JP2021195430A - Coating agent, protective film, and article having protective film - Google Patents

Abstract

To provide a protective film which is excellent in acid resistance, water repellency, anti-fouling property and slipperiness.SOLUTION: A coating agent contains a dimer diol di(meth)acrylate-based resin, polyfunctional (meth) acrylate-based compounds, and a photopolymerization initiator. A protective film includes a coat layer formed using the coating agent on a base material layer, a base material layer formed using thermoplastic polyurethane, and an adhesive layer formed using at least one resin selected from an acrylic resin, an urethane-based resin, a rubber-based resin and a silicone-based resin on a surface side opposite to a surface side where the coat layer of the base material layer is formed.SELECTED DRAWING: Figure 1

Description

The present invention relates to a protective film mainly for protecting the surface of an article used outdoors.

Articles used outdoors are exposed to ultraviolet rays, wind and rain, and deteriorate or get scratched. Therefore, a protective film that covers the articles is used. As a protective film, for example, it is used by being attached to an automobile body or headlight. In particular, when the film is attached to the headlight portion, the protective film itself needs to maintain transparency for a long period of time from the viewpoint of visibility and safety when irradiated with the light.
In order to solve these problems, a protective film that can easily restore the transparency of a plastic whose transparency has deteriorated due to aging deterioration, weather resistance deterioration, etc. by pasting is disclosed (for example, Cited Document 1). reference.).

However, even when the protective film is used, there is a problem that the film surface is hydrolyzed by acid rain, stain-like coating film erosion occurs, and glossiness and transparency are deteriorated.

International Publication No. 2017/047600

From the above, it is an object of the present invention to obtain a protective film having excellent acid resistance, water repellency, stain resistance, and slipperiness.

The present inventors have conducted diligent studies in order to solve the above problems. As a result, it is presumed that the main causative substance of acid rain damage is strong acid such as concentrated sulfuric acid generated by the volatilization of water, so we tried to strengthen the acid resistance of the coat layer on the surface of the protective film. rice field.
Therefore, we focused on dimerdiol di (meth) acrylate (DDDA), which has a dimer acid skeleton with high hydrophobicity. We have found that DDDA is used as a resin component of a coating agent for a protective film for automobiles to significantly improve sulfuric acid resistance, and completed the present invention.

The coating agent according to the first aspect of the present invention includes a dimerdiol di (meth) acrylate-based resin, polyfunctional (meth) acrylate-based compounds, and a photopolymerization initiator.

The coating agent according to the second aspect of the present invention is the coating agent according to the first aspect of the present invention, wherein the polyfunctional (meth) acrylate compound is a trifunctional acrylate compound.

The protective film 10 according to the third aspect of the present invention is, for example, as shown in FIG. 1, a coat layer formed on a base material layer using the coating agent according to the first or second aspect of the present invention. 12, a base material layer 11 formed by using thermoplastic polyurethane, and an acrylic type, urethane type, rubber type, and silicone type on the surface side opposite to the surface side on which the coat layer of the base material layer is formed. The adhesive layer 13 is formed by using at least one resin selected from the above.
When configured in this way, it becomes a protective film with greatly improved sulfuric acid resistance.
In addition, in this specification, "on the surface side" means that it may be laminated in contact with each other, or it may be laminated through another layer. "On the surface" means to contact and stack.

In the protective film 10 according to the fourth aspect of the present invention, the thermoplastic polyurethane in the protective film 10 according to the third aspect of the present invention is a polycaprolactone-based thermoplastic polyurethane.
With this configuration, the flexibility of the polycaprolactone-based thermoplastic polyurethane can be fully exhibited.

The protective film 10 according to the fifth aspect of the present invention has the acryloyl group at both ends or one end of the coating agent in the protective film 10 according to the third aspect or the fourth aspect of the present invention. Contains at least one reactive silicone compound selected from the siloxane group.

In the protective film 10 according to any one of the third to fifth aspects of the present invention, the protective film 10 according to the sixth aspect of the present invention is further added to the coating agent, fluorosilsesquioxane and fluorosilsesquioki. It contains at least one fluorine compound selected from the group consisting of sun polymers.
With this configuration, the fluorine compound accumulates on the surface of the coat layer, and the surface of the base layer can be modified without impairing the flexibility of the thermoplastic polyurethane of the base layer, resulting in antifouling properties. The protective film 10 has excellent slipperiness.

In the protective film 10 according to the seventh aspect of the present invention, the fluorine compound has a cage-type structure in the protective film 10 according to the sixth aspect of the present invention.
With this structure, the fluorine compound has the property of easily accumulating at the interface between air and solid, and becomes a protective film with increased speed of gathering at the interface between air and solid.

In the protective film 10 according to the eighth aspect of the present invention, in the protective film 10 according to the sixth or seventh aspect of the present invention, the fluorosilsesquioxane polymer has at least one addition polymerizable property. It is an addition polymer of fluorosilsesquioxane having a functional group, or an addition copolymer of fluorosilsesquioxane having one addition-polymerizable functional group and an addition-polymerizable monomer.
With this structure, a protective film using an addition polymer suitable as a fluorosilsesquioxane polymer is obtained.

The automobile body according to the ninth aspect of the present invention is an automobile body in which the protective film 10 according to any one of the third to eighth aspects of the present invention is attached to the surface by the adhesive layer.
With this configuration, the surface of an article such as an automobile body can be protected by a protective film that is uniformly attached following the automobile body. In addition, the surface can be protected from scratches and the like by the thermoplastic polyurethane having high impact resistance. In addition, the antifouling property can be improved by the coat layer. Further, the adhesive layer is excellent in adhesiveness, heat resistance and weather resistance, and there is no adhesive residue after peeling.

The headlight according to the tenth aspect of the present invention is a headlight in which the protective film 10 according to any one of the third to eighth aspects of the present invention is attached to the surface by the adhesive layer.
With this configuration, the surface of the headlight can be protected by the protective film that follows the headlight and is evenly attached. In addition, the surface can be protected from scratches and the like by the thermoplastic polyurethane having high impact resistance. In addition, since the coat layer can be improved in acid resistance and stain resistance, deterioration due to acid rain or the like can be reduced even when used outdoors for a long period of time, and high transparency can be maintained. .. Further, the adhesive layer is excellent in adhesiveness, heat resistance and weather resistance, and there is no adhesive residue after peeling.

By forming a protective layer on the surface of the film using the coating agent of the present invention, a protective film capable of exhibiting high acid resistance without causing appearance defects such as cracks can be obtained.

