JP2020185731A - Protective film and surface protected article - Google Patents

Abstract

To provide a protective film having excellent applicability for an adherend.SOLUTION: A protective film includes: a base material film 11 formed of thermoplastic polyurethane; a surface layer 12 formed on the first face side of the base material film 11; an adhesive layer 13 formed on the second face side, opposite to the first face side, of the base material film 11; and a release film 14 arranged on the face of the side, opposite to the base material film 11, of the adhesive layer 13, in which the surface layer 12 is a cured layer of a curable composition including a urethane (meth)acrylic resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, a fluorosilsesquioxane derivative (c), and a photoinitiator (d), and the release film 14 has arithmetic average roughness (Ra) of 480 nm or more and arithmetic average waviness (Wa) of 120 nm or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a protective film. In particular, it relates to a protective film using thermoplastic polyurethane.

Thermoplastic polyurethane (TPU) having high impact resistance has been conventionally used as a base material for a protective film or the like. Especially in Europe and the United States, the name of paint protection film (PPF) is widely used as a film that protects the body of a car from stone splashes and scratches. For example, 3M's Scotchgard Paint Protection Film.

As a laminate using thermoplastic polyurethane, Patent Document 1 describes a laminate that can be used to protect the surface, particularly to protect the surface of a vehicle (for example, an automobile, an aircraft, a ship) such as a coated surface. The laminate that can be used for is disclosed. The laminate has excellent antifouling properties and sticking properties (time until the remaining air bubbles and blisters after sticking disappear visually), and has the property of being able to suppress adhesive residue. (Paragraph 0006, 0124).

In addition to improving the above characteristics, these laminated bodies are required to further improve workability. As the workability, for example, improvement of complex characteristics such as initial positioning, glue misalignment, reworkability, and liquid drainage can be mentioned.

International Publication No. 2016/010041

Therefore, an object of the present invention is to provide a protective film using thermoplastic polyurethane, which is excellent in workability.

The present inventors have conducted diligent studies to solve the above problems. As a result, by controlling the combination of both the arithmetic mean roughness (Ra) and the arithmetic mean waviness (Wa) of the release film, the workability can be improved, and the appearance defect due to the glue misalignment that occurs during the construction can be prevented. We have found that a protective film that can be suppressed can be formed, and completed the present invention.

The protective film according to the first aspect of the present invention includes, for example, as shown in FIG. 1, a base film 11 formed of thermoplastic polyurethane; and a surface layer formed on the first surface side of the base film 11. 12; and the adhesive layer 13 formed on the second surface side opposite to the first surface side of the base film 11; the peeling provided on the surface of the adhesive layer 13 opposite to the base film 11 The film 14 and; are provided. The surface layer 12 contains a urethane (meth) acrylate resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, a fluorosilsesquioxane derivative (c), and photopolymerization. The curable composition containing the initiator (d) is a cured layer, and the release film 14 has an arithmetic average roughness (Ra) of 480 nm or more and an arithmetic average waviness (Wa) of 120 nm or more. In addition, in this specification, "on the surface side" means that it may be laminated in contact with each other, or it may be laminated through another layer. "On the surface" means to contact and stack.
With this structure, it is possible to have a surface layer having excellent scratch self-healing property and extensibility. That is, the flexibility of the urethane (meth) acrylate-based resin (a) makes it excellent in self-healing and extensibility of scratches. Furthermore, the fluorosilsesquioxane derivative (c) allows the surface layer to have excellent antifouling properties and slipperiness. Further, the release film having an arithmetic mean roughness (Ra) of 480 nm or more and an arithmetic mean swell (Wa) of 120 nm or more facilitates the application of the protective film to the adherend, and the adherend is constructed. Improve the appearance of.

The protective film according to the second aspect of the present invention is the protective film according to the first aspect of the present invention, and the arithmetic mean swell (Wa) is 120 to 600 nm.
With such a configuration, the arithmetic mean waviness (Wa) of the release film can be made more preferable.

The protective film according to the third aspect of the present invention is the protective film according to the first or second aspect of the present invention, wherein the curable composition is the urethane (meth) acrylate-based resin (a). The urethane (meth) acrylate-based compound (b), which does not have the urethane unit and contains a fluorine atom, and the fluorosilsesquioxane derivative (c) in a total amount of 100% by mass. The total of the photopolymerizable acrylic compound (b) containing the resin (a) in a proportion of 20 to 50% by mass, having no urethane unit and containing a fluorine atom, and the fluorosilsesquioxane derivative (c). The amount is contained in a proportion of 50 to 80% by mass.
When configured in this way, the protective film has excellent workability, water repellency, stain resistance, stain resistance durability, oil repellency, flexibility, extensibility, design (smoothness), and low curl after curing. Have a good balance of sex. Such a protective film of the present invention is suitable as a material for PPF.

The protective film according to the fourth aspect of the present invention is the protective film according to the third aspect of the present invention. The urethane (meth) acrylate-based resin (a) has a weight average molecular weight (Mw) of 3,000. The photopolymerizable acrylic compound (b) having a urethane unit of ~ 800,000 and containing a fluorine atom has at least two polymerizable functional groups and is the fluorosilsesquioxane derivative (the fluorosilsesquioxane derivative (). c) has at least one polymerizable functional group.
With this configuration, the urethane (meth) acrylate resin (a) and the (b) or (c) having a polymerizable functional group crosslink with each other. The formed surface layer is fixed by cross-linking, so that dirt can be suppressed from permeating and has excellent antifouling property, and bleed-out is prevented to increase the durability of antifouling property.

The protective film according to the fifth aspect of the present invention is the protective film according to the third or fourth aspect of the present invention, wherein the fluorosilsesquioxane derivative (c) has a cage shape in its structure. Includes structural fluorosilsesquioxane.
With this configuration, the cage-shaped fluorosilsesquioxane has the property of being more likely to accumulate at the interface with air, thus increasing the speed at which it gathers at the interface with air when the surface layer is formed. be able to.

The protective film according to the sixth aspect of the present invention is the protective film according to any one of the first to fifth aspects of the present invention, wherein the adhesive layer is an acrylic type, a urethane type, or a rubber. The release film is composed of at least one resin selected from the based resin and the silicone based resin, and the release film has at least one selected from the fluororesin, the silicone resin, and the long-chain alkyl group-containing carbamate on the surface with respect to the adhesive layer. It is a film coated with two release agents.
With such a configuration, the release film can be easily peeled off from the adhesive layer.

The surface protective article according to the seventh aspect of the present invention is a film obtained by peeling the release film from the protective film according to any one of the first to sixth aspects of the present invention; The peeled film comprises an article attached to the surface by the adhesive layer;
With this configuration, the surface of the article can be protected from scratches and the like by the thermoplastic polyurethane having high impact resistance. Further, when the surface layer which is the outermost surface is scratched, it can be self-repaired, and the outermost surface is also excellent in antifouling property, extensibility and slipperiness. Further, it is possible to suppress the generation of citron skin due to the sticking of the film and improve the appearance of the article to which the film is stuck.

The protective film of the present invention is excellent in workability on the adherend without impairing the flexibility of the thermoplastic polyurethane, and can protect the surface of the adherend.

It is a figure which shows the layer structure of the protective film 200 which concerns on 1st Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each figure, parts that are the same as or correspond to each other are designated by the same or similar reference numerals, and duplicate description will be omitted. Moreover, the present invention is not limited to the following embodiments.

[Protective film 200]
As shown in FIG. 1, the protective film 200 according to the first embodiment of the present invention includes a base film 11 having a surface layer 12 and an adhesive layer 13. The protective film 200 includes a release film 14 at the time of manufacture, but when the protective film 200 is attached to the surface of an article to be adhered, the release film 14 is peeled off and used.

[Base film 11]
As the base film 11, it is desirable to use a film formed of a thermoplastic resin. As the thermoplastic resin, polyurethane resin, polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, polyvinyl chloride Examples thereof include resins such as based resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and norbornene resins. These resins may be used alone or in combination of a plurality of resins. The thermoplastic resin is preferably thermoplastic polyurethane, polycaprolactone (PCL), acrylic acid polymer, polyester, polyacrylonitrile, polyetherketone, polystyrene, polyvinylacetate, or a derivative thereof. The thermoplastic resin is more preferably thermoplastic polyurethane. Examples of thermoplastic polyurethanes are Argotec 49510, Argotec 49510-DV, Nihon Matai Co., Ltd. Esmer URSPX86, Esmer URSPX93, Esmer URSPX98, Seadam Co., Ltd. DUS202, DUS213, DUS235, DUS501, DUS601, DUS601. Examples thereof include DUS203, DUS220, DUS701, XUS2086, XUS2098, DUS451, DUS450, Unigrand XN2001, XN2002, and XN2004 manufactured by Nippon Unipolymer Co., Ltd. Among them, as the polyhydroxy compound, polycaprolactone-based thermoplastic polyurethane using polycaprolactone polyol, polycarbonate-based thermoplastic polyurethane using polycarbonate polyol, and polyether-based thermoplastic polyurethane using polyether polyol are preferable.
The film thickness of the base film 11 is not particularly limited, but when the present invention is used as a protective film, the film thickness of the base film 11 is typically 25 to 300 μm, preferably 100 to 200 μm. It is more preferably 140 to 160 μm. When the film thickness of the base film 11 is 25 μm or more, the mechanical strength of the base film 11 is sufficient, and a layer can be formed on the base material. Further, when the film thickness is 300 μm or less, the thickness of the protective film does not become too thick.

