5 to 80%, and most preferably 74 to 77%. The detailed method for measuring the amount of indentation in this specification is shown in the test examples described later.

[0029] The protective sheet according to this embodiment, having the above-mentioned indentation ratio, tends to easily distribute the load applied to the surface on the coated layer side and to easily satisfy the above-mentioned elongation of coating cracking. Therefore, it exhibits high flexibility and extensibility, tends to easily conform to curved surfaces, and has superior workability. In addition, because it is easier to satisfy the above-mentioned indentation stress, the aforementioned scratch recovery performance is improved.

[0030] Hereinafter, an example of a protective sheet according to this embodiment will be described with reference to the drawings. As shown in Figure 1, the protective sheet 1 according to this embodiment comprises a base material 11 and a coating layer 12 provided on one side of the base material 11. In the protective sheet 1 according to this embodiment, the coating layer 12 forms the outermost layer.

[0031] 1. Each element 1-1. Base material The base material 11 has a coating crack elongation that satisfies the above value, that is, it has the property of not breaking until the coating layer 12 cracks. The breaking elongation of the base material 11 is preferably 100% or more, more preferably 300% or more, particularly preferably 500% or more, and even more preferably 600% or more. There is no particular upper limit to the breaking elongation, but it is usually preferably 10000% or less, more preferably 5000% or less, particularly preferably 2000% or less, and even more preferably 1000% or less. The breaking elongation shall be measured using a tensile testing machine with a measurement width of 15 mm and a measurement length of 50 mm, under conditions of 23°C and 50% RH, and stretched at a tensile speed of 200 mm / min.

[0032] The materials constituting the base material 11 are preferably polyurethane, polyvinyl chloride, polyolefin, etc. Among these, materials containing polyurethane are preferred. In that case, it is preferable that the material contains 10% by mass or more of polyurethane, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit of the content is preferably 100% by mass, but may be 90% by mass or less.

[0033] Polyurethanes such as polyester-based polyurethanes, polyether-based polyurethanes, and polycarbonate-based polyurethanes can be used. Among these, polyester-based polyurethanes are preferred because they have high stretchability and excellent workability. Furthermore, from the viewpoint of high elongation at break, the polyurethane is preferably a thermoplastic elastomer obtained by polymerizing diisocyanate, a low molecular weight diol with a molecular weight of less than 500 as a chain extender, and a high molecular weight diol with a molecular weight of 500 or more and 4000 or less.

[0034] The materials constituting the base material 11 may contain additives such as stabilizers, lubricants, fillers, colorants, processing aids, softeners, metal powders, anti-fogging agents, ultraviolet absorbers, antioxidants, antistatic agents, and twist-resistant agents, as needed. Preferred stabilizers include, for example, Ba-Zn, Cd-Ba, and Sn-based stabilizers. These stabilizers may be used in combination with epoxidized soybean oil, epoxy resins, etc. Preferred softeners include, for example, ethylene / vinyl acetate copolymers and ethylene / vinyl acetate / carbon monoxide copolymers. Furthermore, from the perspective of SDGs, materials with a high biomass content may be used as the materials constituting the base material 11, or materials that are recyclable or reusable may be used, or recycled or reused materials may be used.

[0035] The thickness of the base material 11 is preferably 10 to 300 μm, more preferably 30 to 260 μm, particularly preferably 50 to 220 μm, even more preferably 70 to 200 μm, and most preferably 90 to 180 μm. This ensures protection for the object to be protected, as well as superior conformability to curved surfaces and, consequently, ease of application.

[0036] 1-2. Coating layer The coating layer 12 is preferably made of a material that satisfies the aforementioned physical properties. The coating layer 12 preferably contains a fluorine component and / or a silicone component. This results in water and oil repellency and provides stain resistance. In particular, the coating layer 12 preferably contains a fluorine-based polymer and a silicone component. This improves water and oil repellency while maintaining flexibility, resulting in superior stain resistance. From the perspective of SDGs, the materials constituting the coating layer 12 may be materials with a high biomass content, materials that can be recycled or reused, or recycled or reused materials.

[0037] The coating layer 12 is preferably cured by active energy rays. While thermosetting materials require a seasoning period, active energy ray curing materials do not, thus shortening the lead time to the next process. Furthermore, with thermosetting materials, if curing defects occur, fine roughness occurs on the surface of the coating layer during the seasoning period. However, with active energy ray curing materials, curing is completed immediately after irradiation with active energy rays, thus reducing the risk of defects due to curing defects.

[0038] If the coating layer 12 contains a silicone component, it is preferable that the silicone component is cured by active energy rays. This improves the strength of the formed coating layer 12, makes it more difficult for contaminants to penetrate the coating layer 12, and results in superior stain resistance. Furthermore, if the coating layer 12 contains a fluoropolymer along with the silicone component, it is preferable that the fluoropolymer is also cured by active energy rays. This provides superior stain resistance while exhibiting flexibility and cohesiveness.

