Protective film and protective film with adhesive layer

Abstract

The technical problem of the present invention is to provide a protective sheet that is easy to follow curved surfaces, has excellent workability, and also has excellent scratch repair properties, as well as a protective sheet with an adhesive layer. The solution is a protective sheet (1) having a substrate (11) and a coating (12). When the protective sheet (1) is stretched at a width of 15 mm, a measured length of 50 mm, and a stretching speed of 200 mm / min in an environment of 23°C and 50%RH, the stretching elongation rate is 60% or more such that the substrate (11) does not break but the coating (12) breaks. When the surface of the protective sheet (1) with a thickness of 110~1000 μm or a laminate of the protective sheet (1) is pressed at a speed of 0.01 mm / s to a depth of 100 μm in an area of ​​5 mmφ, the compressive stress is 1 N or more and 8.8 N or less.

Description

Technical Field

[0001] The present invention relates to protective sheets that can be used for the protection of coatings, etc., and protective sheets with adhesive layers. Background Technology

[0002] To improve design and rust resistance, a coating is applied to the surface of exterior automotive components. This coating is frequently damaged by driving scratches, dust or flying stones, fingernails, and luggage. Therefore, to protect the coating, a protective film is sometimes applied to the entire vehicle body; for this purpose, scratch resistance is desirable.

[0003] Furthermore, the protective coating needs to be applied along the car body, which has multiple curved surfaces. Therefore, the protective coating needs to be adaptable to the surface of highly curved areas.

[0004] Patent document 1 discloses a coating protective film with high surface following performance, and patent document 2 discloses an adhesive film with excellent scratch resistance even after extension.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent No. 5989291

[0008] Patent Document 2: Japanese Patent Application Publication No. 2020-125400 Summary of the Invention

[0009] (a) Technical problems to be solved

[0010] However, to date, there is still no protective sheet that combines both the aforementioned workability and scratch resistance. On the other hand, regarding scratch resistance, it can be replaced by the ability of the protective sheet to become invisible within a short period of time, even when a scratch occurs, and the surface of the protective sheet returns to its original state, i.e., scratch repairability.

[0011] The present invention is made in view of the above-mentioned actual situation, and its purpose is to provide a protective sheet that can easily follow curved surfaces, has excellent workability, and also has excellent scratch repair properties, as well as a protective sheet with an adhesive layer.

[0012] (II) Technical Solution

[0013] To achieve the above objectives, firstly, the present invention provides a protective sheet comprising a substrate and a coating. When the protective sheet is stretched at a width of 15 mm, a measured length of 50 mm, and a stretching speed of 200 mm / min in an environment of 23°C and 50%RH, the stretching elongation rate at which the substrate does not break but the coating breaks is 60% or more. When the coating side surface of a protective sheet or a laminate of protective sheets with a thickness of 110 to 1000 μm is pressed at a speed of 0.01 mm / s to a depth of 100 μm over an area of ​​5 mm φ, the compressive stress is 1 N or more and 8.8 N or less (Invention 1).

[0014] The protective sheet of the above-mentioned invention (Invention 1) exhibits high flexibility and elasticity, particularly due to the aforementioned elongation at break of the coating, making it easy to follow curved surfaces and providing excellent workability. Furthermore, the protective sheet, particularly due to the aforementioned compressive stress, ensures that even if scratches occur on the coating, the scratches become invisible within a short time (e.g., 0.1 to 10 minutes), and the surface of the protective sheet easily returns to its original state, demonstrating excellent scratch repair properties.

[0015] In the above invention (Invention 1), it is preferable that the pressing amount (μm) when a 10N load is applied to the surface of the coating side of the protective sheet at a speed of 0.01mm / min on an area of ​​5mmφ is 72% or more and 99.9% or less relative to the thickness (μm) of the protective sheet (Invention 2).

[0016] In the above inventions (Inventions 1 and 2), preferably, the coating contains an organosilicon component (Invention 3).

[0017] In the above inventions (Inventions 1-3), preferably, the coating contains a fluorinated polymer and an organosilicon component (Invention 4).

[0018] In the above inventions (Inventions 3 and 4), preferably, the organosilicon component is formed by curing with active energy rays (Invention 5).

[0019] In the above inventions (Inventions 1 to 5), preferably, the coating is formed by curing with active energy rays (Invention 6).

[0020] In the above inventions (Inventions 1 to 6), preferably, the water contact angle of the surface of the coating side in the protective sheet is 100° or more (Invention 7).

[0021] In the above inventions (Inventions 1 to 7), preferably, the oleic acid contact angle of the surface of the coating side in the protective sheet is 52° or more (Invention 8).

[0022] In the above inventions (Inventions 1 to 8), it is preferred that the substrate is composed of a material containing more than 10% by mass of polyurethane (Invention 9).

[0023] In the above inventions (Inventions 1 to 9), it is preferred that the thickness of the substrate is 10 μm or more and 300 μm or less (Invention 10).

[0024] In the above inventions (Inventions 1 to 10), preferably, the thickness of the coating is 1 μm or more and 50 μm or less (Invention 11).

[0025] Secondly, the present invention provides a protective sheet with an adhesive layer, which includes the protective sheet (Invention 1-11) and an adhesive layer (Invention 12) laminated on the substrate side of the protective sheet.

[0026] (III) Beneficial Effects

[0027] The protective sheet and the protective sheet with adhesive layer of the present invention can easily follow curved surfaces and have excellent workability, while also having excellent scratch repair properties. Attached Figure Description

[0028] Figure 1 This is a cross-sectional view of a protective sheet according to one embodiment of the present invention.

[0029] Figure 2 This is a cross-sectional view of a protective sheet with an adhesive layer according to one embodiment of the present invention.

[0030] Explanation of reference numerals in the attached figures

[0031] 1: Protective sheet; 11: Substrate; 12: Coating; 2: Protective sheet with adhesive layer; 21: Adhesive layer; 22: Release sheet; 23: Protective film. Detailed Implementation

[0032] The following describes the embodiments of the present invention.