[Surface layer 12]
The surface layer 12 includes, for example, a urethane (meth) acrylate-based resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, and a photopolymerization initiator (d). A coating agent containing a curable composition containing a fluorosilsesquioxane derivative (c) is applied onto the surface of the base film 11, and is formed by subsequent drying and curing. Hereinafter, the urethane (meth) acrylate resin (a) may be abbreviated as the component (a). Further, the photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom may be abbreviated as the component (b). Further, the fluorosilsesquioxane derivative (c) may be abbreviated as the component (c). Further, the photopolymerization initiator (d) may be abbreviated as the component (d).
In the surface layer 12, as shown in FIG. 1, the component (b) fc or the component (c) is accumulated on the surface (s1) which is an interface with air. In FIG. 1, the component (b) is shown as fc and the component (c) is shown as ss.
The "curable composition" is a cross-linking component in the coating agent, and refers to the component (a), the component (b), the component (c), and the component (d).
The film thickness of the surface layer 12 is typically 1 to 100 μm, preferably 1 to 50 μm, more preferably 3 to 30 μm, and particularly preferably 5 to 12 μm. When the film thickness of the surface layer 12 is 1 μm or more, the mechanical strength is sufficient, and when the film thickness is 100 μm or less, the thickness of the protective film does not become too thick.

For coating, it is preferable to use a wet coating method in which the coating agent is uniformly coated. As the wet coating method, a gravure coating method, a die coating method, or the like can be used.
In the gravure coating method, a gravure roll with uneven engraving on the surface is dipped in the coating liquid, and the coating agent adhering to the uneven surface of the gravure roll is scraped off with a doctor blade and the liquid is stored in the concave portion for accurate weighing. It is a method of transferring to a base material. By the gravure coating method, a low-viscosity liquid can be thinly coated. The die coating method is a method of coating while pressurizing and extruding a liquid from a coating head called a die. The die coating method enables highly accurate coating. Further, since the liquid is not exposed to the outside air at the time of application, the concentration of the coating agent is unlikely to change due to drying.
Other wet coating methods include spin coating method, bar coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air knife coating method, and curtain coating. Examples include the method and the rod coat method. The coating method can be appropriately selected from these methods according to the required film thickness. By using the wet coating method, coating can be performed at a line speed of several tens of meters per minute (for example, about 20 m / min), so that mass production can be performed and production efficiency can be improved.

[Coating agent]
The coating agent forming the surface layer 12 is a urethane (meth) acrylate resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, and a fluorosilsesquioxane derivative. (C) and a photopolymerization initiator (d) are included. For example, as shown in FIG. 1, when a coating agent is applied onto the base film 11 and cured, a surface layer 12 having excellent self-healing property, antifouling property, and extensibility can be formed.
The fluorosilsesquioxane derivative (c) can improve the antifouling property of the surface layer 12 and impart excellent slipperiness.
The coating agent may further contain a solvent (e) and an additive (f).

[Urethane (meth) acrylate resin (a)]
The urethane (meth) acrylate-based resin (a) is an active energy ray-curable resin having a (meth) acryloyl group and a urethane skeleton, and examples thereof include an ultraviolet curable resin. "(Meta) acryloyl group" means an acryloyl group or a methacryloyl group. The urethane (meth) acrylate-based resin (a) imparts flexibility (flexibility) to the surface layer 12.
The urethane (meth) acrylate-based resin (a) includes an organic isocyanate-based compound (polyisocyanate) having a plurality of isocyanate groups in one molecule and a polyol-based compound (polyhydroxy compound or polyhydric alcohol) having two or more hydroxyl groups. ), And then a hydroxyl group-containing (meth) acrylate-based compound may be further reacted to obtain a radically polymerizable unsaturated group-containing oligomer, prepolymer, or polymer.

In particular, a polycarbonate urethane (meth) acrylate using a polycarbonate polyol as the polyhydroxy compound is preferable. By using the polycarbonate-based urethane (meth) acrylate, the formed surface layer 12 can provide excellent elasticity and toughness.
Alternatively, a polyester urethane (meth) acrylate using a polyester polyol as the polyhydroxy compound is also preferable. By using the polyester urethane (meth) acrylate, the formed surface layer 12 can provide excellent elasticity and toughness.

Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, and triisocyanate. Phenylmethane triisocyanate, Vernock D-750 (trade name: DIC Co., Ltd.), Chris Bonn NK (trade name: DIC Co., Ltd.), Death Module L (trade name: Sumitomo Bayer Urethane Co., Ltd.), Coronate Examples thereof include L (trade name: manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate D102 (trade name: manufactured by Mitsui Takeda Chemical Co., Ltd.), and isocyanate 143L (trade name: manufactured by Mitsubishi Chemical Co., Ltd.).
Examples of the polyhydroxy compound include polycarbonate polyols, polyester polyols, polyether polyols, and polycaprolactone polyols. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin- tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, tri Methylolpropane- tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol- tetrahydrofuran adduct, and dipentaerythritol-ethylene oxide- Examples include propylene oxide adducts.
Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-. Butanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexaneglycol, 1,3-cyclohexaneglycol, 1,4 Examples thereof include -cyclohexaneglycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, and 2,7-decalin glycol.

The hydroxyl group-containing (meth) acrylate-based compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Examples thereof include di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid and pentaerythritol tri (meth) acrylate.

The urethane (meth) acrylate-based resin (a) can be synthesized by a known method. As an example, a predetermined amount of polyisocyanate and a polycarbonate polyol are reacted under the condition of 70 ° C. to 80 ° C. until the residual isocyanate concentration reaches a predetermined amount, and then a predetermined amount of molecules further contain one or more hydroxyl groups. It can be obtained by adding (meth) acrylate and reacting in the presence of a polymerization inhibitor (for example, hydroquinone monomethyl ether) at 70 ° C to 80 ° C until the residual isocyanate concentration becomes 0.1% by mass or less. ..

The weight average molecular weight (Mw) of the urethane (meth) acrylate-based resin (a) is typically in the range of 3,000 to 800,000, preferably in the range of 5,000 to 20,000. Within this range, flexibility can be imparted to the surface layer 12. When it is 3,000 or more, the crosslink density in the surface layer 12 does not become too high.

[Photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom]
The photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom has at least two polymerizable functional groups without a urethane unit and a monomer or an oligomer if it has a fluorine atom. , Prepolymer, or polymer. As a substance containing the photopolymerizable acrylic compound (b) which does not have a urethane unit and contains a fluorine atom, a perfluoropolyether having a (meth) acryloyl group can be mentioned. In the present invention, the photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom does not include the following fluorosilsesquioxane derivative (c).

Examples of the perfluoropolyether include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked. The divalent fluorocarbon groups having 1 to 3 carbon atoms may be of one type or a combination of two or more types.
Specific examples of the perfluoropolyether chain include those represented by the following formula (1).

In the above formula (1), X is the following formulas (1-1) to (1-5). Further, X may be any one of the following formulas (1-1) to (1-5), and two or more of the following formulas (1-1) to (1-5) may be used. It may have. For example, a structure having two or more of the following formulas (1-1) to (1-5) as X is represented by − (CF ₂ CF ₂ −O) _n − (CF ₂ −O) _n −. There is a structure that can be used. When the X includes two or more types of structures represented by the formulas (1-1) to (1-5), it has a random structure or a block structure composed of- (X-O) -structural units. May be good. Further, n is an integer of 2 to 200 representing a repeating unit.

The photopolymerizable acrylic compound (b) which does not have a urethane unit and contains a fluorine atom preferably has a polymerizable functional group at least at both ends. The polymerizable functional group is not particularly limited as long as it is a radically polymerizable group. For example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylicamide, N-vinylamide, malein. Acid esters, fumaric acid esters, N-substituted maleimides and the like are included, with groups containing (meth) acrylic or styryl being preferred. (Meta) Acrylic is a general term for acrylic and methacrylic, and means acrylic or methacrylic.

The photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom can be synthesized by a known method.
The content of the photopolymerizable acrylic compound (b) which does not have a urethane unit and contains a fluorine atom is the photopolymerizable of the urethane (meth) acrylate resin (a) and which does not have a urethane unit and contains a fluorine atom. It is 50 to 80% by mass, preferably 50 to 70% by mass, per 100% by mass of the total amount of the acrylic compound (b).

The photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom may be composed of one kind of photopolymerizable acrylic compound, and at least one kind of fluorine atom-containing photopolymerizable acrylic. It may be composed of two or more kinds of photopolymerizable acrylic compounds including a system compound.
Examples of the photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom include a photocurable acrylic monomer having a fluorine atom in the molecule, or an oligomer such as Optool DAC-HP (Daikin Industries, Ltd.). ), Megafuck RS-75 (manufactured by DIC Co., Ltd.), Viscort V-3F (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and other commercially available fluorine-based (meth) acrylate compounds can be used.

[Fluorosylsesquioxane derivative (c)]
The fluorosilsesquioxane derivative (c) may be any of a monomer, an oligomer, a prepolymer, and a polymer as long as it has at least one polymerizable functional group.
-Fluorosilsesquioxane monomer Silsesquioxane is a general term for polysiloxanes represented by [(R-SiO _1.5 ) n] (R is an arbitrary substituent). The structure of this silsesquioxane is generally classified into a random type structure, a ladder type structure, and a cage type structure according to its Si—O—Si skeleton. Further, the cage type structure is classified into T8, T10, T12 type and the like according to the number of Si contained.
The fluorosilsesquioxane may have a property of easily accumulating at the interface between air and a solid (or liquid) in a hydrophobic atmosphere (for example, in air). A fluorosilsesquioxane that accumulates at the interface can fully exert the effects of the present invention. Due to the excellent surface accumulation characteristics of fluorosilsesquioxane, the surface modification of the surface layer 12 can be effectively performed in a small amount.

As an example of fluorosilsesquioxane, a fluorosilsesquioxane monomer having a molecular structure represented by the following formula (2) can be mentioned.