[0039] Preferably, the coating layer 12 is formed by curing a composition (hereinafter sometimes referred to as "coating layer composition C") containing an active energy ray-curable fluororesin (A) and an active energy ray-curable silicone compound (B) using active energy rays. This makes it easier to satisfy the aforementioned physical properties, resulting in superior workability and scratch recovery, as well as superior stain resistance. Furthermore, a seasoning period is not required after the formation of the coating layer 12.

[0040] (1) Each component (1-1) Active energy ray curable fluororesin (A) As the active energy ray curable fluororesin (A), a fluorine-containing resin having constituent units derived from fluorine-containing monomers and constituent units derived from crosslinkable monomers is preferred. Specific examples of fluorine-containing monomer units include fluoroolefins such as fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, and perfluoro-2,2-dimethyl-1,3-dioxol; fluorinated alkyl ester derivatives of (meth)acrylic acid; and fluorinated vinyl ethers. As the crosslinkable monomer, in addition to (meth)acrylate monomers, examples include (meth)acrylate monomers having carboxyl groups, hydroxyl groups, amino groups, sulfonic acid groups, etc. In this specification, (meth)acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.

[0041] The active energy ray-curable fluororesin (A) is preferably an active energy ray-curable silicon-containing fluororesin. This makes it easier to satisfy the aforementioned physical properties, resulting in improved workability and scratch recovery, as well as even better stain resistance.

[0042] The active energy ray curable silicon-containing fluororesin is preferably a silsesquioxane compound having an active energy ray curable functional group and a fluorine atom. The silsesquioxane compound is preferably one in which the majority of its structure is based on the structural formula [RSiO 1.5 This is a general term for polysiloxane compounds represented by ](where each R independently represents any organic group, and two or more Rs may be linked to each other), and includes ladder-shaped silsesquioxane compounds, cage-shaped silsesquioxane compounds, amorphous silsesquioxane compounds, etc. Among these, cage-shaped silsesquioxane compounds are preferred.

[0043] Examples of commercially available cage-like silsesquioxane compounds having an active energy ray-curable functional group and a fluorine atom include, for example, JNC Petrochemical Co., Ltd.'s "Sila-Max® XC0199-40", "Sila-Max® XC0208-40", and "Sila-Max® XC0212-40".

[0044] A cage-like silsesquioxane compound having an active energy ray-curable functional group and a fluorine atom can be produced, for example, by reacting a cage-like silsesquioxane compound having a reactive group and a fluorine atom (preferably a fluoroalkyl group) with a reactive silicone (preferably a reactive polydimethylsiloxane having a reactive functional group at one or both ends of a linear siloxane chain).

[0045] The content of the active energy ray-curable fluororesin (A) in the coating layer composition C is preferably 50 to 99.9% by mass, more preferably 60 to 99% by mass, particularly preferably 70 to 98.5% by mass, even more preferably 80 to 98% by mass, and most preferably 90 to 97.5% by mass. This makes it easier to satisfy the aforementioned physical properties, resulting in superior workability and scratch recovery, as well as superior stain resistance.

[0046] (1-2) Active energy ray curable silicone compound (B) Examples of active energy ray curable silicone compounds (B) include radical addition type silicones having alkenyl and mercapto groups in the molecule, hydrosilylation reaction type silicones having alkenyl and hydrogen atoms, cationic polymerization type silicones having epoxy groups, and radical polymerization type silicones having (meth)acryloyl groups. Among these, radical polymerization type silicone compounds having (meth)acryloyl groups are preferred.

[0047] Examples of radical polymerization type silicone compounds include compounds represented by the following general formula (1). [ka]

[0048] In general formula (1), R represents a hydrogen atom, a methyl group, a hydrosilyl group, or a methoxy group, and X represents an integer from 0 to 1,200. At least one of the methyl groups in general formula (1) is substituted with an alkyl group containing a (meth)acryloyl group.

[0049] Alkyl groups containing a (meth)acryloyl group include -(CH2) y A group represented by -O-CO-C(R')=CH2 (where y is an integer from 2 to 8, preferably 3 or 4, and R' represents a hydrogen atom or a methyl group) is preferred. In general formula (1), the methyl group not substituted with an alkyl group containing a (meth)acryloyl group may be substituted with a (poly)ether alkyl, aralkyl, long-chain fatty acid ester, higher fatty acid ester, higher fatty acid amide, etc.

[0050] As a radical polymerization type silicone compound having a (meth)acryloyl group, a silicone-modified polyurethane (meth)acrylate, in which a polyorganosiloxane and a polyurethane (meth)acrylate are covalently bonded together, can also be preferred.

[0051] Examples of commercially available active energy ray-curable silicone compounds (B) include "Shiko (registered trademark) UV-AF100" from Mitsubishi Chemical Corporation; "UMS-182," "UMS-992," "RMS-044," and "RMS-083" from Chisso Corporation; "X-22" and "X-24" from Shin-Etsu Chemical Co., Ltd.; and "GS1015" from Toagosei Chemical Co., Ltd. These active energy ray-curable silicone compounds (B) may be used individually or in combination of two or more.

