Photopolymerizable coating composition and product using same

Abstract

Provided is a coating film having improved weathering resistance.　Provided is a photopolymerizable coating composition containing a component (a) that is a urethane (meth)acrylate, a component (b) that is a photopolymerizable (meth)acrylic compound, and a component (c) that is a photostabilizer represented by formula (2), said composition containing the component (a) and the component (b) as photopolymerizable components. Relative to the total amount of photopolymerizable components, the component (a) is blended at a quantity of 1-50 parts by weight and the component (b) is blended at a quantity of 50-99 parts by weight. If the total amount of the component (a) and the component (b) is 100 parts by weight, the component (c) is blended at a quantity of 1-20 parts by weight. The component (b) includes a component (b1) that is a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by formula (1), a component (b2) that is a reactive silicone, and a component (b3) that is a photopolymerizable acrylic compound not having a urethane unit and having neither a fluorine atom nor an Si atom.

Description

Photopolymerizable coating composition and its use

[0001] The present invention relates to a photopolymerizable coating composition that can be used as a material for laminates such as top coat layers for various articles, surface protection films, decorative films, and paint protection films, and to products using the same.

[0002] BACKGROUND ART Laminate materials such as top coat layers, surface protection films, decorative films, and paint protection films are frequently used on the surfaces of various articles, including vehicles such as automobiles and motorcycles, as well as ships, buildings, electrical products, exhibits, interior decorations, furniture, factory equipment, industrial equipment, and medical equipment, for various purposes such as surface protection and as an alternative to paint.

[0003] Among these, paint protection film (PPF) is a film-like product used to protect the surfaces of industrial products used outdoors. The basic structure of PPF is a laminate comprising at least two layers: a substrate made of a flexible, transparent resin film and an adhesive layer. PPF is typically supplied to the market in the form of a laminate, further comprising a coating layer on the side of the substrate opposite the adhesive layer to enhance the substrate's stain resistance and scratch resistance, and a release layer on the side of the adhesive layer opposite the substrate. When using PPF, first cut the PPF to fit the surface of the industrial product to be protected, and then adhere the adhesive layer of the cut PPF to the surface to be protected. Products coated with PPF are protected from various external stimuli, such as soiling and scratches caused by wind, rain, dust, sand, river water, microorganisms, and contact and excretion of animals, plants, and insects, without damaging their paint, shape, or appearance. Specifically, PPF acts as a cushion to absorb pressure and impacts from the outside world, and PPF repels rainwater and dirt, thereby reducing the impact of external stimuli on the product itself.

[0004] PPF was originally developed for industrial products used in harsh environments, such as airplanes, but is now becoming increasingly popular as a surface protection material for automobiles, motorcycles, and other vehicles. For example, coating the roof, hood, front, doors, and trunk doors of an automobile with PPF can protect the body from bird droppings, dead insects, cat paw prints, vandalism, scratches caused by carrying luggage, and scratches caused by flying stones, all of which plague drivers. PPF can typically be used for a relatively long period of time, as dirt on the PPF surface can be easily removed by washing the PPF-coated surface with water. After a certain period of use, PPF can be easily peeled off the body and replaced with new PPF.

[0005] With the recent spread of automobiles, motorcycles, and other vehicles around the world, there is a demand for PPF that can be used in a wider range of environments, for example, in cold, tropical, and more severe climates than arid regions. Furthermore, as the PPF market expands, there is a demand for PPF that can be applied more easily and appropriately by workers without special skills. Therefore, PPF in recent years is required to have various performance characteristics, such as flexibility to adapt to the varied surface shapes of automobiles and motorcycles, durability to withstand external stimuli over a long period of time, transparency and smoothness that do not impair the appearance of the product itself, and easy peelability when replacing.

[0006] For example, Patent Document 1 describes a PPF that has excellent adhesion properties and minimizes adhesive residue by laminating a base film and an adhesive layer with controlled surface roughness. However, this PPF does not specifically address the antifouling layer that is added to the surface of the base film, and there are problems with its practicality for use in automobiles and motorcycles, where appearance is important.

[0007] For example, Patent Document 2 describes a PPF in which a first layer containing polyurethane, a second layer containing thermoplastic polyurethane, and a third layer containing a pressure-sensitive adhesive are laminated in this order. However, even this PPF requires further improvement in its performance.

[0008] JP 2016-20079 A JP 2008-539107 A

[0009] As such, there is room for improvement in the prior art PPF technology. The present inventors focused on weather resistance, which was not considered in the prior art, as a performance to be improved, namely, the ability to maintain the original surface shape even after long-term use in harsh outdoor environments. The present inventors aimed to improve this weather resistance by modifying the coating material that constitutes the outermost surface of a laminate such as PPF.

[0010] As a result, the inventors discovered that an acrylic photopolymerizable coating composition containing a specific photopolymerizable component and a light stabilizer can produce a coating film (coating layer) that maintains its surface shape for a long period of time when used in an outdoor environment. Furthermore, the inventors discovered that a coating layer made of a cured product of this photopolymerizable coating composition can be used as a laminate such as PPF. That is, the present invention is as follows.

[0011] (Invention 1) A photopolymerizable coating composition comprising: component (a): a urethane (meth)acrylate; component (b): a photopolymerizable (meth)acrylic compound; and component (c): a light stabilizer represented by formula (2), wherein components (a) and (b) are contained as photopolymerizable components, and are mixed in a ratio of 1 to 50 parts by weight of component (a) and 50 to 99 parts by weight of component (b) relative to the total amount of the photopolymerizable components, and component (c) is mixed in a ratio of 1 to 20 parts by weight when the total amount of components (a) and (b) is taken as 100 parts by weight, and wherein component (b) comprises: component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by formula (1), component (b2): a reactive silicone, and component (b3): ​​a photopolymerizable acrylic compound that has no urethane units and has neither a fluorine atom nor a Si atom.

