TW202003745A - Protective film and method for producing same - Google Patents

Abstract

The present invention addresses the problem of providing a protective film which uses a resin containing a thermoplastic polyurethane, and which is suppressed in adhesive residue, while exhibiting excellent contamination resistance, impact resistance, workability, anti-glare properties and bonding characteristics. A protective film according to the present invention is provided with: a base film which is formed of a resin that contains a thermoplastic polyurethane; and an adhesive layer. This protective film is configured such that: the base film has a surface layer, in which the thermoplastic polyurethane and a curable resin composition coexist, on a second surface that is on the reverse side of a first surface; the curable resin composition contains a curable resin and at least one fluorine compound that is selected from the group consisting of fluorosilsesquioxanes and fluorosilsesquioxane polymers; and an impact resistance-imparting layer is formed on the first surface of the base film, or alternatively, the gloss value of the second surface of the base film is less than 20. The thickness of base film is 50[mu]m~300[mu]m, the thickness of impact resistance-imparting layer is 20[mu]m~300[mu]m, the thickness of adhesive layer is 10[mu]m~100[mu]m, the surface roughness of adhesive layer is 300nm~800nm.

Description

Protective film and its manufacturing method

The present invention relates to a protective film for protecting the surface of floor boards (floors) and the like. In particular, there is a protective film using thermoplastic polyurethane.

Since the beginning, thermoplastic polyurethane (TPU) with high impact strength has been used as a base material for protective films and the like.

As a protective film using thermoplastic polyurethane, Patent Document 1 discloses a multi-layer film for protecting the surface, for example, a film for protecting the surface (for example, coated surface) of vehicles such as automobiles, airplanes, and ships. . More specifically, there is disclosed a multi-layer surface protective film having a polyurethane-like layer on the uppermost part of the thermoplastic polyurethane layer after being back-processed with a pressure-sensitive adhesive (paragraph 0001).

In addition, Patent Document 2 discloses a surface protection film including: a base film formed of thermoplastic polyurethane; and an adhesive layer formed on one side of the base film. The surface of the thermoplastic polyurethane contains at least one fluorine compound selected from the group consisting of fluorosesquioxane and fluorosesquioxane polymer, and a hardening resin, which has antifouling Sex. These surface protective films, for example, in addition to imparting antifouling properties to the surface of painted boards such as automobiles, improving the adhesion characteristics to the painted boards, and further improving heat resistance and weather resistance, films and pastes when peeled from the painted boards The agent is not left on the attachment site, etc. for the purpose of protecting the surface of the coating surface of vehicles such as automobiles and the like, and therefore does not have anti-glare properties and anti-slip properties suitable for the protection of the surface of floors and the like. In addition, a protective film having more excellent impact resistance and workability is required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Special Publication No. 2008-539107 [Patent Literature 2] International Publication No. 2016/010041 Manual

[Problems to be solved by the invention] Therefore, an object of the present invention is to provide a protective film using a thermoplastic polyurethane-containing resin and having excellent stain resistance and impact resistance. Furthermore, the subject of this invention is providing a protective film excellent in workability. Furthermore, an object of the present invention is to provide a protective film having excellent anti-glare properties. Furthermore, an object of the present invention is to provide a protective film having excellent adhesion characteristics and suppressing paste residue. [Means to solve the problem]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, it has been found that the use of the following laminate as a protective film has an excellent effect that the existing protective film does not have (not only excellent stain resistance and impact resistance, but also by having an impact resistance-imparting layer, excellent construction can be obtained By setting the surface layer to a specific gloss value, a protective film with respect to shape followability and matt feeling can be obtained, and the present invention has been completed. The laminate is composed of a fluorine-containing compound and a curable resin The surface layer of the product is combined with an adhesive layer that improves the adhesion characteristics and has no paste residue when peeled off, and the surface layer is impregnated with a substrate film formed of a resin containing thermoplastic polyurethane While forming.

The protective film of the first aspect of the present invention includes: a base film formed of a resin containing thermoplastic polyurethane; and an adhesive layer, the base film being on the side opposite to the first surface The second surface side has a surface layer in which the resin containing the thermoplastic polyurethane and the curable resin composition are mixed, and the curable resin composition contains a compound selected from the group consisting of fluorine sesquisiloxane and fluorine sesqui At least one fluorine compound in the group consisting of a siloxane polymer and a curable resin having an impact resistance-imparting layer formed on the first surface side of the base film or the second surface of the base film The gloss value on the side is less than 20.

In this specification, the term "on the side of the surface" means that it can be laminated in contact with each other, or it can be laminated through another layer, or it can have a layer on the inner side of the surface. The so-called "on the surface" refers to contact and build up.

With such a structure, the fluorine compound will accumulate on the surface of the surface layer (that is, the second surface), and the surface of the base film can be modified without compromising the flexibility of the thermoplastic polyurethane, which becomes A protective film with excellent dirt resistance and impact resistance.

The protective film of the second aspect of the present invention includes the base film formed of a resin containing a thermoplastic polyurethane and the impact resistance-imparting layer in the protective film of the first aspect of the present invention. , Formed on the first surface side of the base film; and an adhesive layer formed on the opposite side of the impact resistance-imparting layer from the base film surface side, the base film on the first surface The second surface side having the opposite side has a surface layer in which the resin containing the thermoplastic polyurethane and the curable resin composition are mixed, and the curable resin composition contains a At least one fluorine compound in the group consisting of alkane and fluorosilsesquioxane polymer, and a hardening resin.

With such a structure, the impact resistance-imparting layer becomes a protective film excellent in impact resistance and workability.

The protective film according to the third aspect of the present invention includes the base film formed from a resin containing thermoplastic polyurethane and the adhesive layer to form the protective film according to the first aspect of the present invention. On the first surface side of the base film, the base film has a resin and a curable resin including the thermoplastic polyurethane on the second surface side opposite to the first surface A surface layer in which a composition is mixed, the curable resin composition containing at least one fluorine compound selected from the group consisting of fluorosesquioxane and fluorosesquioxane polymer, and a curable resin, The gloss value of the second side of the base film is less than 20.

With such a configuration, the second surface of the base film has an uneven shape, and when the gloss value of the second surface side of the base film is less than 20, it becomes a protective film excellent in anti-glare properties.

The protective film of the fourth aspect of the present invention is the protective film of any of the first aspect to the third aspect of the present invention, wherein the impact resistance-imparting layer contains a polyester resin and a polyolefin. At least one kind of resin, fluorosesquioxane or fluorosesquioxane polymer has a cage structure, the curable resin contains at least one compound having a (meth)acryloyl group, and the adhesive layer contains At least one resin selected from acrylic, urethane, rubber, and silicone.

With such a structure, it becomes a protective film using a resin suitable as an impact resistance-imparting layer. In addition, the fluorine compound has the property of being easily aggregated at the interface of air and solid, and thus serves as a protective film that increases the rate of accumulation at the interface of air and solid. Furthermore, since the resin containing the (meth)acryloyl group contained in the curable resin penetrates into the resin containing the thermoplastic polyurethane, it becomes integrated with the base film without impairing the existing thermoplastic A flexible surface layer of polyurethane. Therefore, although the protective film of the two-layer structure generally has a low elongation and is prone to cracking, the protective film of the present invention has a high elongation at break, and does not generate a crack even when the elongation is set to, for example, 100%. Moreover, it becomes a protective film using resin suitable as an adhesive layer.

The protective film of the fifth aspect of the present invention is the protective film of any of the first aspect to the fourth aspect of the present invention, wherein the fluorosilsesquioxane polymer has at least one Addition polymer of fluorosilsesquioxane with addition polymerizable functional group, or addition copolymer of fluorosilsesquioxane with at least one addition polymerizable functional group and other addition polymerizable monomers .

With such a configuration, it becomes a protective film using an addition polymer suitable as a fluorosilsesquioxane polymer.

In the protective film of the sixth aspect of the present invention, in the protective film of any one of the first to fifth aspects of the present invention, the content ratio of the curable resin composition is from the surface The surface of the layer is formed so as to gradually decrease into the base film.

Fluorine compounds have the property of being easily aggregated at the interface between air and solid, and the curable resin penetrates into the resin containing thermoplastic polyurethane, so the content ratio of the curable resin composition is from the surface of the surface layer of the base film Gradually decrease into the substrate film. Therefore, it becomes a surface layer integrated with the base film without impairing the flexibility of the conventional thermoplastic polyurethane.

The protective film of the seventh aspect of the present invention is in the protective film of any one of the first aspect, the second aspect, and the fourth aspect to the sixth aspect of the present invention. The gloss value of the second side of the material film is less than 20.

With such a configuration, the second surface of the base film has a concave-convex shape, and the gloss value of the second surface side of the base film is less than 20, making it suitable for surface protection such as flooring materials with excellent anti-glare properties Protective film.

The protective film of the eighth aspect of the present invention is the protective film of any one of the first to seventh aspects of the present invention, and the thickness of the base film is 50 μm to 300 μm.

With such a structure, by having a base film with a thickness of 50 μm to 300 μm, it becomes a protective film excellent in mechanical strength and workability.

The protective film of the ninth aspect of the present invention is provided with the impact resistance in the protective film of any one of the first, second and fourth to eighth aspects of the present invention The thickness of the layer is 20 μm to 300 μm.

With such a structure, by having an impact resistance-imparting layer with a thickness of 20 μm to 300 μm, it becomes a protective film excellent in impact resistance and workability.

In the protective film of the tenth aspect of the present invention, in the protective film of any of the first aspect to the ninth aspect of the present invention, the thickness of the adhesive layer is 10 μm to 100 μm. The surface roughness is from 300 nm to 800 nm.

With such a configuration, by having an adhesive layer with a surface roughness of 300 nm to 800 nm and a thickness of 10 μm to 100 μm, it becomes a protective film having excellent adhesiveness and suppressing paste residue when the protective film is peeled off. In addition, in this specification, "surface roughness" means the arithmetic average roughness R(a) unless there is a special description. In addition, the adhesive layer also serves as a buffer layer on the surface of the protective film and the adherend, so that the adhesive layer exists without defects, which can reduce the impact of the impact phenomenon on the adherend in the field of protective films used for the above-mentioned purposes.

The layered body for a protective film of the eleventh aspect of the present invention is on the surface of the adhesive layer opposite to the base film with respect to the protective film of any of the first to tenth aspects of the present invention There is a release film on the upper layer, and the surface roughness of the surface of the release film facing the adhesive layer is 350 nm to 850 nm.

With such a configuration, the surface roughness of the adhesive layer can be set to 300 nm to 800 nm by the release film having a surface roughness of 350 nm to 850 nm when manufacturing the protective film. In addition, the adhesive surface of the adhesive layer can be protected by a release film after manufacturing.

In the layered body for a protective film of the twelfth aspect of the present invention, in the layered body for a protective film of the eleventh aspect of the present invention, the adhesive layer is held for a period of 10 to 120 minutes after the peeling film is peeled off The irregular shape of the surface roughness is shown.

With such a structure, when bonding to the adherend to be the target, the depressing part of the adhesive layer of the adjacent unattached part is used for rapid defoaming on one side, and the surface of the removed adhesive gradually joins with the adherend Stick. Furthermore, after the bonding, the uneven shape is easily disappeared with the assistance of the applied pressure, and follows the adherend to be uniformly attached.

In the 13th aspect of the present invention, the laminate for a protective film in the 11th aspect or the 12th aspect of the present invention, a release film is applied on the surface facing the adhesive layer, At least one release agent from a fluorine-based resin, a silicone resin, and a long-chain-containing urethane.

With such a configuration, it is easy to peel off the release film from the adhesive layer.

The surface protection article of the fourteenth aspect of the present invention is the following surface protection article, including: the protective film of any one of the first to tenth aspects of the present invention; and the protective film by Items attached to the surface with an adhesive layer.

With such a configuration, the coating on the surface of the article can be protected by the disappearance of the uneven shape and following the protective film to which the article is evenly attached. In addition, the thermoplastic polyurethane with high impact strength can protect the surface from damage and the like. Furthermore, since the surface layer of the base film has an uneven shape, the anti-glare property is excellent, and the texture of the article is not impaired. In addition, the surface layer can improve the antifouling property. Furthermore, the adhesive layer is excellent in adhesiveness, excellent in heat resistance and weather resistance, and has no paste residue after peeling.

The method for manufacturing a protective film according to a fifteenth aspect of the present invention is a method for manufacturing a protective film, including: a step of providing a base film formed of a resin containing thermoplastic polyurethane; a step of forming an adhesive layer; A step of applying a curable resin composition on the second surface of the base film opposite to the first surface, and impregnating the base film with the curable resin composition; and The step of irradiating active energy rays or heating the curable resin composition, the curable resin composition containing at least one selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers A fluorine compound and a curable resin, and further includes a step of forming an impact resistance-imparting layer on the first surface side of the base film, or a step of making the gloss value of the second surface side of the base film less than 20 .

With such a structure, an adhesive layer excellent in adhesion can be formed. Furthermore, a surface layer in which a part of the base film is mixed with the curable resin composition can be formed without impairing the flexibility possessed by the thermoplastic polyurethane. Furthermore, the surface layer can be formed from a fluorine compound having excellent surface aggregation characteristics without impairing the flexibility of the thermoplastic polyurethane, and the surface layer can improve the antifouling property.

The method for manufacturing the protective film of the sixteenth aspect of the present invention in the method for manufacturing the protective film of the fifteenth aspect of the present invention includes: providing a base material formed of a resin containing a thermoplastic polyurethane The step of the film; the step of forming an impact resistance-imparting layer on the first surface side of the base film; the step of forming an adhesive layer on the side of the impact resistance-imparting layer opposite to the side of the base film; the base film The step of coating the curable resin composition on the second surface opposite to the first surface, and impregnating the curable resin composition into the substrate film; and irradiating the curable resin composition with activity An energy ray or a step of heating; the curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin.

With such a structure, the impact resistance-imparting layer becomes a protective film excellent in impact resistance and workability.

The manufacturing method of the protective film of the 17th aspect of this invention in the manufacturing method of the protective film of the 15th aspect of this invention includes providing the base material formed of the resin containing thermoplastic polyurethane. A film step; a step of forming an adhesive layer on the first surface side of the base film; applying a curable resin composition on a second surface of the base film opposite to the first surface, A step of permeating the curable resin composition into the base film; and a step of irradiating the active resin line with an active energy ray or heating the curable resin composition; the curable resin composition At least one fluorine compound in the group consisting of silicone and fluorosilsesquioxane polymer, and the curable resin, the gloss value of the second side of the base film is less than 20.