[0052] The content of the active energy ray-curable silicone compound (B) in the coating layer composition C is preferably 0.1 to 50 parts by mass, more preferably 1 to 35 parts by mass, particularly preferably 2 to 20 parts by mass, and even more preferably 3 to 12 parts by mass, per 100 parts by mass of the active energy ray-curable fluororesin (A). This results in superior stain resistance.

[0053] (1-3) Photopolymerization initiator (D) When ultraviolet light is used as the active energy ray for curing the coating layer composition C, it is preferable that the coating layer composition C contains a photopolymerization initiator (D). This allows the coating layer composition C to be cured efficiently, and also reduces the polymerization curing time and the amount of ultraviolet light required.

[0054] Examples of photopolymerization initiators (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl Examples include ruanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one. These may be used individually or in combination of two or more.

[0055] The amount of photopolymerization initiator (D) in the coating layer composition C is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of active energy ray curable fluororesin (A) and active energy ray curable silicone compound (B). This makes it easier to satisfy the aforementioned physical properties and results in superior workability and scratch recovery.

[0056] (1-4) Various additives The coating layer composition C may optionally contain various commonly used additives, such as light stabilizers, oxygen absorbers, antioxidants, softeners, colorants, ultraviolet absorbers, infrared absorbers, antistatic agents, fillers, refractive index adjusters, etc. However, from the viewpoint of seasoning-free application, it is preferable not to contain thermal crosslinking agents, and more preferably substantially free of them. Even if thermal crosslinking agents are included, their content is preferably 0.01% by mass or less.

[0057] (2) Preparation of the coating layer composition Coating layer composition C can be manufactured by mixing an active energy ray-curable fluororesin (A) and an active energy ray-curable silicone compound (B), and optionally adding a photopolymerization initiator (D), additives, etc. Furthermore, by appropriately adding a diluent solvent, it can be prepared as a coating solution for coating layer composition C.

[0058] Examples of the diluent solvents used include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ethers such as propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve.

[0059] The concentration and viscosity of the coating solution of the coating layer composition C prepared in this manner are not particularly limited, as long as they are within the range of coating, and can be appropriately selected depending on the situation. For example, the coating layer composition C is diluted to a concentration of 10 to 60% by mass. Note that the addition of a diluent is not a necessary condition when obtaining the coating solution; if the coating layer composition C has a viscosity suitable for coating, a diluent may be omitted.

[0060] (3) Formation of the coating layer To form the coating layer 12, it is preferable to apply the coating solution of the coating layer composition C to one side of the substrate 11, heat and dry it as appropriate, and then irradiate the resulting coating film with active energy rays.

[0061] Methods for applying the coating solution of the coating layer composition C include, for example, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.

[0062] When performing heat drying, the heating temperature is preferably 70 to 150°C, and particularly preferably 80 to 125°C. The heating time is preferably 10 seconds to 10 minutes, and particularly preferably 20 seconds to 5 minutes.

[0063] Active energy rays refer to electromagnetic waves or charged particle beams that possess energy quanta, specifically including ultraviolet rays and electron beams. Among active energy rays, ultraviolet rays are particularly preferred because they are easy to handle.

[0064] Ultraviolet irradiation can be performed using high-pressure mercury lamps, Heraeus H lamps, xenon lamps, etc., with an illuminance of 30 to 1000 mW / cm². 2 Preferably, it is 60-600 mW / cm². 2 It is more preferable that the light intensity be 50-10000 mJ / cm². 2 Preferably, the concentration is 100-5000 mJ / cm². 2It is more preferable that the concentration be 150-2000 mJ / cm². 2 It is particularly preferable that this is the case. On the other hand, electron beam irradiation can be performed by an electron beam accelerator or the like, and the electron beam irradiation dose is preferably about 10 to 1000 krad.

[0065] (4) Physical properties (4-1) Thickness The thickness of the coating layer 21 is preferably 1 to 50 μm, more preferably 2 to 30 μm, particularly preferably 3 to 20 μm, even more preferably 3.5 to 12 μm, and most preferably 4 to 8 μm. This makes it easier to satisfy the aforementioned physical properties, resulting in improved workability and superior scratch recovery. Furthermore, if a silicone component is included, the stain resistance will be even better.

[0066] (4-2) Water contact angle The water contact angle of the surface of the coating layer 21 is preferably 100° or more, more preferably 100.5° to 160°, and particularly preferably 101° to 140°. This results in superior stain resistance, and in particular superior stain resistance against water-based stains. The water contact angle refers to the angle on the side containing the water droplet, when a water droplet is placed on the surface of the coating layer, between the tangent of the water droplet at the point of contact with the surface of the coating layer and the surface of the coating layer.