[0033] [Protective Film]

[0034] One embodiment of the protective sheet of the present invention comprises a substrate and a coating. When the protective sheet of this embodiment is stretched at a width of 15 mm, a measurement length of 50 mm, and a tensile speed of 200 mm / min in an environment of 23°C and 50% RH, the tensile elongation (hereinafter sometimes referred to as "coating breakage elongation") where the substrate does not break but the coating breaks is preferably 60% or more. Detailed methods for measuring the coating breakage elongation in this specification are described in the test examples below.

[0035] Furthermore, the compressive stress when the coated surface of the protective sheet of this embodiment is pressed at a speed of 0.01 mm / s to a depth of 100 μm over an area of ​​5 mm φ is preferably 1 to 8.8 N. Here, the thickness of the protective sheet to be measured is set to be in the range of 110 to 1000 μm. When this thickness is insufficient for a single protective sheet, multiple protective sheets are stacked in such a way that they fall within this thickness range. The detailed method for measuring the compressive stress in this specification is described in the test examples below.

[0036] The protective sheet of this embodiment exhibits high flexibility and elasticity, particularly due to the aforementioned elongation at break of the coating, making it easy to follow curved surfaces and providing excellent workability. Furthermore, the protective sheet of this embodiment, particularly due to the aforementioned compressive stress, ensures that even if scratches occur on the coating, the scratches become invisible within a short time (e.g., 0.1 to 10 minutes), and the surface of the protective sheet easily returns to its original state, demonstrating excellent scratch repair properties.

[0037] From the perspective of workability, the elongation at break of the coating is preferably 65% ​​or more, particularly preferably 70% or more, further preferably 75% or more, and most preferably 80% or more. There is no particular upper limit to the elongation at break of the coating, but it is generally preferred to be 150% or less, more preferably 140% or less, and particularly preferably 130% or less.

[0038] Furthermore, from the perspective of scratch repairability, the pressing stress is more preferably 3 to 8.7 N, particularly preferably 5 to 8.6 N, and even more preferably 7 to 8.5 N, wherein 8.1 to 8.4 N is preferred.

[0039] For the protective sheet of this embodiment, the ratio (%) of the pressing amount (μm) to the thickness (μm) of the protective sheet when a 10N load is applied to the surface of the coated side at a rate of 0.01 mm / min over an area of ​​5 mmφ is preferably 72-99.9%, more preferably 72.5-99%, particularly preferably 73-90%, further preferably 73.5-80%, and most preferably 74-77%. The detailed method for measuring the pressing amount in this specification is as described in the test examples below.

[0040] The protective sheet of this embodiment, by having the aforementioned pressing ratio, tends to easily disperse the load applied to the coating side surface, and easily meets the aforementioned coating elongation at break. Therefore, it exhibits high flexibility and elasticity, tends to easily follow curved surfaces, and has superior workability. Furthermore, since it is easy to meet the aforementioned pressing stress, the aforementioned scratch repair performance is superior.

[0041] The following description, with reference to the accompanying drawings, illustrates an example of the protective sheet of this embodiment. Figure 1As shown, the protective sheet 1 of this embodiment includes a substrate 11 and a coating 12 disposed on one side of the substrate 11. In the protective sheet 1 of this embodiment, the coating 12 forms the outermost layer.

[0042] 1. Various elements

[0043] 1-1. Substrate

[0044] The substrate 11 is a material whose elongation at break of the coating meets the above-mentioned value, that is, it has the property that it will not break until the coating 12 breaks. The elongation at break of the substrate 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 limitation on the upper limit of the elongation at break, but it is generally preferred to be 10000% or less, more preferably 5000% or less, particularly preferably 2000% or less, and even more preferably 1000% or less. In addition, the elongation at break is the value measured by using a tensile testing machine at a tensile speed of 200 mm / min with a measurement width of 15 mm and a measurement length of 50 mm in an environment of 23°C and 50%RH.

[0045] Materials constituting the substrate 11 may preferably include polyurethane, polyvinyl chloride, polyolefins, etc. Among them, materials containing polyurethane are preferred. In this case, it is preferable to contain 10% by mass or more of polyurethane, more preferably 30% by mass or more of polyurethane, particularly preferably 40% by mass or more of polyurethane, and even more preferably 50% by mass or more of polyurethane. The upper limit of this content is preferably 100% by mass, but may also be 90% by mass or less.

[0046] Polyurethane can be polyester-based, polyether-based, or polycarbonate-based. Among these, polyester-based polyurethane, which has high elongation and excellent workability, is preferred. Furthermore, from the perspective 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 but less than 4000.

[0047] The materials constituting the substrate 11 may also contain additives such as stabilizers, lubricants, fillers, colorants, processing aids, softeners, metal powders, antifogging agents, ultraviolet absorbers, antioxidants, antistatic agents, and flame retardants, as needed. As stabilizers, Ba-Zn based, Cd-Ba based, and Sn based stabilizers are preferred, for example. These stabilizers can be used simultaneously with epoxidized soybean oil, epoxy resins, etc. As softeners, ethylene / vinyl acetate copolymers or ethylene / vinyl acetate / carbon monoxide copolymers are preferred, for example. Furthermore, from the perspective of SDGs (Sustainable Development Goals), materials constituting the substrate 11 can be materials with high bio-based content, recyclable or reusable materials, or materials that have already been recycled or reused.

[0048] The thickness of the substrate 11 is preferably 10-300 μm, more preferably 30-260 μm, particularly preferably 50-220 μm, and even more preferably 70-200 μm, wherein preferably 90-180 μm. This ensures protection of the object being protected, while also providing superior surface conformability and workability.

[0049] 1-2. Coating

[0050] The coating 12 is preferably made of a material that satisfies the aforementioned physical properties.