With such a configuration, the second surface of the base film has a concave-convex shape, and when the gloss value of the second surface side is less than 20, it becomes a protective film excellent in anti-glare properties. [Effect of invention]

The protective film of the present invention has antifouling properties and impact resistance. Therefore, by attaching a protective film to buildings such as floor boards, the floor boards and the like can be protected when tableware and the like fall, and it is easy to wipe off the adhesion around the water and the like dirt. The protective film of the present invention has an impact resistance-imparting layer, is excellent in workability, and can shorten work time and cost. In addition, the protective film of the present invention can prevent the reflection of external light (sunlight, etc.) due to the extinction shape on the surface, and does not impair the original design of the floor plate and the like. Furthermore, when the protective film is damaged, if the film is peeled off, it becomes the same clean material as the new product. In this case, since the protective film can be peeled without damaging the material, the time for reattaching the protective film and the cost due to the re-repair of the floor and the like are reduced.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In addition, in each figure, the same or similar parts are denoted by the same or similar symbols, and repeated explanations are omitted. In addition, the present invention is not limited to the following embodiments.

[Protection film 10] As shown in FIG. 1, the protective film 10 of the first embodiment of the present invention includes a base film 11 including a surface layer 12, an impact resistance-imparting layer 15 and an adhesive layer 13. In another aspect, as shown in FIG. 2, the protective film 10 of the first embodiment of the present invention includes a base film 11 including a surface layer 12 and an adhesive layer 13. The protective film 10 is provided with a peeling film 14 at the time of manufacture, but is used by peeling off the peeling film 14 when attaching to the surface of an article to be adhered.

[Base film 11] The base film 11 is a film formed of a resin containing thermoplastic polyurethane.

<Thermoplastic Polyurethane> As the thermoplastic polyurethane used in the present invention, it is preferable that the rubber elastic polymer having a urethane bond in the molecular structure has thermoplasticity by using the diol component as the following The short-chain diol and the long-chain diol, and diisocyanate as main raw materials are obtained by subjecting a diamine as a chain extender to addition polymerization reaction if necessary.

Examples of short-chain diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and so on. The long-chain diol is a compound having two hydroxyl groups in one molecule and having a molecular weight of about 200 to 10,000, and examples thereof include polyether diol, polyester diol, and polycarbonate diol. Specifically, examples of the polyether glycol include polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, and polytetramethylene glycol. Examples of polyester diols include condensation-based polyester diols produced by the dehydration condensation reaction of dibasic acids and diols, and lactone-based polyesters obtained by ring-opening polymerization of ε-caprolactone. Alcohol etc.

Examples of the diisocyanate include aromatic groups such as toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and xylylene diisocyanate. Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ionic acid diisocyanate, hydrogenated diphenyl diisocyanate, hydrogenated xylylene diisocyanate, etc. In the case of non-yellowing thermoplastic polyurethane, aliphatic diisocyanate can be preferably used.

In addition, the Shore hardness of the thermoplastic polyurethane is preferably Shore A hardness 40 or more and Shore D hardness 65 or less. If the Shore A hardness is 40 or more, even if the thermoplastic polyurethane itself is at room temperature, it will not show adhesiveness, so it is easy to wind up into a film shape. On the other hand, if the Shore D hardness is 65 or less, It will not be excellent and better.

<Resin> The base film 11 is preferably a film formed of a thermoplastic resin as a resin. As the thermoplastic resin, a polyurethane-based resin other than thermoplastic polyurethane may be included. The polyurethane-based resin can be arbitrarily selected from those with low hardness to those with high hardness, and can be preferably used. In addition to the polyurethane-based resin, other thermoplastic resins may be further included. Examples of the thermoplastic resin other than the polyurethane-based resin include polyester-based resins and acetate-based resins. Polyether resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin Resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, polyphenylene sulfide-based resins, norbornene-based resins, polydiene-based resins, high cohesion due to the use of metal ions Resins such as molecular ionomers. Specifically, it is preferably polycaprolactone (Polycaprolactone, PCL), acrylic polymer, polyester, polyacrylonitrile, polyetherketone, polystyrene, polyvinyl acetate, or derivatives of these resins. These resins may be used alone or in combination. The thermoplastic resin can be synthesized by a known method or a commercially available product.

In the case of using a thermoplastic polyurethane and a thermoplastic resin other than thermoplastic polyurethane in combination, there is no limitation as long as the effect of the present invention is not hindered, and the mixing ratio thereof may be, for example, 1:99 ~99:1 (weight ratio), preferably 50:50 ~ 90:10 (weight ratio).

(Optional) Furthermore, the thermoplastic polyurethane may contain well-known additives within a range that does not hinder its physical properties. Examples of additives include antioxidants such as phenol-based heat stabilizers, phosphorus-based heat stabilizers, and sulfur-based heat stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, anti-fogging agents, and anti-blocking agents. Agent. One or two or more of the additives may be used. The proportion of the additive is 0.1% by weight to 80% by weight relative to the total amount of the thermoplastic resin, preferably 0.1% by weight to 50% by weight, and more preferably 0.1% by weight to 30% by weight.

<film thickness> The film thickness of the base film 11 is not particularly limited, and the film thickness of the base film is preferably 50 μm to 300 μm, and more preferably 100 μm to 200 μm. If the thickness of the base film is 50 μm or more, the mechanical strength of the base material is sufficient, and a layer can be formed on the base material. In addition, if the film thickness is 300 μm or less, the thickness of the protective film does not become too thick.

<Extinction> Since the second surface of the base film 11 has an uneven shape, it can have a matt feeling. In this way, even if the protective film is attached, it will not damage the original design of the article. The shape of the unevenness of the base film 11 can be changed according to the characteristics and the like required in the attached article, and is not limited. For example, as the arithmetic average roughness R(a), it is usually 0.1 μm to 100 μm, preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 10 μm. Furthermore, the uneven shape can be obtained by performing matting treatment (surface treatment) such as embossing on the surface side of the base film. In addition, the matting property can be changed according to the characteristics and the like required in the attached article, and is not limited. For example, when matting property is required, it is the 60° gloss value of the surface of the protective film after being adhered to the floor and other articles, Usually less than 20, preferably 15 or less, or 10 or less. The lower limit of the 60° gloss value is not particularly limited, but it can be set to 0.5 or more in practical use, and typically 1.0 or more. In addition, when gloss is required (when matting is not required), the 60° gloss value of the surface of the protective film after being adhered to an article such as a floor is usually 20 or more, preferably 25 or more , Can also be more than 30. The upper limit of the 60° gloss value is not particularly limited. In practice, it can be set to 100 or less, and typically 50 or less. The 60° gloss value can be measured using a commercially available gloss meter under the condition of a measurement angle of 60°.

Hereinafter, an example of a method for producing a resin film having an uneven shape obtained by the film transfer method used in the present invention is shown.

The resin film having a concave-convex shape obtained by the film transfer method used in the present invention can be obtained by adding the separator 7 and the separator for film transfer (concavo-convex) to the single side of the molten resin extruded from a flat die The transfer film 8) is manufactured by cooling rollers (Figure 2).

As the separator used in the present invention, a polyethylene terephthalate film or paper can be used. In the case where the separator cannot be easily peeled from the laminated film obtained by pressing and laminating the separator and the resin, it is preferable to perform a peeling treatment on the surface of the polyethylene terephthalate film or paper. Examples of the method of the peeling treatment include a method of applying a silicone-based, fluorine-based, or long-chain alkyl group-containing urethane-based peeling agent on its surface, and a polyolefin such as polyethylene or polypropylene. The method of film lamination.

As the separator for film transfer used in the present invention, a plastic film (for example, polyethylene terephthalate film or polyolefin film such as polyethylene or polypropylene as a thermoplastic) or paper can be used. Regarding the unevenness of the separator for film transfer, a method of mixing fillers (such as silica, alumina, calcium carbonate, etc.) into the polyethylene terephthalate film can form fine Bump. In the case where the separator cannot be easily peeled off in the laminated film obtained by pressing and laminating the separator for film transfer and the thermoplastic elastomer, the polyethylene terephthalate film or The surface of the paper is peeled off. Examples of the method of the peeling treatment include a method of applying a silicone-based, fluorine-based, or long-chain alkyl group-containing urethane-based peeling agent on its surface, and a polyolefin such as polyethylene or polypropylene. The method of film lamination.

In addition, regarding the separator for film transfer used in the present invention, the surface of the polyethylene terephthalate film or paper is coated with a filler (such as silica, alumina, calcium carbonate, etc.). The release agent can form fine irregularities.

Furthermore, the separator for film transfer used in the present invention can be sandblasted on a plastic film (such as polyethylene terephthalate film or polyolefin film such as polyethylene or polypropylene as a thermoplastic) or The surface of the paper laminated with a polyolefin film such as polypropylene has fine irregularities. When the separator cannot be easily peeled from the laminated film obtained by pressing and laminating the separator for film transfer and the thermoplastic elastomer, it is preferable to perform the process on the surface of the separator for film transfer Stripping treatment. Examples of the method of the peeling treatment include a method of applying a silicone-based, fluorine-based, or long-chain alkyl-containing urethane-based peeling agent to the surface.

In addition, the separator for film transfer used in the present invention can be thermally transferred to a plastic film (such as polyethylene terephthalate film or polyethylene or polypropylene as a thermoplastic) by using an embossing roller Polyolefin film) or paper laminated with a polyolefin film such as polypropylene has fine irregularities on the surface.

Hereinafter, an example of a method for producing a resin film having an uneven shape obtained by the embossing roller transfer method used in the present invention is shown.

The resin film having a concave-convex shape obtained by the embossing roll transfer method used in the present invention can be pressed when the separator 7 is added to one side of the molten resin extruded from a flat die and passes through the cooling roller 3 The embossing roller 4 is manufactured by transferring the unevenness of the surface of the embossing roller to one side of the thermoplastic resin (FIG. 3 ).

The manufacturing method of the resin film not having an uneven shape can be manufactured in the same manner as the manufacturing method of the resin film having an uneven shape except that the uneven shape is not implemented.

[Impact resistance imparting layer 15] <Resin> As shown in FIG. 1, the impact resistance-imparting layer 15 is formed on the opposite side to the surface layer of the base film 11 that has been subjected to antifouling treatment (or antifouling treatment) by the surface layer 12. The impact resistance-imparting layer may be formed directly on the surface of the base film 11, or may be laminated between the base film 11 and another layer. The impact resistance-imparting layer 15 is not particularly limited as long as it is a layer that imparts impact resistance. For example, it is preferable to use a film formed of a resin such as polyester-based resin or polyolefin-based resin. Preferably, resins, such as polyethylene terephthalate, polyethylene, and polypropylene, are mentioned. One or two or more resins can be used. The resin and the film formed from the resin can be synthesized by a known method or a commercially available product.

(Optional) In addition, the impact resistance-imparting layer may contain well-known additives within a range that does not hinder its physical properties. Examples of additives include antioxidants such as phenol-based heat stabilizers, phosphorus-based heat stabilizers, and sulfur-based heat stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, anti-fogging agents, and anti-blocking agents. Agent. One or two or more of the additives may be used. The proportion of additives is 0.1% by weight to 80% by weight relative to the total amount of resin, preferably 0.1% by weight to 50% by weight, and more preferably 0.1% by weight to 30% by weight.

<film thickness> The film thickness of the impact resistance-imparting layer 15 is not particularly limited, but is preferably 20 μm to 300 μm, and more preferably 50 μm to 200 μm. If the film thickness of the impact resistance-imparting layer is 20 μm or more, the impact resistance is sufficient, and the workability of the protective film is improved. In addition, if the film thickness is 300 μm or less, the thickness of the protective film does not become too thick.

With the impact resistance-imparting layer 15, excellent impact resistance can be obtained. Furthermore, stiffness (hardness) is given to the protective film, and construction workability is improved. The stiffness of the film can be changed according to the attached article and the like, and is not limited. For example, as a rigidity value, it is usually 20 mN or more, preferably 35 mN or more. The upper limit of the rigidity value is not particularly limited, but it can be set to 250 mN or less in practice, and typically 200 mN or less. The stiffness value can be measured using a commercially available ring stiffness tester as the collapse resistance value under the ring.

[Surface layer 12] In order to form the surface layer 12, first, a coating agent containing a curable resin composition is applied to the surface of the base film 11.

<Coating agent> The curable resin composition penetrates into the base film 11 and is mixed with a part of the base film 11. By drying and curing, a part of the base film 11 is integrated with the curable resin composition to form the surface layer 12. The surface layer 12 is configured so that the content ratio of the curable resin composition gradually decreases from the surface of the surface layer 12 into the base film 11. Therefore, a protective film with a high elongation at break can be formed, and even if the protective film is stretched, cracks are not generated. The curable resin composition is a composition containing at least one fluorine compound selected from the group consisting of fluorosesquioxane and fluorosesquioxane polymer, and a curable resin. The fluorine compound and the curable resin can be synthesized by a known method or a commercially available product. In addition, the coating agent can be prepared by directly preparing a curable resin composition as a solid component (active ingredient), and separately preparing a mixture with a solvent or the like.

When the total amount of the fluorine compound and the curable resin is set to 100% by weight, the curable resin composition preferably contains 0.01% to 20% by weight of the fluorine compound. The content of the fluorine compound is preferably 0.1% by weight to 10% by weight, and more preferably 1% by weight to 5% by weight. If it is 0.01% by weight or more (more preferably 0.5% by weight or more), sufficient antifouling property can be imparted to the surface layer 12. In addition, in order to obtain the effect of the present invention, it is preferable to contain a fluorine component (in terms of fluorine atom content) of 0.001 to 4% by weight based on 100% by weight of the fluorine compound and the curable resin. It is preferably 0.01% by weight to 2% by weight, and more preferably 0.1% by weight to 1% by weight. When the total amount of the fluorine compound and the curable resin is set to 100% by weight, the curable resin composition preferably contains 80% to 99.9% by weight of the curable resin. The content of the curable resin is preferably 90% by weight to 99.9% by weight, and more preferably 95% by weight to 99% by weight.

For the application of the coating agent containing the curable resin composition, it is preferable to use a wet coating method in which the fluorine compound and the curable resin are uniformly applied. As the wet coating method, a gravure coating method, a die coating method, or the like can be used. The gravure coating method is a method of immersing an intaglio roll having an uneven engraving process on the surface in a coating liquid, and scraping off the coating agent adhering to the uneven portion on the surface of the intaglio roll with a doctor blade The solution accumulates in the recess, thereby accurately metering and transferring to the substrate. With the gravure coating method, a low viscosity solution can be applied thinly. The die coating method is a method in which the solution is pressed out from a coating head called a die and applied on one side. The die coating method enables high-precision coating. Furthermore, the solution is not exposed to outside air during coating, so it is less likely that the concentration of the coating agent will change due to drying. Other wet coating methods include spin coating method, bar coating method, reverse roll method, roll coating method, slit coating method, dipping method, spray coating method, and kiss coating method, Reverse anastomosis coating method, air knife coating method, curtain coating method, rod coating method, etc. The coating method can be appropriately selected from these methods according to the necessary film thickness. Furthermore, by using a wet coating method, coating can be performed at a linear speed of several tens of meters per minute (for example, about 20 m/min), so mass production is possible, and production efficiency can be improved.