[0067] (4-3) Oleic acid contact angle The oleic acid contact angle of the surface of the coating layer 21 is preferably 52° or more, more preferably 52.5° to 120°, and particularly preferably 53° to 90°. This results in superior stain resistance, and in particular superior stain resistance against oil-based stains. The oleic acid contact angle refers to the angle on the side containing the oleic acid droplet when the droplet is placed on the surface of the coating layer, and the angle formed between the tangent of the droplet at the point of contact with the surface of the coating layer and the surface of the coating layer.

[0068] 2. Physical properties of the protective sheet (1) Thickness The thickness of the protective sheet 1 is preferably 10 to 1000 μm, more preferably 30 to 600 μm, particularly preferably 50 to 300 μm, even more preferably 70 to 200 μm, and most preferably 90 to 180 μm. This ensures protection for the object to be protected, as well as superior conformability to curved surfaces and, consequently, ease of application. It also provides superior scratch recovery.

[0069] (2) Haze value The haze value of protective sheet 1 is preferably 10% or less, more preferably 5% or less, particularly preferably 1% or less, even more preferably 0.6% or less, and most preferably 0.4% or less. This helps to suppress any damage to the appearance of the object to which protective sheet 1 is applied. The lower limit of the above haze value is not particularly limited, but 0% is most preferable, but 0.01% or more is preferable, and particularly preferably 0.1% or more. The haze values ​​in this specification are values ​​measured in accordance with JIS K7136:2000, and the specific test methods are as shown in the test examples described later.

[0070] (3) Total light transmittance The total light transmittance of protective sheet 1 is preferably 80% or more, more preferably 84% or more, particularly preferably 88% or more, and even more preferably 90% or more. This helps to prevent damage to the appearance of the object to which protective sheet 1 is applied. The upper limit of the total light transmittance is not particularly limited, but 100% is most preferable, but 99.9% or less is preferable, and particularly preferably 99% or less. The total light transmittance in this specification is a value measured in accordance with JIS K7361-1:1997, and the specific test method is as shown in the test examples described later.

[0071] [Protective sheet with adhesive layer] An adhesive protective sheet according to one embodiment of the present invention comprises a protective sheet according to the above-described embodiment and an adhesive layer laminated on the substrate-side surface of the protective sheet. The adhesive protective sheet according to this embodiment can be attached to an object to be protected via the adhesive layer and can be easily installed.

[0072] Hereinafter, an example of a protective sheet with an adhesive layer according to this embodiment will be described with reference to the drawings. As shown in Figure 2, the protective sheet with an adhesive layer 2 according to this embodiment comprises a protective sheet 1 having a base material 11 and a coating layer 12, an adhesive layer 21 laminated on the surface of the protective sheet 1 facing the base material 11, a release sheet 22 laminated on the side of the adhesive layer 21 opposite to the protective sheet 1, and a protective film 23 laminated on the side of the coating layer 12 opposite to the base material 11.

[0073] The release sheet 22 protects the adhesive surface of the adhesive layer 21 until the adhesive protective sheet 2 is used, and is peeled off when the adhesive protective sheet 2 is applied (especially immediately before application). The protective film 23 protects the coating layer 12 until the adhesive protective sheet 2 is used, and is peeled off when the adhesive protective sheet 2 is applied (especially immediately before application).

[0074] 1. Each element 1-1. Protective sheet The protective sheet 1 in this embodiment is the protective sheet 1 according to the embodiment described above.

[0075] 1-2. Adhesive layer The adhesive layer 21 in this embodiment is not particularly limited as long as it can adhere the protective sheet 1 to the object to be protected and does not hinder workability. The type of adhesive constituting the adhesive layer 21 may be any of the following: acrylic adhesive, polyester adhesive, polyurethane adhesive, rubber adhesive, silicone adhesive, etc. Furthermore, the adhesive may be of emulsion type, solvent type, or solvent-free type, and may be of crosslinked type or non-crosslinked type. It may also be thermosetting (thermally crosslinkable) or active energy ray curable. Among these, acrylic adhesives that have excellent adhesive properties, optical properties, etc., are preferred.

[0076] As an acrylic adhesive, a (meth)acrylic acid ester polymer is preferably used, in which an alkyl (meth)acrylate ester is the main monomer component, and a monomer copolymerizable with the alkyl (meth)acrylate ester is copolymerized with the alkyl (meth)acrylate ester as needed. Furthermore, it is preferable that the (meth)acrylic acid ester polymer be crosslinked with a crosslinking agent. In addition, it is preferable to include additives such as ultraviolet absorbers, infrared absorbers, silane coupling agents, antistatic agents, colorants, and optical modifiers as needed.

[0077] Furthermore, from the perspective of the SDGs, the materials constituting the adhesive layer 21 may be materials with a high biomass content, materials that can be recycled or reused, or recycled or reused materials.