[0051] The coating 12 preferably contains fluorine and / or silicone components. This provides water and oil repellency, resulting in antifouling properties. It is particularly preferred that the coating 12 contains fluorinated polymers and silicone components. This provides flexibility while simultaneously enhancing water and oil repellency, resulting in superior antifouling properties. Furthermore, from the perspective of SDGs, materials constituting the coating 12 can be highly bio-based, recyclable, or reusable.

[0052] The coating 12 is preferably formed by curing with active energy rays. While thermosetting materials require a curing period, active energy ray curing eliminates this requirement, thus shortening the lead time until the next process. Furthermore, in thermosetting materials, poor curing can result in fine roughness on the coating surface during the curing period. However, in active energy ray curing, curing is completed immediately after irradiation with active energy rays, reducing the risk of defects caused by poor curing.

[0053] When coating 12 contains an organosilicon component, the organosilicon component is preferably cured by active energy radiation. This increases the strength of the resulting coating 12, making it less susceptible to penetration by contaminants and providing superior stain resistance. Furthermore, when coating 12 contains both an organosilicon component and a fluoropolymer, the fluoropolymer is also preferably cured by active energy radiation. This provides both flexibility and cohesion, while also enhancing stain resistance.

[0054] The coating 12 is preferably formed by curing a composition (hereinafter sometimes referred to as "coating composition C") containing an active energy ray-curable fluoropolymer resin (A) and an active energy ray-curable silicone compound (B) with active energy ray curable silicone compound (B). This readily satisfies the aforementioned physical properties, resulting in superior workability and scratch repair properties, as well as superior stain resistance. Furthermore, no curing period is required after the coating 12 is formed.

[0055] (1) Each ingredient

[0056] (1-1) Active energy radiation-cured fluoropolymer resin (A)

[0057] As an active energy ray-curable fluorinated resin (A), examples preferably include fluorinated resins having structural units derived from fluorinated monomers and structural units derived from crosslinking monomers. Specific examples of fluorinated monomer units include fluoroolefins such as vinylidene fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, and perfluoro-2,2-dimethyl-1,3-dioxane; fluorinated alkyl ester derivatives of (meth)acrylic acid; and fluorinated vinyl ethers. As crosslinking monomers, in addition to (meth)acrylic acid ester monomers, examples include (meth)acrylic acid ester monomers having carboxyl, hydroxyl, amino, or sulfonic acid groups. Furthermore, in this specification, (meth)acrylic acid refers to both acrylic acid and methacrylic acid. Other similar terms are also used.

[0058] The active energy ray-curable fluorinated resin (A) is preferably an active energy ray-curable silicone-containing fluorinated resin. This makes it easier to meet the aforementioned physical properties, resulting in superior workability and scratch repair properties, as well as superior stain resistance.

[0059] The preferred active energy radiation-curable silicon-containing fluorine resin is a silsesquioxane compound with functional groups and fluorine atoms possessing active energy radiation curability. Silsesquioxane compounds are characterized by a structure largely composed of the structural formula [RSiO]. 1.5 [R represents any independent organic group, and two or more Rs can be linked together.] This is a general term for polysiloxane compounds, including ladder-shaped silsesquioxane compounds, basket-shaped silsesquioxane compounds, and amorphous silsesquioxane compounds. Among them, basket-shaped silsesquioxane compounds are preferred.

[0060] Commercially available products that are basket-shaped silsesquioxane compounds with functional groups and fluorine atoms that have active energy radiation curing properties include, for example, JNC petro chemical Co., Ltd.’s “Sila-Max (registered trademark) XC0199-40”, “Sila-Max (registered trademark) XC0208-40”, and “Sila-Max (registered trademark) XC0212-40”.

[0061] Basket-shaped silsesquioxane compounds with functional groups and fluorine atoms that have active energy radiation curability can be manufactured, for example, by reacting a basket-shaped silsesquioxane compound with reactive groups and fluorine atoms (preferably fluoroalkyl) with a reactive organosilicon (preferably a reactive polydimethylsiloxane with reactive functional groups at one or both ends of a straight-chain siloxane chain).

[0062] The content of the active energy ray-curable fluoropolymer resin (A) in the coating composition C is preferably 50-99.9% by mass, more preferably 60-99% by mass, particularly preferably 70-98.5% by mass, further preferably 80-98% by mass, and most preferably 90-97.5% by mass. This makes it easier to meet the aforementioned physical properties, resulting in better workability and scratch repair properties, as well as superior stain resistance.

[0063] (1-2) Active energy radiation-curable organosilicon compounds (B)

[0064] Examples of organosilicon compounds (B) that can be cured by active energy rays include free radical addition compounds having alkenyl and thiol groups within the molecule, hydrosilylation reaction compounds having alkenyl groups and hydrogen atoms, cationic polymerization compounds having epoxy groups, and free radical polymerization compounds having (meth)acryloyl groups. Among these, free radical polymerization compounds having (meth)acryloyl groups are preferred.

[0065] As free radical polymerizable organosilicon compounds, examples include compounds represented by the following general formula (1).

[0066] [Chemical Formula 1]

[0067]

[0068] In general formula (1), R represents a hydrogen atom, methyl, silyl or methoxy, 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.

[0069] As an alkyl group containing (meth)acryloyl, -(CH2) is preferred. yThe group represented by -O-CO-C(R')=CH2 (y represents an integer from 2 to 8, preferably 3 or 4. R' represents a hydrogen atom or a methyl group.) In addition, in general formula (1), the methyl group not substituted by an alkyl group containing (meth)acryloyl can be replaced by (poly)ether alkyl, aralkyl, long-chain fatty acid ester, higher fatty acid ester, higher fatty acid amide, etc.

[0070] As a free radical polymerizable organosilicon compound having a (meth)acryloyl group, organosilicon-modified polyurethane (meth)acrylate monomers formed by covalent bonding of polyorganosiloxanes and polyurethane (meth)acrylate monomers are also preferred examples.