<Curable resin composition> (Curable resin) The curable resin contained in the curable resin composition is a resin that is cured by ultraviolet irradiation, electron beam irradiation, heating, or the like. Examples of the curable resins include silicone resins, acrylic resins, methacrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, urethane resins, polyimides, and polyetherimides. , Polyamide amide imine, phenol resin, alkyd resin, urea resin, bismaleimide resin, polyester urethane resin, polyether urethane resin, etc. Among these curable resins, from the viewpoint of productivity, an active energy ray-curable resin that is formed into a film and is cured by an active energy ray in a short time is preferable. Here, the active energy ray refers to an energy ray that can decompose an active species-generating compound to generate an active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, and electron beams. More preferably, it is an ultraviolet curable resin. The ultraviolet curable resin is usually used by adding a photopolymerization initiator. Examples of the photopolymerization initiator include various benzoin derivatives, benzophenone derivatives, and phenyl ketone derivatives. The addition amount of the photopolymerization initiator is preferably set to 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin.

Specific examples of the curable resin include: (meth)acrylate monomers, unsaturated polyester resins, polyester (meth)acrylate resins, epoxy (meth)acrylate resins, and (meth)acrylate amines Resins having unsaturated bonds capable of radical polymerization, such as urethane resins. These resins may be used alone or in combination. Particularly preferred is a resin having a (meth)acryloyl group with more than one function.

(Resin with unsaturated bonds capable of radical polymerization) ·(Meth)acrylate monomer Examples of the (meth)acrylate monomers include compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols. For example, polyalkylene glycol di(meth)acrylate, ethylene glycol (meth)acrylate, propylene glycol (meth)acrylate, polyethylidene polytrimethylolpropane di(methyl) ) Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, Trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate , Tetramethylolmethane tetra(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a (meth)acrylate in the functional group among the compounds which have a silsesquioxane skeleton is also mentioned.

·Unsaturated polyester resin Examples of unsaturated polyester resins include resins obtained by dissolving a condensation product (unsaturated polyester) obtained by esterification of a polyol with an unsaturated polybasic acid (and optionally a saturated polybasic acid) in a polymerizable monomer. The unsaturated polyester can be produced by polycondensation of unsaturated acids such as maleic anhydride and glycols such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, itaconic acid, or an anhydride thereof can be used as the acid component, and it can be combined with ethylene glycol, propylene glycol, or diethylene glycol as the alcohol component. , Dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2 -Reaction of polyols such as dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, and Polyacids or anhydrides thereof that do not have a polymerizable unsaturated bond, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc., are also added as acid components if necessary And the manufactured unsaturated polyester.

·Polyester (meth)acrylate resin Examples of polyester (meth)acrylate resins are: (1) The terminal of the epoxy compound containing α,β-unsaturated carboxylic acid ester and the saturated polybasic acid and/or unsaturated polybasic acid and polyol is a carboxyl group (Meth)acrylate obtained from the reaction of polyester; (2) the reaction of (meth)acrylic acid ester containing hydroxyl group with polyester with carboxyl end obtained from saturated polyacid and/or unsaturated polyacid and polyol (Meth)acrylic acid ester; (3) (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with a hydroxyl-terminated polyester obtained from a saturated polyacid and/or unsaturated polyacid and a polyol. Examples of saturated polybasic acids that can be used as raw materials for polyester (meth)acrylates include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Polyacid or its anhydride which does not have a polymerizable unsaturated bond, and polymerizable unsaturated polyacid or its anhydride such as fumaric acid, maleic acid, itaconic acid and the like. Furthermore, the polyol component is the same as the unsaturated polyester.

·Epoxy (meth)acrylate resin Examples of the epoxy (meth)acrylate resin include compounds having a polymerizable unsaturated bond produced by ring-opening reaction of a compound having a glycidyl group with a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid (Vinyl ester) A resin obtained by dissolving in a polymerizable monomer. The vinyl ester is produced by a well-known method, and examples thereof include an epoxy (meth)acrylate obtained by reacting an unsaturated monobasic acid such as acrylic acid or methacrylic acid with an epoxy resin. In addition, bisphenol (such as type A) or adipic acid, sebacic acid, dimer acid (Haridimer (Haridimer) 270S: Harima Chemicals (Harima Chemicals) (shares)) and other two The metabolic acid reacts with various epoxy resins to impart flexibility. Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolac-type glycidyl ethers, and the like.

·(Meth)acrylate urethane resin The (meth)acrylic urethane resin is an active energy ray-curable resin having a (meth)acryloyl group and having a urethane skeleton, and examples thereof include ultraviolet-curable resins. (Meth)acrylic urethane resin is particularly good for imparting flexibility (flexibility) to the cured film. (Meth)acrylic acid urethane resins can also be oligomers, prepolymers, polymers containing free radically polymerizable unsaturated groups that can be obtained by combining polyisocyanates with polyhydroxy compounds or polyhydric compounds After the alcohols are reacted, the hydroxyl-containing (meth)acrylic compound is further reacted. It is particularly preferable to use polycarbonate-based acrylic urethanes of polycarbonate-based polyols for polyols. By using polycarbonate-based acrylic urethane, the resulting cured film can provide excellent stretchability and toughness.

Specific examples of the polyisocyanate include: 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, Xylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Barnock D-750 (trade name: manufactured by DIC (stock)), Chrisbon (Crisvon) NK (trade name: manufactured by DIC (share)), Desmodule L (trade name: manufactured by Sumitomo Bayer Urethane (share)), gram Coronate L (trade name: manufactured by Japan Polyurethane Industry Co., Ltd.), Takenate D102 (trade name: manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonaite (Isonate) 143L (trade name: manufactured by Mitsubishi Chemical Corporation), etc. Examples of the polyhydroxy compound include polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, and the like, and specific examples include glycerin-ethylene oxide adducts and glycerin-epoxy Propane adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct Adducts, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct Products, dipentaerythritol-tetrahydrofuran adducts, dipentaerythritol-ethylene oxide-propylene oxide adducts, etc. Specific examples of the polyols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3. -Adducts of butanediol, bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexane Glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, p-xylene glycol, dicyclohexyl-4,4-diol, 2,6-decalindiol, 2 , 7-decalin, etc. The hydroxyl group-containing (meth)acrylic compound is not particularly limited, but is preferably a hydroxyl group-containing (meth)acrylate, specifically, for example, 2-hydroxyethyl (meth)acrylate, (Meth)acrylic acid-2-hydroxypropyl ester, (meth)acrylic acid-3-hydroxybutyl ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tri(hydroxyethyl Radical) isocyanuric acid di(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.

The (meth)acrylate urethane resin can be synthesized by a known method. As an example, a (meth)acrylate urethane resin can be obtained by subjecting a given amount of organic polyisocyanate (a) and polycarbonate polyol (b) to 70°C to 80°C The reaction is performed in such a way that the remaining isocyanate concentration becomes a predetermined amount, and then a predetermined amount of (meth)acrylate (c) containing more than one hydroxyl group in the molecule is added to the polymerization inhibitor (for example, hydroquinone monomethyl ether) The reaction is carried out at 70°C to 80°C until the residual isocyanate concentration reaches 0.1% by weight or less. The weight average molecular weight (Mw) of the (meth)acrylate urethane resin is 3,000 to 500,000, preferably 5,000 to 200,000. By setting to this range, the cured film can be given flexibility. In the case of 3,000 or more, the crosslink density in the cured film does not become too high.

The curable resin contained in the curable resin composition is preferably a resin containing at least one compound having the (meth)acryloyl group. The molecular weight of the resin having a (meth)acryloyl compound is 50 to 30,000, more preferably 50 to 5,000. Compounds with a (meth)acryloyl group with a molecular weight of 50 to 30,000 easily penetrate into the interior of the thermoplastic polyurethane and integrate with the thermoplastic polyurethane, but will not harm the existing thermoplastic polyamine The softness of carbamate. Regarding the curable resin contained in the curable resin composition, a resin having a compound having a (meth)acryloyl group may be added separately from the above resin, or as long as the molecular weight is within an appropriate range, it may be included only A resin including a resin having a (meth)acryloyl group. The content of the resin having the (meth)acryloyl group in the curable resin is 40% by weight to 100% by weight, preferably 50% by weight to 100% by weight.

(Resin hardened by reactions other than free radical polymerization) As specific examples of the curable resin, in addition to the (meth)acryloyl group-containing curable resin, a resin that is cured by a reaction other than radical polymerization, that is, active energy ray curable or thermosetting Cationic polymerizable resin, anionic polymerizable resin, addition polymerizable resin, polycondensation resin, ring-opening polymerizable resin, thermosetting resin other than cation polymerizable, etc. These resins may be used alone or in combination.

·Cationic polymerizable resin, anionic polymerizable resin Examples of the cationic polymerizable resin and anionic polymerizable resin include compounds having a cationic polymerizable functional group such as vinyl ether group, propylene ether group, oxetanyl group, oxetanyl group, and vinylaryl group; and vinyl groups. Compounds with anionic polymerizable functional groups such as carboxyl groups and cyanoacryloyl groups. Furthermore, examples of the cationic polymerizable resin include bisphenol-based epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and other epoxy resins, oxetane resins, and vinyl ethers. Resin.

Examples of the addition polymerizable resin, polycondensation resin, and ring-opening polymerizable resin include the following. ·Addition polymerizable resin The addition polymerizable resin includes, for example, an active hydrogen-containing compound such as polyurethane produced by polymerization, and examples thereof include low molecular weight diols [ethylene glycol, propylene glycol, 1,4-butanediol, 1 , 6-hexanediol, etc.]; polyether diol [the exemplified low molecular weight diol alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts, alkylene oxide Ring-opening polymer (polytetramethylene glycol, etc.)]; polyester diol [aliphatic dicarboxylic acid (adipic acid, maleic acid, dimerized linoleic acid, etc.) or aromatic dicarboxylic acid ( Phthalic acid, terephthalic acid, etc.) Condensed polyester diol with the exemplified low molecular weight diol, polylactone diol obtained by ring-opening polymerization of ε-caprolactone, etc.]; low molecular weight two Amine (isophorone diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, etc.). Examples of the diisocyanate include aromatic diisocyanates (toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, etc.), and alicyclic diisocyanates (isophorone diisocyanate, Dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, diisocyanate methylcyclohexane, etc.), aliphatic diisocyanate (hexamethylene diisocyanate, etc.), etc. In addition, it may include active hydrogen-containing compounds with more than three functions (polyols such as trimethylolpropane, pentaerythritol, and sorbitol; polyamines such as diethylenetriamine and triethylenetetramine; amino alcohols such as triethanolamine, etc.) And/or polyisocyanates with more than three functions [triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, one to three adduct of trimethylolpropane and hexamethylene diisocyanate, hexamethylene Combination of methyl diisocyanate cyclic terpolymer, etc.]. Examples of the epoxy compound include: phenol ether-based glycidyl compounds (diglycidyl ethers such as bisphenol A and bisphenol F); ether-based glycidyl compounds (diglycidyl ether, triglycidyl ether of glycerin, Polyallyl glycidyl ether, etc.); ester glycidyl compounds [copolymers of glycidyl (meth)acrylate and ethylenically unsaturated monomers (acrylonitrile, etc.)]; glycidyl amines (pair (Glycidyl ether of aminophenol, etc.), non-glycidyl epoxy compounds (epoxidized polyolefin, epoxidized soybean oil, etc.), etc. Examples of the epoxy hardener include polyamines and polycarboxylic acids (anhydrides). Examples of the polyamines include aliphatic polyamines (alkylene diamines such as ethylenediamine and tetramethylenediamine, polyalkylene polyamines such as diethylenetriamine and triethylenetetramine, and alkylene Alkylaminopropylamines, aminoethylethanolamines, and other alkyl or hydroxyalkylamines, xylenediamine and other aromatic ring-containing aliphatic amines, polyoxypropylene polyamines and other polyether polyamines, etc. ); aliphatic polyamines containing alicyclic or heterocyclic rings (N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophorone diamine, etc.); aromatic polyamines ( Phenylenediamine, toluenediamine, diaminodiphenylmethane, etc.); polyamide polyamines (condensates of the polyamines and dimer acids); benzoguanamine and/or alkylguanamine And its modified products; and dicyandiamide (dicyandiamide), etc.

·Polycondensation resin Examples of the polycondensable resin include: polyester-like aliphatic dicarboxylic acid ester-based polymers (polybutylene adipate, polyethylene adipate, etc.) produced by polymerization; polycarbonate; and Two or more co-esters of these polymers or the compounds that make up these polymers and alkylene oxides (polyethylene glycol, polypropylene glycol, etc.), low molecular crosslinking agents with more than three functions (trimethylolpropane , Glycerin, trimellitic acid, etc.). Polyamides include: 6-nylon, 6,6-nylon, 6,10-nylon, 11-nylon, 12-nylon, 4,6-nylon, etc. and two or more kinds of co-amides of these nylons Or a co-condensation polymer of a compound that constitutes these polymers, a compound that constitutes a polyester, an alkylene oxide (polyethylene glycol, polypropylene glycol, etc.), or a low molecular crosslinking agent (trimellitic acid, etc.) with more than three functions. The polyimide system may include: polycondensates of pyromellitic acid and 1,4-diaminobenzene; co-condensation polymers of the compounds constituting these polyimides and the compounds constituting the polyimide, that is, poly Amidimide, etc. In addition to these compounds having two or less functional groups in the molecule, they also include polymerizable compounds having three or more functional groups and forming a cross-linked structure by polymerization. Examples include: active hydrogen-containing compounds with more than three functions (polyols such as trimethylolpropane, pentaerythritol, and sorbitol; polyamines such as diethylenetriamine and triethylenetetramine; and amino alcohols such as triethanolamine. ), trimellitic acid and/or more than three functional polyisocyanates [triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, trimethylolpropane and hexamethylene diisocyanate one to three Adducts, cyclic trimers of hexamethylene diisocyanate, etc.] combinations, etc.

·Ring-opening polymerizable resin Examples of the ring-opening polymerizable resin include lactones such as γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone, ε-caprolactam, and encaprolactone Endoamides such as enantholactam and lauryl lactam

Furthermore, as an example of the resin hardened by a reaction other than radical polymerization, a silsesquioxane derivative represented by the following formula (A-1) to formula (A-3) may be mentioned.

[Chemical 1]

In formula (A-1) to formula (A-3), R is independently hydrogen, any hydrogen may be substituted with fluorine and is not adjacent -CH ₂ -carbon which may be substituted with -O- or cycloalkylene C1-C45 alkyl, C4-C8 cycloalkyl, substituted or unsubstituted aryl. In the benzene ring of the substituted aryl group, any hydrogen may be substituted with an alkyl group having 1 to 10 carbon atoms, halogen, or fluorine. R ^{1 is} independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl. At least one X is a group having hydrogen or a polymerizable functional group, and the remaining X is a group defined in the same manner as R ¹ . In the case where R is hydrogen, only one X may be hydrogen. When X is a polymerizable functional group, at least two X are preferably a polymerizable functional group. These compounds can be synthesized by well-known manufacturing methods. For example, refer to Japanese Patent No. 5050473.