[0078] The thickness of the adhesive layer 21 is preferably 1 to 200 μm, more preferably 5 to 120 μm, particularly preferably 10 to 80 μm, and even more preferably 15 to 40 μm. This makes it easier to obtain good adhesion, workability, reworkability, etc.

[0079] 1-3. Release Sheet Examples of release sheets 22 include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(meth)acrylic acid copolymer film, ethylene-(meth)acrylic acid ester polymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Crosslinked films of these materials can also be used. Furthermore, laminated films of these materials may also be used. From the perspective of SDGs, materials with a high biomass content may be used as the material constituting the release sheet, materials that can be recycled or reused may be used, or recycled or reused materials may be used.

[0080] It is preferable that the release surface (the surface in contact with the adhesive layer 21) of the release sheet 22 is subjected to a release treatment. Examples of release agents used in the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax-based release agents.

[0081] There are no particular restrictions on the thickness of the release sheet 22, but it is preferably 10 to 250 μm, and more preferably 20 to 150 μm.

[0082] 1-4. Protective film The protective film 23 is not particularly limited as long as it can protect the coating layer 12 of the protective sheet 1. For example, the protective film 23 may be made from a polyester film such as polyethylene terephthalate film, or a polyolefin film such as polyethylene film or polypropylene film, with an adhesive layer made of a weak adhesive provided on one side of the base material. From the perspective of SDGs, the materials constituting the protective film 23 may be materials with a high biomass content, materials that can be recycled or reused, or recycled or reused materials.

[0083] There are no particular restrictions on the thickness of the protective film 23, but it is preferably 5 to 250 μm, and more preferably 10 to 150 μm.

[0084] 2. Manufacturing method One example of manufacturing the adhesive-coated protective sheet 2 is to first attach a protective film 23 to the surface of the coating layer 12 of the protective sheet 1. Meanwhile, an adhesive layer 21 is formed on the release surface of the release sheet 22, and the exposed surface of the formed adhesive layer 21 is bonded to the surface of the protective sheet 1 facing the base material 11. Alternatively, the adhesive layer 21 may be formed on the surface of the protective sheet 1 facing the base material 11, and the exposed surface of the formed adhesive layer 21 may be bonded to the release surface of the release sheet 22.

[0085] The adhesive layer 21 can be formed by conventional methods, usually by applying an adhesive coating solution and performing heat treatment or curing as necessary.

[0086] Methods for applying the adhesive coating solution include, for example, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.

[0087] 3.Applications The adhesive protective sheet 2 according to this embodiment is easy to apply to curved surfaces, offers excellent workability, and has superior scratch recovery properties, making it suitable for protecting the coatings of moving objects, particularly automobiles and motorcycles. When the adhesive protective sheet 2 has antifouling properties, it is particularly suitable for use on moving objects and buildings used outdoors. In addition to protecting coatings, it can also be used on glass windows of moving objects and buildings. Furthermore, it can be used for protecting the coatings, housings, and transparent components of various electronic devices (personal computers, smartphones, tablets, etc.) and electrical appliances. Moreover, it can be used for protecting various optical components, particularly flexible displays and stretchable displays.

[0088] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit it. Accordingly, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention.

[0089] For example, other layers may be interposed between the base material 11 and the coating layer 12 in protective sheet 1, and other layers may also be interposed between the base material 11 and the adhesive layer 21 in protective sheet 2 with an adhesive layer. Furthermore, the release sheet 22 may be omitted.

[0090] In this specification, when "X~Y" (where X and Y are any numbers) is written, unless otherwise specified, it includes the meaning of "greater than or equal to X and less than or equal to Y," as well as "preferably greater than X" or "preferably less than Y." Similarly, when "greater than or equal to X" (where X is any number) is written, unless otherwise specified, it includes the meaning of "preferably greater than X," and when "less than or equal to Y" (where Y is any number) is written, unless otherwise specified, it also includes the meaning of "preferably less than Y." [Examples]

[0091] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0092] [Example 1] 1. Preparation of the coating liquid for the coat layer To 100 parts by mass (in terms of solid content) of an ultraviolet-curable silicon-containing fluororesin (manufactured by JNC Petrochemical Co., Ltd., product name "Sila-Max XC0199-40") as an active energy ray-curable fluororesin (A), 5.0 parts by mass (in terms of solid content) of an ultraviolet-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "Purple Light UV-AF100") as an active energy ray-curable silicone compound (B) was mixed, and this was used as the coating liquid for the coat layer composition.

[0093] 2. Production of the protective sheet On one surface of a polyurethane resin film (manufactured by Seiko Chemical Co., Ltd., product name "Lucks Skin F9700ES-150C", thickness: 150 μm, elongation at break: 700%) as the base material, the coating liquid for the coat layer composition prepared above was applied by a bar coater and dried at 80°C for 1 minute to form a coating film. Then, with respect to the coating film, ultraviolet irradiation was performed at an illuminance of 80 mW / cm 2 , a light quantity of 200 mJ / cm 2 in a nitrogen atmosphere to form a coat layer with a thickness of 4 μm, and this was used as the protective sheet (thickness: 154 μm).