[0012]

[0013] (In formula (1), R ｆ １ ~R ｆ ７are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen may be replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl or alkyl may be replaced by fluorine or trifluoromethyl, and A １ is a group represented by formula (1-1) or formula (1-2).

[0014]

[0015] (In formula (1-1), Y ３ is alkylene having 2 to 10 carbon atoms, and R ６ is hydrogen, linear alkyl having 1 to 5 carbon atoms, branched alkyl having 3 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms.

[0016]

[0017] (In formula (1-2), Y ４ is a single bond or alkylene having 1 to 10 carbon atoms.

[0018]

[0019] (In formula (2), n is an integer of 4 to 12, each R is independently alkyl having 1 to 5 carbon atoms or alkoxy having 4 to 10 carbon atoms, and Me is methyl.)

[0020] (Invention 2) The component (b1) contains a structural unit derived from γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane represented by formula (1-3),

[0021]

[0022] The photopolymerizable coating composition of Invention 1, wherein the component (b2) is a polyorganosiloxane compound containing terminal vinyl groups.

[0023] (Invention 3) The photopolymerizable coating composition of Invention 1, further comprising component (d): an ultraviolet absorber.

[0024] (Invention 4) The photopolymerizable coating composition of Invention 2, further comprising component (d): an ultraviolet absorber.

[0025] (Invention 5) The photopolymerizable coating composition of Invention 1, further comprising component (e): a fluorine-based surfactant.

[0026] (Invention 6) The photopolymerizable coating composition of Invention 2, further comprising component (e): a fluorine-based surfactant.

[0027] (Invention 7) A laminate comprising a coating layer made of a cured product of the photopolymerizable coating composition of any one of Inventions 1 to 6 and a substrate layer in contact with each other.

[0028] (Invention 8) A laminate comprising a coating layer made of a cured product of the photopolymerizable coating composition of any one of Inventions 1 to 6, a substrate layer made of thermoplastic polyurethane, and an adhesive layer made of a pressure-sensitive adhesive, which are bonded together in this order.

[0029] (Invention 9) An article having the laminate of Invention 8 attached to a surface by the adhesive layer.

[0030] The good surface shape of the coating film (coating layer) obtained from the photopolymerizable coating composition of the present invention is maintained even after long-term outdoor use, and therefore the laminate of the present invention has excellent weather resistance.

[0031] Fig. 1 is a diagram showing an example of the laminate of the present invention, and Fig. 2 is a diagram showing an example of the laminate of the present invention used as a PPF.

[0032] [1. Photopolymerizable Coating Composition] The photopolymerizable coating composition of the present invention contains, as essential components, component (a): urethane (meth)acrylate, component (b): photopolymerizable (meth)acrylic compound, and component (c): light stabilizer represented by formula (2), and contains the above components (a) and (b) as photopolymerizable components. In the photopolymerizable coating composition of the present invention, the above components (a) and (b) may be in a diluted state or may be in a state consisting of undiluted polymers. In the description, "(meth)acrylate" means acrylate or methacrylate, "(meth)acrylo" means acrylo or methacrylo, and "(meth)acrylic" means acrylic or methacrylic.

[0033] In the present invention, from the viewpoint of maintaining the good surface shape of the coating film (coating layer) even after long-term use in an outdoor environment, i.e., from the viewpoint of excellent weather resistance, the components (a) and (b) are mixed in such a manner that, relative to the total amount of the photopolymerizable components, the components (a) and (b) are 1 to 50 parts by weight of the component (a) and 50 to 99 parts by weight of the component (b), preferably 1 to 30 parts by weight of the component (a) and 70 to 99 parts by weight of the component (b). Furthermore, from the viewpoint of maintaining the good surface shape of the coating film (coating layer) even after long-term use in an outdoor environment, i.e., from the viewpoint of excellent weather resistance, the components (c) are mixed in such a manner that, relative to the total amount of the components (a) and (b) is 100 parts by weight, the components (c) are 1 to 20 parts by weight, preferably 1 to 10 parts by weight.

[0034] [Component (a): Urethane (meth)acrylate] The urethane (meth)acrylate used as the component (a) is a general term for an oligomeric compound having a reactive (meth)acryloyl group at its terminal, which is obtained by reacting an isocyanate compound, a polyol, a hydroxyl group-containing (meth)acrylic monomer, and an isocyanate group-containing (meth)acrylic monomer.

[0035] The urethane (meth)acrylate used in the present invention is typically an ultraviolet-curable urethane (meth)acrylate, and is preferably a urethane (meth)acrylate obtained by reacting (i) an isocyanate compound consisting of an aliphatic isocyanate compound and / or an alicyclic isocyanate compound, (ii) one or more polyol compounds selected from an ester-based polyol, (iii) an ether-based polyol, or (iv) a polycarbonate-based polyol, and (v) a (meth)acrylate compound having a hydroxyl group.

[0036] (i) Examples of the aliphatic isocyanate compounds include hexamethylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of the alicyclic isocyanate compounds include isophorone diisocyanate, 4,4'-dicyclohexylmethane isocyanate, and hydrogenated xylylene diisocyanate.

[0037] (ii) Examples of the ester polyol include ester compounds obtained by reacting diols with dicarboxylic acid. Examples of the diols include 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol. Examples of the dicarboxylic acid include sebacic acid, adipic acid, dimer acid, succinic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, and citraconic acid, and anhydrides thereof may also be used.

[0038] (iii) Examples of ether polyols include polyether diols, poly(oxytetramethylene) glycols, and poly(oxybutylene) glycols. Specific examples of the polyether diols include polypropylene glycols, polyethylene glycols, polytetramethylene glycols, and propylene-modified polytetramethylene glycols.

[0039] (iv) Examples of polycarbonate polyols include reaction products of carbonate derivatives and diols. Examples of the carbonate derivatives include diallyl carbonates such as diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. Examples of the diols include the compounds described above.