That is, among the random type structure, the ladder type structure, and the cage type structure which are the structures of silsesquioxane, the cage type structure is particularly preferable. When fluorosilsesquioxane having a cage structure is used, the speed of accumulation at the interface can be increased as compared with that of other structures.
Considering the availability, it is preferable to use any one of T8 type, T10 type and T12 type.
The substituent (R) in the above formula [(R-SiO _1.5 ) n] is preferably a fluoroalkyl group (R _f ). Considering the solubility in a solvent, the carbon number of R _f is preferably 1 to 8. R _f may be a straight chain group or a branched group. Specifically, as a linear group, -CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , as a branched group, -CH ₂ CH ₂ CF (CF ₃ ) ₂ , -CH ₂ CH (CF ₃ ) CF ₂ CF ₃ , -CH (CF ₃ ) CH ₂ CF ₂ CF ₃ , -CH ₂ C (CF ₃ ) ₂ CF ₃ , -C (CF ₃ ) ₂ CH ₂ CF ₃ -CH ₂ CH ₂ CF ₂ CF (CF ₃ ) ₂ , -CH ₂ CH ₂ CF (CF ₃ ) CF ₂ CF ₃ , and -CH ₂ CH ₂ C (CF ₃ ) ₂ CF ₃ etc. It can be exemplified. R _f may be different groups or all may be the same group.

The above formula (2) exemplifies fluorosilsesquioxane having "3- (methacryloyloxy) propyl" in one Si, but the present invention is not limited to this polymerizable functional group. For example, when the position of "3- (methacryloyloxy) propyl" is Z, this position can be replaced with another functional group. Specifically, as Z, hydrogen, hydroxy, alkenyl, or halogen (chlorine, bromine, iodine), alkoxy, phenoxy, polyalkyleneoxy, -COOH, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkenyl. Oxycarbonyl, Oxylanyl, 3,4-Epoxycyclohexyl, Oxetanyl, Oxetanilen, -NH-, -NH ₂ , -CN, -NCO, Alkynyl, Cycloalkoxy, Acryloyloxy, Methacryloyloxy, Urethaneacryloyl, Urethanemethacryloyl, -SH and It can be based on any of −PH ₂ . Further, Z may be the above group (hydrogen to −PH ₂ ) via an alkylene. The alkylene bonded to Si is not particularly limited, but an alkylene having 1 to 8 carbon atoms is preferable, and a propylene having 3 carbon atoms is particularly preferable. However, the selection range does not include groups having alkanoyloxy, groups having sulfonyl halides, and groups having α-haloester groups.
Particularly preferred is fluorosilsesquioxane, which has at least two polymerizable functional groups attached to Si. For example, in the above formula (2), fluorosilsesquioxane having "3- (methacryloyloxy) propyl" in one Si is exemplified, but this "3- (methacryloyl)" is illustrated in one or more other Sis. More preferably, it is a fluorosilsesquioxane having "oxy) propyl". Further, the polymerizable functional group is preferably a radically polymerizable functional group.

-Fluorosilsesquioxane oligomer, prepolymer, polymer In the following, the fluorosilsesquioxane oligomer, prepolymer, and polymer are collectively referred to as a fluorosilsesquioxane polymer.
The fluorosilsesquioxane polymer can be a monopolymer of fluorosilsesquioxane if the functional group is a polymerizable group, and other common monomers (eg, additions). It can also be a copolymer with a polymerizable monomer). It may be a copolymer of fluorosilsesquioxanes having different polymerizable groups. At this time, any known method can be adopted as the polymerization method. As described above, the fluorosilsesquioxane used in the coating agent may be a fluorosilsesquioxane polymer.
However, the polymerized fluorosilsesquioxane polymer has at least one polymerizable functional group. Further, the polymerizable functional group is preferably a radically polymerizable functional group.

That is, the fluorosilsesquioxane of the above formula (2) may have an addition-polymerizable functional group as Z. Alternatively, it may have an addition-polymerizable functional group as Z via an alkylene. Examples of addition polymerizable functional groups include groups having terminal olefin type or internal olefin type radically polymerizable functional groups; groups having cationically polymerizable functional groups such as vinyl ether and propenyl ether; and vinyl carboxyl, cyanoacryloyl and the like. A group having an anionic polymerizable functional group is included, and a radically polymerizable functional group is preferable.

The above radically polymerizable functional group is not particularly limited as long as it is a radically polymerizable group, for example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylicamide, N-. Vinyl amide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like are included, and a group containing (meth) acrylic or styryl is preferable. (Meta) Acrylic is a general term for acrylic and methacrylic, and means acrylic or methacrylic.

Examples of the above-mentioned radically polymerizable functional group having (meth) acrylic include a group represented by the following formula (3). In the formula (3), Y ¹ represents an alkylene having 2 to 10 carbon atoms, preferably an alkylene having 2 to 6 carbon atoms, and more preferably propylene. Further, X represents hydrogen or an alkyl having 1 to 3 carbon atoms, and preferably hydrogen or methyl.

Further, examples of the above-mentioned radically polymerizable functional group having styryl include a group represented by the following formula (4). In the formula (4), Y ² represents a single bond or an alkylene having 1 to 10 carbon atoms, preferably a single bond or an alkylene having 1 to 6 carbon atoms, and more preferably a single bond or ethylene. Further, vinyl is bonded to any carbon of the benzene ring, and is preferably bonded to the carbon at the para position with respect to Y ² .

Some addition-polymerizable monomers have a crosslinkable functional group and some do not have a crosslinkable functional group. The addition-polymerizable monomer having a crosslinkable functional group may be any compound having one or more addition-polymerizable double bonds, and may be, for example, any of a vinyl compound, a vinylidene compound, and a vinylene compound. Often, more specifically, (meth) acrylic acid compounds, styrene compounds and the like are exemplified.

Examples of the above (meth) acrylic acid compounds include (meth) acrylic acid and (meth) acrylic acid esters, as well as (meth) acrylic acid amides, (meth) acrylonitrile and the like.

An example of the (meth) acrylic acid compound of the addition-polymerizable monomer is a (meth) acrylate having a crosslinkable functional group. Examples of such crosslinkable functional groups include epoxies such as glycidyl and epoxycyclohexyl, oxetanyl, isocyanato, acid anhydrides, carboxyls, and hydroxyls, with preference given to epoxies such as glycidyl and oxetanyl. Specific examples of the (meth) acrylate having a crosslinkable functional group include hydroxyalkyl (meth) acrylates such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; Epoxy-containing (meth) acrylates such as glycidyl (meth) acrylates; alicyclic epoxy-containing (meth) acrylates such as 3,4-epoxycyclohexylmethyl (meth) acrylates; 3-ethyl-3- (meth) acryloyloxymethyloxetane Oxetanyl-containing (meth) acrylates such as 2- (meth) acryloyloxyethyl isocyanate; γ- (methacryloyloxypropyl) trimethoxysilane; (meth) acrylate-2-aminoethyl, 2- (2-bromopropionyloxy) ethyl (Meta) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate; 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-pi) Peridinyloxy) ethane, 1-(4-((4- (meth) acryloxy) ethoxyethyl) phenylethoxy) piperidine, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2, 2,6,6-Pentamethyl-4-piperidyl (meth) acrylate; and the like are included.

An example of the above-mentioned styrene compound having an addition-polymerizable double bond is a styrene compound having a crosslinkable functional group. Specific examples of such crosslinkable functional groups include epoxies such as glycidyl, oxetanyl, halo, amino, isocyanato, acid anhydride, carboxyl, hydroxyl, thiol, syroxy and the like.
Examples of styrene compounds having crosslinkable functional groups include o-aminostyrene, p-styrenechlorosulfonic acid, styrenesulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2 -(2-Bromoisobutyryloxy) styrene, 1-(2-((4-vinylphenyl) methoxy) -1-phenylethoxy) -2,2,6,6-tetramethylpiperidine and the following formula Contains compounds that

In addition to the above-mentioned addition-polymerizable monomer, in order to control compatibility with a curable resin, leveling property, amount of crosslinkable functional groups in the copolymer, etc., other than the above-mentioned addition-polymerizable monomer as necessary. The addition-polymerizable monomer of can also be used in combination.

As the addition-polymerizable monomer having no crosslinkable functional group, a (meth) acrylic acid compound having one addition-polymerizable double bond and having no crosslinkable functional group and one addition-polymerizable di Examples thereof include styrene compounds having a heavy bond and no crosslinkable functional group. Specific examples of such (meth) acrylic acid compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylates, nonyl (meth) acrylates, decyl (meth) acrylates, dodecyl (meth) acrylates and stearyl (meth) acrylates; aryls such as phenyl (meth) acrylates and toluyl (meth) acrylates. (Meta) acrylate; arylalkyl (meth) acrylate such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate. Meta) acrylate; ethylene oxide adduct of (meth) acrylic acid; and the like.

Specific examples of the (meth) acrylic acid compound having one addition-polymerizable double bond and no crosslinkable functional group include trifluoromethylmethyl (meth) acrylate and 2-trifluoromethyl. Ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, Diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and Includes fluoroalkyl (meth) acrylates such as 2-perfluorohexadecylethyl (meth) acrylates and the like.

Further, an example of a (meth) acrylic acid compound having one addition-polymerizable double bond and no crosslinkable functional group is a (meth) acrylic acid compound having a silsesquioxane skeleton. Specific examples of the (meth) acrylic acid compound having such a silsesquioxane skeleton include 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3]. , 9.1} 5,15.1.1 ^7,13 ] ^{Octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9. 5.1.1 ^{3,9.1 5,15} . 1 ^7,13 ] ^{Octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-hepta) isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9, 11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3, 5,7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate , 3 - [(3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane -1- yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15. 1 ^7,13 ] Octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1] .1 ^{3,9.1 5,15.1 7,13} ] ^{Octasiloxane-} 1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5, 7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane -1- Lee Luoxy) dimethylsilyl] propyl (meth) acrylate and the like are included. Specific examples of the styrene compound having one addition-polymerizable double bond and no crosslinkable functional group include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene; and the like.

Examples of the above-mentioned styrene compound having an addition-polymerizable double bond and no crosslinkable functional group further include a styrene compound containing silsesquioxane. Examples of styrene induction containing such silsesquioxane include 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3, 9} .. 1 ^5,15 . 1 ^7,13 ] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] Octasiloxane, and 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] ^Octasiloxane having a 4-vinylphenyl group (T8 type silsesquioxane) such as octasiloxane; and 3- (3,5,7,9,11,13,15-heptaethylpenta) cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13 , 15-hepta isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9 , 11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5, 7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3 - (( 3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane - 1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15. 1 ^7,13 ] Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^{3,] 9} .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, and 3 - ((3,5,7,9,11,13,15- heptaphenyl penta cyclo [9 .5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) such as dimethylsilyl) ethylstyrene, 4-vinylphenyl ethyl Octasiloxane (T8 type silsesquioxane); and the like.