The protective film of the present invention has better acid resistance than the coat layer. Further, by incorporating a fluorine compound in the coat layer, it has high water repellency, antifouling property and slipperiness. Further, by attaching the protective film of the present invention to the surface of an adherend (object to be attached) such as a headlight, these surfaces can be protected.

It is a figure which shows the layer structure of the protective film 10 which concerns on the 2nd Embodiment of this invention.

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

[Coating agent]
The coating agent of the present invention includes a dimerdiol di (meth) acrylate-based resin, polyfunctional (meth) acrylate-based compounds, and a photopolymerization initiator. For example, as shown in FIG. 1, by applying a coating agent on the base material layer 11 and curing it, a coat layer 12 having excellent acid resistance and extensibility can be formed. The coating agent may further contain a fluorine compound and a reactive silicone compound as an antifouling agent. The antifouling agent can improve the antifouling property of the coat layer 12 and impart excellent slipperiness. The coating agent may further contain a solvent and an additive. Among the components contained in the coating agent, the dimerdiol di (meth) acrylate-based resin, the polyfunctional (meth) acrylate-based compound, and the photopolymerization initiator may be referred to as a curable component.

[Protective film 10]
As shown in FIG. 1, the protective film 10 according to the first embodiment of the present invention includes a base material layer 11 provided with a coat layer 12 and an adhesive layer 13. The protective film 10 includes a release film 14 at the time of manufacture, but when the protective film 10 is attached to the surface of a headlight which is an adherend, the release film 14 is peeled off and used.

[Coat layer 12]
The coat layer 12 contains a dimerdiol di (meth) acrylate-based resin, a polyfunctional (meth) acrylate-based compound, a photopolymerization initiator, and a coating agent containing a reactive silicone compound and a fluorine compound as optional components. It is applied on the surface of the base material layer 11 and then dried and cured to form it. When the reactive silicone compound and the fluorine compound are contained, in the coat layer 12, the silicone and fluorine contained in the reactive silicone compound and the fluorine compound are accumulated at the interface with air. The film thickness of the coat layer 12 is typically 0.5 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm, and particularly preferably 1 to 5 μm. When the film thickness of the coat layer 12 is 0.5 μm or more, the acid resistance performance is sufficient, and when the film thickness is 100 μm or less, the thickness of the protective film does not become too thick.

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

[Base material layer 11]
The base material layer 11 is formed by using thermoplastic polyurethane. Examples of the thermoplastic polyurethane include polycaprolactone-based thermoplastic polyurethane using polycaprolactone polyol as a polyhydroxy compound, polycarbonate-based thermoplastic polyurethane using polycarbonate polyol, and polyether-based thermoplastic polyurethane using polyether polyol. Of these, polycaprolactone-based thermoplastic polyurethane can be preferably used. Specific examples of the thermoplastic polyurethane are Argotec 49510, Argotec 49510-DV, Nihon Matai Esmer URSPX86, Esmer URSPX93, Esmer URSPX98, Seadam DUS202, DUS213, DUS235, DUS501, DUS601. , DUS203, DUS220, DUS701, XUS2086, XUS2098, DUS451, DUS450, Unigrand XN2001, XN2002, XN2004, Nupro N4900, Okura Industrial SNY97-CLB, DinZing PP277 + 375, PP386 + 375 can be mentioned.

The film thickness of the base material layer 11 is not particularly limited, but the film thickness of the base material layer 11 is typically 25 to 300 μm, preferably 100 to 200 μm, and more preferably 100 to 150 μm. .. When the film thickness of the base material layer 11 is 25 μm or more, the mechanical strength of the base material layer becomes sufficient, and it becomes possible to form a layer on the base material layer. Further, when the film thickness is 300 μm or less, the thickness of the protective film does not become too thick.

[Dimerdiol di (meth) acrylate resin]
The dimerdiol di (meth) acrylate resin is an active energy ray-curable resin having a (meth) acryloyl group and dimer acid as a basic skeleton, which is a dimer of an unsaturated fatty acid having 18 carbon atoms. Yes, for example, an ultraviolet curable resin can be mentioned. "(Meta) acryloyl group" means an acryloyl group or a methacryloyl group. The dimerdiol di (meth) acrylate-based resin imparts acid resistance to the coat layer 12.
The dimerdiol di (meth) acrylate resin can be obtained by a general ester synthesis method such as a dehydration condensation method, an acid chloride method, or a transesterification method.
Dimer diol is a saturated alkylene diol having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid obtained from vegetable oil to obtain dimer acid, and then further distilling and purifying. be.
Further, an active energy ray-curable resin having trimeric acid as a basic skeleton, which is a trimerate of an unsaturated fatty acid having 54 carbon atoms, can also be obtained by the same reaction or the like, and imparts acid resistance to the coat layer 12. be able to.

[Polyfunctional (meth) acrylate compounds]
Polyfunctional (meth) acrylate compounds are compounds having two or more (meth) acryloyl groups. "(Meta) acryloyl group" means an acryloyl group or a methacryloyl group.
Examples of the polyfunctional (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, trimethylol propanedi (meth) acrylate, trimethylol propanetri (meth) acrylate, EO-modified trimethylol propanetri (meth) acrylate, PO-modified trimethylol propanetri (meth) acrylate, EO, PO-modified trimethylol propanetri. (Meta) Acrylate, Dimethylol Tricyclodecandi (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Ethylene Glycol Di (Meta) Acrylate, Tetraethylene Glycol Di (Meta) Acrylate, Phenyl Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol diacrylate, 1,3-adamantandimethanol di (1) Meta) acrylate, o-xylylene range (meth) acrylate, m-xylylene range (meth) acrylate, p-xylylene range (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloyloxy) isocyanurate , Bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified 2,2-bis (4-((meth) acryloxy) phenyl ) Propane, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, EO, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane and the like. Speaking of the trade names of Toagosei Chemical Industry Co., Ltd., Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245, Aronix M-305, M- 306, Aronix M-309, Aronix M-313, Aronix M-315, Aronix M-321, Aronix M-325, M-350, M-360 and the like can be mentioned.

[Photopolymerization initiator]
The photopolymerization initiator is not particularly limited, but a photoradical polymerization initiator that generates radicals with active energy rays can be used, and examples thereof include 1-hydroxycyclohexylphenyl ketone, benzophenone, Michler's ketone, and 4,4'-bis ( Diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropio Phenyl, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl]- 2-Molholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate isoamyl, 4,4 ′ -Di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (3', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4) ′ -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'- Phenyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2-( p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chloropheni) Le) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4- Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholino) Propionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-) Il) -Phenyl) Titanium, 3,3', 4,4'-Tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′ -Di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxycarbonyl) benzophenone, 4 , 4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] Phenyl} -2-methyl-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide. These compounds may be used alone, or a mixture of two or more thereof may be used. The content of the photoradical polymerization initiator is preferably 0.01 to 20 parts by weight with respect to the total amount (100 parts by weight) of the photoradical polymerizable resin. More preferably, it is 1 to 10 parts by weight.