[0094] [Examples 2 to 3] The coating liquid for the coat layer composition was prepared in the same manner as in Example 1, except that the mixing amount of the active energy ray-curable silicone compound (B) was changed as shown in Table 1. Then, using the coating liquid for the coat layer composition, a protective sheet was manufactured in the same manner as in Example 1.

[0095] [Example 4] 100 parts by mass (based on solid content) of an ultraviolet-curable silicon-containing fluororesin (manufactured by JNC Petrochemical Co., Ltd., product name "Sila-Max XC0199-40") as an active energy ray-curable fluororesin (A) was mixed with 5.0 parts by mass (based on solid content) of an ultraviolet-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "Shiko UV-AF100") as an active energy ray-curable silicone compound (B) and 1.0 part by mass (based on solid content) of 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (D1) as a photopolymerization initiator (D), and this was used as the coating solution for the coating layer composition.

[0096] Using the coating solution of the coating layer composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0097] [Example 5] A coating solution for the coating layer composition was prepared in the same manner as in Example 4, except that the amount of photopolymerization initiator (D) was changed as shown in Table 1. Then, a protective sheet was manufactured using this coating solution for the coating layer composition in the same manner as in Example 1.

[0098] [Example 6] A coating solution for the coating layer composition was prepared in the same manner as in Example 4, except that the photopolymerization initiator (D) was changed to 2,2-dimethoxy-2-phenylacetophenone (D2). Then, a protective sheet was manufactured using the coating solution for the coating layer composition in the same manner as in Example 1.

[0099] [Comparative Example 1] As the coating solution for the coating layer composition, only an ultraviolet-curable silicon-containing fluororesin (manufactured by JNC Petrochemical Co., Ltd., product name "Sila-Max XC0199-40") (dissolved in a mixed solvent of propylene glycol monomethyl ether and methyl ethyl ketone (solid content concentration 40% by mass)) was used as the active energy ray-curable fluororesin (A), and a protective sheet was manufactured in the same manner as in Example 1.

[0100] [Comparative Example 2] 100 parts by mass (based on solid content) of ultraviolet-curable silicon-containing fluororesin (manufactured by JNC Petrochemical Co., Ltd., product name "Sila-Max XC0199-40") as an active energy ray-curable fluororesin (A) was mixed with 5.0 parts by mass (based on solid content) of polyether-modified silicone (manufactured by Dow-Toray, Inc., product name "DOWSIL SH28 PAINT ADDITIVE") as a surface modifier, and this was used as the coating solution for the coating layer composition.

[0101] Using the coating solution of the coating layer composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0102] [Comparative Example 3] 100 parts by mass (based on solid content) of polyfunctional acrylate (manufactured by SARTOMER COMPANY, product name "SR399E") was mixed with 5.0 parts by mass (based on solid content) of an ultraviolet-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "Shiko UV-AF100") as an active energy ray-curable silicone compound (B), and 1.0 part by mass (based on solid content) of 2,2-dimethoxy-2-phenylacetophenone (D2) as a photopolymerization initiator (D), and this was used as the coating solution for the coating layer composition.

[0103] Using the coating solution of the coating layer composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0104] [Test Example 1] (Measurement of coating crack elongation) The protective sheets manufactured in the examples and comparative examples were cut to 15 mm x 100 mm and used as samples. These samples were set in a precision universal testing machine (Shimadzu Corporation, product name "AG-IS") with a jig distance (measurement length) of 50 mm, and a tensile test was performed in accordance with JIS K7127:1999, under conditions of 23°C and 50% RH relative humidity, at a tensile speed of 200 mm / min. The tensile elongation (%) at which the coating layer cracked without the substrate breaking was measured as the coating crack elongation (%). The results are shown in Table 2.

[0105] The tensile elongation is calculated using the following formula. Tensile elongation (%) = (distance elongated / distance between fixtures (measured length)) × 100

[0106] [Test Example 2] (Measurement of indentation stress) An optical adhesive layer (Lintec Corporation, product name "OPTERIA MO-3014", adhesive thickness: 25 μm, total light transmittance: >90%, haze value: <1.0%) was laminated to the substrate side of the protective sheets manufactured in the examples and comparative examples. The protective sheets were then attached to a soda-lime glass plate (Nippon Sheet Glass Co., Ltd., 0.7 mm) via this adhesive layer to create a laminate having the configuration of a coating layer / substrate / adhesive layer / glass plate.

[0107] Under conditions of 23°C and 50% RH relative humidity, a texture analyzer (Stable Micro Systems, product name "TA.XT.Plus") was used to press a probe (part number: P / 5S, tip shape: spherical, size: 5 mm in diameter, material: stainless steel) as a jig against the surface of the coating layer of the laminate. The stress (N) was measured when the probe was pressed to a depth of 100 μm at a pressing speed of 0.01 mm / second, and this was defined as the indentation stress (N). The results are shown in Table 2.