[0071] Commercially available active energy-curable silicone compounds (B) include, for example, "UV-AF100" manufactured by Mitsubishi Chemical Corporation; "UMS-182", "UMS-992", "RMS-044", and "RMS-083" manufactured by Chisso Corporation; "X-22" and "X-24" manufactured by Shin-Etsu Chemical Co., Ltd.; and "GS1015" manufactured by TOAGOSEI CO., LTD. These active energy-curable silicone compounds (B) can be used alone or in combination of two or more.

[0072] The content of the active energy radiation-curable organosilicon compound (B) in the coating composition C is preferably 0.1 to 50 parts by weight, more preferably 1 to 35 parts by weight, particularly preferably 2 to 20 parts by weight, and even more preferably 3 to 12 parts by weight, relative to 100 parts by weight of the active energy radiation-curable fluorinated resin (A). This results in superior antifouling properties.

[0073] (1-3) Photopolymerization initiator (D)

[0074] When ultraviolet light is used as the active energy ray for curing coating composition C, coating composition C preferably contains a photopolymerization initiator (D). This allows for efficient curing of coating composition C and reduces polymerization curing time and the amount of ultraviolet light irradiated.

[0075] 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-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2 2-Methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligomeric [2-hydroxy-2-methyl-1[4-(-1-methylvinyl)phenyl]acetone], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one), etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0076] Relative to 100 parts by mass of the combined amount of the active energy radiation-curable fluorinated resin (A) and the active energy radiation-curable silicone compound (B), the content of the photopolymerization initiator (D) in the coating 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. This makes it easier to meet the aforementioned physical properties, and provides superior workability and scratch repair properties.

[0077] (1-4) Various additives

[0078] The coating composition C may contain various commonly used additives, such as light stabilizers, oxygen absorbers, antioxidants, softeners, colorants, ultraviolet absorbers, infrared absorbers, antistatic agents, fillers, and refractive index modifiers, as needed. Furthermore, from the perspective of eliminating curing time, it is preferable to not contain thermal crosslinking agents, and more preferably, to contain virtually no thermal crosslinking agents. Even if thermal crosslinking agents are present, their content is preferably 0.01% by mass or less.

[0079] (2) Preparation of coating composition

[0080] By mixing an active energy ray-curable fluoropolymer resin (A) with an active energy ray-curable organosilicon compound (B), and adding photopolymerization initiator (D), additives, etc., as needed, a coating composition C can be manufactured. Furthermore, by appropriately adding a diluent, a coating liquid of the coating composition C can be prepared.

[0081] As diluents for the above-mentioned purposes, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and vinyl 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 solvents such as ethyl cellosolves.

[0082] The concentration and viscosity of the coating liquid of the coating composition C prepared in this manner are not particularly limited as long as they are within the coatable range, and can be appropriately selected according to the situation. For example, the coating composition C can be diluted to a concentration of 10 to 60% by mass. In addition, adding diluents when obtaining the coating liquid is not necessary. If the coating composition C has a coatable viscosity, diluents may not be added.

[0083] (3) Formation of coating

[0084] To form coating 12, it is preferable to apply the coating liquid of coating composition C to one side of substrate 11, heat and dry it appropriately, and then irradiate the resulting coating film with active energy rays.

[0085] Methods for applying the coating liquid of composition C for coating can include, for example, bar coating, blade coating, roller coating, scraper coating, die coating, gravure coating, etc.

[0086] When performing heat drying, the heating temperature is preferably 70~150℃, and more preferably 80~125℃. In addition, the heating time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.

[0087] Reactive energy rays refer to active energy rays containing energy quanta within electromagnetic waves or charged particle beams. Specifically, examples include ultraviolet light and electron beams. Among reactive energy rays, ultraviolet light, which is particularly easy to manipulate, is preferred.

[0088] Ultraviolet (UV) irradiation can be achieved using high-pressure mercury lamps, Heraeus H lamps, xenon lamps, etc. The optimal UV irradiation intensity is 30–1000 mW / cm². 2 More preferably 60~600mW / cm 2 Furthermore, the preferred light intensity is 50~10000 mJ / cm².2 More preferably, it is 100~5000 mJ / cm 2 The preferred value is 150~2000 mJ / cm³. 2 On the other hand, electron beam irradiation can be performed using an electron beam accelerator or the like, and the preferred irradiation dose is around 10 to 1000 krad.

[0089] (4)Physical properties

[0090] (4-1) Thickness

[0091] The thickness of coating 21 is preferably 1~50μm, more preferably 2~30μm, particularly preferably 3~20μm, and even more preferably 3.5~12μm, wherein 4~8μm is preferred. This makes it easier to meet the aforementioned physical properties, resulting in better workability and scratch repair. Furthermore, the presence of organosilicon components enhances its anti-fouling properties.

[0092] (4-2) Water contact angle

[0093] The water contact angle of the coating 21 surface is preferably 100° or more, more preferably 100.5° to 160°, and particularly preferably 101° to 140°. This results in superior antifouling properties, especially against waterborne contaminants. Furthermore, the water contact angle refers to the angle between the tangent of the water droplet at the contact point of the coating surface and the coating surface, including the side containing the water droplet, when a water droplet is placed still on the coating surface.

[0094] (4-3) Oleic acid contact angle

[0095] The oleic acid contact angle of the surface of coating 21 is preferably 52° or more, more preferably 52.5° to 120°, and particularly preferably 53° to 90°. This results in superior antifouling properties, especially against oil-based contaminants. Furthermore, the oleic acid contact angle refers to the angle between the tangent of the droplet at the contact portion of the coating surface and the coating surface, including the droplet side, when an oleic acid droplet is placed on the surface of the coating.

[0096] 2. Physical properties of the protective film

[0097] (1) Thickness

[0098] The thickness of the protective sheet 1 is preferably 10~1000μm, more preferably 30~600μm, particularly preferably 50~300μm, and even more preferably 70~200μm, with a preferred thickness of 90~180μm. This ensures excellent protection of the object being protected, while also providing superior surface conformability and workability. Furthermore, it offers superior scratch repair properties.