[Fluorine compound]
As the fluorine compound, at least one selected from the group consisting of fluorosilsesquioxane and fluorosilsesquioxane polymers can be used.
-Fluorosilsesquioxane Fluorosylsesquioxane may be any of a monomer, an oligomer, a prepolymer, and a polymer as long as it has at least one polymerizable functional group. The fluorosilsesquioxane may have a property of easily accumulating at the interface between air and a solid (or liquid) in a hydrophobic atmosphere (for example, in air). Further, if the fluorosilsesquioxane is accumulated at the interface, the effect of the present invention can be fully exerted. Due to such excellent surface accumulation characteristics of fluorosilsesquioxane, the surface modification of the coat layer 12 can be effectively performed in a small amount.
As the fluorosilsesquioxane used in the present invention, a compound _{in which the substituent (R) in the formula [(R-SiO 1.5} ) n] is replaced with a fluoroalkyl group (R ^f ) can be used. Specifically, as an example of fluorosilsesquioxane, fluorosilsesquioxane having a molecular structure having a cage-type structure represented by the following formula (2) can be mentioned.

In the formula (2), ^{the carbon number of R f} is preferably 1 to 8 in consideration of the solubility in a solvent. R ^f may be a linear group or a branched group. Specifically, as a linear group, -CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , as a branched group, -CH ₂ CH ₂ CF (CF ₃ ) ₂ , -CH ₂ CH (CF ₃ ) CF ₂ CF ₃ , -CH (CF ₃ ) CH ₂ CF ₂ CF ₃ , -CH ₂ C (CF ₃ ) ₂ CF ₃ , -C (CF ₃ ) ₂ CH ₂ CF ₃ -CH ₂ CH ₂ CF ₂ CF (CF ₃ ) ₂ , -CH ₂ CH ₂ CF (CF ₃ ) CF ₂ CF ₃ , -CH ₂ CH ₂ C (CF ₃ ) ₂ CF ₃ etc. are exemplified. can do. It should be ^{noted that R f} may be a different group or all may be the same group.

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

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

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

The above radically polymerizable functional group is not particularly limited as long as it is a radically polymerizable group, and is, for example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-. It contains vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like, and a group containing (meth) acrylic or styryl is preferable. Here, (meth) acrylic is a general term for acrylic and methacryl, and means acrylic or methacrylic.
Examples of the above-mentioned radically polymerizable functional group having (meth) acrylic include a group represented by the following formula (3). In the formula (3), Y ¹ represents an alkylene having 2 to 10 carbon atoms, preferably an alkylene having 2 to 6 carbon atoms, and more preferably propylene. Further, X represents hydrogen or an alkyl having 1 to 3 carbon atoms, preferably hydrogen or methyl.

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

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

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

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

An example of the above-mentioned styrene compound having an addition-polymerizable double bond is a styrene compound having a crosslinkable functional group. Specific examples of such crosslinkable functional groups include epoxies such as glycidyl, oxetanyl, halos, aminos, isocyanatos, acid anhydrides, carboxyls, hydroxyls, thiols and syroxys.
Examples of styrene compounds having a crosslinkable functional group include o-aminostyrene, p-styrenechlorosulfonic acid, styrenesulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2 -(2-Bromoisobutyryloxy) styrene, 1-(2-((4-vinylphenyl) methoxy) -1-phenylethoxy) -2,2,6,6-tetramethylpiperidine and the following formula Contains the following compounds.

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

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

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

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

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

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

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

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

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

The polymer is an addition polymer of fluorosilsesquioxane or an addition copolymer with another addition-polymerizable monomer, and in the case of a copolymer, a constitutive copolymer such as block copolymer. It may be a coalescence or a random copolymer, but is preferably a random copolymer. Further, the polymer may have a crosslinked structure or may be a graft copolymer.

The content of the fluorine compound is relative to the total amount of the fluorine-based compound containing the dimerdiol di (meth) acrylate-based resin, the polyfunctional (meth) acrylate-based compound, and the photopolymerization initiator as required. It is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. When it is 0.1% by weight or more, the antifouling property of the coat layer 12 can be improved and slipperiness can be imparted, and when it is 10% by weight or less, the flexibility of the coat layer 12 is lowered and the self-repairing property is improved. You can avoid being inferior.

[solvent]
The dimerdiol di (meth) acrylate-based resin, polyfunctional (meth) acrylate-based compound, photopolymerization initiator, and fluorine compound contained as necessary in the coating agent of the present invention can be used as a solvent such as an organic solvent. It may be dissolved and used. The solvent is not particularly limited. A general organic solvent or the like can be used. Specific examples of the solvent include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.). ), Ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol-based solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile-based solvents (acetonitrile, propionitrile, benzonitrile, etc.) Etc.), ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethyl, etc.) Acetamide), hydrochlorofluorocarbon-based solvent (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) -based solvent (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon-based solvent (perfluoropentane, per). Fluorohexane), alicyclic hydrofluorocarbon solvent (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorosolvent (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic fluorosolvent (α, α, Α-Trifluorotoluene, hexafluorobenzene), water and the like.

These solvents may be used alone or in combination of two or more. For example, a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone can be mentioned. By adding a solvent such as methyl ethyl ketone, the workability of homogenizing the solution can be improved when the coating agent is prepared. In addition, the coating agent can be stabilized by improving the solubility. The mixing ratio (based on weight) can be, for example, in the range of methyl isobutyl ketone / methyl ethyl ketone = 1 to 99/99 to 1, preferably in the range of 20 to 80/80 to 20. The content of the solvent is preferably 20 to 500 parts by weight, more preferably 50 to 400 parts by weight, based on the total amount (100 parts by weight) of the coating agent forming the coat layer.

[Additive]
Various additives may be added to the coating agent, if necessary. For example, a filler may be added in order to impart hardness and scratch resistance of the coating layer. A leveling agent for improving the coatability and a reactive silicone for improving the squeegee property at the time of construction may be added. In addition, additives such as a weather resistant agent and an antifoaming agent may be added.
More specifically, an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, a wettability improver, as long as the effect of the coat layer formed by the coating agent is not adversely affected. Optional such as surfactants, plasticizers, UV absorbers (weather resistant agents), light stabilizers (weather resistant agents), antioxidants, antistatic agents, silane coupling agents, inorganic fillers (silica, alumina, etc.), organic fillers, etc. The component of may be further contained in the coating agent.