In addition, the group having a polymerizable functional group represented by X is not particularly limited as long as it is a functional group capable of addition polymerization, ring-opening polymerization, or polycondensation, and may be exemplified. : Oxetanyl, oxetanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanyl, acrylic or (meth)acrylic, alkenyl, amine , 2-oxapropane-1,3-diacyl (2-oxapropane-1,3-dioyl), etc. In addition, when there are a plurality of polymerizable functional groups, they may be the same group or different groups. Specifically, the groups represented by the following formula (a) to formula (h) can be exemplified.

[Chem 2]

In formulae (a) to (h), R ² is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. One -CH ₂ -in the alkylene group may be substituted with -O- or 1,4-phenylene group. Furthermore, R ³ is hydrogen or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen.

· Thermosetting resins other than cationic polymerizable Examples of thermosetting resins other than cation polymerizable include phenol resin, alkyd resin, melamine resin, epoxy resin, urea resin, unsaturated polyester resin, urethane resin, thermosetting polymer Acetylene imide and silicone resin. These resins may be used alone or in combination. Specifically, in terms of processability, bisphenol A type epoxy resin, bisphenol F type epoxy resin, multifunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, Epoxy resins such as glycidyl ester epoxy resin, polymer epoxy resin, biphenyl epoxy resin, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified Melamine resins such as melamine resins, methylbutyl mixed etherified melamine resins, polyisocyanate compounds with two or more isocyanate groups (O=C=NRN=C=O), and polyols with two or more hydroxyl groups Carbamates obtained from the reaction of compounds (HO-R'-OH), polyamines (H2N-R"-NH2), water and other compounds with active hydrogen (-NH2, -NH, -CONH-, etc.) Department of resin. Epoxy-based resins are excellent in heat resistance and chemical resistance, melamine-based resins are excellent in heat resistance, hardness, and transparency, and urethane-based resins are excellent in low-temperature curability, and can be appropriately selected and used.

The resin hardened by a reaction other than radical polymerization is particularly preferably a cationic polymerizable resin. By using cationic polymerization, the hardening reaction can be accelerated, which is preferable at the time of manufacture. In addition, depending on the type of cationic polymerization initiator used, it is possible to appropriately select which of light and heat to perform cationic polymerization.

The content of the resin hardened by reactions other than radical polymerization depends on the type of resin or the characteristics to be imparted to the cured film. For example, the content of the resin cured by a reaction other than radical polymerization is preferably 10% by weight to 90% by weight with respect to the total weight (100% by weight) of the curable resin composition forming the cured film. More preferably, it is 20% by weight to 70% by weight. If the content of the resin hardened by a reaction other than radical polymerization is 10% by weight to 90% by weight, the cured film after curing can maintain excellent hardness, toughness, and heat resistance.

(Photopolymerization initiator) The photopolymerization initiator is not particularly limited. As long as it is an initiator that generates free radicals through active energy rays. Compounds that can be used as active energy ray polymerization initiators are benzophenone, Michlerone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, iso Propylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylacetonone, 2-hydroxy-2-methyl-4' -Isopropyl phenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethyl Benzylbenzyldiphenylphosphine 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(tris Chloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyrene Group)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(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)benzothiazole, 2-mercaptobenzene Thiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2, 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromo Phenyl)-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-morpholinylpropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2 ,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(third butylperoxycarbonyl)benzophenone, 3, 3',4 ,4'-tetra(third hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(third butylperoxycarbonyl)benzophenone , 3,4'-bis(methoxycarbonyl)-4,3'-bis(third butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3 '-Di (third butyl peroxycarbonyl) benzophenone and so on. These compounds can be used alone, and it is effective to use two or more of them in combination. The content of the photopolymerization initiator is preferably 0.01% by weight to 20% by weight relative to the total weight of the radically polymerizable resin (100% by weight). More preferably, it is 1% to 10% by weight.

(Cationic polymerization initiator) The cationic polymerization initiator may be a compound that can release a substance that initiates cationic polymerization by active energy ray irradiation or thermal energy. Examples of the cationic polymerization initiator include a carboxylic acid, an amine, an anhydride compound or an acid generator, preferably a double salt or its derivative as an onium salt releasing Lewis acid.

Representative compounds of the cationic polymerization initiator include salts of cations and anions represented by the following formula (1). [A] ^m+ [B] ^m- (1)

In formula (1), the cation [A] ^{m+ is} preferably an onium ion, and is represented by the following formula (2), for example. [(α) _a Q] ^m+ (2) In formula (2), α is an organic group having 1 to 60 carbon atoms and may contain atoms other than a few carbon atoms. a is an integer of 1-5. A alphas are independent and may be the same or different. In addition, it is preferable that at least one α is an organic group having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. In addition, when the valence of Q in cation [A] ^m+ is set to q, m=aq (where N=N is operated with a valence of 0).

On the other hand, the anion [B] ^{m- is} preferably a halide complex, and is represented by the following formula (3), for example. [LX _b ] ^m- (3) In formula (3), L is a metal or semimetal (Metalloid) as the central atom of the halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom. b is an integer of 3-7. In addition, when the valence of L in the anion [LX _b ] ^m- is p, m=bp. Specific examples of the anion [LX _b ] ^m- represented by formula (3) include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), and hexafluoro Arsenate (AsF ₆ ), hexachloroantimonate (SbCl ₆ ), etc.

In addition, as the anion [B] ^m- , an anion represented by the following formula (4) can also be preferably used. L, X, b are the same as described above. [LX _b-1 (OH)] ^m- (4)

Examples of anions [B] ^m- further include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluene Sulfonate anion, trinitrobenzenesulfonate anion, etc.

Regarding the cationic polymerization initiator in the present invention, among such onium salts, further preferred are the aromatic onium salts exemplified in the following (I) to (III). Among these aromatic onium salts, one kind may be used alone, or two or more kinds may be used in combination. (A) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate. (B) Diarylphosphonium salts such as diphenylphosphonium hexafluoroantimonate, bis(4-methylphenyl)phosphonium hexafluorophosphate, bis(4-third butylphenyl)phosphonium hexafluorophosphate . (C) Triphenylammonium hexafluoroantimonate, tris(4-methoxyphenyl)ammonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylammonium hexafluoroantimonate, di Phenyl-4-thiophenoxyphenyl alkane hexafluorophosphate, 4,4'-bis(diphenylamyl) phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis (Diphenyl alkynyl) phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy) phenyl alkynyl] phenyl sulfide-bis-hexafluoroantimony Acid salt, 4,4'-bis[bis(β-hydroxyethoxy)phenyl amidyl] phenyl sulfide-bis-hexafluorophosphate, 4-[4'-(benzyl) phenyl sulfide Yl]phenyl-di-(4-fluorophenyl)ammonium hexafluoroantimonate, 4-[4'-(benzyl)phenylthio]phenyl-di-(4-fluorophenyl)ammonium Hexafluorophosphate and other triaryl alum salts.

Furthermore, the cationic polymerization initiator in the present invention may be a mixture of iron aromatic hydrocarbon complex or aluminum complex and silanols such as triphenylsilanol. Examples of iron arene complexes include (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl ) Benzene]-iron-hexafluorophosphate and the like, and examples of aluminum complexes include aluminum tris (acetone acetone), aluminum tris (ethyl acetoacetate), aluminum tris(salicylic aldehyde), and the like.

Among the above, from a practical point of view, the cationic polymerization initiator according to the embodiment of the present invention is preferably an aromatic tungsten salt, an aromatic manganese salt, or an iron aromatic hydrocarbon complex.

Examples of the cationic polymerization initiator that generates cationic species by ultraviolet irradiation include hexafluoroantimonate, pentafluorohydroxyantimonate, hexafluorophosphate, and hexafluoroarsenate. The cationic polymerization initiator can also be used, for example: UVACURE 1590 (trade name: Daicel-Cytec (made by Daicel-Cytec)), CD-1010, CD-1011, CD-1012 (Both trade names: manufactured by Sartomer, USA), Irgacure 264 (trade name: manufactured by BASF), CIT-1682 (trade name: manufactured by Soda Japan) and other cities Sales.

Examples of the cationic polymerization initiator that generates cationic species by performing heat treatment include aryldiazonium salts, arylphosphonium salts, arylsulfonium salts, and allene-ion complexes. The cationic polymerization initiator can be preferably used, for example: PP-33, CP-66, CP-77 (all trade names: manufactured by ADEKA (stock)), FC-509 (trade name: 3M), UVE1014 (trade name: manufactured by GE), Sun-aid SI-60L, Sun-aid SI-80L, Sun-aid SI-100L, Sang Sun-aid SI-110L, Sun-aid SI-150L (both trade names: Sanshin Chemical Industry Co., Ltd.), CG-24-61 (trade name: BASF Japan ( BASF Japan)) and other commercially available products. Furthermore, it may be a compound of a chelate compound of a metal such as aluminum or titanium and a acetic acid or diketone and a silanol such as triphenylsilanol, or a chelate of a metal such as aluminum or titanium and a acetic acid or diketone Compound compounds and phenolic compounds such as bisphenol S.

In particular, Sun-aid SI-60L can set the heating temperature at the time of curing to a relatively low temperature (80°C to 150°C), and it has excellent storage stability, so it is excellent and preferable for film formation.

The content of the cationic polymerization initiator is preferably 0.01% to 20% by weight relative to the total weight (100% by weight) of the cationically polymerizable resin. It is more preferably 0.2% by weight to 10% by weight.

(Solvent) The fluorine compound and the curable resin used in the coating agent of the present invention may be used by being dissolved in a solvent such as an organic solvent. The solvent is not particularly limited as long as the effect of the present invention is not hindered. Common organic solvents and the like can be used.

Specific examples of the solvent include hydrocarbon-based solvents (benzene, toluene, etc.), ether-based solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon-based solvents (dichloromethane, Chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol) Etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethyl carbonate, propyl carbonate, etc.), acetyl Amine solvents (N,N-dimethylformamide, N,N-dimethylacetamide), hydrochlorofluorocarbon compounds (HCFC-141b, HCFC-225), hydrofluorocarbons Compounds (hydrofluorocarbons, HFCs) based solvents (HFCs with carbon numbers 2 to 4, 5 and 6 or more), perfluorocarbon based solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon based solvents (fluorine Cyclopentane, fluorocyclobutane), oxygen-containing fluorine-based solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine-based solvents (α,α,α-trifluorotoluene, hexafluorobenzene ),water. These solvents may be used alone or in combination of two or more.

The content of the solvent is 20 parts by weight to 500 parts by weight with respect to the total amount (100 parts by weight) of the curable resin composition forming the cured film. It is preferably 50 parts by weight to 300 parts by weight.

(Optional) In addition to the above, additives can also be added to the coating agent. For example, in order to impart hardness and scratch resistance to the film, a filler may be added. In order to improve the applicability, leveling agents can also be added. In addition, additives such as weathering agents and defoamers can also be added. In more detail, the coating agent may further contain an active energy ray sensitizer, a polymerization inhibitor, and a polymerization initiation aid within a range that does not adversely affect the effect of the cured film formed by the coating agent , Leveling agent, wetness improver, surfactant, plasticizer, ultraviolet absorber, antioxidant, antistatic agent, silane coupling agent, inorganic filler, organic filler, etc. represented by silica or alumina .

Examples of the leveling agent include commercially available acrylic surface modifiers BYK-350, BYK-352, BYK-354, BYK-356, BIK Gram (BYK)-381, BYK-392, BYK-394, BYK-3441, BYK-3440, BYK-3550 (all goods Name: Made by BYK Chemie Japan (stock). Examples of weathering agents include: benzotriazoles, hydroxyphenyl triazines, benzophenones, salicylates, cyanoacrylates, triazines, or dibenzoyl m-benzene Diphenols. These ultraviolet absorbers may be used alone, or a plurality of ultraviolet absorbers may be used in combination. The ultraviolet absorber is preferably appropriately selected in accordance with the type or combination of ultraviolet rays to be absorbed.

A silicon compound can also be added to the coating agent as a surface improvement component. For example, a general surface modifier containing a silicone compound as a main component can be used. Examples of silicone compounds include: BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by BYK Chemie Japan), TEGOLA (TEGO) Rad) 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2500, TEGO Rad 2600, TEGO Rad 2600, TEGO Rad Rad) 2700 (both trade names: manufactured by Evonic Degussa Japan), 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 (all trade names: Shin-Etsu Chemical Industry Co., Ltd.), etc.

Other resin components can also be added to the paint. Examples include thermoplastic resins and rubber. By adding thermoplastic resin and rubber as other resins, the original characteristics of the resin (mechanical physical properties, surface/interface characteristics, compatibility, etc.) can be modified.

Examples of the thermoplastic resin used in the coating agent include the following compounds.

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 ether, polyphenylene sulfide, poly lanthanum, polyether lanolin, polyether ether ketone, polyarylate (U polymer (U Polymer): Unitica (share) trade name, Vectra (Vectra): Polyplastics (share plastic trade name, etc.), polyimide (Capton) (Kapton): Toray (share) trade name, Orum (AURUM): Mitsui Chemicals (share) trade name, etc.), polyether amide imide and polyamide amide imide.

Polyamides such as Nylon 6, Nylon 6,6, Nylon 6,10, Nylon MXD6, Nylon 6,T (all trade names: manufactured by Dupond (share)).

Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene 2,6-naphthalene dicarboxylate.

Furthermore, fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride.

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

Examples of the curing process for curing the curable resin include curing processes such as ultraviolet irradiation, heating, and electron beam irradiation. In addition, when the coating film contains a solvent, it is usually preferable to heat the coating film within a range of 70°C to 200°C for a few minutes to several tens of minutes to remove the solvent remaining in the coating film and then harden it. deal with. For hardening by ultraviolet irradiation, as long as the ultraviolet (Ultraviolet, UV) lamp (such as high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, high-power metal halide lamp) is irradiated to the coating liquid for a short time (a few seconds to several In the range of ten seconds) ultraviolet rays with a wavelength of 200 nm to 400 nm are sufficient. In addition, as for the hardening by heating, for example, it may be heated at a temperature of usually 180°C to 250°C, preferably 200°C to 250°C. At this time, when an oven is used, heating may be performed for 30 minutes to 90 minutes, and when a hot plate is used, heating may be performed for 5 minutes to 30 minutes. In addition, as for hardening by electron beam irradiation, the coating liquid may be irradiated with a low-energy electron beam from a self-shielding low-energy electron accelerator of 300 keV or less.

The surface layer 12 is formed by integrating a part of the base film 11 with the curable resin composition. That is, the curable resin composition is contained on the second surface side of the base film. Since the concentration of the curable resin composition gradually decreases toward the inside of the base film 11, the boundary between the portion of the base film 11 that is mixed with the curable resin composition and the portion that is not mixed becomes unclear. Therefore, as an example, regarding the coating amount of the coating agent on the surface layer 12, the curable resin composition (active ingredient) is preferably 0.5 g/m ² to 20 g/m ² , and more preferably 1.0 g/m ² ~10 g/m ² .