[0108] [Test Example 3] (Measurement of indentation amount) A laminate was fabricated in the same manner as in Test 2. Under a temperature of 23°C and a relative humidity of 50%RH, a texture analyzer (Stable Micro Systems, product name "TA.XT.Plus") was used to press a probe (product number: P / 5S, tip shape: spherical, size: diameter 5 mm, material: stainless steel) as a jig against the surface of the coating layer of the laminate. A load was continuously applied at an indentation speed of 0.01 mm / second, and the indentation depth (μm) was measured when the load reached 10 N and was held for 5 seconds. This was defined as the indentation amount (μm).

[0109] Next, the ratio (%; indentation percentage) of the measured indentation amount (μm) to the thickness (μm) of the protective sheet was calculated. The results are shown in Table 2.

[0110] [Test Example 4] (Measurement of haze value) The haze values ​​(%) of the protective sheets manufactured in the examples and comparative examples were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH7000") in accordance with JIS K7136:2000. The results are shown in Table 2.

[0111] [Test Example 5] (Measurement of total light transmittance) The total light transmittance (%) of the protective sheets manufactured in the examples and comparative examples was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH7000") in accordance with JIS K7361-1:1997. The results are shown in Table 2.

[0112] [Test Example 6] (Measurement of water contact angle) The water contact angle on the surface of the coating layer of the protective sheets manufactured in the examples and comparative examples was measured using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., DM-701) under the following conditions. The results are shown in Table 2. • Droplet volume of purified water: 2 μl ·Measurement time: 3 seconds after dropping • Image analysis method: θ / 2 method

[0113] [Test Example 7] (Measurement of Oleic Acid Contact Angle) The oleic acid contact angle on the surface of the coating layer of the protective sheets manufactured in the examples and comparative examples was measured using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., DM-701) under the following conditions. The oleic acid used was that manufactured by Tokyo Chemical Industry Co., Ltd. The results are shown in Table 2. • Droplet volume of oleic acid: 2 μl ·Measurement time: 3 seconds after dropping • Image analysis method: θ / 2 method

[0114] [Test Example 8] (Evaluation of workability) A (meth)acrylic acid ester polymer was prepared by copolymerizing 95 parts by mass of n-butyl acrylate and 5 parts by mass of acrylic acid using a solution polymerization method. The molecular weight of this (meth)acrylic acid ester polymer was measured by a method described later and found to be 500,000 (weight-average molecular weight (Mw)). 100 parts by mass of the obtained (meth)acrylic acid ester polymer (solids content) was mixed with 0.01 parts by mass of an epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "TETRAD-X"), thoroughly stirred, and diluted with toluene to obtain a coating solution for an adhesive composition.

[0115] The adhesive composition coating solution obtained in the above process was applied using a knife coater to the release sheet (thickness: 38 μm) obtained by releasing one side of a polyethylene terephthalate film with a silicone-based release agent. The coated layer was then heated at 90°C for 1 minute to form an adhesive layer (thickness: 20 μm). The adhesive layer on the release sheet was laminated onto the substrate side of the protective sheets produced in the examples and comparative examples to create a laminate having the configuration of a coating layer / substrate / adhesive layer / release sheet, and this was used as a sample.

[0116] The release sheet was peeled off from the above sample, and the side with the exposed adhesive layer was manually applied to the surface of the driver's side door of commercially available automobiles 1 (Honda Motor Co., Ltd., Fit) and automobile 2 (Toyota Motor Corporation, Aqua) using a squeegee to apply the protective sheet.

[0117] The workability was then evaluated according to the following criteria. The results are shown in Table 2. For protective sheets that received a "○" rating, they could be successfully applied to the entire surface of the vehicle body in both Vehicle 1 and Vehicle 2. ○...In both automobile 1 and automobile 2, the protective sheet was able to conform well to the curved surface of the door and be applied to it, and there were no defects such as wrinkles in the protective sheet, resulting in a successful application. ×...In either vehicle 1 or vehicle 2, or both vehicle 1 and vehicle 2, the protective sheet did not conform well to the curved surface of the door, resulting in defects such as wrinkles in the protective sheet, making it unsuitable for practical use.

[0118] Here, the weight-average molecular weight (Mw) mentioned above is the weight-average molecular weight in polystyrene terms, measured using gel permeation chromatography (GPC) under the following conditions (GPC measurement). <Measurement conditions> • Measuring device: Tosoh Corporation, HLC-8320 • GPC column (passes through in the following order): Manufactured by Tosoh Corporation TSK Gel Super H-H TSK gel superHM-H TSK Gel Super H2000 • Measurement solvent: tetrahydrofuran ·Measurement temperature: 40℃

[0119] [Test Example 9] (Evaluation of wound healing) The surface of the coating layer of the protective sheets manufactured in the examples and comparative examples was rubbed back and forth 20 times with a brass brush. Then, it was visually determined whether the scratches disappeared over time. The scratch recovery was then evaluated according to the following criteria. The results are shown in Table 2. 〇...The wound disappeared within a few minutes. ×...The scar remained.