As an example of the leveling agent, as commercially available products, acrylic surface conditioners BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, BYK-3550 (trade name: manufactured by Big Chemie Japan Co., Ltd.) can be mentioned.
Examples of silicone-based surface conditioners include BYK-UV3500, BYK-UV-3570 (trade names: manufactured by Big Chemie Japan Co., Ltd.), TEGO Rad2100, 2200N, 2250, 2500, 2600, and 2700 (all of which). Product name: Evonik Degussa Japan Co., Ltd., X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X -22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22 -8201, X-22-2426, X-22-164A, X-22-164C (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

Examples of the weather resistant agent include ultraviolet absorbers such as benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, dibenzoylresorcinols, and light stabilizers.

Examples of benzotriazoles include TINUVIN PS, TINUVIN 99-2, TINUVIN326, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130, and TINUVINCarbofect manufactured by BASF. Examples of hydroxyphenyltriazines include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 manufactured by BASF. Examples of benzophenones include 1413 manufactured by ADEKA and Sumisorb 130 manufactured by Sumika Chemtex. Examples of salicylates include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of cyanoacrylates include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and ethyl 2-cyano-3,3-diphenyl acrylate. Examples of triazines include LA-46 and LA-F70 manufactured by ADEKA, and examples of dibenzoyl resorcinols include 4,6-dibenzoyl resorcinol. These UV absorbers may be used alone or in combination of a plurality of UV absorbers. It is preferable to appropriately select the type and combination of the ultraviolet absorbers based on the wavelength of the ultraviolet rays to be absorbed.

The light stabilizers (HALS) include TINUVIN (registered trademark) 5100 (neutral type general-purpose HALS) and TINUVIN292 (compound name: bis (1,2,2,6,6-pentamethyl-4-)) manufactured by BASF. Piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN152 (compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,) 2,6,6-Tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), TINUVIN144 (Compound name: Bis (1,2,2,6) 6-Pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate), TINUVIN123 (compound name: decanodic acid, bis (2,) Reaction product of 2,6,6-tetramethyl-1- (octyloxy) -4 piperidinyl) ester (in the presence of 1,1-dimethylethylhydroperoxide and octane)), TINUVIN111FDL (about 50%, TINUVIN622, compound name). : (Butandiic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl) in the presence of ethanol), about 50%, CHIMSORB119, compound name: N-N'-N''-N' '' -Tetrax (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazine-2-yl) -4,7-diazadecan-1 , 10-Diamine), or Adecaster LA series manufactured by Adeca Co., Ltd., specifically, LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 (((5) -5555), LA-62). 5) -5711), LA-67 ((5) -5755), LA-82 ((5) -6023), LA-87 ((5) -6022). The numbers in parentheses are the existing chemical substance numbers.

As an example of the inorganic filler, the commercially available products include MEK-ST-40, MEK-ST-L, MEK-ST-ZL, PGM-AC-2140Y, PGM-AC-4130Y, AS-200, AS-520 manufactured by Nissan Chemical Industries. , CIK Nanotech Anatase TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ , Cobalt Blue, Mikuni Color Zirconium Oxide, Barium Titanate, Titanium Oxide, Silica, Alumina, MUA Filler.
Examples of organic fillers include Sekisui Plastics Industrial Tech Polymer MBX Series, SBX Series, Negami Industrial Art Pearl Crosslinked Acrylic Beads, Art Pearl Crosslinked Urethane Beads, and Aica Kogyo Ganz Pearl.
These fillers may be used alone or in combination of a plurality of fillers.

Reactive Silicone Compounds Reactive silicone compounds are a group of silicone compounds, also referred to as reactive silicone oils and polysiloxane-based macromonomers. In the field of polymer synthesis, these are used as raw materials for block copolymers and graft copolymers, as resin modifiers, and paint modifiers. This component can improve the surface smoothness of the coating agent of the present invention and improve the squeegee property at the time of construction. As such a component, a polyorganosiloxane compound containing a terminal vinyl group is preferable, and a polydimethylsiloxane macromonomer having a methacryloyl group at the terminal is more preferable.
Other components may be added to the coating agent of the present invention. Examples of other components include thermoplastic resins and rubber. By adding a thermoplastic resin and rubber, the characteristics of the coat layer (mechanical characteristics, surface / interface characteristics, compatibility, etc.) can be modified.
For example, X-22-164A (molecular weight 860, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.), X-24. -164E (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.) , Silaplane FM-7711 (manufactured by JNC Co., Ltd.), Silaplane FM-07721 (manufactured by JNC Co., Ltd.), Silaplane FM-7725 (manufactured by JNC Co., Ltd.), Silaplane 0711 (manufactured by JNC Co., Ltd.) , One-ended silaplane FM-0721 (molecular weight 5000, manufactured by JNC Co., Ltd.), One-ended silaplane FM-0725 (molecular weight 10,000, manufactured by JNC Co., Ltd.), One-ended silaplane TM-0701 (molecular weight 423,) JNC Co., Ltd.), One-ended silaplane TM-0701T (molecular weight 423, manufactured by JNC Co., Ltd.), BYK-UV3500 (manufactured by Big Chemie Japan Co., Ltd.), BYK-UV3510 (manufactured by Big Chemie Japan Co., Ltd.) , BYK-UV3570 (manufactured by Big Chemie Japan Co., Ltd.), TEGO Rad2100 (manufactured by Tegokemy Service), TEGO Rad2200N (manufactured by Tegokemy Service), TEGO Rad2250 (manufactured by Tegokemy Service), TEGO Rad2500 (manufactured by Tegokemy Service) , TEGO Rad2600 (manufactured by Tegokemy Service), TEGO Rad2600 (manufactured by Tegokemy Service), TEGO Rad2700 (manufactured by Tegokemy Service) and the like.

Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, and poly-4-. Methylpentene, syndiotactic polystyrene, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitica Co., Ltd. trade name, Vectra: Polyplastics Co., Ltd.) Product name, etc.), Polyimide (Capton: Toray Co., Ltd. product name, AURUM: Mitsui Chemicals Co., Ltd. product name, etc.), Polyetherimide and Polyamidoimide, Nylon 6, Nylon 6, 6, Nylon 6, 10, Polyimide such as nylon MXD6, nylon 6, T (trade name: manufactured by DuPont Co., Ltd.), polyethylene terephthalate, polybutylene terephthalate, polyester such as polyethylene 2,6-naphthalenedicarboxylate, and polytetrafluoroethylene, Fluorescent resins such as polyvinylidene fluoride can be mentioned.