Further, as an addition-polymerizable monomer other than the addition-polymerizable monomer, it has a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxides such as ethylene oxide and propylene oxide. , A macromonomer having one polymerizable double bond is also exemplified.

Examples of addition-polymerizable monomers also include compounds having two addition-polymerizable double bonds. Examples of compounds having two add-polymerizable double bonds are 1,3-butanediol = di (meth) acrylate, 1,4-butanediol = di (meth) acrylate, 1,6-hexanediol = di. (Meta) acrylate, polyethylene glycol = di (meth) acrylate, diethylene glycol = di (meth) acrylate, neopentyl glycol = di (meth) acrylate, triethylene glycol = di (meth) acrylate, tripropylene glycol = di (meth) Acrylate, hydroxypivalic acid ester Neopentyl glycol = di (meth) acrylate, trimethylpropan = di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol = di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol Di (meth) acrylates of compounds and di (meth) acrylate-based monomers such as bis [(meth) acryloyloxypropyl] tetramethyldisiloxane and divinylbenzene are included.
Further exemplified are macromonomers having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxides such as ethylene oxide and propylene oxide, and having two polymerizable double bonds. To.

Examples of the addition-polymerizable monomer also include compounds having three or more addition-polymerizable double bonds. Examples of compounds having three or more addition-polymerizable double bonds are trimethylolpropane = tri (meth) acrylate, pentaerythritol = tri (meth) acrylate, pentaerythritol = tetra (meth) acrylate, dipentaerythritol = mono. Hydroxypenta (meth) acrylate, tris (2-hydroxyethyl isocyanate) = tri (meth) acrylate, tris (diethylene glycol) trimerite = tri (meth) acrylate, 3,7,14-tris [(((meth) acryloyloxypropyl) ) Dimethylsiloxy)]-1,3,5,7,9,11,14-Heptaethyltricyclo [7.3.3.1 ^5,11 ] Heptasiloxane, 3,7,14-Tris [(((((() Meta) Acryloyloxypropyl) Dimethylsiloxy)] -1,3,5,7,9,11,14-Heptaisobutyltricyclo [7.3.3.1 ^5,11 ] Heptasiloxane, 3,7,14- Tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisooctyl lycyclo [7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-Tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyllycyclo [7.3.3.1 ^{5, 11} ] Propylsiloxane, 3,7,14-Tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptaphenyltricyclo [7.3. 3.1 ^5,11 ] Heptasiloxane, octakis (3- (meth) acryloyloxypropyldimethylsiloxy) octacilsesquioxane and octakis (3- (meth) acryloyloxypropyl) octacilsesquioxane are included.
Further exemplified are macromonomers having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxides such as ethylene oxide and propylene oxide, and having three or more polymerizable double bonds. Will be done.

The addition-polymerizable monomer is preferably a (meth) acrylic acid compound, more preferably a (meth) acrylic acid ester, and even more preferably a lower alkyl (for example, 1 to 3 carbon atoms) of (meth) acrylic acid. ) Esters, esters having crosslinkable functional groups, etc.

The fluorosilsesquioxane derivative (c) is an addition polymer of fluorosilsesquioxane or an addition copolymer with another addition-polymerizable monomer, and when it is a copolymer, it is a block copolymer. It may be a constitutive copolymer such as, or a random copolymer, but it is preferably a random copolymer. Further, the fluorosilsesquioxane derivative (c) may have a crosslinked structure or may be a graft copolymer.

The curable composition comprises a urethane (meth) acrylate-based resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, and a fluorosilsesquioxane derivative (c). A photopolymerizable acrylic compound (b) containing a urethane (meth) acrylate-based resin (a) in a proportion of 20 to 50% by mass, having no urethane unit, and containing a fluorine atom per 100% by mass of the total amount of The total amount of the fluorosilsesquioxane derivative (c) is contained in a proportion of 50% by mass or more and less than 80% by mass, preferably 50% by mass or more and less than 70% by mass.
The content of the fluorosilsesquioxane derivative (c) is a urethane (meth) acrylate resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, and fluorosilsesqui. It is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the oxane derivative (c). When it is 0.1% by mass or more, the antifouling property of the surface layer 12 can be improved and slipperiness can be imparted, and when it is 10% by mass or less, the flexibility of the surface layer 12 is lowered and the self-healing property is improved. You can avoid being inferior.

[Photopolymerization Initiator (d)]
The photopolymerization initiator (d) may be any kind of initiator (active energy ray polymerization initiator) that generates radicals with active energy rays, and is not particularly limited. For example, an alkylphenone-based photopolymerization initiator and the like can be mentioned.
Examples of the compound used as the photopolymerization initiator (d) include 1-hydroxycyclohexylphenylketone, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, and the like. 2-Ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1,4-ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4' -Tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 4- [pn, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -S-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) Benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-bi Imidazole, 2 , 2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) ) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3-( 2-Methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (η5-2,4-) Cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) Benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3, 4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2-Hyrodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, and bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide and the like can be mentioned. These compounds may be used alone, or a mixture of two or more thereof may be used.
The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to the total amount (100 parts by mass) of the radically polymerizable resin. More preferably, it is 1 to 10 parts by mass.

[Solvent (e)]
In the present invention, the above-mentioned component (a), component (b), component (c), and component (d) contained in the coating agent may be used by being dissolved in a solvent such as an organic solvent. The solvent is not particularly limited. A general organic solvent or the like can be used.
Specific examples of the solvent include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.). ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetriform, propionitrile, benzonitrile, etc.) Etc.), ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethyl, etc.) Acetamide), hydrochlorofluorocarbon-based solvent (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) -based solvent (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon-based solvent (perfluoropentane, per) Fluorohexane), alicyclic hydrofluorocarbon solvent (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorosolvent (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic fluorosolvent (α, α, Α-Trifluorotoluene, hexafluorobenzene), and water. These may be used alone or in combination of two or more. For example, a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone can be mentioned. By adding a solvent such as methyl ethyl ketone, which is expected to increase the solubility in the resin, in addition to methyl isobutyl ketone, the workability of solution homogenization can be improved when the coating agent is prepared. In addition, the coating agent can be stabilized by improving the solubility. The mixing ratio (based on mass) can be, for example, in the range of methyl isobutyl ketone / methyl ethyl ketone = 1 to 99/99 to 1, preferably in the range of 20 to 80/80 to 20.

The content of the solvent is 20 to 500 parts by mass with respect to the total amount (100 parts by mass) of the curable composition forming the surface layer. It is preferably 50 to 400 parts by mass.

[Additive (f)]
Additives may be added to the coating agent in addition to the above. For example, a filler may be added in order to impart hardness and scratch resistance of the film. A leveling agent may be added to improve the coatability. In addition, additives such as a weather resistant agent and an antifoaming agent may be added.
More specifically, an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, a wettability improver, as long as the effect of the cured film formed by the coating agent is not adversely affected. Any component such as surfactant, plasticizer, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent, silane coupling agent, inorganic filler typified by silica or alumina, organic filler, etc. can be further used as a coating agent. It may be contained.

As an example of the leveling agent, there are commercially available acrylic surface conditioners BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, , BYK-3550 (both trade names: manufactured by Big Chemie Japan Co., Ltd.) and the like.
As silicone-based surface conditioners, BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by Big Chemie Japan Co., Ltd.), TEGO Rad2100, 2200N, 2250, 2500, 2600, 2700 (all are commercial products). Name: Ebonic Degusa Japan Co., Ltd., X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22 -1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201 , X-22-2426, X-22-164A, X-22-164C (trade names: manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

Examples of weather resistant agents include UV absorbers of benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, or dibenzoylresorcinols.
Examples of benzotriazoles include BASF TINUVIN PS, TINUVIN 99-2, TINUVIN326, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130, TINUVINCarboproject, and examples of hydroxyphenyltriazines, BASF TINUVIN400, TINUVIN400, TINUVIN4 , And TINUVIN479 and the like.
Examples of benzophenones include 1413 manufactured by ADEKA Corporation and Sumisorb 130 manufactured by Sumika Chemtex Co., Ltd.
Examples of salicylates include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate and the like.
Examples of cyanoacrylates include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3-diphenyl acrylate and the like.
Examples of triazines include LA-46 and LA-F70 manufactured by ADEKA CORPORATION.
Examples of dibenzoyl resorcinols include 4,6-dibenzoyl resorcinol and the like.
These UV absorbers may be used alone or in combination of a plurality of UV absorbers. It is preferable that the type and combination of the ultraviolet absorbers are appropriately selected based on the wavelength of the ultraviolet rays to be absorbed.

The light stabilizers (HALS) include TINUVIN (registered trademark) 5100 (neutral type general-purpose HALS) and TINUVIN292 (compound name: bis (1,2,2,6,6-pentamethyl-4-)) manufactured by BASF. Piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN152 (compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2, 1-cyclohexyloxy-2,) 2,6,6-Tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), TINUVIN144 (Compound name: Bis (1,2,2,6) 6-Pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate), TINUVIN123 (compound name: decanodic acid, bis (2,2) Reaction product of 2,6,6-tetramethyl-1- (octyloxy) -4 piperidinyl) ester (in the presence of 1,1-dimethylethylhydroperoxide and octane)), TINUVIN111FDL (about 50%, TINUVIN622, compound) Name: (butan diacid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl) in the presence of ethanol), about 50%, CHIMASSORB119, compound name: N-N'-N "-N '''-Tetrakiss (4,56-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazine-2-yl) -4,7-diazadecan- 1,10-Diamine) or Adecaster LA series manufactured by Adeca Co., Ltd., specifically, LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 ( (5) -5711), LA-67 ((5) -5755), LA-82 ((5) -6023), LA-87 ((5) -6022) and the like can be mentioned. The numbers in parentheses are the existing chemical substance numbers.