[0040] (v) Examples of acrylate compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0041] In producing such a urethane acrylate, the essential components, i.e., an isocyanate compound, a polyol compound, and an acrylate compound having a hydroxyl group, can be charged and reacted all at once. Alternatively, a (meth)acrylate compound having a hydroxyl group can be reacted with the isocyanate compound to produce a prepolymer having an excess of isocyanate groups, and the remaining isocyanate groups can then be reacted with a polyol compound.

[0042] Alternatively, an isocyanate compound may be reacted with a polyol compound to produce a prepolymer having an excess of isocyanate groups, and then the remaining isocyanate groups may be reacted with a (meth)acrylate compound having a hydroxyl group. The urethane (meth)acrylate produced by these methods preferably has a polyurethane chain.

[0043] In the present invention, commercially available products such as Shikoh UT-5569 (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., AUP-838 (trade name) manufactured by Tokushiki Corporation, RUA-062S, RUA-058SY2, RUA-012, and RUA-075 (trade names) manufactured by Asia Industries Co., Ltd., and P7-532 (trade name) manufactured by Kyoeisha Chemical Co., Ltd. can be used.

[0044] [Component (b): Photopolymerizable (meth)acrylic compounds] The photopolymerizable coating composition of the present invention contains component (b): photopolymerizable (meth)acrylic compounds as a component that photopolymerizes with component (a). Component (b) includes component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by formula (1), component (b2): a reactive silicone, and component (b3): ​​a photopolymerizable acrylic compound that does not have a urethane unit and does not have either a fluorine atom or a Si atom. However, component (b) does not contain component (a). Components (b1), (b2), and (b3) are mixed in a diluted state or in a state consisting of undiluted polymers.

[0045] There are no particular restrictions on the proportions of the components (b1), (b2), and (b3) in the component (b). Generally, the components (b1) and (b2) are blended together so that the total amount of the components (b1) and (b2) is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of the total amount of the component (b), with the component (b3) accounting for the remainder. Generally, the component (b2) is combined in an amount of 0.1 to 10 times, preferably 0.2 to 5 times, the weight of the component (b1). In the present invention, a synergistic effect can be achieved by using the component (b2) in combination with the component (b1).

[0046] [Component (b1): Photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative]

[0047] The component (b1) contained in the component (b) used in the present invention has a fluorosilsesquioxane structure and is generally classified into a random structure, a ladder structure, or a cage structure depending on its Si—O—Si skeleton. Among these, a photopolymerizable (meth)acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by formula (1) is particularly preferred.

[0048]

[0049] In formula (1), R ｆ １ ~R ｆ７ are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen may be replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl or alkyl may be replaced by fluorine or trifluoromethyl, and A １ is a group represented by formula (1-1) or formula (1-2). The meaning of the phrase "at least one methylene in the fluoroalkyl may be replaced by oxygen" is shown below as an example. For example, when the terminal of the fluoroalkyl is C ４ H ９ -, in which at least one methylene is replaced with oxygen, includes C ３ H ７ -O-, CH ３ -O-(CH ２ ) ２ -, CH ３ -O-CH ２ In this way, the term "at least one" means "at least one selected without distinction." In consideration of the stability of the compound, it is preferable that oxygen atoms are not adjacent to each other. ３ -O-O-CH ２ -, rather than oxygen and oxygen are not adjacent ３ -O-CH ２ --O-- is preferred.

[0050] Preferably, R in formula (1) ｆ １ ~R ｆ ７are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy)propyl, pentafluorophenylpropyl, pentafluorophenyl, or α,α,α-trifluoromethylphenyl.

[0051] More preferably, R in formula (1) ｆ １ ~R ｆ ７ are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

[0052]

[0053] In formula (1-1), Y ３ is alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, and R ６ is hydrogen, straight or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms.

[0054]

[0055] In formula (1-2), Y ４ is a single bond or alkylene having 1 to 10 carbon atoms.

[0056] The fluorosilsesquioxane derivative (1) is produced by the following method: First, a silicon compound (3) having a trifunctional hydrolyzable group, represented by formula (3), is hydrolyzed in an oxygen-containing organic solvent in the presence of an alkali metal hydroxide, followed by polycondensation to produce a compound (4) represented by formula (4).

[0057]

[0058]

[0059] In formula (4), M is not particularly limited as long as it is an alkali metal, such as lithium, sodium, potassium, or cesium.

[0060] R in formulas (3) and (4) １ and R ２ are each independently R in the above formula (1). ｆ １ ~R ｆ ７ and X is a linear or branched fluoroalkyl having 1 to 20 carbon atoms, in which at least one methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms, in which at least one hydrogen may be replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms, in which at least one hydrogen in the aryl or alkyl may be replaced by fluorine or trifluoromethyl; １ ~X ３ is a hydrolyzable group.

[0061] Preferably, R in formulas (3) and (4) １ and R ２ are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy)propyl, pentafluorophenylpropyl, pentafluorophenyl, or α,α,α-trifluoromethylphenyl.

[0062] More preferably, R in formulas (3) and (4) １ and R ２ are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

[0063] Next, the compound (4) is reacted with a compound (5) represented by formula (5) to obtain the fluorosilsesquioxane derivative (1).

[0064]

[0065] Group X in formula (5) ４ is a group represented by the above formula (1-1) or formula (1-2).

[0066] Among such fluorosilsesquioxane derivatives (1), γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane represented by formula (6) is preferred.

[0067]

[0068] The introduction of a fluorosilsesquioxane derivative (1), such as γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane, into a coating layer can further improve the antifouling function of the coating layer. When the fluorosilsesquioxane derivative (1) is incorporated into a photopolymerizable (meth)acrylic compound, the fluorosilsesquioxane derivative (1) may be directly mixed with other photopolymerizable (meth)acrylic compounds, or an oligomer produced by crosslinking and / or polymerizing the fluorosilsesquioxane derivative (1) with a photopolymerizable (meth)acrylic compound may be mixed with other photopolymerizable acrylic compounds.