The coating agent used to form the coat layer 12 needs to be liquid. Therefore, when the coating agent contains a solid substance, it may be dissolved in a solvent and used as a liquid as described above. The concentration of the curable component in the coating agent can be selected so that the viscosity of the coating agent becomes a viscosity corresponding to the coating method such as a wet coating method. The concentration is preferably 1 to 80% by weight, more preferably 3 to 60% by weight. The concentration of the curable component in the coating agent can be adjusted by using a solvent. As the solvent, for example, a general organic solvent such as methyl ethyl ketone and methyl isobutyl ketone can be used. When the coating agent contains a fluorine compound and the solubility in the solvent is lowered due to the length of the fluoroalkyl group contained in the fluorine compound or the like, a fluorine-based organic solvent may be used.

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

[Adhesive layer 13]
As shown in FIG. 1, the adhesive layer 13 is formed by applying an adhesive on the side opposite to the surface of the base material layer 11 provided with the coat layer 12. The adhesive layer 13 may be formed directly on the surface of the base material layer 11 or may be laminated with the base material layer 11 via another layer. As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 13, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like can be used. Acrylic adhesives with excellent heat resistance and weather resistance are preferable for applications that require long-term durability from the viewpoint of product design. The pressure-sensitive adhesive layer 13 is provided with irregularities on the surface of the pressure-sensitive adhesive in terms of sticking characteristics to an article to be adhered.

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

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

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

The weight average molecular weight (Mw) of the acrylic copolymer is 50,000 to 2 million, preferably 100,000 to 1,500,000, more preferably 150,000 to 1,000,000. 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.

In order to apply the composition to be the adhesive layer 13 to the release film 14 or the base material layer 11, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a roll coating method, a die coating method, which are usually performed, are used. It can be performed by a knife coating method, an air knife coating method, a hot melt coating method, a curtain coating method, or the like. The thickness of the adhesive layer 13 is typically 10 to 100 μm, preferably 15 to 50 μm, more preferably 25 to 45 μm, and particularly preferably 35 to 40 μm in terms of adhesion after application. be.

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

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

Examples of the article as an adherend to which the protective film of the present invention is attached include lighting equipment such as automobiles, aircrafts, and ships. Transparency of various body parts of these articles, especially flying debris (eg sand, stones, etc.), endangered parts such as insects (eg, front hood tip and other tip surfaces, rocker panels, etc.) It is effective in protecting the coated surface of various plastic parts.

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

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

Next, a polymer containing γ-methacetic propylhepta (trifluoropropyl) -T8-silsesquioxane unit was produced by the following procedure. Γ-Methyloxypropylhepta (trifluoropropyl) -T8-silsesquioxane (5) obtained by the above method in a four-necked flask with an internal volume of 200 mL equipped with a reflux condenser, a thermometer and a dropping funnel. 36.65 g, methyl methacrylate (MMA) 18.33 g, 2-hydroxyethyl methacrylate (HEMA) 27.49 g, one-ended methacryloxy group-modified dimethyl silicone (FM-0721, molecular weight about 6,300) 9.16 g. , 2-Butanone (MEK) 106.4 g was introduced and sealed with nitrogen. It was set in an oil bath kept at 95 ° C. and refluxed, and oxygen was removed for 10 minutes. Then, a solution of 0.70 g of 2,2'-azobisisobutyronitrile (AIBN) and 0.08 g of mercaptoacetic acid (AcSH) dissolved in 7.0 g of MEK was introduced and kept at the reflux temperature. Polymerization was started. After the polymerization for 3 hours, a solution in which 0.70 g of AIBN was dissolved in 7.0 g of MEK was introduced, and the polymerization was continued for another 5 hours. After completion of the polymerization, 65 mL of modified alcohol (Solmix AP-1, manufactured by Japan Alcohol Trading Co., Ltd.) was added to the polymerization solution, and then the polymer was poured into 1300 mL of Solmix AP-1 to precipitate the polymer. The supernatant was removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to separate the product.
15.0 g of product, 0.015 g of MEHQ, 0.0263 g of DBTDL, 130 g of ethyl acetate were introduced into a four-necked flask with an internal volume of 200 mL equipped with a reflux condenser, a thermometer and a septum cap, and a nitrogen seal was introduced. did. It was set in an oil bath kept at 48 ° C. and the temperature was raised. Then, when the liquid temperature reached 45 ° C., 15.9 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced and the reaction was started. After reacting for 6 hours, the mixture was cooled to room temperature and 10.0 g of MeOH was introduced to complete the reaction. After completion of the reaction, 65 mL of Solmix AP-1 was added to the reaction solution, and then the reaction was poured into 1300 mL of Solmix AP-1 to precipitate the reaction product. The supernatant is removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to contain 11.8 g of γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane unit, side chain. A polymer having an acryloyl group (XUA008) was obtained. The weight average molecular weight determined by GPC analysis of XUA008 was 45,000, and the molecular weight distribution was 1.7.

[Dimerdiol di (meth) acrylate]
The dimerdiol di (meth) acrylate derived from the dimerdiol was prepared by the following method. Dimerdiol (Cropol 2033, 284.4 g, 500 mmol) was dissolved under nitrogen in dry acetone (450 ml) in a 1 liter three-necked flask equipped with a mechanical stirrer and a dropping funnel. I let you. Triethylamine (101.2 g, 1 mol) was added to this solution and the solution was cooled to 4 ° C. on an ice bath. Acryloyl chloride (90.5 g, 1 mol) solvated in dry acetone (100 ml) was added to the dropping funnel and added dropwise to the stirring reaction solution over a 60-minute process while maintaining an internal temperature of T <10 ° C. After stirring this solution on ice for another 2 hours, the temperature was returned to room temperature and the mixture was stirred for 4 hours. Most of the solvent was removed by evaporation and the residual residue was solvated in CH ₂ Cl ₂ (1 liter). Furthermore, the solution was washed with a 5% HCl aqueous solution (800 ml) and _H 2 O (1200ml). The organic materials were isolated, dried over anhydrous MgSO ₄ and filtered, after solvent removal by an evaporator, to give a dimer diol di (meth) acrylate (DDDA).