The surface layer 12 is formed by applying a curable resin composition containing a fluorine compound and a curable resin, contains a fluorine compound, and further contains a curable resin. Fluorine compounds have the property of easily gathering at the interface between air and solid in a hydrophobic environment (for example, in air). It is considered that the reason is that the fluorine compound containing a fluorine group has higher hydrophobicity than the resin, and therefore is attracted to the air side. Therefore, during the coating process, the fluorine compound accumulates near the surface of the surface layer 12, and the concentration of the fluorine compound is biased toward the surface side. As a result, an inclined structure of the fluorine compound concentration is formed near the surface of the surface layer 12. In addition, since the fluorine compound has excellent characteristics as an antifouling material, the antifouling property of the surface of the surface layer 12 can be improved.

<Fluorine compound> The fluorine compound contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers.

(Fluorosilsesquioxane) Silsesquioxane is a general term for polysiloxanes represented by [(R-SiO _1.5 )n] (R is an arbitrary substituent). The structure of the silsesquioxane corresponds to its Si-O-Si framework and is generally classified into a random structure, a ladder structure, and a cage structure. Furthermore, cage structures are classified into T8 type, T10 type, T12 type, etc. according to the amount of Si contained. The fluorine silsesquioxane used in the protective film of the present invention may be any silsesquioxane having fluorine atoms and having a property of easily accumulating at the interface between air and solid in a hydrophobic environment (for example, in air). As long as it is fluorosilsesquioxane accumulated at the interface, the effect of the present invention can be sufficiently exhibited. With such excellent surface aggregation characteristics of fluorosilsesquioxane, the surface of the surface layer 12 can be modified in a small amount and efficiently.

Among them, as an example, particularly preferred is fluorosilsesquioxane having a molecular structure represented by the following formula (I).

[Chemical 3]

That is, among the random structure, the trapezoidal structure, and the cage structure as the structure of sesquisiloxane, the cage structure is particularly preferable. If the cage-type structure of fluorosilsesquioxane is used, the rate of aggregation at the interface can be higher than those of other structures. Considering the ease of acquisition, any one of the T8 type, T10 type, and T12 type is preferable. The substituent (R) in the formula [(R-SiO _1.5 )n] is preferably a fluoroalkyl group (R _f ). Considering the solubility in the solvent, the carbon number of R _f is preferably 1-8. R _f may be a linear group or a branched group. Specifically, linear groups can be exemplified by: -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 , the branched group can be exemplified: -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 , -CH ₂ CH ₂ C(CF ₃ ) ₂ CF ₃ etc. Furthermore, R _f may be different groups, or all may be the same group.

In the above formula (I), exemplified is a fluorosilsesquioxane having "3-(methacryloxy)propyl" on one Si, but it is not limited to this functional group. For example, when the position of "3-(methacryloyloxy)propyl" is Z, the position can be substituted with another functional group. Specifically, Z can be set to any of the following groups: hydrogen, hydroxyl, alkenyl, or halogen (chlorine, bromine, iodine), alkoxy, phenoxy, polyalkyleneoxy, -COOH, 2- Oxapropane-1,3-diacyl, alkoxycarbonyl, alkenyloxycarbonyl, oxetanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanyl, -NH-, -NH ₂ , -CN, -NCO, alkenyl, cycloalkenyl, acryloyloxy, methacryloyloxy, carbamate acryloyl, carbamate methacrylic Acyl, -SH and -PH ₂ . Furthermore, Z can also be set as the group mentioned as the specific example of the said Z which interposes an alkylene group. The alkylene group bonded to Si is not particularly limited, and it is preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 3 carbon atoms. Among them, the selection range does not include a group having an alkoxy group, a group having a halogenated sulfonyl group, and a group having an α-haloester group.

(Fluorosilsesquioxane polymer) When the functional group is a polymerizable group, the fluorosilsesquioxane polymer contained in the curable resin composition can be set as a single polymer of fluorosilsesquioxane, or it can be set as a single amount with other normal Copolymers such as addition polymerizable monomers. It may also be set as a copolymer of fluorosesquioxanes having different polymerizable groups. In this case, any known method can be used for the polymerization method. In this manner, the fluorosesquioxane used in the protective film of the present invention may also be a fluorosesquioxane polymer.

That is, the fluorosilsesquioxane of the formula (I) may have an addition polymerizable functional group as Z. Or, it may have an addition polymerizable functional group as Z through the alkylene group. Examples of addition polymerizable functional groups include: terminal olefin type or internal olefin type groups having radical polymerizable functional groups; groups having cationic polymerizable functional groups such as vinyl ether and propylene ether; and vinyl carboxyl groups, The group having an anionic polymerizable functional group such as a cyanoacryloyl group preferably includes a radical polymerizable functional group.

The radical polymerizable functional group is not particularly limited as long as it is a group that undergoes radical polymerization, and includes, for example, methacryl, propenyl, allyl, styryl, and α-methylbenzene Vinyl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleate, fumarate, N-substituted maleimide, etc. Among them, a group having a (meth)acrylic group or a styryl group is preferred. Here, the (meth)acrylic group is a general term for an acrylic group and a methacrylic group, and refers to an acrylic group and/or a methacrylic group. The following is the same.

Examples of the radical polymerizable functional group having a (meth)acrylic group include groups represented by the following formula (II). In formula (II), Y ¹ represents a C2-C10 alkylene group, preferably a C2-C6 alkylene group, and more preferably a C-propylene group. In addition, X represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and preferably represents hydrogen or methyl.

In addition, examples of the radical polymerizable functional group having a styrene group include a group represented by the following formula (III). In formula (III), Y ² represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond or an ethyl group. In addition, the vinyl group is bonded to any carbon of the benzene ring, and is preferably bonded to the para-position carbon relative to Y ² .

[Chemical 4]

(Additionally polymerizable single volume) Among the addition polymerizable monomers, there are a monomer having a crosslinkable functional group and a monomer having no crosslinkable functional group. ·Additionally polymerizable monomer with crosslinkable functional group The addition polymerizable monomer having a crosslinkable functional group may be a compound having one or more addition polymerizable double bonds, and may be, for example, a vinyl compound, a vinylidene compound, or a vinylene compound Any one of the base compounds can be more specifically exemplified by a (meth)acrylic compound or a styrene compound.

Examples of the (meth)acrylic compound include (meth)acrylic acid amide, (meth)acrylonitrile and the like in addition to (meth)acrylic acid and (meth)acrylic acid ester.

As an example of the (meth)acrylic compound of the said addition polymerizable monomer, there is a (meth)acrylate which has a crosslinkable functional group. Examples of the crosslinkable functional group include epoxy groups such as glycidyl group and epoxycyclohexyl group, oxetanyl group, isocyanate, acid anhydride, carboxyl group and hydroxyl group, etc., preferably epoxy groups such as glycidyl group or Oxetanyl. The specific examples of the (meth)acrylate having a crosslinkable functional group include: (meth)acrylic acid; (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester Hydroxyalkyl (meth)acrylate; glycidyl (meth)acrylate and other epoxy-containing (meth)acrylate; (meth)acrylic acid-3,4-epoxycyclohexyl methyl ester and other (Meth)acrylates of alicyclic epoxy groups; (meth)acrylates containing oxetanyl groups such as 3-ethyl-3-(meth)acryloxymethyloxetane ; 2-(meth)acryl oxyethyl isocyanate; γ-(methacryl oxypropyl) trimethoxysilane; (meth)acrylic acid 2-aminoethyl, (meth)acrylic acid -2-(2-bromopropionyloxy) ethyl ester, (meth)acrylic acid-2-(2-bromoisobutyl acetyloxy) ethyl ester; 1-(meth)acrylic acetyloxy-2-benzene Yl-2-(2,2,6,6-tetramethyl-1-piperidinyloxy)ethane, 1-(4-((4-(methyl)propenyloxy)ethoxyethyl )Phenylethoxy)piperidine, (meth)acrylic acid-1,2,2,6,6-pentamethyl-4-piperidinyl ester, (meth)acrylic acid-2,2,6,6- Pentamethyl-4-piperidinyl ester, etc.

Examples of the styrene compound having one addition polymerizable double bond include a styrene compound having a crosslinkable functional group. Specific examples of the crosslinkable functional group include epoxy groups such as glycidyl group, oxetanyl group, halogen group, amine group, isocyanate, acid anhydride, carboxyl group, hydroxyl group, thiol, silaneoxy group and the like. Examples of the styrene compound having a crosslinkable functional group include: o-amino styrene, p-styrene chlorosulfonic acid, styrene sulfonic acid and its salts, vinyl phenyl methyl dithiocarbamate ( vinyl phenyl methyl dithiocarbamate), 2-(2-bromopropionyloxy) styrene, 2-(2-bromoisobutylamide) styrene, 1-(2-((4-vinylphenyl)methyl Oxy)-1-phenylethoxy)-2,2,6,6-tetramethylpiperidine or a compound represented by the following formula.

[Chem 5]

In addition to the addition polymerizable monomers, the addition polymerizable monomers may be used in combination as needed in order to control compatibility with the curable resin, leveling properties, the amount of crosslinkable functional groups in the copolymer, and the like. Addition polymerizable single volume other than volume.

·Additionally polymerizable monomers without crosslinkable functional groups Examples of the addition polymerizable singular body having no crosslinkable functional group include: (meth)acrylic compounds having one addition polymerizable double bond and no crosslinkable functional group, and one addition polymerizable double A styrene compound that does not have a crosslinkable functional group. Specific examples of the (meth)acrylic compound include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth ) Butyl acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, N-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (meth) ) Alkyl (meth)acrylate such as dodecyl acrylate, stearyl (meth)acrylate; aryl (meth)acrylate such as phenyl (meth)acrylate, toluene (meth)acrylate ; (Meth)acrylic acid benzyl ester and other (meth)acrylic acid aryl alkyl ester; (meth)acrylic acid-2-methoxyethyl ester, (meth)acrylic acid-3-methoxypropyl ester, (meth Group) alkoxyalkyl (meth)acrylate such as 3-methoxybutyl acrylate; ethylene oxide adducts of (meth)acrylic acid and the like.

The specific example of the (meth)acrylic compound having one addition polymerizable double bond and having no crosslinkable functional group further includes: (meth)acrylic acid trifluoromethyl methyl ester, (meth)acrylic acid- 2-trifluoromethyl ethyl ester, (meth)acrylic acid-2-perfluoroethyl ethyl ester, (meth)acrylic acid-2-perfluoroethyl-2-perfluorobutyl ethyl ester, (meth) Perfluoroethyl acrylate, trifluoromethyl (meth)acrylate, (meth)acrylic acid-diperfluoromethyl methyl ester, (meth)acrylic acid-2-perfluoromethyl-2-perfluoroethyl ethyl Esters, 2-perfluorohexyl ethyl (meth)acrylate, 2-perfluorodecyl ethyl (meth)acrylate, 2-perfluorohexadecyl ethyl (meth)acrylate, etc. Group) fluoroalkyl acrylate, etc.

Furthermore, examples of the (meth)acrylic compound having one addition polymerizable double bond and having no crosslinkable functional group include a (meth)acrylic compound having a silsesquioxane skeleton. The specific example of the (meth)acrylic compound having a silsesquioxane skeleton includes: 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^{3, 9.1 5,15.1 7,13} ) octasiloxan-1-yl)propyl (meth)acrylate, 3-(3,5,7,9,11,13,15-heptaisobutyric acid yl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] silicon eight oxo-l-yl) propyl (meth) acrylate, 3- (3,5,7,9, 11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^{3,9.1 , 15.1 7,13} ]octasiloxan-1-yl)propyl (meth)acrylate, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9.1 .1 ^5,15 .1 ^7,13 ]octasiloxan-1-yl)propyl (Meth)acrylate, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^{3,9.1 , 15.1 7,13} ]octasiloxane Alkan-1-yl)propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^{3,9.1 .5,15} .1 ^7,13 ) octasiloxan-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11,13,15- Heptaisobutyl pentacyclo[9.5.1.1 ^{3,9.1 , 15} .1 ^7,13 ]octasiloxan-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-yl Oxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1 ^3,9 . 1 ^5,15 .1 ^7,13 ]octasiloxan-1-yloxy)dimethylsilyl]propyl (meth)acrylate, 3-[(3,5,7,9,11, 13,15- seven phenyl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] silicon eight oxo-1-yloxy) dimethyl silicon alkyl] propyl (meth) Acrylic esters, etc. Specific examples of the styrene compound having one addition polymerizable double bond and having no crosslinkable functional group include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, and the like.

Examples of the styrene compound having one addition polymerizable double bond and having no crosslinkable functional group further include styrene compounds containing silsesquioxane. The styrene derivative containing silsesquioxane contains: 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^{3 ,9.1} .1 ^15,15 .1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutyl pentacyclo[ 9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] Octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctane yl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] siloxane eight silicon, 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- seven phenyl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] and the like having eight silicon alumoxane eight silicon alumoxane is 4-vinylphenyl (T8 type sesqui Siloxane); and 3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^{3,9.1 .15,1 7,13} ]octasiloxane -1-yl) ethyl styrene, 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) ethyl styrene, 3-(3,5,7,9,11,13,15-heptaisooctyl pentacyclic [9.5.1.1 3,9.1 ^{.5 5,15} .1 ^7,13 ) octasiloxan-1-yl) ethyl styrene, 3-(3,5,7,9,11,13,15-heptacyclopentyl pentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxan-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5. 1.13,9.15,15.17,13]octasiloxan-1-yl)ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1 ^{3 ,9.1} .1 ^15,15 .1 ^7,13 ]octasiloxane-1-oxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9,11,13, 15 seven-isobutyl-pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] silicon eight oxo-1-yloxy) dimethyl silicon alkyl) ethylstyrene, 3- ( (3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-oxy) di Methylsilyl) ethyl styrene, 3-((3,5,7,9,11,13,15 - seven cyclopentyl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] Silicon eight oxo-1-yloxy) dimethyl silicon alkyl) styrene and ethyl 3 - (( 3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-oxy)dimethyl Silane) ethyl styrene and the like, octasiloxane T8 type silsesquioxane with 4-vinylphenylethyl) etc.

Furthermore, addition polymerizable singular bodies other than the addition polymerizable singular body can also be exemplified by having: styrene, (meth)acrylate, silicone and alkylene oxide, such as ethylene oxide, The main chain derived from propylene oxide, etc., and has a polymerized double bond of giant single body.

Examples of the addition-polymerizable unit mass also include compounds having two addition-polymerizable double bonds. Examples of compounds having two addition polymerizable double bonds include: 1,3-butanediol=di(meth)acrylate, 1,4-butanediol=di(meth)acrylate, 1, 6-Hexanediol=di(meth)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, hydroxytrimethylacetate neopentyl glycol = di(meth)acrylate, trimethylol Propane = di(meth)acrylate, bis[(meth)acryloyloxyethoxy]bisphenol A, bis[(meth)acryloyloxyethoxy]tetrabromobisphenol A, bis [(Meth)acryloyloxypolyethoxy]bisphenol A, 1,3-bis(hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol=di (Meth) acrylate, hydroxy trimethyl acetate dipentyl methacrylate, di (meth) acrylate and bis [(meth) acrylic propyl propyl] tetramethyl disilaxane and other two (Meth)acrylic ester-based monolithic body, divinylbenzene. Furthermore, it can also be exemplified: having a main chain derived from styrene, (meth)acrylate, silicone and alkylene oxide, such as ethylene oxide, propylene oxide, etc., and having two polymerizable double bonds Giant single volume.