[0069] In general, a polymer having fluorosilsesquioxane derivative (1) units is prepared in advance by copolymerizing the fluorosilsesquioxane derivative (1) with one or more (meth)acrylate copolymerization components selected from monofunctional acrylates, difunctional acrylates, and polyfunctional acrylates, and this polymer is used as part of the photopolymerizable (meth)acrylic compounds. In this case, the polymer having fluorosilsesquioxane derivative (1) units is blended in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, relative to the photopolymerization component.

[0070] As the one or more (meth)acrylate copolymerization components described above, compounds generally called photocurable acrylic monomers can be used, for example, monofunctional acrylates such as (meth)acrylic acid, (meth)acrylic acid esters and hydroxy group-containing (meth)acrylic acid esters, difunctional acrylates such as (poly)alkylene glycol di(meth)acrylates, trifunctional or higher polyfunctional acrylates such as pentaerythritol triacrylate, and oligomers obtained by polymerizing these.

[0071] [Component (b2): Reactive Silicone] The component (b2): reactive silicone contained in the component (b) used in the present invention is a group of silicone compounds also known as reactive silicone oil or polysiloxane macromonomer. These are used in the field of polymer synthesis as raw materials for block copolymers and graft copolymers, as modifiers for molding resins, and as modifiers for paints. This component (b2) improves the surface smoothness of the photopolymerizable coating composition of the present invention.

[0072] As the component (b2), a polyorganosiloxane compound containing a terminal vinyl group is preferred, and a polydimethylsiloxane macromonomer having a terminal methacryloyl group is more preferred.

[0073] [Component (b3): ​​Photopolymerizable acrylic compound without urethane units and without fluorine or silicon atoms] The photopolymerizable coating composition of the present invention contains component (b3): ​​a photopolymerizable acrylic compound without urethane units and without fluorine or silicon atoms, as a crosslinking agent or copolymerizable monomer that photopolymerizes with at least one of the above-mentioned components (a), (b1), and (b2). This component (b3) contributes to the extension of the polymerization chain during curing of the photopolymerizable coating composition of the present invention. The resin component primarily composed of component (b3) contributes to the strength of the coating film (coating layer) produced by the curing. Such component (b3) can be selected from various compounds and products available as photopolymerizable acrylic compounds or solutions containing the same, and there is no limit to the type.

[0074] The component (b3) may be supplied to the photopolymerizable coating composition of the present invention in a form in which it has been previously mixed with one or more selected from the components (a), (b1), and (b2). Alternatively, a copolymer obtained by reacting at least a portion of the component (b3) with one or more selected from the components (a), (b1), and (b2) may be supplied to the photopolymerizable coating composition of the present invention.

[0075] [Component (c): Light Stabilizer Represented by Formula (2)] The component (c) used in the present invention is a light stabilizer containing a compound represented by formula (2). In formula (2), n is an integer of 4 to 12, each R is independently alkyl having 1 to 5 carbon atoms or alkoxy having 4 to 10 carbon atoms, and Me is methyl. In formula (2), preferably, n is an integer of 6 to 12, each R is independently alkyl having 1 to 3 carbon atoms or alkoxy having 6 to 8 carbon atoms, more preferably, n is an integer of 6 to 10, and each R is independently linear alkyl having 1 to 3 carbon atoms or linear alkoxy having 6 to 8 carbon atoms, or cyclohexyloxy. Preferred examples of the component (c) include TINUVIN 765 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate), TINUVIN 292 (compound name: a mixture of approximately 75% by weight of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and approximately 25% by weight of methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate), and TINUVIN 123 (compound name: reaction product of decanedioic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester (in the presence of 1,1-dimethylethyl hydroperoxide and octane)), both of which are trade names of BASF.

[0076] [Component (d): Ultraviolet Absorber] The photopolymerizable coating composition of the present invention can further contain component (d): an ultraviolet absorber. Examples of component (d) include ultraviolet absorbers such as benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, and dibenzoylresorcinols.

[0077] Examples of benzotriazoles include TINUVIN PS, TINUVIN 99-2, TINUVIN 326, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, and TINUVIN Carboprotect, both manufactured by BASF. Examples of hydroxyphenyltriazines include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479, both manufactured by BASF. Examples of benzophenones include ADEKASTAB1413, both manufactured by ADEKA Corporation, and Sumisorb130, both manufactured by Sumika Chemtex Co., Ltd. Examples of salicylates include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of cyanoacrylates include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and ethyl 2-cyano-3,3-diphenylacrylate. Examples of triazines include ADEKASTAB LA-46 and ADEKASTAB LA-F70 (trade names) manufactured by ADEKA Corporation, and an example of dibenzoylresorcinols is 4,6-dibenzoylresorcinol. These ultraviolet absorbers may be used alone or in combination. It is preferable to appropriately select the type and combination of ultraviolet absorbers based on the wavelength of ultraviolet light to be absorbed. The photopolymerizable coating composition of the present invention preferably contains 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, of the component (d) per 100 parts by weight of the total amount of the photopolymerizable components, the components (a) and (b), so that the good surface shape of the coating film (coating layer) can be maintained even after long-term use in an outdoor environment, i.e., from the viewpoint of excellent weather resistance.

[0078] [Component (e): Fluorine-Based Surfactant] The photopolymerizable coating composition of the present invention can further contain the above-mentioned component (e): a fluorine-based surfactant. This component (e) is a monomer or oligomer having a fluorine atom and a photopolymerizable unsaturated group in its chemical structure, and refers to a group of materials known in the coatings field as fluorine-based additives, fluorine-based surfactants, fluorine-based surface modifiers, etc. For convenience, in this specification, the above-mentioned component (e) will be referred to as a "fluorine-based surfactant," which is one of the general terms.