[Preparation of coating agent A0]
As the dimerdiol di (meth) acrylate resin, 27.7% by weight of the "dimerdiol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above was used, and as a trifunctional acrylate compound, Toa XUA008 (effective concentration) obtained by the above method in order to impart antifouling and slipperiness by using 64.8% by weight of the ultraviolet curable resin "Aronix M309 (effective concentration: 100% by weight"" manufactured by Synthetic Chemical Co., Ltd. 40.0% by weight) was used in an amount of 0.5% by weight, and FM-7711 (effective concentration of 100% by weight manufactured by JNC) was used in an amount of 0.1% by weight. Further, a dimerdiol di (meth) acrylate-based resin and 3 The total weight of the functional acrylate compounds was 100 parts by weight, and 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent A0 shown in Table 1 was obtained.

[Preparation of coating agent B0]
As the dimerdiol di (meth) acrylate resin, 27.8% by weight of the "dimerdiol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above is used, and as a trifunctional acrylate compound, Toa FM-7711 (JNC) is used as a reactive silicone compound to impart antifouling and slipperiness by using 65.1% by weight of the ultraviolet curable resin "Aronix M309 (effective concentration: 100% by weight"" manufactured by Synthetic Chemical Co., Ltd. The effective concentration (100% by weight) was used in an amount of 0.1% by weight. Further, the total weight of the dimerdiol di (meth) acrylate-based resin and the trifunctional acrylate-based compound was set to 100 parts by weight. 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent B0 shown in Table 1 was obtained.

[Preparation of coating agent C0]
As the dimer diol di (meth) acrylate resin, 46.2% by weight of the "dimer diol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above was used, and as a trifunctional acrylate compound, Toa XUA008 (effective concentration: 100% by weight) obtained by the above method in order to further impart antifouling and slipperiness by using 46.3% by weight of the ultraviolet curable resin "Aronix M309 (effective concentration: 100% by weight"" manufactured by Synthetic Chemical Co., Ltd. ( (Effective concentration 30.0% by weight) was used at 0.5% by weight, and FM-7711 (effective concentration 100% by weight manufactured by JNC) was used at 0.1% by weight. The total weight of the acrylate-based resin and the trifunctional acrylate-based compound is 100 parts by weight, whereas 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of the methylisobutylketone as a diluent are used. added.
In this way, the coating agent C0 shown in Table 1 was obtained.

[Preparation of coating agent D0]
As the dimer diol di (meth) acrylate resin, 9.2% by weight of the "dimer diol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above was used, and as a trifunctional acrylate compound, Toa 83.3% by weight of UV curable resin (trifunctional acrylate) "Aronix M309 (effective concentration: 100% by weight"" manufactured by Synthetic Chemical Co., Ltd. is used, and in order to further impart antifouling and slipperiness, the above method is used. The obtained XUA008 (effective concentration 30.0% by weight) was used in an amount of 0.5 parts by weight, and FM-7711 (effective concentration of 10.0% by weight manufactured by JNC) was used in an amount of 0.1% by weight. Further, the total weight of the dimerdiol di (meth) acrylate-based resin and the trifunctional acrylate-based compound is 100 parts by weight, whereas 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" is used as a diluent. 30 parts by weight of methyl isobutyl ketone was added.
In this way, the coating agent D0 shown in Table 1 was obtained.

[Preparation of coating agent E0]
As the dimer diol di (meth) acrylate resin, 92.5% by weight of the "dimer diol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above is used to further impart antifouling and slipperiness. In order to use 0.5 parts by weight of XUA008 (effective concentration 30.0% by weight) obtained by the above method and 0.1% by weight of FM-7711 (effective concentration 100% by weight manufactured by JNC). did. Further, 100 parts by weight of the dimerdiol di (meth) acrylate resin was added, and 7.5 parts by weight of the photopolymerization initiator "Irgacure127" and 30% by weight of methyl isobutyl ketone were added as a diluent. ..
In this way, the coating agent E0 shown in Table 1 was obtained.

[Preparation of coating agent F0]
As the dimerdiol di (meth) acrylate resin, 27.7% by weight of the "dimerdiol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above was used, and Toa was used as a trifunctional acrylate compound. XUA008 (effective concentration: 100% by weight) obtained by the above method is used in order to impart antifouling and slipperiness by using 64.8% by weight of the ultraviolet curable resin "Aronix M309 (effective concentration: 100% by weight") manufactured by Synthetic Chemical Co., Ltd. An effective concentration of 30.0% by weight) was used in an amount of 0.5 parts by weight, and FM-7711 (effective concentration of 100% by weight manufactured by JNC) was used in an amount of 0.1% by weight. Further, a dimerdiol di (meth) acrylate-based resin was used. To 100 parts by weight, 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent F0 shown in Table 1 was obtained.

[Preparation of coating agent G0]
As trifunctional acrylate compounds, 92.5% by weight of UV curable resin "Aronix M309 (effective concentration: 100% by weight") manufactured by Toa Synthetic Chemical Co., Ltd. is used, and in order to further impart antifouling and slipperiness, XUA008 (effective concentration 30.0% by weight) obtained by the above method was used in an amount of 0.5% by weight, and FM-7711 (effective concentration 100% by weight manufactured by JNC) was used in an amount of 0.1% by weight. The functional acrylate compounds were made up to 100 parts by weight, and 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent G0 shown in Table 2 was obtained.

[Preparation of coating agent H0]
92.5% by weight of UV curable resin "Aronix M402 (effective concentration: 100% by weight") manufactured by Toa Synthetic Chemical Co., Ltd., which is a 5,6 functional acrylate compound, is used to further impart antifouling and slipperiness. XUA008 (effective concentration 30.0% by weight) obtained by the above method was used in an amount of 0.5% by weight, and FM-7711 (effective concentration of 100% by weight manufactured by JNC) was used in an amount of 0.1% by weight. The amount of the 5,6-functional acrylate compounds was 100 parts by weight, and 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent H0 shown in Table 2 was obtained.

[Preparation of coating agent I0]
As the dimerdiol di (meth) acrylate resin, 64.7% by weight of the "dimerdiol di (meth) acrylate (effective concentration: 100% by weight)" synthesized above was used, and the 5,6 functional acrylate compounds were used. A certain UV curable resin "Aronix M402 (effective concentration: 100% by weight") manufactured by Toa Synthetic Chemical Co., Ltd. was used in an amount of 27.8% by weight. Further, in order to impart antifouling and slipperiness, it was obtained by the above method. 0.5% by weight of XUA008 (effective concentration 30.0% by weight) and 0.1% by weight of FM-7711 (effective concentration 100% by weight manufactured by JNC) were used. Further, a dimerdiol di (meth) acrylate-based resin was used. And 100 parts by weight of the 5,6 functional acrylate compounds, 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone as a diluent were added.
In this way, the coating agent I0 shown in Table 2 was obtained.