Examples of the addition-polymerizable unit mass also include compounds having three or more addition-polymerizable double bonds. Examples of compounds having three or more addition polymerizable double bonds include: trimethylolpropane=tri(meth)acrylate, pentaerythritol=tri(meth)acrylate, pentaerythritol=tetra(meth)acrylic acid Ester, dipentaerythritol = monohydroxypenta (meth) acrylate, tri (2-hydroxyethyl isocyanate) = tri (meth) acrylate, tri (diethylene glycol) trimellitate = tri (methyl ) Acrylate, 3,7,14-tris[((((meth)acryloxypropyl)dimethylsiloxy))-1,3,5,7,9,11,14-hepta Tricyclo[7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-tris[(((meth)acryloxypropyl)dimethylsiloxy)]-1,3, 5,7,9,11,14-heptaisobutyl tricyclo[7.3.3.1 ^5,11 ]heptasiloxane, 3,7,14-tri[((((meth)acryloxypropyl)) Dimethylsiloxy))-1,3,5,7,9,11,14-heptaisooctyl tricyclo[7.3.3.1 ^5,11 ]heptasiloxane, 3,7,14-tris[ (((Meth)acryloxypropyl) dimethylsiloxy))-1,3,5,7,9,11,14-heptacyclopentyl tricyclo[7.3.3.1 ^5,11 ] Heptasiloxane, 3,7,14-tris[((((meth)acryloxypropyl)dimethylsiloxy))-1,3,5,7,9,11,14-seven Phenyltricyclo[7.3.3.1 ^5,11 ] heptasiloxane, octa(3-(meth)acryloxypropyl dimethylsiloxy) octasesquisiloxane and octa(3-( Methyl) propylene acetyloxypropyl) sesquisiloxane. Furthermore, it can be exemplified by having a main chain derived from styrene, (meth)acrylate, silicone and alkylene oxide, such as ethylene oxide, propylene oxide, etc., and having three or more polymerizable bis A huge single volume of keys.

The addition polymerizable monomer is preferably a (meth)acrylic compound, more preferably a (meth)acrylic acid ester, and further preferably a lower alkyl (eg, carbon number 1-3) ester of (meth)acrylic acid or having Crosslinkable functional group esters, etc.

The fluorosilsesquioxane polymer is an addition polymer of fluorosilsesquioxane or an addition copolymer with other addition polymerizable monomers. In the case of a copolymer, it may be block copolymerization The iso-sequential copolymer may also be a random copolymer, preferably a random copolymer. In addition, the polymer may have a cross-linked structure or a graft copolymer.

[Adhesive layer 13/Release film 14] As shown in FIG. 2, the adhesive layer 13 is formed by applying an adhesive on the side opposite to the surface layer of the base film 11 that has been subjected to antifouling treatment (or antifouling treatment) by the surface layer 12. The adhesive layer may be formed directly on the surface of the base film 11, or may be laminated between the base film 11 and other layers. As another layer, for example, as shown in FIG. 1, the impact resistance-imparting layer 15 can be cited.

<Adhesive> The adhesive used for the adhesive layer 13 is not limited as long as it does not hinder the effects of the present invention, and acrylic adhesives, rubber adhesives, urethane adhesives, silicone adhesives, and the like can be used. These adhesives can be used alone or in combination. The adhesive can be synthesized by a known method or a commercially available product. From the aspect of product design, in applications requiring long-term durability, an acrylic adhesive excellent in heat resistance and weather resistance is preferred. In the adhesive layer 13 of the present invention, the surface of the adhesive is provided with irregularities in terms of the adhesive properties of the article to be adhered.

·Acrylic adhesive Examples of the acrylic adhesive include acrylic adhesives containing an acrylic copolymer obtained by copolymerizing a monomer component having a functional group such as a carboxyl group or a hydroxyl group with a monomer component mainly composed of an acrylate . Examples of acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( Isobutyl meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, (meth)acrylic acid Hexyl ester, 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, (meth) Dodecyl acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate , Heptadecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, (meth)acrylic acid Isobornyl ester, 1-adamantyl (meth)acrylate, etc. One or more of these (meth)acrylic acid alkyl esters can be used.

The following monomer components can be copolymerized with the alkyl (meth)acrylate. Examples of copolymerizable monomer components include itaconic acid, maleic acid, crotonic acid, methacrylic acid, fumaric acid, (meth)acrylic acid, carboxyethyl (meth)acrylate, (meth)acrylic acid Carboxyl-containing monomers such as carboxypentyl ester; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- (meth)acrylic acid Hydroxyhexyl, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl) methacrylate Monomers containing hydroxyl groups; glycidyl group-containing monomers such as glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile ; (Meth)acrylic acid-N,N-dimethylaminoethyl, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl(meth)acrylic Acetamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, (meth)acrylamide Morpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N -Vinyl-1,3-dioxazin-2-one, N-vinyl-3,5-morpholinedione, N-cyclohexylmaleimide, N-phenylmaleimide, Nitrogen-containing monomers such as N-propenylpyrrolidine and tert-butylaminoethyl (meth)acrylate; monomers such as styrene or styrene derivatives, vinyl acetate, etc. One or more of these monomers may be copolymerized with (meth)acrylate as needed, and used.

The adhesive used in the present invention preferably contains, for example, at least one selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate, and one selected from the group consisting of acrylic acid and methacrylic acid At least one carboxyl group-containing monomer. In order to improve heat resistance and weather resistance, the adhesive used in the present invention is, for example, by adding hard components such as methyl acrylate and vinyl acetate to increase the glass transition temperature (Tg). Examples of such hard components for adjusting the glass transition temperature include methyl acrylate, vinyl acetate, methyl methacrylate, and acrylonitrile. Furthermore, in order to further improve various physical properties such as weather resistance, an ultraviolet absorber, a light stabilizer, etc. may be added as necessary. The proportion of the hard component relative to the total amount of the adhesive is 10% by weight to 80% by weight, preferably 20% by weight to 70% by weight, and more preferably 30% by weight to 60% by weight.

The weight average molecular weight (Mw) of the acrylic copolymer is 50,000 to 2 million, preferably 100,000 to 1.5 million, and more preferably 150,000 to 1 million. The number average molecular weight (Mn) is 10,000 to 500,000, preferably 10,000 to 400,000, and more preferably 10,000 to 300,000. The dispersion value is 1-20, preferably 1-15, and more preferably 2-10. The glass transition temperature is -70°C to 0°C, preferably -40°C to 0°C, more preferably -30°C to 0°C, and particularly preferably -20°C to 0°C.

Examples of rubber-based adhesives include natural rubber, grafted natural rubber, polyisoprene, polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene, and styrene. -Butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene butene-styrene block copolymer, styrene-ethylene propylene-styrene block copolymer Segment copolymer.

Examples of the urethane-based adhesive include a polyurethane-based adhesive obtained by condensing a compound having an isocyanate group and a hydroxyl group with each other. Examples of compounds having isocyanate groups (isocyanates) include: Tolylene Diisocyanate (TDI), diphenyl Methane Diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), naphthalene diisocyanate Isocyanate (Naphthalene Diisocyanate, NDI), etc. Examples of the compound (polyol) having a hydroxyl group include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol, and polyethylene Butanediol azelate, polycaprolactone diol, etc.

Silicone-based adhesives can also be used in either peroxide-hardening type or addition molding type.

When the composition to be the adhesive layer 13 is applied to the release film 14 or the base film 11, the gravure coating method, bar coating method, spray coating method, spin coating method, roll coating method, The die coating method, knife coating method, air knife coating method, hot melt coating method, curtain coating method, etc. are performed. In terms of adhesion after attachment, the thickness of the adhesive layer 13 is 10 μm to 100 μm, preferably 15 μm to 50 μm, and more preferably 25 μm to 45 μm.

For the adhesive layer 13, the surface roughness is physically formed by transferring the roughness by attaching the peeling film 14 formed with roughness. The surface roughness of the adhesive layer 13 with good adhesion characteristics is an arithmetic average roughness R(a)=300 nm to 800 nm, preferably 350 nm to 750 nm, and more preferably 400 nm to 700 nm.

For the peeling film 14, for example, a plastic film such as a polyester-based resin or a polyolefin-based resin, cellophane, and translucent paper (glassine paper), etc., that have undergone caulking treatment can be used. Furthermore, it can be used for polyethylene terephthalate, polyethylene, polypropylene coated with a stripping agent such as fluorine-based resin, silicone-based resin, long-chain alkyl group-containing urethane on one or both sides Resin film, etc. The release film can be synthesized by a known method or a commercially available product. The thickness of the release film varies slightly depending on the material used, but it is usually 10 μm to 250 μm, preferably 20 μm to 200 μm.

The surface irregularities formed on the peeling film 14 are arithmetic mean roughness R(a)=350 nm to 850 nm, preferably 400 nm to 800 nm, and more preferably 450 nm to 750 nm. A well-known method can be used for the method of forming irregularities. Furthermore, the arithmetic average roughness R(a) means that only the reference length (lowercase L in the following formula) is extracted from the roughness curve in the direction of its average line, and the average line from the extracted part to The absolute values of the deviations of the measurement curves are added up and averaged. The effect of a damage on the measured value becomes very small and stable results can be obtained, so it is better.

[Number 1]

The adhesive layer of the present invention can maintain unevenness during a short period of time (10 minutes to 120 minutes immediately after peeling, preferably 20 minutes to 90 minutes, particularly preferably 30 minutes to 60 minutes) after peeling from the peeling film After the shape and size, after it starts to be attached to the adherend to be the object, the shape is easily disappeared with the assistance of the applied pressure, and follows the adherend and adheres uniformly. Another feature of this attachment is that when a peeling film that does not have the surface roughness as described above is used, the uneven shape is prematurely damaged and loses uniformity when attached to the adherend, which also prevents the removal of bubbles and blisters Sex. For the protective film having the adhesive layer of the present invention, at the time of bonding, the concave part of the adhesive layer of the adjacent unattached part is used for rapid defoaming (the bubble is removed and the adhered body is adhered to the adherend body) . In addition, in the case of using this type of attachment method, even if the bubble is gradually extended for long-term use after the attachment is completed, it will rarely occur, and it will not cause the actual use of the protective film between the adherend and the adhesive layer The local physical defects caused by bubbles or the chemical defects containing air (oxygen) are extended, and the initial mechanical properties (crumb resistance, impact resistance), initial heat resistance, initial weather resistance are basically maintained when used for a long time. Properties, and further initial peelability (no paste residue), a novel and epoch-making protective film was discovered.

[Protection film] The protective film of the present invention has high water repellency and antifouling properties by the surface layer, and has high adhesion properties to articles such as floor boards by the adhesive layer. In addition, by applying unevenness to the base film, the reflectance can be suppressed, the reflection of light can be suppressed, and the matting feeling can be provided. Furthermore, the curable resin penetrates into the interior of the thermoplastic polyurethane to form a surface layer integrated with a part of the base film. Therefore, the elongation at break is high, and even if the surface of the article to be adhered has a complicated shape such as a curved surface, it can be easily attached. In addition, it has excellent impact resistance. Furthermore, by having an impact resistance-imparting layer, it has excellent workability. Furthermore, by controlling the surface roughness of the adhesive surface, the adhesion characteristics to the adherend (water and air defoaming) are significantly improved. Furthermore, since the adhesive layer is excellent in heat resistance and weather resistance, no paste remains after peeling. [Laminate for protective film] The laminate for a protective film of the present invention protects the adhesive surface of the adhesive layer until it is attached to the adherend by the release film with high releasability, and therefore can be circulated and transported without deteriorating the adhesiveness.

[Surface protection article] The surface protection article of the second embodiment of the present invention will be described. As described above, the protective film of the present invention has excellent antifouling properties, impact resistance, antiglare properties, and adhesive properties. Therefore, by attaching it to various adherends (articles) that require coating surface protection, it does not damage the articles. Design and protect items. The adherend (article) to which the protective film of the present invention is attached is not limited, and examples thereof include building materials, buildings (internal materials such as floor surfaces, wall surfaces, and patios, etc.), and displays. The adherend (article) to which the protective film of the present invention is attached is preferably a floor material.

[Manufacturing method of protective film] The method for manufacturing the protective film of the second embodiment of the present invention will be described. The manufacturing method of the protective film of the present invention includes the steps of: providing a base film formed of a resin containing thermoplastic polyurethane; forming an adhesive layer; and the opposite side of the base film from the first surface The step of applying the curable resin composition on the second surface to allow the curable resin composition to penetrate the substrate film; and the step of irradiating the active energy ray or heating the curable resin composition. The curable resin composition contains At least one fluorine compound in the group consisting of free fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin, and further comprising forming impact resistance on the first surface side of the base film The step of imparting a property to the layer, or the step of making the gloss value of the second surface side of the base film less than 20. Each step of the method for producing a protective film of the present invention can be performed based on a well-known method and the method described in this specification, except that the protective film has the above-mentioned specific configuration. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these. The characteristic evaluation results of the protective film are shown below.

[Production Example 1: Synthesis of Polymer A-1] To a nitrogen-sealed four-necked round-bottom flask equipped with a refluxer and a dropping funnel, add compound A (25 g), Silaplane FM0721 (6.25 g, manufactured by JNC), methacrylic acid 2-Hydroxyethyl ester (18.75 g), methyl methacrylate (12.5 g), and methyl ethyl ketone (61.97 g) were refluxed and degassed using an oil bath for 15 minutes, and then put in azobisisobutyronitrile (0.477 g), a solution of thioglycolic acid (0.054 g) dissolved in methyl ethyl ketone (4.78 g) to start polymerization. Three hours after the start of polymerization, azobisisobutyronitrile (0.477 g) was dissolved in methyl ethyl ketone (4.29 g) and added, and a solution of the copolymer obtained by aging for 5 hours was obtained. Furthermore, after p-methoxyphenol (0.16 g) as a polymerization inhibitor and dibutyltin dilaurate (0.154 g, manufactured by Showa Denko Co., Ltd.) were dissolved in methyl ethyl ketone (1.54 g) and added, Using a dropping funnel, Karenz AOI (26.43 g) was added dropwise in such a way that the liquid temperature changed from 35°C to 50°C, and after dripping, it was aged at 45°C for 3 hours. After adding methanol (9 g) for treatment, p-methoxyphenol (0.16 g) was further added and diluted with methyl isobutyl ketone (107.34 g) to obtain 30 of the target polymer A-1. Weight% solution. The obtained polymer A-1 had a weight average molecular weight: Mw 42,000 and a polydispersity index: Mw/Mn1.9. The weight average molecular weight and polydispersity index are gel permeation chromatography (Gel Permeation Chromatography, GPC, model: Alliance 2695, manufactured by Waters), column: Shodex GPC KF-804L×2 Root (in series), protective column: KF-G) determination.