[0079] Component (e) is preferably a nonionic compound that does not separate into components in the photopolymerizable coating composition of the present invention, has high solubility in various organic solvents (e.g., ether-based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents), and contains 0.01 to 80% by weight of fluorine.

[0080] The preferred component (e) is a perfluoropolyether compound having a perfluoropolyether skeleton and a photopolymerizable unsaturated group at one or both ends. The perfluoropolyether skeleton may be, for example, —(O—CF ２ CF ２ ) -, -(OCF ２ CF ２ CF ２ )-, or -(O-CF ２ C (CF ３ The photopolymerizable unsaturated group is not particularly limited, and examples thereof include (meth)acryloyl, (meth)acryloyloxy, vinyl, and allyl groups, and from the viewpoint of reactivity with the component (a) and the component (b), a (meth)acryloyl group is preferred.

[0081] Examples of such component (e) that can be used include "Megafac (registered trademark) RS-75" (trade name manufactured by DIC Corporation), "KY-1203" (trade name manufactured by Shin-Etsu Chemical Co., Ltd.), "FLUOROLINK AD1700" and "FLUOROLINK MD700" (trade names manufactured by Solvay Solexis K.K.), "OPTOOL DAC-HP" (trade name manufactured by Daikin Chemical Industries, Ltd.), and "CN4000" (trade name manufactured by Sartomer).

[0082] The photopolymerizable coating composition of the present invention can contain generally 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, of the component (e) relative to 100 parts by weight of the total amount of the photopolymerizable components (a) and (b).

[0083] [2. Polymerization Initiator] The polymerization initiator used for curing the photopolymerizable coating composition of the present invention can be any photopolymerization initiator available in the market without limitation. Examples of such photopolymerization initiators include polymers of hydroxyketones such as {2-hydroxy-2-methyl-1-phenylpropanone}, 1-hydroxydicyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-{4(2-hydroxyethoxy)phenyl}-2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphineoxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide.

[0084] [3. Additives] Various additives may be added to the photopolymerizable coating composition of the present invention as needed. For example, a filler may be added to impart hardness and scratch resistance to the coating layer. A leveling agent may be added to improve coatability. Other additives such as weathering agents and antifoaming agents may also be added. More specifically, the photopolymerizable coating composition may further contain optional components such as active energy ray sensitizers, polymerization inhibitors, polymerization initiator aids, leveling agents, wettability improvers, surfactants, plasticizers, light stabilizers other than component (c), antioxidants, antistatic agents, silane coupling agents, inorganic fillers (such as silica and alumina), and organic fillers, as long as they do not adversely affect the effects of the coating layer formed from the photopolymerizable coating composition.

[0085] Examples of light stabilizers other than the component (c) include hindered benzoate-based light stabilizers and hindered amine-based light stabilizers (HALS) other than the component (c).

[0086] Examples of the hindered benzoate light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and 2,4-di-t-amylphenyl-3,5-di-t-butyl-4-hydroxybenzoate. Examples of hindered amine light stabilizers (HALS) other than the above component (c) include BASF's trade name: TINUVIN (registered trademark) 5100 (a neutral general-purpose HALS), TINUVIN 152 (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), and TINUVIN 144 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl] methyl]butylmalonate), TINUVIN 111FDL (a mixture of about 50% by weight, TINUVIN 622, compound name: (butanedioic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl)ethanol), and about 50% by weight, CHIMASSORB 119, compound name: N-N'-N''-N'''-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine), or ADEKA STAB (trade name, manufactured by ADEKA Corporation) LA series, specifically LA-52 ((5)-6116), LA-57 ((5)-5555), LA-62 ((5)-5711), LA-67 ((5)-5755), LA-82 ((5)-6023), LA-87 ((5)-6022). The numbers in parentheses are the numbers of existing chemical substances.

[0087] [4. Use of Photopolymerizable Coating Composition] The photopolymerizable coating composition of the present invention can be applied to the surface of various articles, followed by curing and drying, to form a coating film (coating layer) that imparts antifouling and water-repellent properties to the surface of the article. There are no particular restrictions on the articles on which the coating layer can be formed, but laminates are particularly advantageous in that the liquid photopolymerizable coating composition of the present invention can be easily applied. Among laminates, PPF, which is required to have antifouling and water-repellent properties, is particularly useful as a laminate utilizing the coating layer.

[0088] The layer structure, manufacturing method and uses of the laminate provided with the coating layer will be described in detail below.

[0089] [Coating Layer] The coating layer constituting the laminate of the present invention is composed of a polymer obtained by curing the above-mentioned photopolymerizable coating composition on the substrate layer in the presence of a polymerization initiator. The thickness of the coating layer is generally 1 to 100 μm, preferably 2 to 50 μm, and more preferably 3 to 30 μm. The structure of the polymer constituting such a coating layer is complex and cannot be expressed by a single constituent unit or a uniform structural formula. In the present invention, the polymer constituting the coating layer is defined by the photopolymerizable compound contained in the above-mentioned photopolymerizable coating composition.

[0090] [Substrate Layer] As the substrate layer constituting the laminate of the present invention, it is desirable to use a film formed of a thermoplastic resin. Examples of thermoplastic resins include polyurethane resins, polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and norbornene resins. Specifically, thermoplastic polyurethane, polycaprolactone (PCL), acrylic acid polymers, polyester, polyacrylonitrile, polyether ketone, polystyrene, polyvinyl acetate, or derivatives thereof are preferred. These resins may be used alone or in combination.