As an example of the inorganic filler, commercially available products include MEK-ST-40, MEK-ST-L, MEK-ST-ZL, PGM-AC-2140Y, PGM-AC-4130Y, AS-200, manufactured by Nissan Chemical Industries, Ltd. AS-520, Anatase TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ , Cobalt Blue, Zirconium Oxide, Barium Titanate, Titanium Oxide, Silica, Alumina, and MUA Filler manufactured by CIK Nanotech Co., Ltd. And so on.
Examples of organic fillers include Sekisui Plastics Co., Ltd. Techpolymer MBX series, SBX series, Negami Kogyo Co., Ltd. Art Pearl cross-linked acrylic beads, Art Pearl cross-linked urethane beads, and Aika Kogyo Co., Ltd. Ganz Pearl. Can be mentioned.
These fillers may be used alone or in combination of a plurality of fillers.

Other resin components may be added to the coating agent. For example, thermoplastic resin and rubber can be mentioned.
By adding a thermoplastic resin or rubber as other resins, the original properties of the resin (mechanical properties, surface / interface properties, compatibility, etc.) can be modified.

Examples of the thermoplastic resin can be exemplified as follows.
Polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultra-high molecular weight polyethylene, poly-4-methylpentene, syndiotactic polystyrene, Polyacetal, Polycarbonate, Polyphenylene oxide, Polyphenylene sulfide, Polysulfone, Polyethersulfone, Polyetheretherketone, Polyarylate (U polymer: Unitica Co., Ltd. trade name, Vectra: Polyplastics Co., Ltd. trade name, etc.), Polyimide ( Capton: Toray Co., Ltd. trade name, AURUM: Mitsui Chemicals Co., Ltd. trade name, etc.), Polyethyleneimide and Polycarbonateimide.
Polyamides such as nylon 6, nylon 6,6, nylon 6,10, nylon MXD6, nylon 6,T (all trade names: manufactured by DuPont Co., Ltd.).
Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene 2,6-naphthalenedicarboxylate.
In addition, fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride.

The curable composition used for the surface layer 12 is used as a coating agent for coating on the base film. Therefore, the coating agent is preferably liquid. When the curable composition is a solid, it may be dissolved in a solvent and used as a coating agent as described above.
The concentration of the curable composition in the coating agent can be selected so that the viscosity of the coating agent becomes a viscosity corresponding to the coating method such as the wet coating method. The concentration is preferably 1 to 80% by mass, more preferably 3 to 60% by mass. The concentration of the curable composition in the coating agent can be adjusted by using a solvent. As the solvent, for example, a general organic solvent such as methyl ethyl ketone and methyl isobutyl ketone can be used. If the solubility in the solvent is reduced due to the length of the fluoroalkyl group contained in the fluorine compound contained in the curable composition, a fluorine-based organic solvent may be used. Further, other known additives such as a leveling agent such as a surfactant may be added to the coating agent, if necessary. By adding a leveling agent, the surface tension of the coating agent can be controlled, and surface defects that occur during layer formation such as repellents and craters can be suppressed.

Examples of the curing treatment for curing the curable composition include curing treatments such as ultraviolet irradiation, heating, and electron beam irradiation. When the coating film contains a solvent, the coating film is usually heated in the range of 70 to 200 ° C. for several tens of minutes to remove the solvent remaining in the coating film, and then the curing treatment is performed. Is preferable. Curing by ultraviolet irradiation is performed by applying ultraviolet rays having a wavelength of 200 to 400 nm from a UV lamp (for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, or a high-power metal halide lamp) to the coating liquid for a short time (several seconds to several tens of seconds). Within the range) It may be irradiated. Further, for curing by electron beam irradiation, a low energy electron beam may be irradiated to the coating liquid from a self-shielding type low energy electron accelerator of 300 keV or less.

The photopolymerizable acrylic compound (b) and the fluorosilsesquioxane derivative (c), which do not have a urethane unit and contain a fluorine atom, are air and solid (or liquid) in a hydrophobic atmosphere (for example, in air). It has the property of easily accumulating at the interface of. It is considered that this is because the component (b) and the component (c) containing a fluorine atom have higher hydrophobicity than the resin and are therefore attracted to the air side. Therefore, in the coating process, the component (b) and the component (c) are accumulated near the surface of the surface layer 12, and the concentrations of the component (b) and the component (c) are biased toward the surface side. As a result, the vicinity of the surface of the surface layer 12 forms an inclined structure of the concentrations of the component (b) and the component (c) as shown in FIG.
Further, since the component (b) and the component (c) have excellent properties as an antifouling material, the antifouling property of the surface of the surface layer 12 can be enhanced.

[Adhesive layer 13]
As shown in FIG. 1, the adhesive layer 13 is formed by applying an adhesive to the opposite surface side of the base film 11 which has been antifouled (or antifouled) by the surface layer 12. It may be formed directly on the surface of the base film 11, or may be laminated with the base film 11 via another layer.
As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 13, acrylic-based, urethane-based, rubber-based, and silicone-based pressure-sensitive adhesives can be used. Acrylic adhesives with excellent heat resistance and weather resistance are preferable for applications that require long-term durability from the viewpoint of product design.
In the adhesive layer 13 of the present invention, unevenness is provided on the surface of the adhesive from the viewpoint of workability on the article to be adhered.

Examples of the acrylic pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive containing an acrylic copolymer obtained by copolymerizing a monomer component mainly composed of an acrylic acid ester with a monomer component having a functional group such as a carboxyl group or a hydroxyl group. ..
Examples of the acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meta) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate , Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, ecocil (meth) acrylate, isobornyl Examples thereof include (meth) acrylate and 1-adamantyl (meth) acrylate. One kind or two or more kinds of these alkyl (meth) acrylates can be used.

The following monomer components can be copolymerized with the above alkyl (meth) acrylate. Examples of the copolymerizable monomer component include carboxyl groups such as itaconic acid, maleic acid, crotonic acid, isocrotonic acid, fumaric acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. Monomers contained; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acrylic acid Hydrolyl group-containing monomers such as 8-hydroxyoctyl, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) -methylacrylate; glycidyl (meth) acrylate, methylglycidyl Glycidyl group-containing monomers such as (meth) acrylate; cyanoacrylate-based monomers such as acryliconitrile and metaacrylonitrile; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acrylic morpholine, N-vinyl-2-piperidone, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione, N-cyclohexylmaleimide , N-phenylmaleimide, N-acryloylpyrrolidin, nitrogen-containing monomers such as t-butylaminoethyl (meth) acrylate, styrene and styrene derivatives, monomers such as vinyl acetate and the like. If necessary, one kind or two or more kinds of these monomers can be copolymerized with a (meth) acrylic acid ester and used.

The pressure-sensitive adhesive used in the present invention is, for example, at least one selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate, and at least one carboxyl group selected from the group consisting of acrylic acid and methacrylic acid. It preferably contains a containing monomer.
The pressure-sensitive adhesive used in the present invention may contain, for example, methyl acrylate, vinyl acetate, methyl methacrylate, acrylonitrile, or the like in order to improve heat resistance and weather resistance. In addition, in order to further improve various physical properties such as weather resistance, an ultraviolet absorber, a light stabilizer and the like may be added as necessary. The ratio of addition is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass with respect to the total amount of the pressure-sensitive adhesive.

The weight average molecular weight (Mw) of the acrylic copolymer is preferably 50,000 to 2 million, more preferably 100,000 to 1.5 million, and even more preferably 150,000 to 1,000,000. The number average molecular weight (Mn) is preferably 10,000 to 500,000, more preferably 10,000 to 400,000, and even more preferably 10,000 to 300,000.

In order to apply the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 13 to the release film 14 or the base film 11, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a roll coating method, and a die coating method are usually performed. , Knife coating method, air knife coating method, hot melt coating method, curtain coating method and the like.
The thickness of the adhesive layer 13 is typically 10 to 100 μm, preferably 15 to 50 μm, more preferably 25 to 45 μm, and particularly preferably 35 to 40 μm in terms of adhesion after sticking. is there.

The adhesive layer 13 physically forms surface irregularities by laminating the release film 14 on which the irregularities are formed and transferring the irregularities.

[Release film 14]
As the release film 14, for example, a polyethylene terephthalate, polyethylene, or polypropylene resin film coated on one side or both sides with a release agent such as a fluorine-based resin, a silicone-based resin, or a long-chain alkyl group-containing carbamate can be used. it can. Alternatively, a paper having a seal treatment such as a plastic film such as a polyester resin or a polyolefin resin, cellophane, or glassine paper can be used.
The thickness of the release film 14 varies slightly depending on the material used, but is typically preferably 10 to 250 μm, more preferably 20 to 200 μm, and even more preferably 50 to 75 μm.

The surface unevenness formed on the release film 14 has an arithmetic mean roughness (Ra) of typically 480 nm or more, preferably 480 to 850 nm, more preferably 480 to 800 nm, and an arithmetic mean swell (). Wa) is typically 120 nm or more, preferably 120 to 600 nm, more preferably 120 to 500 nm, and particularly preferably 120 to 450 nm.