Compound A has a molecular structure represented by the following formula (IV).

[化6]

[Production Example 2: Preparation of Coating Agent A] Polymer A-1 (2.22 g), pentaerythritol triacrylate (57.46 g), 1,6-hexanediol diacrylate (3.19 g), acrylic urethane with acrylic carbamate functionality Ester oligomer (6.02 g), α-hydroxyacetophenone photopolymerization initiator (3.19 g), methyl isobutyl ketone (97.91 g), ethyl acetate (56.67 g) were added to 0.5 L scale (Scale) stainless steel bottles were stirred with a stirring blade for 1 hour to obtain a coating agent A having a solid component (active component) of 30% by weight.

[Production Example 3: Preparation of Adhesive A] It contains 40 to 55 parts by weight of butyl acrylate, 40 to 55 parts by weight of methyl acrylate, 1 to 15 parts by weight of vinyl acetate, and 0.1 to 3 parts by weight of carboxyl group-containing To the acrylic adhesive A of the acrylate copolymer, 30 parts by weight of ethyl acetate was added, and the mixture was stirred at 23° C. for 30 minutes using a stirring blade to adjust the solid content to 23% by weight and the viscosity to 1000 CPS. The weight average molecular weight (Mw) of Adhesive A is 550,000, and the glass transition temperature is -16°C.

[Production Example 4: Preparation of thermoplastic polyurethane film A] As a raw material for thermoplastic polyurethane films, ESTAN (ALB CL87A-V, manufactured by Lubrizol Corporation, MI: 5.0 g/10 min) was used, and extruded using small biaxial mixing The device (made by TECHNOVEL, KZW15TW) is processed into a film. The device consists of an extruder, a supply section and a die. The extruder is equipped with L/D45 screw. The mold has an adjustable opening with a width of 150 mm and a flange clearance of 0.1 mm to 1.0 mm. The temperature of the extruder head was set at 200°C. Water was used at the exit of the mold, and the film was taken up onto a mirror-finished 20°C metal cooling roll. At this time, a protective peeling film made of polyethylene terephthalate was sandwiched on the opposite side, and the embossed rubber roller was pressed to form a single-sided wrinkled sheet (surface roughness of 1 μm) (Figure 3). Thereafter, a thermoplastic polyurethane film A with a thickness of 100 μm or a thickness of 200 μm was obtained by cooling to 20°C.

[Production Example 5: Preparation of thermoplastic polyurethane film B] As a raw material for thermoplastic polyurethane films, ESTAN (ALB CL87A-V, manufactured by Lubrizol Corporation, MI: 5.0 g/10 min) was used, and extruded using small biaxial mixing The device (made by TECHNOVEL, KZW15TW) is processed into a film. The device consists of an extruder, a supply section and a die. The extruder is equipped with L/D45 screw. The mold has an adjustable opening with a width of 150 mm and a flange clearance of 0.1 mm to 1.0 mm. The temperature of the extruder head was set at 200°C. Water was used at the exit of the mold, and the film was taken up onto a mirror-finished 20°C metal cooling roll. At this time, the protective peeling film made of polyethylene terephthalate was sandwiched on the opposite surface, and the rubber roller subjected to surface polishing was pressed to form a sheet with a smooth surface. Thereafter, by cooling to 20° C., a thermoplastic polyurethane film B with a thickness of 100 μm was obtained.

[Production Example 6: PET laminate thermoplastic polyurethane A] The protective release film made of polyethylene terephthalate of the thermoplastic polyurethane film A (thickness 100 μm) substrate obtained in Production Example 4 was peeled, and the polyurethane was peeled off on the side of the peeled surface Resin-based adhesive (manufactured by Aica Kogyo; mixed with main agent (5 g), hardener (0.50 g), ethyl acetate (5 g)) using coating rod No. 6 (RDS Webers (Manufactured by RDS Webster) is applied to the surface and dried at 80°C for 2 minutes. Thereafter, a 100 μm PET film (PET manufactured by Toyobo; A4300) was pressure-bonded using a rubber roller and cured at 40° C. for 3 days to obtain a PET laminate thermoplastic polyurethane A.

[Production Example 7: PET laminate thermoplastic polyurethane B] The protective release film made of polyethylene terephthalate of the thermoplastic polyurethane film B substrate obtained in Production Example 5 was peeled off, and the urethane resin-based adhesive ( Manufactured by Aica Kogyo; prepared by mixing main agent (5 g), hardener (0.50 g), ethyl acetate (5 g)) using coating rod No. 6 (RDS Webster) Co., Ltd.) coated on the surface and dried at 80°C for 2 minutes. Thereafter, a 100 μm PET film (PET manufactured by Toyobo; A4300) was pressure-bonded using a rubber roller and cured at 40° C. for 3 days to obtain a PET laminate thermoplastic polyurethane B.

[Production Example 8: PET laminate thermoplastic polyurethane C] The protective release film made of polyethylene terephthalate of the thermoplastic polyurethane film A (thickness 100 μm) substrate obtained in Production Example 4 was peeled, and the polyurethane was peeled off on the side of the peeled surface Resin-based adhesive (manufactured by Aica Kogyo; mixed with main agent (5 g), hardener (0.50 g), ethyl acetate (5 g)) using coating rod No. 6 (RDS Webers (Manufactured by RDS Webster) is applied to the surface and dried at 80°C for 2 minutes. Thereafter, a 50 μm PET film (PET manufactured by Toray; lumirror) was pressure-bonded using a rubber roller, and cured at 40° C. for 3 days to obtain a PET laminate thermoplastic polyurethane C.

[Production Example 9: PET laminate vinyl chloride resin substrate A] A urethane resin-based adhesive (Aica Kogyo) was applied to a pleated sheet made of translucent vinyl chloride (trade name: EA911AG, manufactured by Esko Corporation, thickness 300 μm) ) Manufacture; using the main agent (5 g), hardener (0.50 g), ethyl acetate (5 g) mixed preparation) using the coating rod No. 6 (manufactured by RDS Webster) applied to The surface was dried at 80°C for 2 minutes. Thereafter, a 100 μm PET film (PET manufactured by Toyobo; A4300) was pressure-bonded using a rubber roller and cured at 40° C. for 3 days to obtain PET vinyl chloride resin substrate A.

[Example 1A: Preparation of laminate 1A] On the opposite side of the pleated surface of the prepared PET laminate thermoplastic polyurethane film A, the prepared preparation was applied by die coating Adhesive A was dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light quantity: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 1A.

[Example 2A: Preparation of laminate 2A] On the prepared PET laminate thermoplastic polyurethane film B, the prepared adhesive A was applied by die coating at 70°C for 3 minutes Dry under conditions to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent No. 6 (manufactured by RDS Webster) was used to apply the coating agent A on the surface opposite to the surface on which the adhesive was applied, under the condition of 90° C.×3 minutes To dry. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 2A.

[Example 3A: Preparation of laminate 3A] On the surface opposite to the wrinkled surface of the prepared PET laminate thermoplastic polyurethane film C, the prepared preparation was applied by die coating Adhesive A was dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 3A.

[Comparative Example 1A: Preparation of laminate 4A] On the opposite side of the pleated surface of the prepared PET laminate thermoplastic polyurethane film A, the prepared preparation was applied by die coating Adhesive A was dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. After that, using the coating rod No. 6 (manufactured by RDS Webster) on the creped surface, apply 30% by weight of solid content (active ingredient) adjusted with ethyl acetate as a dilution solvent Phlucid 300C (ultraviolet-curable acrylic resin paint; manufactured by China Paint), dried at 90°C for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 4A.

[Comparative Example 2A: Preparation of laminate 5A] The prepared thermoplastic polyurethane film A was peeled off with a protective release film made of polyethylene terephthalate and applied by die coating on the peeled surface side. The prepared adhesive A was applied and dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 5A.

[Comparative Example 3A: Preparation of laminate 6A] On the surface opposite to the wrinkled surface of the PET laminate vinyl chloride resin substrate A prepared in Production Example 9, the preparation was applied by die coating. The adhesive A was dried at 70℃×3 minutes to form a 38 μm adhesive layer. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light quantity: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 6A.

[Comparative Example 4A: Preparation of laminate 7A] A translucent polyethylene terephthalate sheet (trade name: PET U4 manufactured by Teijin Co., Ltd., thickness 200 μm) was prepared by die coating. The adhesive A was dried at 70℃×3 minutes to form a 38 μm adhesive layer. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent No. 6 (manufactured by RDS Webster) was used to apply the coating agent A on the surface opposite to the surface on which the adhesive was applied, under the condition of 90° C.×3 minutes To dry. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 7 A.

[Comparative Example 5A] The residential floor used for evaluation purposes was set to Comparative Example 5A.

[Table 1] Table 1

[experiment method] (1) Oil resistance (marking ink resistance) Use a black oily marker (manufactured by Sharpie) to describe the surface layer of the laminate, evaluate the rejection of oily ink, and use Dusper K-3 (manufactured by Otsu Industries (Co., Ltd.)) )'S erasability. Set those without wiping residue to ○, and those with wiping residue to ×. (2) Alkali resistance & acid resistance (I) Evaluation of acid resistance Place the absorbent cotton fully impregnated with 10% citric acid aqueous solution on the surface layer of the laminate, cover with a watch glass, and leave it for 18 hours. After 18 hours, the surface state after wiping the surface with absorbent cotton was observed and compared with the untreated person. A person with no deterioration on the surface is set to ○, and a person with deterioration is set to ×. (Ii) Evaluation of alkali resistance On the surface layer of the laminate, absorbent cotton sufficiently saturated with a 5% sodium hypochlorite solution (trade name: Haiter (registered trademark), manufactured by Kao Co., Ltd.) was placed, and the alkali resistance evaluation was performed in the same manner as the acid resistance evaluation. A person with no deterioration on the surface is set to ○, and a person with deterioration is set to ×.

(3) Floor As a floor for residential use used for evaluation purposes, a multilayer floor in which a plywood and a decorative veneer on which wood grain is printed on is attached to a base material is used. (4) Monkey Wrench drop indentation test Apply 1 L of water to the adhesive layer side of the protective film after peeling off the peeling film from the laminate and the floor (width 50 mm, length 150 mm, thickness 12 mm). For the adhesive layer of the laminate, use rubber. The squeegee squeezes out water on one side and sticks to the floor. Afterwards, it was left at room temperature for 18 h for a drop test. Measure the concavity when the adjustable wrench (TRUSCO made 375 mm, weight 1.27 kg) was dropped from a height of 100 cm. (Based on Japanese Industrial Standards (JIS) A 1408) The presence or absence of indentation on the surface of the floor material after peeling off the laminate was observed, and those without indentation were designated as ○, and those with indentation were designated as ×.

(5) Taber abrasion Using a method similar to the above (4), the protective film after peeling off the peeling film from the laminate was attached to the floor, and Taber abrasion was evaluated. Taber abrasion strength is measured according to JIS K 5400. Specifically, at a time point after a total rotation speed of 2000 rpm, visually evaluate whether or not the abrasion has started to reach the surface of the floor material, the person who has not caused abrasion is set to ○, and the person who has abrasion is set to x. The evaluation conditions at this time are as follows. Device: Yata Seiki Co., Ltd. (TaberABRASER) Abrasion wheel: CS-0+S-42 (coarse paper) × 2 Load: 500 g ^f Rotation speed: 60 rpm Vacuum distance: 3 mm Remarks: Every 500 Change the abrasion wheel to a new product measurement environment: 23°C 50%RH The sample used in the test uses a sample that is conditioned for 24 hours in a constant temperature and humidity machine using 23°C×50%RH. (6) Adhesive force For the protective film after peeling off the peeling film from the laminated body cut to a width of 25 mm and a length of 200 mm, use a 2 kg rubber roller at a moving speed of 5 mm/s to the SUS304 board ( 50 mm in width, 150 mm in length, and 1.2 mm in thickness. Surface grinding is finished). After storing in an environment of 23°C±2°C and 50±5%RH for 24 hours, use a tensile tester (Strograph VG, manufactured by Toyo Seiki Co., Ltd.) and load 100 N on the crosshead 1. Measure the adhesive force of the protective film attached to the coating board at a crosshead speed of 300 mm/min.

(7) Evaluation of extinction After the protective film was attached to the floor in the order described in (4) above, the glossiness (gloss value) of 60° was measured using a gloss meter (VG 2000, manufactured by Nippon Denshoku) based on JIS Z8741-1997. (8) Ease of observation of the wood grain of the floor Ten adult men and women in their 20s to 40s attached the protective films produced in the examples and comparative examples to the floor for residential use, and visually evaluated whether the appearance of the wood grain of the floor was damaged. The evaluation criteria are as follows. It is set as ○ for 7 or more adult men and women, △ for 3 to 6 persons, and × for 2 or less persons.

(9) Paste residue The protective film is attached to the floor (50 mm in width, 150 mm in length, and 1.2 mm in thickness) in the same manner as (4) above. Thereafter, after leaving it at room temperature for 1 day, it was heated in an oven set at 80°C for 24 hours, and after leaving it at room temperature for more than 1 hour, the protective film attached to the coating board was peeled off, and the coating was visually observed The status of the board. The determination is made using the following criteria. ○: No paste remains on the painted surface. △: There is a slight residue of paste on the painted surface. ×: The paste remains on the entire painted surface. (10) Stiffness When constructing the floor, the stiffness (hardness) of the membrane becomes necessary. The stiffness of the membrane greatly improves the construction workability. As an indicator of the stiffness of the film, a ring is formed, a ring stiffness tester (manufactured by Toyo Seiki Co., Ltd.) is used, the width of the sample is set to 3 mm, the effective length is set to 80 mm, and the compression speed is 3.5 mm/ Determine the collapse resistance value (stiffness value) required to squeeze the ring by 10 mm in seconds. If the rigidity value is 30 mN or more, a substantial improvement in workability is confirmed.

Regarding Comparative Example 1A in which the coating agent A of Example 1A was replaced with a coating compound containing no fluorine compound, the stain resistance (oil resistance, acid resistance, and alkali resistance) was insufficient. In addition, cracks were observed in the appearance, the matting feeling was insufficient, and the appearance of the floor surface was impaired. It is considered that this is due to insufficient penetration of the coating agent into the base film and accumulation on the base, thereby impairing the anti-glare property. Regarding Comparative Example 2A that does not use the impact resistance-imparting layer of Example 1A, impact resistance (indentation test) and stiffness are insufficient. It is believed that it is caused by the absence of an impact-resistant layer. Regarding Comparative Example 3A in which the base film of Example 1A was replaced with polyvinyl chloride, impact resistance (indentation test) was insufficient. This is considered to be caused by the poor impact resistance of the base film compared to the polyurethane resin. In addition, pollution resistance (oil resistance, acid resistance, alkali resistance) is insufficient. The reason for this is considered to be that the coating agent penetrates into the base film in a large amount, and the content ratio of the curable resin composition cannot gradually decrease from the surface of the surface layer into the base film. Regarding Comparative Example 4A in which the base material film of Example 1A was replaced with a PET sheet and no impact resistance-imparting layer was used, impact resistance (indentation test) and impact resistance (Tabel wear) were insufficient. It is considered that this is because the base film has poor impact resistance compared to the polyurethane resin and does not contain an impact resistant layer. Compared with Comparative Example 5A not containing a protective film, Example 1A is excellent in stain resistance and impact resistance, and exhibits the same appearance as the floor surface. In addition, Example 3 in which the thickness of the impact resistance-imparting layer (PET layer) was 50 μm thinner than Example 1A was excellent in contamination resistance and impact resistance as in Example 1A, and exhibited the same appearance as the floor surface. Example 2A has excellent stain resistance and impact resistance as in Example 1A, but exhibits a glossy feeling on the surface. In addition, the protective films of Example 1A, Example 2A, and Example 3A had sufficient stiffness and excellent workability. Furthermore, the adhesiveness is also excellent, and there is little paste residue.