[0099] (2) Haze value

[0100] The haze value of the 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 allows for the suppression of appearance damage to the object to which the protective sheet 1 is applied. The lower limit of the haze value is not particularly limited, but is most preferably 0%, more preferably 0.01% or more, and particularly preferably 0.1% or more. Furthermore, the haze value in this specification is a value measured according to JIS K7136: 2000, and the specific test method is described in the test examples below.

[0101] (3) Total transmittance

[0102] The total light transmittance of the 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 allows for the suppression of surface damage to the object to which the protective sheet 1 is applied. The upper limit of the above-mentioned total light transmittance is not particularly limited, but is most preferably 100%, more preferably 99.9% or less, and particularly preferably 99% or less. Furthermore, the total light transmittance in this specification is a value measured according to JIS K7361-1: 1997, and the specific test method is described in the test examples below.

[0103] [Protective sheet with adhesive layer]

[0104] One embodiment of the present invention provides a protective sheet with an adhesive layer comprising the protective sheet of the aforementioned embodiment and an adhesive layer laminated on the substrate side of the protective sheet. The protective sheet with the adhesive layer of this embodiment can be easily attached to the object to be protected via the adhesive layer, allowing for simple installation.

[0105] The following description, with reference to the accompanying drawings, illustrates an example of a protective sheet with an adhesive layer according to this embodiment. Figure 2 As shown, the protective sheet 2 with adhesive layer in this embodiment includes: a protective sheet 1 having a substrate 11 and a coating 12, an adhesive layer 21 laminated on the substrate 11 side of the protective sheet 1, a release sheet 22 laminated on the adhesive layer 21 on the opposite side of the protective sheet 1, and a protective film 23 laminated on the coating 12 on the opposite side of the substrate 11.

[0106] The release liner 22 protects the adhesive surface of the adhesive layer 21 until the use of the protective sheet 2 with the adhesive layer, and is peeled off during application to the protective sheet 2 with the adhesive layer (especially just before application). Similarly, the protective film 23 protects the coating 12 until the use of the protective sheet 2 with the adhesive layer, and is peeled off during application to the protective sheet 2 with the adhesive layer (especially just before application).

[0107] 1. Various elements

[0108] 1-1. Protective film

[0109] The protective sheet 1 in this embodiment is the same as the protective sheet 1 in the aforementioned embodiment.

[0110] 1-2. Adhesive layer

[0111] In this embodiment, the adhesive layer 21 allows the protective sheet 1 to be attached to the object being protected, and there are no particular limitations as long as it does not hinder workability. The type of adhesive constituting the adhesive layer 21 can be any of acrylic adhesives, polyester adhesives, polyurethane adhesives, rubber adhesives, silicone adhesives, etc. Furthermore, the adhesive can be any of emulsion type, solvent type, or solvent-free type, and can be any of cross-linked type or non-cross-linked type. Additionally, it can be thermosetting (thermally cross-linked) or radioactive energy cured. Among these, acrylic adhesives with excellent adhesive properties and optical properties are preferred.

[0112] As an acrylic adhesive, a (meth)acrylate polymer is preferably used, with alkyl (meth)acrylate as the main monomer component, and copolymerized with monomers that can copolymerize with alkyl (meth)acrylate as needed. Furthermore, the (meth)acrylate polymer is preferably crosslinked by a crosslinking agent. Additionally, additives such as ultraviolet absorbers, infrared absorbers, silane coupling agents, antistatic agents, colorants, and optical modifiers are preferably included as needed.

[0113] In addition, from the perspective of SDGs, the materials constituting the adhesive layer 21 can be materials with high bio-based content, materials that are recyclable or reusable, or materials that have been recycled or reused.

[0114] The thickness of the adhesive layer 21 is preferably 1~200 μm, more preferably 5~120 μm, particularly preferably 10~80 μm, and even more preferably 15~40 μm. This facilitates the acquisition of good adhesion, workability, and reworkability.

[0115] 1-3. Peeling sheets

[0116] Examples of release sheets 22 include polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polyethylene naphthalate films, polybutylene terephthalate films, polyurethane films, ethylene vinyl acetate films, ionomer resin films, ethylene-(meth)acrylate copolymer films, ethylene-(meth)acrylate polymer films, polystyrene films, polycarbonate films, polyimide films, and fluoropolymer films. Crosslinked films of these films can also be used. Furthermore, laminated films of these films can also be used. Additionally, from the perspective of SDGs, materials constituting the release sheet can be materials with high bio-based content, recyclable or reusable materials, or materials that have been recycled or reused.

[0117] Preferably, 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 for the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.

[0118] The thickness of the release strip 22 is not particularly limited, but it is preferably 10~250μm, more preferably 20~150μm.

[0119] 1-4. Protective film

[0120] The protective film 23 is not particularly limited as long as it can protect the coating 12 of the protective sheet 1. For example, the protective film 23 can be a film with a polyester film such as polyethylene terephthalate film, a polyolefin film such as polyethylene film, or a polypropylene film as the substrate, and an adhesive layer composed of a micro-adhesive is provided on one side of the substrate. Furthermore, from the perspective of SDGs, the materials constituting the protective film 23 can be materials with high bio-based content, recyclable or reusable materials, or materials that have been recycled or reused.

[0121] The thickness of the protective film 23 is not particularly limited, but it is preferably 5 to 250 μm, more preferably 10 to 150 μm.

[0122] 2. Manufacturing method

[0123] As one manufacturing example of the protective sheet 2 with an adhesive layer, a protective film 23 is first attached to the surface of the coating 12 of the protective sheet 1. On the other hand, an adhesive layer 21 is formed on the peeling surface of the release liner 22, and the exposed surface of the formed adhesive layer 21 is bonded to the surface of the protective sheet 1 on the substrate 11 side. Alternatively, the adhesive layer 21 may be formed on the surface of the protective sheet 1 on the substrate 11 side, and the exposed surface of the formed adhesive layer 21 may be bonded to the peeling surface of the release liner 22.