As a method for forming the unevenness on the release film 14, a known method can be used. A matte layer may be formed on polyethylene terephthalate as a base material. The mat layer may be applied once, twice, three times, and several times or more. A more uniform surface can be formed by recoating. The filler for the mat may be inorganic particles or synthetic resin particles.
Inorganic particles include silica, alumina, barium sulfate, talc, mica powder, aluminum hydroxide, calcium hydroxide, calcium carbonate, boron nitride, aluminum borate, aluminum titanate, barium titanate, strontium titanate, calcium titanate, Examples thereof include magnesium titanate, bismuth titanate, titanium oxide, barium titanate, and calcium zirconate. As the silica, silica such as amorphous silica, molten silica, crystalline silica, synthetic silica, and hollow silica is preferable.
Examples of the synthetic resin particles include acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, styrene beads, urethane acrylic beads, polyester beads, polyethylene beads and the like.
The average particle size is typically preferably 1 to 200 μm, more preferably 1 to 100 μm, and even more preferably 1 to 50 μm. The amount added is typically preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, still more preferably 0.5 to 50% by mass, based on 100% by mass of the binder resin. It is 15% by mass. Two or more types of fillers having different average particle sizes may be mixed. The "average particle size" refers to the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

Arithmetic mean roughness (Ra) is a roughness curve measured in accordance with JIS B 0601-2001, and only the reference length (lower L in the formula below) is extracted in the direction of the average line, and this extraction is performed. The absolute value of the deviation from the average line of the part to the measurement curve is summed and averaged. It is preferable because the influence of one scratch on the measured value is very small and stable results can be obtained. The measurement results were evaluated based on the definition and display of the surface roughness of JIS B 0601.

The arithmetic mean swell (Wa) is the arithmetic mean height at the reference length of the swell curve as a contour curve, which is measured according to JIS B 0601-2001. The waviness curve is a contour curve obtained by sequentially applying contour curve filters with cutoff values λf and λc to the cross-sectional curve, and is not the fine unevenness represented by the roughness curve, but the unevenness on a larger scale (that is, the waviness). It represents. The measurement results were evaluated based on the definition and display of the surface roughness of JIS B 0601.

The protective film of the present invention has excellent self-healing property, high water repellency / antifouling property, stretchability, and slipperiness in the surface layer. In addition, the surface layer can smooth the surface, suppress the reflectance, and give a glossy feeling. Further, since the adhesive surface of the adhesive layer is protected by a highly peelable release film until it is attached to the adherend, it can be distributed and transported without deteriorating the adhesiveness.
Further, the protective film of the present invention controls the arithmetic mean roughness (Ra) and the arithmetic mean waviness (Wa) of the release film to improve the workability on the adherend and the adherend to which the protective film is attached. The appearance can be improved. For example, when installing on a car body, a release film secures an appropriate flow path for the construction liquid on the protective film, making it easier for the construction liquid to drain quickly, maintaining appropriate adhesion to the body, and facilitating construction. At the same time, it is possible to suppress the cause of poor appearance such as adhesive misalignment.

[Surface protection article]
The surface protection article according to the second embodiment of the present invention will be described. Examples of the article as an adherend to which the protective film of the present invention is attached include automobiles, aircrafts, ships and the like. Coating various body parts of these articles, especially parts at risk such as flying debris (eg sand, stones, etc.), insects (eg, front hood tip and other tip surfaces, rocker panels, etc.) Effective for surface protection.
In addition, it can be used, for example, in windows, building materials, digital signage, packaging, and office supplies, and can be used in a wide range of fields such as electronics, security, and industry. Further, in the fields of nursing care and medical care, it can be applied to packing waste and protecting the surface of medical equipment. In addition, since the surface of the protected article can be smoothed, the design can be improved.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the following examples.

[Production of polymer containing γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane unit]
First, γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane was synthesized by the following procedure.
Trifluoropropyltrimethoxysilane (100 g), THF (500 mL), deionized water (10.5 g), and sodium hydroxide in a 1 L 4-neck flask equipped with a reflux condenser, thermometer, and dropping funnel. (7.9 g) was charged and heated with an oil bath from room temperature to a temperature at which THF refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Then, the flask was pulled up from the oil bath, allowed to stand at room temperature overnight, set in the oil bath again, and concentrated by heating under constant pressure until a solid was precipitated.
The precipitated product was collected by filtration using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm. Next, the obtained solid was washed once with THF and dried in a vacuum dryer at 80 ° C. for 3 hours to obtain 74 g of a colorless powder solid.
The obtained solid matter (65 g), dichloromethane (491 g), and triethylamine (8.1 g) were placed in a 4-necked flask having an internal volume of 1 L equipped with a reflux condenser, a thermometer, and a dropping funnel, and placed in an ice bath. It was cooled to 3 ° C. Next, γ-methacryloxypropyltrichlorosilane (21.2 g) was added, and after confirming that the heat generation had subsided, the mixture was withdrawn from the ice bath and aged overnight at room temperature. After washing with ion-exchanged water three times, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and magnesium sulfate was removed by filtration. It was concentrated with a rotary evaporator until a viscous solid was precipitated, 260 g of methanol was added, and the mixture was stirred until it became a powder. The powder was filtered using a pressure filter equipped with a 5 μm filter paper and dried at 65 ° C. for 3 hours in a vacuum dryer to obtain 41.5 g of a colorless powdery solid. The GPC of the obtained individual was measured by ¹ H-NMR, and the production of γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane (5) represented by the following formula (5) was confirmed. ..

Next, a polymer containing γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane unit was produced by the following procedure. Γ-Methyloxypropylhepta (trifluoropropyl) -T8-silsesquioxane (5) obtained by the above method in a four-necked flask with an internal volume of 200 mL equipped with a reflux condenser, a thermometer, and a dropping funnel. ) Is 36.65 g, methyl methacrylate (MMA) is 18.33 g, 2-hydroxyethyl methacrylate (HEMA) is 27.49 g, and one-terminal methacryloxy group-modified dimethyl silicone (FM-0721, molecular weight is about 6,300) is 9. 106.4 g of 16 g and 2-butanone (MEK) were introduced and sealed with nitrogen. It was set in an oil bath kept at 95 ° C., refluxed, and oxygenated for 10 minutes. Then, a solution of 0.70 g of 2,2'-azobisisobutyronitrile (AIBN) and 0.08 g of mercaptoacetic acid (AcSH) dissolved in 7.0 g of MEK was introduced and kept at the reflux temperature. Polymerization was started. After the polymerization for 3 hours, a solution in which 0.70 g of AIBN was dissolved in 7.0 g of MEK was introduced, and the polymerization was continued for another 5 hours. After completion of the polymerization, 65 mL of modified alcohol (Solmix AP-1, manufactured by Japan Alcohol Trading Co., Ltd.) was added to the polymerization solution, and then poured into 1300 mL of Solmix AP-1 to precipitate the polymer. The supernatant was removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to separate the products.
15.0 g of product, 0.015 g of MEHQ, 0.0263 g of DBTDL, 130 g of ethyl acetate were introduced into a four-necked flask with an internal volume of 200 mL equipped with a reflux condenser, a thermometer and a septum cap, and nitrogen sealed. did. The temperature was raised by setting in an oil bath maintained at 48 ° C. Then, when the liquid temperature reached 45 ° C., 15.9 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced and the reaction was started. After reacting for 6 hours, the reaction was completed by cooling to room temperature and introducing 10.0 g of MeOH. After completion of the reaction, 65 mL of Solmix AP-1 was added to the reaction solution, and then the reaction product was precipitated by pouring into 1300 mL of Solmix AP-1. The supernatant is removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to contain 11.8 g of γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane unit, side chain. A polymer having an acryloyl group (XUA008) was obtained. The weight average molecular weight determined by GPC analysis of XUA008 was 45,000, and the molecular weight distribution was 1.7.

[Preparation of coating agent]
The following components (a), component (b), and component (c) were used as the curable composition.
Ingredient (a): As the urethane acrylate, a UV curable self-healing paint "AUP-1852 (concentration of urethane acrylate as an active ingredient: 48.0% by mass)" manufactured by Tokushiki Co., Ltd. was used.
Ingredient (b): As a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, an ultraviolet curable resin (5-functional or higher) manufactured by Nippon Kayaku Co., Ltd. "KAYARAD DPCA-120" ( (Consists of a polymerizable acrylic compound that does not have a urethane unit) and DIC Co., Ltd.'s fluorine-containing UV-reactive surface modifier "Megafuck RS75" (a polymerizable acrylic compound that does not have a urethane unit and contains fluorine Contains the compound at a concentration of 40.0% by mass)
Ingredient (c): As the fluorosilsesquioxane derivative (c), XUA008 obtained by the above method was used.
The component (a) was mixed with 49.2% by mass, the component (b) with 13% by mass, and the component (c) with 37.8% by mass, for a total of 50.8% by mass. Further, as a diluent, 5 parts by mass of the photopolymerization initiator (d) "Irgacure 127" with respect to 100 parts by mass of the curable composition (component (a), component (b), and component (c)) was added. Solvent (e) 2-propanol was added so as to contain the above curable composition at a concentration of 30% by mass.