[Example 1B: Preparation of laminate 1B] The surface of the prepared thermoplastic polyurethane film A (thickness 200 μm) on the opposite side from the wrinkled surface was coated by die coating. The prepared adhesive A was dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 1B.

[Comparative Example 1B: Preparation of laminate 2B] The surface of the thermoplastic polyurethane film A (thickness 200 μm) prepared on the opposite side from the wrinkled surface was coated by die coating. The prepared adhesive A was dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. After that, using the coating rod No. 6 (manufactured by RDS Webster) on the creped surface, apply 30% by weight of solid content (active ingredient) adjusted with ethyl acetate as a dilution solvent Phlucid 300C (ultraviolet-curable acrylic resin paint; manufactured by China Paint), dried at 90°C for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 2B.

[Comparative Example 2B: Preparation of laminate 3B] Apply the prepared adhesive A on the opposite side of the prepared thermoplastic polyurethane film A (thickness 200 μm) from the creped surface by die coating, at 70°C×3 Dry in minutes to form an adhesive layer of 38 μm. Furthermore, a 75 μm thick polyethylene terephthalate film (peeling film A, surface roughness: 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer with a rubber roller. Then, it was cured for one day in an environment of 45°C to obtain a laminate 3B.

[Comparative Example 3B: Preparation of laminate 4B] The wrinkled surface of the wrinkled processed translucent vinyl chloride sheet (trade name: EA911AG, manufactured by Esko Corporation, thickness 300 μm) is On the opposite side, the prepared adhesive A was applied by die coating, and dried at 70°C for 3 minutes to form an adhesive layer of 38 μm. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent A was applied to the wrinkled surface using the coating rod No. 6 (manufactured by RDS Webster), and dried at 90° C. for 3 minutes. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 4B.

[Comparative Example 4B: Preparation of laminate 5B] A translucent polyethylene terephthalate sheet (trade name: PET U4 manufactured by Teijin Co., Ltd., thickness 200 μm) was prepared by die coating. The adhesive A was dried at 70℃×3 minutes to form a 30 μm adhesive layer. Furthermore, using a rubber roller, a 75 μm-thick polyethylene terephthalate film (peeling film A, surface roughness 716 nm), which had been peeled off with silicone resin, was pressure-bonded to the adhesive layer at 45°C 1 day curing in the environment. Thereafter, the coating agent No. 6 (manufactured by RDS Webster) was used to apply the coating agent A on the surface opposite to the surface on which the adhesive was applied, under the condition of 90° C.×3 minutes To dry. Thereafter, a conveyor-type ultraviolet irradiation device (cumulative light amount: 850 mJ/cm ² ) equipped with an H-bulb (H-Bulb) manufactured by Fusion was used for photohardening to obtain a laminate 5B.

[Comparative Example 5B] The residential floor used for evaluation purposes is set to Comparative Example 5B.

[Table 2] Table 2

[experiment method] About (1) Oil resistance (Marking ink resistance), (2) Alkali resistance & acid resistance (i) Acid resistance evaluation, (3) Flooring, (5) Taber abrasion, (6) Adhesion, (7) Matting The evaluation of the feeling, (8) the ease of observing the wood grain of the floor, and (9) the residue of the paste were tested in the same manner as the test method described above. In addition to this, the test was conducted in the following manner.

(2) Alkali resistance & acid resistance (Ii) Evaluation of alkali resistance On the surface layer of the laminate, a cotton wool sufficiently saturated with a 10% sodium hypochlorite solution was placed, and the alkali resistance evaluation was performed in the same manner as the acid resistance evaluation.

(4) Falling ball indentation test Apply 1 L of water to the surface of the protective film after peeling off the peeling film from the adhesive layer of the laminate and the floor (width 50 mm, length 150 mm, thickness 12 mm). Use 1 L for the adhesive layer of the laminate. The rubber squeegee squeezes out water while sticking to the floor. Afterwards, it was left at room temperature for 18 h for the ball drop test. The indentation when dropping a steel ball having a weight of about 530 g and a diameter of about 51 mm from a height of 75 cm was measured. (Based on JIS A 1408) The presence or absence of indentation on the surface of the floor material after peeling off the laminate was observed, and those without indentation were designated as ○, and those with indentation were designated as ×.

Regarding Comparative Example 1B in which the coating agent A of Example 1B was replaced with a coating compound containing no fluorine compound, the stain resistance (oil resistance) was insufficient. In addition, cracks were observed in the appearance, the matting feeling was insufficient, and the appearance of the floor surface was impaired. It is considered that this is due to insufficient penetration of the coating agent into the base film and accumulation on the base, thereby impairing the anti-glare property. Regarding Comparative Example 2B that does not use the coating agent A of Example 1B, the stain resistance (oil resistance, acid resistance, alkali resistance) is insufficient. It is believed that this is caused by the surface of the base film not being modified by the coating agent. Regarding Comparative Example 3B in which the base film of Example 1B was replaced with polyvinyl chloride, the impact resistance (falling ball indentation test) was insufficient. This is considered to be caused by the poor impact resistance of the base film compared to the polyurethane resin. In addition, pollution resistance (oil resistance, acid resistance, alkali resistance) is insufficient. The reason for this is considered to be that the coating agent penetrates into the base film in a large amount, and the content ratio of the curable resin composition cannot gradually decrease from the surface of the surface layer into the base film. Regarding Comparative Example 4B in which the base film of Example 1B was replaced with polyethylene terephthalate, the impact resistance (falling ball indentation test) was insufficient. This is considered to be caused by the poor impact resistance of the base film compared to the polyurethane resin. In addition, the impact resistance (Tabel wear) is insufficient, the matting feeling is insufficient, and the appearance of the floor surface is impaired. It is considered that this is due to the fact that the coating agent does not penetrate the substrate film and accumulates on the substrate. Compared with Comparative Example 5B which does not use the protective film of Example 1B, Example 1B is excellent in stain resistance and impact resistance, and exhibits the same appearance as the floor surface. In addition, the protective film of Example 1B was excellent in adhesive force and had little paste residue.

For the publications cited in this specification, and all documents including Japanese patent applications and Japanese patents, each document is specifically indicated and incorporated into this case for reference, and the entire content described in this specification is the same The limits are incorporated in the present invention for reference.

The use of nouns and the same indicators used in connection with the description of the present invention (especially in relation to the following patent applications) is understood to involve singular and Plural both. The sentences "include", "have", "contain" and "contain" can be understood as open end terms (that is, the meaning of "including ~ but not limited") unless otherwise specified. As long as the detailed description of the numerical ranges in this specification is not specifically indicated in this specification, it is only intended to function as a shorthand notation for individually describing the values within the range. If the values are listed one by one in this specification Generally incorporated into the manual. All methods described in this specification can be performed in any appropriate order as long as they are not specifically pointed out in this specification or do not clearly contradict the context. All examples or illustrative expressions used in this specification (such as "etc.") are only intended to better explain the present invention unless specifically claimed, and are not intended to limit the scope of the present invention. Any wording in the specification cannot be understood as representing an element that is not described in the scope of the patent application that is indispensable for implementing the present invention.

In this specification, in order to implement the present invention, a preferred embodiment of the present invention will be described including the best mode known to the inventor. For those skilled in the art, after reading the above description, the modifications of these preferred embodiments can be clarified. The present inventor envisions that a skilled person would suitably apply such a modification, and plans to implement the present invention by methods other than those specifically described in this specification. Therefore, as permitted by the reference law, the present invention includes all changes and equivalents of the contents described in the scope of patent applications attached to this specification. Furthermore, as long as it is not specifically pointed out in this specification or does not clearly contradict the context, any combination of the above-mentioned elements in all the modifications is included in the present invention.

1‧‧‧Extruder 2‧‧‧flat die 3‧‧‧cooling roller 4‧‧‧embossing roller 5‧‧‧pressure roller 6‧‧‧ pinch roller 7‧‧‧ Separator 8‧‧‧Concave and convex transfer film 9‧‧‧membrane with irregular shape 10‧‧‧Protection film 11‧‧‧ Base film 12‧‧‧Surface layer 13‧‧‧ Adhesive layer 14‧‧‧ peeling film 15‧‧‧Impact resistance imparting layer s1‧‧‧surface ss‧‧‧fluoro compounds

FIG. 1 is a diagram showing the structure of a laminate for a protective film having an impact resistance-imparting layer according to an eleventh embodiment of the present invention. A of FIG. 1 shows an example of a film (flat type) that does not have an uneven shape on the surface. B of FIG. 1 shows an example of a film (matte type) having an uneven shape on the surface. 2 is a diagram showing the structure of a laminate for a protective film having an uneven surface on the surface without an impact resistance-imparting layer according to an eleventh embodiment of the present invention. FIG. 3 is a diagram showing a film-forming step of the laminated film of the present invention. An example of a method for manufacturing a film having an uneven shape obtained by a film transfer method is shown. Fig. 4 is a diagram showing a film-forming step of the laminated film of the present invention. An example of a method of manufacturing a film having an uneven shape obtained by an embossing roll transfer method.

10‧‧‧Protection film

11‧‧‧ Base film

12‧‧‧Surface layer

13‧‧‧ Adhesive layer

14‧‧‧ peeling film

15‧‧‧Impact resistance imparting layer

s1‧‧‧surface

ss‧‧‧fluoro compounds

Claims (17)

A protective film, including: A substrate film formed of a resin containing thermoplastic polyurethane; and Adhesive layer, The base film has a surface layer in which a resin containing the thermoplastic polyurethane and a curable resin composition are mixed on the second surface side opposite to the first surface, The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin, It has an impact resistance-imparting layer formed on the first surface side of the base film, or the gloss value of the second surface side of the base film is less than 20. The protective film as described in item 1 of the patent application scope includes: The base film is formed of a resin containing thermoplastic polyurethane; An impact resistance-imparting layer formed on the first surface side of the base film; and an adhesive layer formed on the side opposite to the base film surface side of the impact-resistant imparting layer, The base film has a surface layer in which a resin containing the thermoplastic polyurethane and a curable resin composition are mixed on the second surface side opposite to the first surface, The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin. The protective film as described in item 1 of the patent application scope includes: A substrate film formed of a resin containing thermoplastic polyurethane; and An adhesive layer formed on the first surface side of the base film, The base film has a surface layer in which a resin containing the thermoplastic polyurethane and a curable resin composition are mixed on the second surface side opposite to the first surface, The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin, The gloss value of the second side of the base film is less than 20. The protective film according to item 1 of the patent application range, wherein the impact resistance-imparting layer contains at least one resin selected from polyester resins and polyolefin resins, The fluorosesquioxane or the fluorosesquioxane polymer has a cage structure, The curable resin contains at least one compound having a (meth)acryloyl group, The adhesive layer includes at least one resin selected from the group consisting of acrylic, urethane, rubber, and silicone. The protective film according to item 1 of the patent application scope, wherein the fluorosesquioxane polymer is an addition polymer of fluorosesquioxane having at least one addition polymerizable functional group, or has at least one An addition copolymer of fluorosilsesquioxane with addition polymerizable functional group and addition polymerizable monomer. The protective film according to item 1 of the patent application range, wherein the content ratio of the curable resin composition is configured to gradually decrease from the surface of the surface layer into the base film. The protective film according to item 1 of the patent application range, wherein the gloss value of the second surface side of the base film is less than 20. The protective film according to item 1 of the patent application range, wherein the thickness of the base film is 50 μm to 300 μm. The protective film according to item 1 of the patent application range, wherein the impact resistance-imparting layer has a thickness of 20 μm to 300 μm. The protective film according to item 1 of the patent application scope, wherein the thickness of the adhesive layer is 10 μm to 100 μm, The surface roughness of the adhesive layer is 300 nm to 800 nm. A layered body for a protective film, which is different from the protective film as described in any one of items 1 to 10 of the patent application scope, A peeling film is deposited on the surface of the adhesive layer opposite to the base film, The surface roughness of the surface of the release film facing the adhesive layer is 350 nm to 850 nm. The laminate for a protective film according to item 11 of the patent application range, wherein the adhesive layer maintains the uneven shape showing the surface roughness for a period of 10 minutes to 120 minutes after the peeling film is peeled off . The laminate for a protective film according to item 11 of the patent application range, wherein the peeling film is coated on the surface facing the adhesive layer with a resin selected from the group consisting of fluorine-based resin, silicone resin and long-chain At least one release agent in the acid ester. A surface protection article, including: The protective film as described in any one of claims 1 to 10; and The protective film is attached to the surface of the article by the adhesive layer. A method for manufacturing a protective film, including: The step of providing a substrate film formed of a resin containing thermoplastic polyurethane; Steps to form an adhesive layer; The step of applying a curable resin composition on the second surface of the base film opposite to the first surface, and impregnating the base film with the curable resin composition; and The step of irradiating active energy rays or heating the curable resin composition, The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin, Furthermore, a step of forming an impact resistance-imparting layer on the first surface side of the base film or a step of making the gloss value of the second surface side of the base film less than 20 are included. The method for manufacturing a protective film as described in item 15 of the patent application scope includes: The step of providing a substrate film formed of a resin containing thermoplastic polyurethane; A step of forming an impact resistance-imparting layer on the first surface side of the base film; A step of forming an adhesive layer on the side opposite to the surface of the base material film of the impact resistance-imparting layer; The step of applying a curable resin composition on the second surface of the base film opposite to the first surface, and impregnating the base film with the curable resin composition; and A step of irradiating active energy rays or heating the curable resin composition; The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin. The method for manufacturing a protective film as described in item 15 of the patent application scope includes: The step of providing a substrate film formed of a resin containing thermoplastic polyurethane; The step of forming an adhesive layer on the first surface side of the base film; The step of applying a curable resin composition on the second surface of the base film opposite to the first surface, and impregnating the base film with the curable resin composition; and A step of irradiating active energy rays or heating the curable resin composition; The curable resin composition contains at least one fluorine compound selected from the group consisting of fluorosesquioxanes and fluorosesquioxane polymers, and a curable resin, The gloss value of the second surface side of the base film was less than 20.

Images