[0120] [Test Example 10] (Evaluation of stain resistance) (1) Oil-based pen In the examples and comparative examples, the surface of the protective sheet's coating layer was marked with an oil-based pen (Zebra Corporation, product name "Mackie Black"). The surface of the protective sheet's coating layer was then dry-wiped with a non-woven fabric wiper (Asahi Kasei Corporation, product name "Bencott S-2"), and the degree to which the oil-based pen marks could be removed was visually determined. The stain resistance (oil-based pen) was then evaluated according to the following criteria. The results are shown in Table 2. ○...It could be easily wiped away. △...It was possible to wipe it off to some extent, but the writing marks were still visible. ×...It couldn't be wiped off.

[0121] (2) Carbon Black A carbon black aqueous dispersion (carbon black content: 5% by mass) was dropped onto the surface of the coating layer of the protective sheets manufactured in the examples and comparative examples (dropping volume: 0.5 mL), and then dried. Afterward, the surface of the coating layer of the protective sheets was washed with running water, and it was visually determined whether or not the carbon black residue had been removed. The antifouling properties (carbon black) were then evaluated according to the following criteria. The results are shown in Table 2. ○...Carbon black residue could be easily removed. △...Some of it was removed, but traces of carbon black were still visible. ×...The carbon black residue could not be removed.

[0122] [Test Example 11] (Seasoning Evaluation) When manufacturing the protective sheets for the examples and comparative examples, the pencil hardness of the coating layer surface of the protective sheets was measured immediately after UV irradiation to form the coating layer (day 0) and 30 days later. The pencil hardness was measured using an electric pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., product name "No. 553-M1") in accordance with JIS K5600. The seasoning was then evaluated based on the following criteria. The results are shown in Table 2. T... The pencil hardness was the same immediately after the coating layer was formed (day 0) and 30 days later (= no seasoning required). N... The pencil hardness was higher after 30 days than immediately after the coating layer was formed (day 0) (= seasoning is necessary).

[0123] [Table 1]

[0124] [Table 2]

[0125] As is clear from Table 2, the protective sheets manufactured in the examples were excellent in terms of ease of installation, scratch recovery, and stain resistance, and seasoning was not required. [Industrial applicability]

[0126] The protective sheet according to the present invention is suitable, for example, as a protective sheet for protecting the paint film of an automobile or the like. [Explanation of Symbols]

[0127] 1… Protective sheet 11...Base material 12…Court layer 2…Protective sheet with adhesive layer 21…Adhesive layer 22…Release sheet 23… Protective film

Claims

1. A protective sheet comprising a base material and a coating layer, When the protective sheet is stretched in an environment of 23°C and 50% RH with a width of 15 mm, a measurement length of 50 mm, and a tensile speed of 200 mm / min, the tensile elongation at which the base material does not break but the coating layer cracks is 60% or more. The indentation stress when the surface of the protective sheet or laminate of the protective sheet, having a thickness of 110 to 1000 μm, is pressed to a depth of 100 μm at a speed of 0.01 mm / second over an area of ​​5 mmφ is between 1 N and 8.8 N. A protective sheet characterized by the following features.

2. The protective sheet according to claim 1, characterized in that the ratio of the amount of indentation (μm) when a 10N load is applied to the surface of the protective sheet on the coated layer side at a speed of 0.01 mm / min over an area of ​​5 mmφ to the thickness (μm) of the protective sheet is 72% or more and 99.9% or less.

3. The protective sheet according to claim 1, characterized in that the coating layer contains a silicone component.

4. The protective sheet according to claim 1, characterized in that the coating layer contains a fluorine-based polymer and a silicone component.

5. The protective sheet according to claim 3 or 4, characterized in that the silicone component is obtained by active energy ray curing.

6. The protective sheet according to claim 1, characterized in that the coating layer is cured by active energy rays.

7. The protective sheet according to claim 1, characterized in that the water contact angle of the surface on the coating layer side of the protective sheet is 100° or more.

8. The protective sheet according to claim 1, characterized in that the oleic acid contact angle of the surface on the coating layer side of the protective sheet is 52° or more.

9. The protective sheet according to claim 1, characterized in that the base material is made of a material containing 10% by mass or more of polyurethane.

10. The protective sheet according to claim 1, characterized in that the thickness of the substrate is 10 μm or more and 300 μm or less.

11. The protective sheet according to claim 1, characterized in that the thickness of the coating layer is 1 μm or more and 50 μm or less.

12. The protective sheet described in claim 1, The adhesive layer laminated on the substrate side surface of the protective sheet and A protective sheet with an adhesive layer, equipped with [a specific feature / feature].

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