[0124] The adhesive layer 21 can be formed using conventional methods, typically by applying an adhesive coating solution and then subjecting it to heat treatment or curing as required.

[0125] Methods for applying coating liquid as an adhesive include, for example, rod coating, blade coating, roller coating, scraper coating, die coating, gravure coating, etc.

[0126] 3. Applications

[0127] The protective sheet 2 with an adhesive layer in this embodiment easily follows curved surfaces and has excellent workability, as well as excellent scratch repair properties, making it suitable for protecting coatings on mobile objects, especially automobiles or motorcycles. When the protective sheet 2 with the adhesive layer has anti-fouling properties, it is particularly suitable for mobile objects or buildings used outdoors. Furthermore, in addition to protecting coatings, it can also be used for glass windows on mobile objects or buildings. Further, it can be used for coating protection, housing protection, and protection of transparent components in various electronic devices (personal computers, smartphones, tablets, etc.) or electrochemical products. In addition, it can be used for the protection of various optical components, especially flexible displays and retractable displays.

[0128] The embodiments described above are provided for ease of understanding of the present invention and are not intended to limit the present invention. Therefore, the elements disclosed in the above embodiments also include all design modifications or equivalents that fall within the scope of the present invention.

[0129] For example, there may be other layers between the substrate 11 and the coating 12 in the protective sheet 1, or between the substrate 11 and the adhesive layer 21 in the protective sheet 2 with the adhesive layer. In addition, the release liner 22 may be omitted.

[0130] Furthermore, unless otherwise specified, the use of "X~Y" (where X and Y are arbitrary numbers) in this specification refers to "X or more but less than Y," and also includes "preferably greater than X" or "preferably less than Y." Additionally, unless otherwise specified, the use of "X or more" (where X is any number) includes "preferably greater than X," and the use of "Y or less" (where Y is any number) also includes "preferably less than Y."

[0131] Example

[0132] Hereinafter, the present invention will be further described in detail using examples, etc., but the scope of the present invention is not limited to these examples, etc.

[0133] [Example 1]

[0134] 1. Preparation of the coating liquid for the coating composition

[0135] 5.0 parts by weight (converted to solids content) of a UV-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "UV-AF100") which is an active energy ray-curable silicone compound (B) and 100 parts by weight (converted to solids content) of a UV-curable silicone fluoropolymer resin (manufactured by JNC petro chemical Co., Ltd., product name "Sila-Max XC0199-40") which is an active energy ray-curable fluoropolymer resin (A) are mixed together to form a coating liquid for a coating composition.

[0136] 2. Manufacturing of the protective film

[0137] The coating solution of the above-prepared coating composition was applied to one side of a polyurethane resin film (manufactured by SEIKOH CHEMICALS CO.,LTD., product name "LUCKSKIN F9700ES-150C", thickness: 150 μm, elongation at break: 700%), which served as the substrate, using a bar coater, and dried at 80°C for 1 minute to form a coating film. Then, the coating film was subjected to an illuminance of 80 mW / cm² under a nitrogen atmosphere. 2 The light intensity is 200 mJ / cm 2 It is exposed to ultraviolet light to form a coating with a thickness of 4μm, which is used as a protective film (thickness: 154μm).

[0138] [Examples 2-3]

[0139] Except for changing the mixing amount of the active energy ray curable organosilicon compound (B) as shown in Table 1, the coating liquid for the coating composition was prepared in the same manner as in Example 1. Then, using the coating liquid for the coating composition, a protective sheet was manufactured in the same manner as in Example 1.

[0140] [Example 4]

[0141] 5.0 parts by weight (converted to solids content) of a UV-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "UV-AF100") as an active energy ray-curable silicone compound (B) and 1.0 parts by weight (converted to solids content) of 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one (D1) as a photopolymerization initiator (D) were mixed with 100 parts by weight (converted to solids content) of a UV-curable silicone-containing fluoropolymer resin (manufactured by JNC petro chemical Co., Ltd., product name "Sila-Max XC0199-40") as an active energy ray-curable fluoropolymer resin (A) to form a coating liquid for a coating composition.

[0142] Using the coating liquid of the coating composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0143] [Example 5]

[0144] Except for changing the mixing amount of photopolymerization initiator (D) as shown in Table 1, the coating liquid of the coating composition was prepared in the same manner as in Example 4. Then, using the coating liquid of the coating composition, a protective sheet was manufactured in the same manner as in Example 1.

[0145] [Example 6]

[0146] Except for changing the photopolymerization initiator (D) to 2,2-dimethoxy-2-phenylacetophenone (D2), the coating liquid of the coating composition was prepared in the same manner as in Example 4. Then, using the coating liquid of the coating composition, a protective sheet was manufactured in the same manner as in Example 1.

[0147] [Comparative Example 1]

[0148] As the coating liquid for the coating composition, only an ultraviolet-curable silicone fluoropolymer (manufactured by JNC petro chemical Co., Ltd., product name "Sila-MaxXC0199-40") (a substance dissolved in a mixed solvent of propylene glycol monomethyl ether and methyl ethyl ketone (solid component concentration of 40% by mass)) was used as the active energy ray curable fluorine resin (A), and a protective sheet was manufactured in the same manner as in Example 1.

[0149] [Comparative Example 2]

[0150] 5.0 parts by weight (converted to solids content) of polyether-modified silicone (manufactured by Dow Toray, product name "DOWSIL SH28 PAINT ADDITIVE") as a surface modifier and 100 parts by weight (converted to solids content) of UV-curable silicone-containing fluoropolymer (manufactured by JNC petro chemical Co., Ltd., product name "Sila-Max XC0199-40") as an active energy ray-curable fluoropolymer (A) were mixed and used as a coating liquid for the coating composition.