[Preparation of release film 1]
With respect to the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass). 5% by mass of silica powder having an average particle diameter of 12 μm (manufactured by Maruto Co., Ltd.), 2.5% by mass of silica powder having an average particle diameter of 22 μm (manufactured by Maruto Co., Ltd.), and silica having an average particle diameter of 36 μm. Coating liquid (liquid component is 125 parts by mass of ethyl acetate with respect to 100 parts by mass of "XS-870") which is made by mixing powder (manufactured by Maruto Co., Ltd.) in 2.5% by mass. Part addition) was applied using Mayer bar count: # 14, heat-dried at 130 ° C. for 30 seconds, and the mat layer was heat-cured to obtain a heat-cured film.
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Preparation of release film 2]
For the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass) A mixture of 5% by mass of silica powder having an average particle diameter of 12 μm (manufactured by Maruto Co., Ltd.) and 5.0% by mass of silica powder having an average particle diameter of 22 μm (manufactured by Maruto Co., Ltd.) is mixed. The coating liquid (the liquid component is 100 parts by mass of "XS-870" and 125 parts by mass of ethyl acetate is added) is applied using Mayer bar count: # 14, and the temperature is 130 ° C. for 30 seconds. The matte layer was heat-cured under the conditions of (1) to obtain a heat-cured film.
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Preparation of release film 3]
With respect to the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass). A coating liquid (liquid component is 100 parts by mass of "XS-870") prepared by mixing a mixture of silica powder (manufactured by Maruto Co., Ltd.) having an average particle diameter of 36 μm in an amount of 10% by mass. , 125 parts by mass of ethyl acetate was added) was applied using Mayer bar count: # 14, and the mat layer was heat-dried at 130 ° C. for 30 seconds to obtain a heat-cured film. ..
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Preparation of release film 4]
With respect to the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass). A coating liquid (liquid component is 100 parts by mass of "XS-870") prepared by mixing a mixture of silica powder (manufactured by Maruto Co., Ltd.) having an average particle diameter of 12 μm in an amount of 10% by mass. , 125 parts by mass of ethyl acetate was added) was applied using Mayer bar count: # 14, and the mat layer was heat-dried at 130 ° C. for 30 seconds to obtain a heat-cured film. ..
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Preparation of release film 5]
For the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass). A mixture of 5.0% by mass of silica powder having an average particle diameter of 12 μm (manufactured by Maruto Co., Ltd.) and 5.0% by mass of silica powder having an average particle diameter of 36 μm (manufactured by Maruto Co., Ltd.). (Liquid component is 100 parts by mass of "XS-870", 125 parts by mass of ethyl acetate is added to 100 parts by mass), which is a mixture of silica, and coated with Mayer bar count: # 14 at 130 ° C. The mat layer was heat-cured to obtain a heat-hardened film.
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Preparation of release film 6]
For the solid content of PET film (Cosmo Shine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 75 μm) and polyvinyl acetate resin (manufactured by DIC Graphics Co., Ltd., trade name “XS-870”, solid content 25% by mass) A mixture of 7.5% by mass of silica powder (manufactured by Maruto Co., Ltd.) having an average particle diameter of 12 μm and 2.5% by mass of silica powder (manufactured by Maruto Co., Ltd.) having an average particle diameter of 22 μm. (Liquid component is 100 parts by mass of "XS-870", 125 parts by mass of ethyl acetate is added to 100 parts by mass), which is a mixture of silica, and coated with Mayer bar count: # 14 at 130 ° C. The mat layer was heat-cured by heating and drying under the condition of 30 seconds to obtain a heat-cured film.
On the obtained thermosetting film, a thermosetting silicone composition (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-830") is applied with a Mayer bar count: # 8, and the coating thickness is 0.4 g after drying. The coating was applied so as to be / m ^2, and the silicone layer was thermoset by heating and drying at 130 ° C. for 30 seconds.

[Making a protective film]
A commercially available acrylic pressure-sensitive adhesive was applied to one side of a base film (Argotec thermoplastic polyurethane film "ARGOGUARD 49510" by die coating and dried at 70 ° C. for 3 minutes. Thus, a 40 μm-thick adhesive was applied to one side of the base film. A layer was formed.
Next, the open surface of the adhesive layer and the prepared release films 1, 2, 3, 4, 5, and 6 were pressure-bonded with a rubber roller, respectively, and cured at 45 ° C. for 1 day. In this way, laminated films A, B, C, D, E, and F in which the base film, the adhesive layer, and the release film were in contact in this order were obtained.
A coating agent was applied to the open surface of the base film. D. S. Webster Wire Bar Coater No. It was applied using 24 and dried at 90 ° C. for 3 minutes. Then, the coating agent was cured at an integrated light intensity of 400 mJ / cm ² using a belt conveyor curing unit (manufactured by Heraeus Co., Ltd.) equipped with a fusion UV lamp. In this way, a surface layer having a thickness of 11 μm is formed on the base film, and the surface layer, the base film, the adhesive layer, and the release film are in contact with each other in this order (Example 1, Example 2, Example 3, Comparative Example). 1. Comparative Example 2 and Comparative Example 3) were obtained.

[Evaluation of protective film]
The obtained protective film was evaluated from the following viewpoints. The results are shown in Table 1.
(1) Arithmetic mean roughness (Ra)
Surface roughness measuring instrument (Alpha-Step D-500 stylus type and optical type surface measurement manufactured by KLA-Tencor, USA) on the surface of the produced release film 1, 2, 3, 4, 5, 6 on the matte surface side. The surface roughness was measured using the device). The arithmetic mean roughness (Ra) was calculated when the evaluation length was 40 mm and the cutoff value was 8 μm.

(2) Arithmetic mean swell (Wa)
The surface side of the prepared release film 1, 2, 3, 4, 5, 6 which was treated with silicone on the matte treatment was subjected to a surface roughness measuring instrument (Alpha-Step D-500 stylus type manufactured by KLA-Tencor, USA). The surface waviness was measured using an optical surface measuring device). The evaluation length was 40 mm, the cutoff values of each contour curve filter were λs = 0.25 μm, λc = 0.08 mm, and λf = 80 μm, and the arithmetic mean swell (Wa) was calculated.

(3) Workability A bonnet for automobiles (Colt 2011 model black manufactured by Mitsubishi Motors Corporation) was prepared as a base material for evaluation of workability and used for evaluation of workability of a protective film. Before use, a car wash towel (microfiber towel manufactured by Kirkland Co., Ltd.) impregnated with isopropyl alcohol was used to remove stains such as oil and fat components adhering to the painted surface of the bonnet. Then, a dry wipe was performed using a dry car wash towel similar to the above to remove isopropyl alcohol and water remaining on the painted surface.
As the protective film, a sample having a width of 210 mm and a length of 300 mm was prepared. When evaluating the workability, the bonnet was attached on the bonnet so that the traveling direction of the bonnet and the vertical direction of the protective film were the same inferred from the traveling direction of the automobile. Further, the rear part is the rear part and the front part is the front part with respect to the traveling direction of the protective film. After peeling off the release film, water (baby shampoo manufactured by Johnson & Johnson Co., Ltd. is diluted 10,000 times on a volume basis) was sprayed on the adhesive layer surface side of the released protective film. In addition, water was sprayed on the bonnet at the place where the protective film was to be bonded, and the protective film was placed on the center of the bonnet so that the open adhesive layer surface side was aligned with the bonnet surface. Then, the workability was evaluated according to the following evaluation items (i) to (iii). The evaluation was performed in an environment of 25 ° C. and a relative humidity of 50%.

(I) Initial positioning When attaching the protective film to the car body (construction), water is sprayed on the car body side and the adhesive layer side of the open protective film, and the protective film is applied to any one place on the car body surface. A part is fixed (pasted), and the protective film is stretched from the fixed point and pasted on the entire vehicle body. Therefore, if a part of the film is not fixed to the vehicle body, the next work cannot be performed, which is an important item for the construction performance of the protective film. In this way, whether or not the protective film can be fixed to the vehicle body at the initial stage and a part of the protective film can be positioned at an arbitrary vehicle body is defined as "initial positioning".
For evaluation, after placing the protective film from which the release film was peeled off on the bonnet, water was also sprayed on the surface layer side of the protective film, and only the vertical width of 100 mm at the rear of the film was applied to a commercially available squeegee (width 100 mm). With a rubber spatula), water was removed by skiing twice in one direction from the center to the left and right sides of both ends. After leaving for 10 seconds, the left and right ends of the front end of the film were picked with both left and right hands (index finger and thumb) and slowly pulled forward. At that time, it was confirmed whether the rear end of the protective film from which the water had been removed did not come off from the surface of the bonnet, and the judgment was made based on the following contents.
++: The rear ends of the fixed protective film do not come off from the bonnet.
+: Only the left and right parts of the rear end of the fixed protective film are peeled off from the bonnet.
-: All the rear ends of the fixed protective film are peeled off from the bonnet.

(Ii) Glue misalignment After the protective film from which the release film has been peeled off is placed on the center of the bonnet, water is also sprayed onto the surface layer side of the protective film, and a commercially available squeegee is used to move forward, backward, left and right from the center of the protective film. A squeegee was performed in one direction towards the end to remove all water. After standing for 5 minutes, the defects of appearance defects (such as sesame granules and craters) that are presumed to have occurred near the bonding interface between the adhesive layer and the bonnet surface are defined as "glue deviation" and are derived from "glue deviation". The presence or absence of the defect was visually confirmed from the surface layer side of the protective film. Furthermore, the number of visually recognized defects was counted and the judgment was made based on the following contents.
++: The number of sesame-grained, crater-like appearance defects is 4 or less.
+: The number of sesame-grained, crater-like appearance defects is 5 to 10.
-: The number of sesame-grained, crater-like appearance defects is 11 or more.

(Iii) Reworkability After the protective film from which the release film has been peeled off is placed on the center of the bonnet, water is also sprayed onto the surface layer side of the protective film, and a commercially available squeegee is used to move forward, backward, left and right from the center of the protective film. A squeegee was performed in one direction towards the end to remove all water. After leaving for 3 minutes, the protective film was peeled off from the bonnet, water was sprayed again on the adhesive layer side of the bonnet and the protective film, and the protective film was attached to the bonnet in the same procedure as described above. The same procedure was repeated once more, and it was confirmed whether the protective film after the third application was fixed to the bonnet coated surface and did not peel off. In addition, this stickability was defined as "reworkability" and the judgment was made based on the following contents.
++: Even if the surface layer of the attached protective film is moved by hand, the protective film does not move and the film edge does not come off from the surface of the coated plate.
+: When the surface layer of the attached protective film is moved by hand, floating occurs only at the edge of the protective film.
-: When the surface layer of the attached protective film is moved by hand, the entire protective film moves and is not fixed to the painted surface.

(Iv) Liquid drainability A 40 mm × 130 mm piece of protective film was prepared. Separately, an aluminum plate (width 50 mm, length 150 mm, thickness 1.2 mm) painted with white paint for automobiles was prepared.
To determine the presence or absence of liquid drainage, add red pigment (Pentel red watercolor polytube) to water (however, baby shampoo manufactured by Johnson & Johnson Co., Ltd. is diluted 10,000 times on a volume basis). A construction liquid was prepared by mixing 0.1 wt%. After spraying the prepared construction liquid, the adhesive layer surface of the protective film is brought into contact with the painted surface, and the protective film is pressed with a commercially available rubber squeegee while removing air bubbles and blisters generated between the protective film and the painted surface. A protective film was attached to the painted plate. Based on the shade of color of the protective film at this time, the degree of drainage of the construction liquid was judged according to the following criteria-: The color remains dark.
+: It remains thin.
++; The color is extremely light.