[0091] A particularly preferred substrate layer is a thermoplastic polyurethane. Examples of trade names of thermoplastic polyurethanes include ArgoGuard (registered trademark) 49510 and ArgoGuard (registered trademark) 49510-DV manufactured by SWM International, Esmer URSPX86, Esmer URSPX93, and Esmer URSPX98 manufactured by Nihon Matai Co., Ltd., DUS202, DUS213, DUS235, DUS501, DUS601, DUS605, DUS614, DUS203, DUS220, DUS701, XUS2086, XUS2098, DUS451, and DUS450 manufactured by Seedam Co., Ltd., and Unigrand XN2001, XN2002, and XN2004 manufactured by Japan Unipolymer Co., Ltd. Among these, polycaprolactone-based thermoplastic polyurethanes using polycaprolactone polyol as the polyhydroxy compound, polycarbonate-based thermoplastic polyurethanes using polycarbonate polyol, and polyether-based thermoplastic polyurethanes using polyether polyol are preferred.

[0092] In the present invention, the thickness of the substrate layer is not particularly limited, but is usually 25 to 300 μm, and preferably 100 to 200 μm.

[0093] [Adhesive Layer] The adhesive layer constituting the laminate of the present invention is made of a pressure-sensitive adhesive. The pressure-sensitive adhesive used in the present invention can be any known adhesive that exhibits adhesiveness at the application temperature of a laminate such as PPF, i.e., at a temperature of about 20 to about 30°C, and is used to bond molded articles made of thermoplastic polyurethane-based materials to articles such as glass, metal, plastic, and paper. Commercially available acrylic pressure-sensitive adhesives and urethane pressure-sensitive adhesives can be used as such pressure-sensitive adhesives, with acrylic pressure-sensitive adhesives being preferred. The thickness of the adhesive layer is not particularly limited, but is typically about 10 to 200 μm.

[0094] [Release Layer] A release layer is preferably further laminated on the adhesive layer constituting the laminate of the present invention. Any known release material can be used as the material for the release layer, without any restrictions. For example, a resin film such as a polyester resin or a polyolefin resin, cellophane paper, glassine paper, or any of these coated with a fluorine-based or silicone-based release agent can be used. The thickness of the release layer is not particularly limited, but is usually about 20 to 200 μm.

[0095] [Protective Layer] The outer surface of the coating layer of the laminate of the present invention can be covered with a protective layer depending on the storage, transportation, and sales form of the laminate. The material of such a protective layer is not limited, and can be appropriately selected from commonly used plastic films such as polyethylene films and release-treated papers.

[0096] [Method for producing laminate] The method for producing the laminate of the present invention can be any method suitable for forming and laminating each layer, without any restrictions. For example, when the laminate of the present invention further has a release layer and a protective layer, the laminate of the present invention can be produced through the following steps.

[0097] First, an adhesive layer is formed on the release-treated surface of the release layer. The open surface of the formed adhesive layer is then brought into close contact with one surface of the substrate layer to produce a laminate in which the substrate layer, adhesive layer, and release layer are in contact in this order. Next, the above-mentioned photopolymerizable coating composition is applied to the open surface of the substrate layer of the resulting laminate, and the coated surface is irradiated with ultraviolet light to cure the photopolymerizable coating composition. Upon completion of curing, a laminate in which the coating layer, substrate layer, adhesive layer, and release layer are in contact in this order is obtained. Furthermore, the open surface of the coating layer is covered with a protective film. Thus, a laminate in which the protective layer, coating layer, substrate layer, adhesive layer, and release layer are in contact in this order is obtained. The resulting laminate is then appropriately cut, wound, and packaged.

[0098] [Surface protection film, decorative film] The laminate of the present invention thus completed can be cut into appropriate length units, stacked, or wound up and used as a surface protection film or decorative film. When applying the laminate, the laminate of the present invention is cut into a shape that matches the shape and size of the painted surface, and the cut laminate is stretched with an appropriate force to make the adhesive layer adhere to the painted surface.

[0099] In the laminate of the present invention, the coating layer, which has excellent strength, smoothness, water repellency, and oil repellency, functions to mitigate external stimuli on the application surface. Meanwhile, the flexible base layer adheres to the application surface via the adhesive layer. After a certain period of use, the laminate can be removed without damaging the surface of the application surface.

[0100] [Production of a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units, an example of component (b1)] First, γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane was synthesized according to the following procedure. Trifluoropropyltrimethoxysilane (100 g), tetrahydrofuran (THF) (500 mL), deionized water (10.5 g), and sodium hydroxide (7.9 g) were charged into a 1 L four-neck flask equipped with a reflux condenser, a thermometer, and a dropping funnel. The mixture was heated in an oil bath from room temperature to the temperature at which the THF refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. The flask was then removed from the oil bath and allowed to stand at room temperature overnight. After that, the flask was placed back into the oil bath and heated and concentrated under constant pressure until a solid precipitated.

[0101] The precipitated product was collected by filtration using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm, and then washed once with THF and dried in a vacuum dryer at 80° C. for 3 hours to obtain 74 g of a colorless powdery solid.

[0102] The obtained solid (65 g), dichloromethane (491 g), and triethylamine (8.1 g) were placed in a 1 L four-neck flask equipped with a reflux condenser, a thermometer, and a dropping funnel, and cooled to 3°C in an ice bath. Next, γ-methacryloxypropyltrichlorosilane (21.2 g) was added, and after confirming that the heat generation had subsided, the flask was removed from the ice bath and aged overnight at room temperature. After washing three times with deionized water, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and the magnesium sulfate was removed by filtration. The mixture was concentrated using a rotary evaporator until a viscous solid precipitated, and 260 g of methanol was added and stirred until a powder was obtained. The powder was filtered using a pressure filter equipped with 5 μm filter paper and dried in a vacuum dryer at 65°C for 3 hours, yielding 41.5 g of a colorless powdery solid. GPC of the obtained solid was analyzed. １ H-NMR measurement was carried out to confirm the production of γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane (6) represented by formula (6).

[0103]

[0104] Next, a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units was synthesized by the following procedure.