[0151] Using the coating liquid of the coating composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0152] [Comparative Example 3]

[0153] 5.0 parts by weight (solid content conversion) of a UV-curable silicone compound (manufactured by Mitsubishi Chemical Corporation, product name "UV-AF100") as an active energy ray-curable silicone compound (B) and 1.0 parts by weight (solid content conversion) of 2,2-dimethoxy-2-phenylacetophenone (D2) as a photopolymerization initiator (D) were mixed with 100 parts by weight (solid content conversion) of a multifunctional acrylate (manufactured by SARTOMER COMPANY, product name "SR399E") to form a coating liquid for a coating composition.

[0154] Using the coating liquid of the coating composition obtained above, a protective sheet was manufactured in the same manner as in Example 1.

[0155] [Experimental Example 1] (Determination of elongation at break of coating)

[0156] The protective sheets manufactured in the examples and comparative examples were cut into 15mm × 100mm pieces and used as samples. These samples were placed in a precision universal testing machine (manufactured by SHIMADZU CORPORATION, product name "AG-IS") with a clamping distance (measurement length) of 50mm, and subjected to a tensile test at 200mm / min at 23°C and 50% RH according to JIS K7127: 1999. The elongation at break (%) when the substrate did not break but the coating cracked was then measured as the coating cracking elongation (%). The results are shown in Table 2.

[0157] In addition, the tensile elongation is calculated using the following formula.

[0158] Elongation (%) = (Distance after elongation / Distance between fixtures (measured length)) × 100

[0159] [Experimental Example 2] (Based on the determination of compressive stress)

[0160] An optical adhesive layer (manufactured by LINTEC Corporation, product name "OPTERIA MO-3014", adhesive thickness: 25 μm, total light transmittance: >90%, haze value: <1.0%) was bonded to the substrate side of the protective sheet manufactured in the examples and comparative examples. The protective sheet was then attached to a soda-lime glass plate (manufactured by NIPPON SHEET GLASS CO., LTD., 0.7 mm) using this adhesive layer, thus creating a laminate consisting of a coating / substrate / adhesive layer / glass plate.

[0161] Under conditions of 23°C and 50%RH, a texture analyzer (manufactured by Stable MicroSystems, product name "TA.XT.Plus") was used to press the surface of the coating of the above-mentioned laminate onto a probe of a fixture (model: P / 5S, tip shape: spherical, size: diameter: 5mm, material: stainless steel) at a pressing speed of 0.01mm / s to a depth of 100μm, and the stress (N) was measured and taken as the pressing stress (N). The results are shown in Table 2.

[0162] [Experimental Example 3] (Determination of Pressing Force)

[0163] The laminate was prepared in the same manner as in Experiment 2. Under conditions of 23°C and 50%RH relative humidity, a texture analyzer (manufactured by Stable Micro Systems, product name "TA.XT.Plus") was used to press the surface of the coating of the above laminate onto a probe of a fixture (model: P / 5S, front end shape: spherical, size: diameter: 5mm, material: stainless steel) at a pressing speed of 0.01mm / s. The pressing depth (μm) at the moment when the load of 10N is held for 5 seconds was measured and taken as the pressing amount (μm).

[0164] Next, the ratio (%) of the measured pressing amount (μm) to the thickness (μm) of the protective sheet was calculated. The results are shown in Table 2.

[0165] [Experimental Example 4] (Determination of Haze Value)

[0166] The haze values ​​(%) of the protective films manufactured in the examples and comparative examples were determined using a haze meter (manufactured by Nippon Denshoku Industries, Co., LTD., product name "NDH7000") according to JIS K7136: 2000. The results are shown in Table 2.

[0167] [Experimental Example 5] (Determination of Total Transmittance)

[0168] The total transmittance (%) of the protective films manufactured in the examples and comparative examples was determined using a haze meter (manufactured by Nippon Denshoku Industries, Co., LTD., product name "NDH7000") according to JIS K7361: 1997. The results are shown in Table 2.

[0169] [Experimental Example 6] (Determination of Water Contact Angle)

[0170] The water contact angle of the coating surface of the protective sheets manufactured in the examples and comparative examples was measured using a fully automated contact angle meter (manufactured by Kyowa Interface Science, Inc., DM-701) under the following conditions. The results are shown in Table 2.

[0171] • Volume of purified water droplets: 2 μl

[0172] • Measurement time: 3 seconds after dropping

[0173] • Image analysis method: θ / 2 method

[0174] [Experimental Example 7] (Determination of Oleic Acid Contact Angle)

[0175] The oleic acid contact angle of the coating surface of the protective sheets manufactured in the examples and comparative examples was measured using a fully automated contact angle meter (manufactured by Kyowa Interface Science, Inc., DM-701) under the following conditions. Oleic acid manufactured by Tokyo Chemical Industry Co., Ltd. was used. The results are shown in Table 2.

[0176] • Droplet volume of oleic acid: 2 μl

[0177] • Measurement time: 3 seconds after dropping

[0178] • Image analysis method: θ / 2 method

[0179] [Experimental Example 8] (Evaluation of constructability)

[0180] A (meth)acrylate polymer was prepared by copolymerizing 95 parts by weight of n-butyl acrylate with 5 parts by weight of acrylic acid using solution polymerization. The molecular weight of the (meth)acrylate polymer was determined using the method described later, and the weight-average molecular weight (Mw) was 500,000. 100 parts by weight of the obtained (meth)acrylate polymer (solid component) was mixed with 0.01 parts by weight of an epoxy crosslinking agent (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-X") and stirred thoroughly. The mixture was then diluted with toluene to obtain a coating solution for the adhesive composition.

[0181] The adhesive composition solution obtained in the above steps was applied to the release-treated surface of a release sheet (thickness: 38 μm) on which one side of a polyethylene terephthalate film had been released using a silicone-based release agent. The coating layer was then heat-treated at 90°C for 1 minute to form an adhesive layer (thickness: 20 μm). The adhesive layer from the release sheet was then laminated onto the substrate side of the protective sheet manufactured in the examples and comparative examples to create a laminate having a coating / substrate / adhesive layer / release sheet structure, which was used as a sample.