[Preparation of coating agent J0]
As the trifunctional acrylate compounds, 64.7% by weight of the ultraviolet curable resin "Aronix M309 (effective concentration: 100% by weight") manufactured by Toa Synthetic Chemical Co., Ltd. is used, and Toa Synthetic is a 5,6 functional acrylate compound. 27.8% by weight of the ultraviolet curable resin "Aronix M402 (effective concentration: 100% by weight)" manufactured by Kagaku Co., Ltd. was used. Further, in order to impart antifouling and slipperiness, XUA008 (effective concentration) obtained by the above method was used. 30.0% by weight) was used in an amount of 0.5 parts by weight, and FM-7711 (effective concentration of 100% by weight manufactured by JNC) was used in an amount of 0.1% by weight. Further, trifunctional acrylate compounds and 5,6-functional compounds were used. To 100 parts by weight of the acrylate compounds, 7.5 parts by weight of the photopolymerization initiator "Irgacure 127" and 30 parts by weight of methyl isobutyl ketone were added as a diluent.
In this way, the coating agent J0 shown in Table 2 was obtained.

[Making a protective film]
A commercially available acrylic pressure-sensitive adhesive (S8721 manufactured by Avery Dennison) was applied to one side of a base material layer (thermoplastic polyurethane film "ARGOGUARD 49510" manufactured by Argotec) by a die coat, and dried at 70 ° C. for 3 minutes. An adhesive layer having a thickness of 40 μm was formed on one side of the above.
Next, the open surface of the adhesive layer and the 75 μm-thick polyethylene terephthalate (release film: release liner) released from the silicone resin were pressure-bonded using a rubber roller and cured at 45 ° C. for 1 day. In this way, protective films A, B, C, D, E, F, G, H, I, and J in which the base material layer, the adhesive layer, and the release film were in contact in this order were obtained.
Photopolymerizable coating agents A0, B0, C0, D0, E0, F0, G0, H0, I0, and J0 were applied to the open surface of the base material layer. D. S. Webster Wire Bar Coater No. 12 was applied and dried at 80 ° C. for 3 minutes. Then, the coating agent was cured at ^{an integrated light intensity of 500 mJ / cm 2} using a belt conveyor curing unit (manufactured by Heraeus) equipped with a fusion UV lamp. In this way, a coat layer having a thickness of 0.5 to 5.0 μm is formed on the base material layer, and the coat layer, the base material layer, the adhesive layer, and the release film layer are in contact with each other in this order (Examples 1 and 2). , Example 3, Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3) were obtained.

[Evaluation of protective film]
The obtained protective film was evaluated from the following viewpoints. The results are shown in Table 1 and Table 2.

1) Thickness (μm) of coat layer (12 in FIG. 1)
The coating layer thickness of the protective film was measured with a scanning electron microscope (SEM).

2) Appearance A piece of 50 mm × 50 mm was cut out from the protective film, and the release film was removed from this piece. As a test substrate, a polycarbonate resin plate (Panlite PC1151, manufactured by Teijin Limited, thickness 2.0 mm) was prepared. After spraying the construction liquid (however, the baby shampoo manufactured by Johnson End Johnson is diluted 10,000 times on a volume basis) on the adhesive layer surface of the protective film piece and the resin plate, the adhesive layer surface of the protective film is applied. The protective film was brought into contact with the test substrate, and the protective film was pressed with a commercially available rubber squeegee while removing air bubbles and water bubbles generated between the protective film and the test substrate, and the protective film was attached to the resin plate. The resin plate to which the protective film was attached was allowed to stand at room temperature until no bubbles or water bubbles were visually observed on the surface. In this way, the test sample was completed.
The surface appearance of the test sample is visually confirmed, and if defects such as cissing defects in the coat layer, whitening, and cracks in the coat layer (12) are confirmed, the appearance is impaired (-). If no defect that impairs the appearance was confirmed, it was marked as (+).

3) Total light transmittance (%)
As an index of the transparency of the protective film, the total light transmittance was measured using a haze meter (NDH-5000SP, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with the JIS K 7631-1 standard. The measurement was performed with the target film attached to a polycarbonate resin plate (Panlite PC1151, thickness 2.0 mm) via the adhesive layer.

^{4) Color The b *} value (transmission SCI) was measured using (SD 7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with the JIS Z 8729 standard as an index of the color of the protective film. The measurement was performed with the target film attached to a polycarbonate resin plate (Panlite PC1151 thickness 2.0 mm) via the adhesive layer.

5) The release liner of the protective film cut into pieces having a breaking elongation of 35 mm × 200 mm was removed, and a protective film in which the coat layer, the base material layer, and the adhesive layer were in contact in this order was prepared. This protective film was pulled and broken by a tensile / compression / bending tester Strograph VG (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The pulling conditions at this time were the initial distance between chucks: 100 mm and the crosshead moving speed: 127 mm / min. The point where a crack was generated in the coat layer (12) of the test sample was visually detected, and the extensibility of the protective film until breaking was determined as the breaking elongation (%) represented by the following formula.
Elongation at break (%) = (Crosshead movement distance to break (mm) / Distance between initial chucks (100 mm)) x 100

6) Adhesion of the coat layer The adhesion of the coat layer (12) to the base material layer (11) was confirmed. The release liner of the protective film cut into pieces of 35 mm × 200 mm was removed, and an evaluation sample in which the coat layer, the base material layer, and the adhesive layer were in contact in this order was prepared. This evaluation difference sample was pulled by a tensile / compression / bending tester Strograph VG (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the operation of the strograph was stopped immediately after a crack was generated in the coat layer (12). At that time, the adhesion between the coat layer and the base material layer was determined by the following determination method.
(++) The coat layer does not peel off from the base material layer even if the surface of the coat layer in which cracks are generated is scratched 5 times with a nail.
(+) When the surface of the coated layer where cracks are generated is scratched 5 times with a nail, a very small amount of the coating film piece of the coat layer is peeled off.
(-) When cracks occur, the coating film of the coat layer peels off from the base material layer.

7) Acid resistance evaluation A sulfuric acid solution (trade name: 64% sulfuric acid, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) adjusted to 0.5% by weight was sprayed onto the coating layer (12) of the protective film at 40 ° C. It was heated on a hot plate and left to stand. After 2 hours, the protective film was taken out from the hot plate, the sulfuric acid component adhering to the surface of the coat layer was washed away with running water, and the acid resistance was evaluated by the following judgment.
(++) There is no change in appearance compared to before the test.
(+) Although there is no deterioration such as whitening, some traces remain.
(-) There is deterioration such as whitening.