[0105] Into a nitrogen-sealed four-neck round-bottom flask equipped with a reflux condenser and a dropping funnel, the above-mentioned γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane (6) (25 g), Silaplane FM-0721 (a polydimethylsiloxane macromonomer having a methacryloxy group at one end and having a number-average molecular weight of Mn 5,000, 6.3 g, trade name of JNC Corporation), 2-hydroxyethyl methacrylate (18.8 g), methyl methacrylate (12.5 g), and methyl ethyl ketone (62 g) were added, and the mixture was refluxed and degassed in an oil bath for 15 minutes. Then, a solution of azobisisobutyronitrile (0.48 g) and mercaptoacetic acid (0.054 g) dissolved in methyl ethyl ketone (4.8 g) was added to initiate polymerization. Three hours after the start of polymerization, azobisisobutyronitrile (0.48 g) was dissolved in methyl ethyl ketone (4.3 g) and added, and the mixture was aged for 5 hours to obtain a copolymer solution. Furthermore, paramethoxyphenol (0.16 g) and dibutyltin dilaurate (0.15 g, manufactured by Resonac Co., Ltd.) were dissolved in methyl ethyl ketone (1.5 g) as polymerization inhibitors and added, followed by dropwise addition of Karenz AOI (acryloyloxyethyl isocyanate, 26.4 g, manufactured by Resonac Co., Ltd.) using a dropping funnel so that the liquid temperature was 35 to 50°C, and the mixture was aged at 45°C for 3 hours after the dropwise addition.

[0106] Methanol (9 g) was then added and treated, after which paramethoxyphenol (0.16 g) was further added, and the mixture was diluted with methyl isobutyl ketone (107.3 g) to obtain a 30 wt % solution of the target polymer (A-1).

[0107] The resulting polymer (A-1) had a weight average molecular weight: Mw 42,000 and a polydispersity index: Mw / Mn 1.9. The weight average molecular weight and polydispersity index were measured using gel permeation chromatography (GPC, model number: Alliance 2695, manufactured by Waters Corporation; column: Shodex GPC KF-804L x 2 (in series), manufactured by Resonac Corporation; guard column: KF-G, manufactured by Resonac Corporation). GPC analysis confirmed that the resulting polymer (A-1) was a polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having acryloyl groups in its side chains.

[0108] Examples 1 to 11, Comparative Examples 1 to 5 Preparation of Photopolymerizable Coating Compositions Photopolymerizable coating compositions of the present invention and comparative photopolymerizable coating compositions were prepared by mixing and stirring the materials according to the compositions shown in Table 1. The materials used are listed below. (Component (a)) P7-532: Urethane acrylate manufactured by Kyoeisha Chemical Co., Ltd., product name: P7-532. (Component (b1)) XUA008: Polymer (A-1) prepared by the method described above. A polymer containing γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane units and having an acryloyl group in the side chain. The parts by weight of XUA008 in Table 1 are the parts by weight of the solid content of a 30 wt% solution of polymer (A-1). (Component (b2)) FM7711: Product name: Silaplane (registered trademark) FM-7711 manufactured by JNC Corporation. Polydimethylsiloxane macromonomer having a number average molecular weight of Mn 1,000 and a methacryloxy group at both ends. FM7725: Trade name: Silaplane (registered trademark) FM-7725, manufactured by JNC Corporation. Polydimethylsiloxane macromonomer having a number average molecular weight of Mn 10,000 and a methacryloxy group at both ends. (Component (b3)) M309: Trade name: Aronix (registered trademark) M309, manufactured by Toagosei Co., Ltd. Trimethylolpropane triacrylate DPCA-120: Trade name: KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd. Caprolactone-modified dipentaerythritol hexaacrylate A-HD-N: Trade name: A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd. 1,6-hexanediol diacrylate. (Component (c)) Tinuvin (registered trademark) 292: Trade name of a light stabilizer manufactured by BASF. TINUVIN 292 (compound name: a mixture of approximately 75% by weight of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and approximately 25% by weight of methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate). (Component (d)) Tinuvin (registered trademark) 479: Trade name of an ultraviolet absorber manufactured by BASF. Hydroxyphenyltriazine-based ultraviolet absorber. Tinuvin (registered trademark) 384-2: Trade name of an ultraviolet absorber manufactured by BASF. Benzotriazole-based ultraviolet absorber. Tinuvin (registered trademark) 400: Trade name of an ultraviolet absorber manufactured by BASF.Hydroxyphenyltriazine-based ultraviolet absorber. (Component (e)) RS-75: UV-reactive surface modifier, fluorine-based additive, product name: Megafac (registered trademark) RS-75, manufactured by DIC Corporation. Oligomer containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups. (Other Components) Photopolymerization initiator: photopolymerization initiator product name: Irgacure (registered trademark) 127, manufactured by BASF. 2-hydroxy-1-(4-((4-(2-hydroxy-2-methylpropanoyl)phenyl)methyl)phenyl)-2-methylpropan-1-one. Tinuvin (registered trademark) 770: light stabilizer product name: bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

[0109] [Production of Laminate] A thermoplastic polyurethane film manufactured by SWM International, trade name: "ArgoGuard (registered trademark) 49510" (thickness: approximately 152 μm) was used as the substrate layer.

[0110] Separately, a commercially available acrylic pressure-sensitive adhesive was applied to a release layer that had been treated with a silicone resin for release, and dried for 5 minutes at 120° C. In this way, a 40 μm thick adhesive layer was formed on one side of the release layer.

[0111] Next, the open surface of the adhesive layer and the base layer were pressed together using a rubber roller, and the resulting mixture was cured for 1 day at 45° C. In this way, a laminate was obtained in which the base layer, adhesive layer, and release layer were contacted in this order.