[0182] Peel the release sheet off the sample and manually apply the exposed adhesive layer side to the surface of the driver's side door of commercially available car 1 (manufactured by Honda Motor Co., Ltd., FIT) and car 2 (manufactured by Toyota Motor Corporation, AQUA) using a scraper.

[0183] Then, the workability was evaluated according to the following evaluation criteria. The results are shown in Table 2. Furthermore, for the protective sheet with an evaluation result of 0, the workability was good for both vehicle 1 and vehicle 2, covering the entire surface of the vehicle body.

[0184] For either car 1 or car 2, the protective sheet can follow and fit well with the curved part of the door, without wrinkles or other defects, allowing for smooth installation.

[0185] ×… For either car 1 or car 2, or for both car 1 and car 2, the protective sheet is difficult to follow the curved part present at the door, and the protective sheet has defects such as wrinkles, and cannot withstand actual use.

[0186] Here, the weight-average molecular weight (Mw) mentioned above is the weight-average molecular weight converted from polystyrene determined by gel permeation chromatography (GPC) under the following conditions (GPC determination).

[0187] <Measurement Conditions>

[0188] • Measuring apparatus: Manufactured by TOSOH CORPORATION, HLC-8320

[0189] • GPC column (passes through in the following order): Manufactured by TOSOH CORPORATION

[0190] TSK gel superH-H

[0191] TSK gel superHM-H

[0192] TSK gel superH2000

[0193] • Solvent for determination: Tetrahydrofuran

[0194] • Measurement temperature: 40℃

[0195] [Experimental Example 9] (Evaluation of Scratch Repairability)

[0196] The coating surface of the protective sheets manufactured in the examples and comparative examples was repeatedly rubbed with a brass brush 20 times. Then, it was visually assessed whether the scratches disappeared over time. The scratch repairability was then evaluated according to the following criteria. The results are shown in Table 2.

[0197] The scratches became invisible within minutes.

[0198] The scratches still remain.

[0199] [Experimental Example 10] (Evaluation of antifouling performance)

[0200] (1) Oil-based pen

[0201] The coating surface of the protective sheets manufactured in the examples and comparative examples was written on using an oil-based pen (manufactured by ZEBRA Co., Ltd., product name "Macky Black"). Then, the coating surface of the protective sheet was wiped dry using a non-woven cloth wiper (manufactured by Asahi Kasei Corporation., product name "BEMCOT S-2"), and the ability to remove the oil-based pen writing was visually assessed. The stain resistance (oil-based pen) was then evaluated according to the following criteria. The results are shown in Table 2.

[0202] 〇…can be easily wiped off.

[0203] △…It can be erased to some extent, but the writing marks can still be identified.

[0204] ×… cannot be erased.

[0205] (2) Carbon black

[0206] A carbon black aqueous dispersion (carbon black content: 5% by mass) was dropped (dropping amount: 0.5 mL) onto the coating surface of the protective sheet manufactured in the examples and comparative examples, and allowed to dry. The coating surface of the protective sheet was then rinsed with running water, and the removal of carbon black traces was visually assessed. The antifouling properties (carbon black) were then evaluated according to the following criteria. The results are shown in Table 2.

[0207] It can easily remove carbon black residue.

[0208] △…can be removed to some extent, but traces of carbon black can still be identified.

[0209] ×…Cannot remove carbon black residue.

[0210] [Experimental Example 11] (Evaluation of Curing)

[0211] During the manufacture of the protective sheets for the examples and comparative examples, the pencil hardness of the coating surface of the protective sheets was measured shortly after ultraviolet irradiation and coating formation (day 0) and 30 days later. The pencil hardness was measured using an electric pencil scratch hardness tester (manufactured by YASUDA SEIKI SEISAKUSHO, LTD., product name "No. 553-M1") according to JIS K5600. The curing was then evaluated based on the following criteria. The results are shown in Table 2.

[0212] The pencil hardness is the same shortly after the coating is formed (day 0) and 30 days later (meaning no curing is required).

[0213] N… The pencil is harder after 30 days compared to shortly after coating formation (day 0) (= requires curing).

[0214] [Table 1]

[0215]

[0216] [Table 2]

[0217]

[0218] As can be clearly seen from Table 2, the protective sheet manufactured in the example has excellent workability, scratch repairability and stain resistance, and does not require curing.

[0219] Industrial applicability

[0220] The protective sheet of the present invention is suitable, for example, as a protective sheet for protecting coatings on automobiles, etc.

Claims

1. A protective sheet, comprising a substrate and a coating, characterized in that, When the protective sheet is stretched at a width of 15 mm, a measurement length of 50 mm, and a tensile speed of 200 mm / min in an environment of 23°C and 50% RH, the tensile elongation rate at which the substrate does not break but the coating cracks is 60% or more. The compressive stress on the coating side surface of the protective sheet or the laminate of the protective sheet with a thickness of 110~1000μm, at a speed of 0.01mm / s to a depth of 100μm, is 1N or more and 8.8N or less.

2. The protective sheet according to claim 1, characterized in that, When a 10N load is applied to the surface of the coating side of the protective sheet at a rate of 0.01mm / min on an area of ​​5mmφ, the amount (μm) is greater than or equal to the thickness (μm) of the protective sheet.

3. The protective sheet according to claim 1, characterized in that, The coating contains organosilicon.

4. The protective sheet according to claim 1, characterized in that, The coating contains fluorinated polymers and organosilicon components.

5. The protective sheet according to claim 3 or 4, characterized in that, The organosilicon component is formed by curing with active energy rays.

6. The protective sheet according to claim 1, characterized in that, The coating is formed by curing with active energy rays.

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

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

9. The protective sheet according to claim 1, characterized in that, The substrate is composed of a material containing more than 10% by mass of polyurethane.

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

11. The protective sheet according to claim 1, characterized in that, The coating thickness is greater than 1 μm and less than 50 μm.

12. A protective sheet with an adhesive layer, comprising the protective sheet of claim 1, and an adhesive layer on the substrate side of the protective sheet.

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