8) Water contact angle measurement; Using distilled water (for nitrogen / phosphorus measurement, manufactured by Kanto Chemical Co., Ltd.) as the probe liquid for the coat layer (12) of the water-repellent protective film, a contact angle meter (Drop Master 400, Kyowa). The contact angle of water in the coat layer of the protective film was measured using Kyowa Interface Science Co., Ltd.

9) Slipperiness: Squeegee sliding test When attaching the protective film to the adherend, after spraying the construction liquid on the film surface, remove the construction liquid while crimping with a squeegee and attach it. At that time, if the slipperiness of the coat layer (12) is low, the squeegee may be caught, the construction workability may be lowered, and the appearance after pasting may be deteriorated. Therefore, a test was conducted to confirm the squeegee slidability of the produced protective film.
Peel off the release film of the laminated body cut to a size of 40 mm in width and 130 mm in length, and spray an aqueous solution of 1 L of water mixed with 2 to 3 drops of baby shampoo (baby whole body shampoo, manufactured by Johnson End Johnson). Spray on the adhesive layer surface side, surface and coating test plate (width 50 mm, length 150 mm, thickness 1.2 mm) coated with black paint for automobiles, and use a rubber squeegee to cover the adhesive layer surface of the laminate with air bubbles and water bubbles. Was extruded and attached to the paint test plate. At that time, the squeegee slidability was determined by the following determination.
(+): The squeegee did not get caught and was attached smoothly.
(-): The squeegee was caught.

10) The release film of the protective film cut out from a piece having an initial adhesive strength of 25 mm × 180 mm was removed. This was used as a test sample. Separately, a polycarbonate plate (Panlite PC1151, width 70 mm, length 150 mm, thickness 1.2 mm) was prepared. The adhesive layer of the test sample was brought into close contact with the coated plate so that the longitudinal direction of the test sample protruded from the polycarbonate plate, and the outer surface of the test sample was pressed with a rubber roller. The pressing conditions were roll weight: 2 kg, roll moving speed: 5 mm / sec, and number of roll presses: one reciprocation over both ends of the test sample. Then, the coated plate to which the test sample was in close contact was stored for 20 minutes in an environment of temperature: 23 ± 2 ° C. and relative humidity: 50 ± 5%. Then, the force required to pull the end of the test sample that was not in close contact with the polycarbonate plate to peel the test sample from the polycarbonate plate was measured as the adhesive force of the test sample. For the above adhesive strength, the end of the test sample is peeled off from the fixed polycarbonate plate with a tensile / compression / bending tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of a crosshead load of 100 N and a crosshead speed of 300 mm / min. It was measured as the maximum stress at the time of.

As shown in Table 1, the protective films produced in Examples 1, 2, 2, 3, and 5 have cracks and the like due to the use of DDDA as a curable component of the coating agent. It was possible to exhibit high acid resistance without causing poor appearance. On the other hand, in Example 4 in which the compounding ratio of DDDA was the lowest, the evaluation of acid resistance was good, but the acid resistance was lowered as compared with Example 1, Example 2, Example 3, and Example 5. It was a tendency. Further, in Example 5 in which only DDDA was used as the coating agent, the adhesion between the coat layer and the base material layer was lowered.

The protective films produced in Examples 1, 2, 3, and 4 are added to DDDA while adjusting the ratio of M309 to enhance the adhesion between the base material layer and the coat layer. It played a role as an anchor coat and was able to improve the adhesion of the coat layer. Therefore, there is less concern that the coat layer will be peeled off even when it is stretched and attached to the adherend, and it is suitable as a protective film for automobiles that can provide a good balance between acid resistance and adhesion of the coat layer. Further, in Example 1, Example 3, Example 4, and Example 5 to which XUA008 is added, the squeegee slipperiness can be further improved as compared with Example 2 in which XUA008 is not added, and the workability is further improved. Was completed.
Even in Example 6 in which the base material layer was different, the same effect was confirmed in improving the acid resistance.
On the other hand, as shown in Table 2, Comparative Example 2, Comparative Example 3, and Comparative Example 4 are acid-resistant by using a 4,5-functional acrylate (manufactured by Aronix M402 Toagosei Co., Ltd.) as a curable component of the coating agent. However, after the coating agent was applied, cracks in the coat layer occurred and the appearance became poor. It seems that the cause is a large difference in hardness between the thermoplastic polyurethane that constitutes the base material layer and the coat layer. Comparative Example 5 (protective film K) and Comparative Example 6 (protective film L) not coated with the coating agent had no acid resistance.

The protective film of the present invention can be used not only for automobile applications but also for windows, digital signage, outdoor touch panels and the like. It can also be used for automobile interiors and indoors, and can also be used for automobile cockpit panels, floorboards, kitchens, bathroom walls, packaging, protection of office supplies, and the like. In addition, since the surface of the protected article can be smoothed, the design can be improved.

10 Protective film 11 Base material layer 12 Coat layer 13 Adhesive layer 14 Release film s1 Surface ss Fluorosylsesquioxane derivative, reactive silicone compound

Claims (10)

A coating agent containing a dimerdiol di (meth) acrylate-based resin, a polyfunctional (meth) acrylate-based compound, and a photopolymerization initiator. The coating agent according to claim 1, wherein the polyfunctional (meth) acrylate compound is a trifunctional acrylate compound. A coat layer formed on a base material layer using the coating agent according to claim 1 or 2, a base material layer formed using thermoplastic polyurethane, and a coat layer of the base material layer are formed. A protective film comprising an adhesive layer formed by using at least one resin selected from an acrylic-based, urethane-based, rubber-based, and silicone-based resin on the surface side opposite to the surface side. The protective film according to claim 3, wherein the thermoplastic polyurethane is a polycaprolactone-based thermoplastic polyurethane. The protective film according to claim 3 or 4, wherein the coating agent further contains at least one reactive silicone compound selected from the group of siloxanes having acryloyl groups at both ends or one end. The protective film according to any one of claims 3 to 5, wherein the coating agent further contains at least one fluorine compound selected from the group consisting of fluorosilsesquioxane and fluorosilsesquioxane polymers. .. The protective film according to claim 6, wherein the fluorine compound has a cage-shaped structure. The fluorosilsesquioxane polymer is an addition polymer of fluorosilsesquioxane having at least one addition-polymerizable functional group, or with fluorosilsesquioxane having one addition-polymerizable functional group. The protective film according to claim 6 or 7, which is an addition copolymer with an addition-polymerizable monomer. An automobile body to which the protective film according to any one of claims 3 to 8 is attached to the surface by the adhesive layer. A headlight in which the protective film according to any one of claims 3 to 8 is attached to the surface by the adhesive layer.

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