[0112] The photopolymerizable coating composition prepared using the above-mentioned materials was applied to the open surface of the substrate layer using a Mayer bar and dried at 80°C for 3 minutes. Thereafter, the coating composition was cured using a Fusion UV lamp-equipped belt conveyor curing unit (manufactured by Heraeus GmbH) with an integrated light dose of 500 mJ / cm. ２ The photopolymerizable coating composition was cured at 100° C. A coating layer having a thickness of 4 μm was formed on the substrate layer. A laminate was obtained in which the coating layer, substrate layer, adhesive layer, and release layer were contacted in this order.

[0113] [Weather resistance test of laminate] The laminate consisting of four layers obtained above was subjected to a QUV test (light source: UVB-313, intensity: 0.71 W / m) using an accelerated weather resistance tester manufactured by Q-Panel. ２Test conditions: UV irradiation at 60°C for 4 hours, then 100% relative humidity at 50°C for 4 hours, one cycle repeated for 8 hours), and the gloss and surface roughness parameters of the irradiated surface of the coating layer of the laminate were measured before and after irradiation.

[0114] [Evaluation of Laminate] (1) Gloss Measurement

[0115] The 60-degree specular gloss (gloss) was measured using a gloss meter "VG7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the standard of JIS Z 8741, and the surface gloss of the coating layer of the laminate was evaluated before the weather resistance test and after 672 hours of the weather resistance test.

[0116] (2) Measurement of Surface Roughness Parameter Using a 3D measuring laser microscope "LEXT OLS5000-SAF" manufactured by Olympus Corporation, measurements were taken at five arbitrary locations on the surface of the coating layer of the laminate before the weather resistance test and after 672 hours of the weather resistance test in accordance with the ISO 25178 standard under the following conditions, and then the surface roughness parameter Sa (arithmetic mean height, μm) was calculated using the attached analysis application and averaged. Objective lens: MPLAPON 20x LEXT Zoom: 1x Image size: 1024 x 1024

[0117]

[0118] As shown in Table 1, the laminates of Examples 1 to 11, in which a coating layer was formed using the photopolymerizable coating composition of the present invention, showed small changes in gloss and surface roughness parameter Sa, i.e., excellent weather resistance, when the light stabilizer represented by formula (2) of component (c) was used. In contrast, the laminates of Comparative Examples 1 to 5, which lacked the light stabilizer represented by formula (2), showed large changes in gloss and surface roughness parameter Sa.

[0119] The photopolymerizable coating composition of the present invention is highly useful as a coating material with excellent weather resistance. Laminates having a coating layer using the photopolymerizable coating composition of the present invention are highly useful as PPFs, etc. PPFs, etc., made from the laminates of the present invention can be expected to be applied to a wide range of applications, including vehicles such as automobiles and motorcycles, as well as ships, buildings, electrical appliances, exhibits, interiors, furniture, factory equipment, industrial equipment, and medical equipment.

[0120] REFERENCE SIGNS LIST 1 Coating layer 2 Base layer 3 Adhesive layer 4 Release layer 5 Laminate 6 Painted surface 7 PPF

Claims

1. A photopolymerizable coating composition comprising: component (a): a urethane (meth)acrylate; component (b): a photopolymerizable (meth)acrylic compound; and component (c): a light stabilizer represented by formula (2), wherein the components (a) and (b) are contained as photopolymerizable components, and the components (a) and (b) are mixed in a ratio of 1 to 50 parts by weight of the component (a) and 50 to 99 parts by weight of the component (b) relative to the total amount of the photopolymerizable components, and the component (c) is mixed in a ratio of 1 to 20 parts by weight when the total amount of the components (a) and (b) is taken as 100 parts by weight, and the component (b) comprises: component (b1): a photopolymerizable acrylic compound having a structural unit derived from a fluorosilsesquioxane derivative represented by formula (1), component (b2): a reactive silicone, and component (b3): ​​a photopolymerizable acrylic compound having no urethane unit and having neither a fluorine atom nor a Si atom. (In formula (1), R ｆ １ ~R ｆ ７ are each independently a linear or branched fluoroalkyl having 1 to 20 carbon atoms, in which at least one methylene may be replaced by oxygen; a fluoroaryl having 6 to 20 carbon atoms, in which at least one hydrogen may be replaced by fluorine or trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms, in which at least one hydrogen in the aryl or alkyl may be replaced by fluorine or trifluoromethyl; １ is a group represented by formula (1-1) or formula (1-2). (In formula (1-1), Y ３ is an alkylene having 2 to 10 carbon atoms, R ６ is hydrogen, a linear alkyl having 1 to 5 carbon atoms, a branched alkyl having 3 to 5 carbon atoms, or an aryl having 6 to 10 carbon atoms. (In formula (1-2), Y ４ is a single bond or an alkylene having 1 to 10 carbon atoms. (In formula (2), n is an integer of 4 to 12, each R is independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 4 to 10 carbon atoms, and Me is methyl.) 2. The component (b1) contains a structural unit derived from γ-methacryloxypropylhepta(trifluoropropyl)-T8-silsesquioxane represented by the formula (1-3), 2. The photopolymerizable coating composition of claim 1, wherein the component (b2) is a polyorganosiloxane compound containing terminal vinyl groups.

3. The photopolymerizable coating composition of claim 1 further comprising component (d): an ultraviolet light absorber.

4. The photopolymerizable coating composition of claim 2 further comprising component (d): an ultraviolet light absorber.

5. The photopolymerizable coating composition of claim 1 further comprising component (e): a fluorosurfactant.

6. The photopolymerizable coating composition of claim 2 further comprising component (e): a fluorosurfactant.

7. A laminate comprising a coating layer made of a cured product of the photopolymerizable coating composition according to any one of claims 1 to 6 and a substrate layer in contact with each other.

8. A laminate comprising a coating layer made of a cured product of the photopolymerizable coating composition according to any one of claims 1 to 6, a substrate layer made of thermoplastic polyurethane, and an adhesive layer made of a pressure-sensitive adhesive, which are bonded in this order.

9. An article having the laminate according to claim 8 attached to a surface by the adhesive layer.