(4) Appearance (i) Strength of yuzu skin feeling A piece of 50 mm × 50 mm was cut out from the protective film, and the release film was removed from this piece. As a coating plate, a hard vinyl chloride resin plate (Capiron, K-5930) coated with a black paint was prepared. After spraying water (however, baby shampoo manufactured by Johnson End Johnson Co., Ltd. is diluted 10,000 times on a volume basis) on the adhesive layer surface of the protective film piece and the painted surface of the painted plate, the protective film The adhesive layer surface of No. 1 was brought into contact with the painted surface, and the protective film was pressed with a commercially available rubber squeegee while removing air bubbles and water bubbles generated between the protective film and the painted surface, and the protective film was attached to the painted plate. The coated plate to which the protective film was attached was allowed to stand at room temperature until no bubbles or water bubbles were visually observed on the surface. In this way, the test sample was completed. Ten adult men and women in their twenties and forties visually evaluated whether the surface of the test sample had a strong yuzu skin feeling and did not impair the appearance. As evaluation criteria, it was judged that 7 or more adult men and women felt (---), 3 to 6 people (-), and 2 or less people (+).

(Ii) Image sharpness test (smoothness)
A piece of 50 mm × 50 mm was cut out from the protective film, and the release film was removed from this piece. As a coating plate, a hard vinyl chloride resin plate (Capiron, K-5930) coated with a black paint was prepared. After spraying water (however, baby shampoo manufactured by Johnson End Johnson Co., Ltd. is diluted 10,000 times on a volume basis) on the adhesive layer surface of the protective film piece and the painted surface of the painted plate, the protective film The adhesive layer surface of No. 1 was brought into contact with the painted surface, and the protective film was pressed with a commercially available rubber squeegee while removing air bubbles and water bubbles generated between the protective film and the painted surface, and the protective film was attached to the painted plate. The coated plate to which the protective film was attached was allowed to stand at room temperature until no bubbles or water bubbles were visually observed on the surface. In this way, the test sample was completed.
The image sharpness test of this test sample was carried out using a mapability measuring device ICM-1T (manufactured by Suga Test Instruments Co., Ltd.) at a reflection angle of 45 °, an optical comb width of 2.0 mm, and an optical comb width of 0.25 mm. By moving the optical comb orthogonal to the ray axis of the reflected light from the test sample, the maximum light amount (M) and the minimum light amount (m) are obtained for the comb widths of 2.0 mm and 0.25 mm, and the image is obtained by the following formula. The sharpness was calculated.
Image sharpness (%) = [(M-m) / (M + m)] x 100
High image sharpness means that the surface of the surface layer is highly smooth. Generally, the exterior parts of automobiles are preferably painted with a glossy appearance and smooth coating. The image sharpness with a width of 2.0 mm correlates with the glossiness, and the image sharpness with a width of 0.25 mm correlates with the state of so-called "orange peel surface". When the image sharpness of the width of 0.25 mm is 45% or more, the surface of the protective film is further improved in gloss and smoothness.

(5) Surface characteristics (i) Self-healing property A piece of 40 mm × 130 mm was cut out from the protective film, and the release film was removed from this piece. Separately, an aluminum plate (width 50 mm, length 150 mm, thickness 1.2 mm) painted with black paint for automobiles was prepared. After spraying water (however, baby shampoo manufactured by Johnson End Johnson Co., Ltd. is diluted 10,000 times on a volume basis) on the adhesive layer surface of the protective film piece and the painted surface of the painted plate, the protective film The adhesive layer surface of No. 1 was brought into contact with the painted surface, and the protective film was pressed with a commercially available rubber squeegee while removing air bubbles and water bubbles generated between the protective film and the painted surface, and the protective film was attached to the painted plate. The coated plate to which the protective film was attached was allowed to stand at room temperature until no bubbles or water bubbles were visually observed on the surface. In this way, the test sample was completed.
Using a surface measuring instrument TYPE14 (manufactured by Shinto Kagaku Co., Ltd.) equipped with a 4-row brass brush manufactured by AS ONE Corporation, the scratching conditions are as follows: pressing pressure: 1000 gf, brush moving speed 3000 mm / min, brush moving path. : The straight reciprocation of 100 mm one way was set to 10 reciprocations, and the surface layer forming the outermost surface of the test sample was scratched. After the completion of the scratching, the surface of the scratched surface layer is visually observed, and the self-healing property of the protective film layer is based on the following criteria based on the time from the end of the scratching to the disappearance of the scratches. Was judged.
+: The scratch disappeared within 1 minute from the end of scratching.
-: Scratches were observed even more than 1 minute after the end of scratching.

(Ii) Antifouling and oil repellent (ink wiping property)
A black oil-based marker (manufactured by Sharpie) was drawn on the surface of the surface layer of the protective film, and how the oil-based ink was repelled was observed. Further, the drawing portion was rubbed with a non-woven fabric (Dasper K-3 manufactured by Ozu Corporation) to observe the wiping property of the oil-based ink. The observation results were judged according to the following criteria.
+: The ink was repelled and wiped off cleanly.
-: Could not wipe off.

(Iii) Elongation at break (extensible)
A piece of 35 mm × 200 mm was cut out from the protective film, the release film was removed, and a protective film in which the surface layer, the base film, and the adhesive layer were in contact in this order was prepared. This protective film was pulled and broken by a tensile / compression / bending tester Strograph VG (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The pulling conditions at this time were the initial distance between chucks: 100 mm and the crosshead moving speed: 127 mm / min. The points where cracks were generated on the surface of the test sample were visually detected, and the extensibility of the protective film until fracture was determined as the elongation at break (%) represented by the following formula.
Elongation at break (%) = (Crosshead movement distance to break (mm) / Initial distance between chucks (100 mm)) x 100

(6) Peeling force of release film A protective film is cut into a size of 25 mm x 200 mm, and under the conditions of 25 ° C. and 65% RH, a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph R type) has a tensile speed of 300 mm. Measure the 180-degree peel strength between the adhesive layer surface side of the release film and the adhesive layer at / min and 50 mm between the cross heads, evaluate three times, and use the average value as the release force [N / 25 mm] of the release film. did.

For the protective film for automobiles, the construction performance on the surface of the body for automobiles is important. When performing construction, spray the construction liquid and apply water to the protective film, apply pressure from above the protective film using a squeegee (rubber spatula), and crimp while draining the construction liquid (water). Therefore, how to efficiently remove the construction liquid intervening between the adhesive layer and the coating plate during squeezing by controlling the surface roughness of the surface of the adhesive layer of the protective film is important in the construction performance. For that purpose, it is important to control the uneven shape of the matte-treated surface of the release film to be transferred to the adhesive layer side of the protective film. We found that Ra (arithmetic mean roughness) and Wa (arithmetic mean waviness) are important factors as evaluation indexes for uneven shapes that have a great effect on workability, and Ra is 480 nm or more on the matte-treated surface side of the release film. The workability of the protective films of Examples 1, 2 and 3 in which Wa was in the range of 120 nm or more was good. On the other hand, if any of the Ra and Wa values was not within the above range, the workability was deteriorated.
The appearance (smoothness) of the protective films of Examples 1 and 2 in which the Wa on the matte-treated surface side of the release film was in the range of 120 to 280 nm was further improved.
In Examples 1, 2 and 3 in which the workability was good, the water drainage property was good. Therefore, there is a correlation between workability and water drainage, and by controlling the shape of the surface of the open adhesive layer after peeling the release film from the mat layer side of the release film side, water can be removed efficiently. It is presumed that it became.

200 Protective film 11 Base film 12 Surface layer 13 Adhesive layer 14 Release film s1 Surface fc Photopolymerizable acrylic compound ss fluorosilsesquioxane derivative that does not have urethane units and contains fluorine atoms

Claims (7)

A base film made of thermoplastic polyurethane and
A surface layer formed on the first surface side of the base film and
An adhesive layer formed on the second surface side opposite to the first surface side of the base film, and
A release film provided on the surface of the adhesive layer opposite to the base film is provided.
The surface layer is a urethane (meth) acrylate resin (a), a photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, a fluorosilsesquioxane derivative (c), and photopolymerization. A layer in which the curable composition containing the initiator (d) is cured.
The release film has an arithmetic mean roughness (Ra) of 480 nm or more and an arithmetic mean swell (Wa) of 120 nm or more.
Protective film. The arithmetic mean swell (Wa) is 120-600 nm.
The protective film according to claim 1. The curable composition includes the urethane (meth) acrylate-based resin (a), the photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom, and the fluorosilsesquioxane derivative (the fluorosilsesquioxane derivative). A photopolymerizable acrylic-based resin containing the urethane (meth) acrylate-based resin (a) in a proportion of 20 to 50% by mass, with the total amount of c) being 100% by mass, and having no urethane unit and containing a fluorine atom. The total amount of the compound (b) and the fluorosilsesquioxane derivative (c) is contained in a proportion of 50 to 80% by mass.
The protective film according to claim 1 or 2. The urethane (meth) acrylate-based resin (a) has a weight average molecular weight (Mw) of 3,000 to 800,000.
The photopolymerizable acrylic compound (b) having no urethane unit and containing a fluorine atom has at least two polymerizable functional groups.
The fluorosilsesquioxane derivative (c) has at least one polymerizable functional group.
The protective film according to claim 3. The fluorosilsesquioxane derivative (c) contains a cage-shaped fluorosilsesquioxane in its structure.
The protective film according to claim 3 or 4. The adhesive layer is composed of at least one resin selected from acrylic, urethane, rubber, and silicone.
The release film was coated with at least one release agent selected from a fluorine-based resin, a silicone-based resin, and a long-chain alkyl group-containing carbamate on the surface with respect to the adhesive layer.
The protective film according to any one of claims 1 to 5. A film obtained by peeling the release film from the protective film according to any one of claims 1 to 6.
An article in which the film from which the release film has been peeled off is attached to the surface by the adhesive layer, and
To prepare
Surface protection article.

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