Laminate and article with laminate

Abstract

Provided is a laminate having excellent stretchability and solvent resistance. A laminate having a base film and a transparent layer, the transparent layer being a layer formed by curing a composition containing a fluorine-containing polymer having a hydroxyl group or a carboxyl group, a non-fluorine polymer, and a curing agent having a functional group that reacts with the hydroxyl group or the carboxyl group, the fluorine-containing polymer having a hydroxyl value or an acid value of 20 mgKOH / g or more, and the content of the fluorine-containing polymer being 30% by mass or less relative to the total content of the fluorine-containing polymer and the non-fluorine polymer.

Description

Technical Field

[0001] This invention relates to laminated bodies and articles with laminated bodies. Background Technology

[0002] For components used in fields such as automotive exterior parts, laminates are sometimes applied for surface protection. Patent Document 1 discloses a protective film for coatings, characterized in that it has an adhesive layer on a supporting substrate, said adhesive layer being formed by blending a specified acrylic polymer with a base polymer comprising a specified styrene-based block polymer.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2000-351952 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] Because these laminates are attached to articles with a desired shape, excellent tensile strength is required. Additionally, excellent solvent resistance is also required to achieve good surface protection.

[0008] The inventors studied the protective film for coating described in Patent Document 1 and found that it was difficult to balance tensile strength and solvent resistance.

[0009] Therefore, the objective of this invention is to provide laminates and articles thereof with excellent tensile strength and solvent resistance.

[0010] Solution for solving the problem

[0011] The inventors conducted in-depth research and found that the problem can be solved using the following configuration.

[0012] [1] A laminate having a substrate film and a transparent layer, wherein the transparent layer is a layer formed by curing a composition, the composition comprising: a fluoropolymer having hydroxyl or carboxyl groups, a non-fluoropolymer, and a curing agent having functional groups that react with the aforementioned hydroxyl or carboxyl groups, wherein the hydroxyl value or acid value of the aforementioned fluoropolymer is 20 mg KOH / g or more, and wherein the content of the aforementioned fluoropolymer in the aforementioned composition is 30% by mass or less relative to the total content of the aforementioned fluoropolymer and the aforementioned non-fluoropolymer.

[0013] [2] According to the laminate of [1], wherein the content of the aforementioned fluoropolymer in the aforementioned composition is less than 5% by mass relative to the total content of the aforementioned fluoropolymer and the aforementioned non-fluoropolymer.

[0014] [3] The laminate according to [1] or [2], wherein the content of the fluorine-containing polymer in the aforementioned composition is 0.1 mass% or more relative to the total content of the fluorine-containing polymer and the non-fluorine polymer.

[0015] [4] The laminate according to [1] to [3], wherein the number average molecular weight of the fluorine-containing polymer is 6,000 or less.

[0016] [5] The laminate according to any one of [1] to [4], wherein the hydroxyl value or acid value of the fluorine-containing polymer is 400 mgKOH / g or less.

[0017] [6] The laminate according to any one of [1] to [5], wherein the fluorine-containing polymer is a fluorine-containing polymer having a hydroxyl group.

[0018] [7] The laminate according to any one of [1] to [6], wherein the fluorine-containing polymer is a fluorine-containing polymer having a hydroxyl group, and the hydroxyl value thereof is 150 mgKOH / g or more.

[0019] [8] The laminate according to any one of [1] to [7], wherein the aforementioned composition contains at least one selected from the group consisting of (meth)acrylic polymers, polyester polymers, polyoxyalkylene polymers, and polycarbonate polymers as the non-fluorine polymer.

[0020] [9] The laminate according to any one of [1] to [8], wherein the non-fluorine polymer has a hydroxyl group.

[0021]

[10] The laminate according to any one of [1] to [9], wherein the aforementioned composition further contains a silicone compound.

[0022]

[11] The laminate according to

[10] , wherein the silicone compound is a silicone oil.

[0023]

[12] The laminate according to any one of [1] to

[11] , wherein the aforementioned composition further contains an ultraviolet absorber.

[0024]

[13] The laminate according to any one of [1] to

[12] , wherein the material constituting the base film contains at least one selected from the group consisting of urethane resins and vinyl chloride resins.

[0025]

[14] An article with a laminate, which has the laminate according to any one of [1] to

[13] .

[0026] Effects of the Invention

[0027] According to the present application, a laminate and an article with the laminate, which are excellent in stretchability and solvent resistance, can be provided. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 A schematic side view showing an example of a layer structure of the laminate of the present application. DETAILED DESCRIPTION

[0029] The meanings of the terms in the present application are as follows.

[0030] The (meth)acrylate is a general term for acrylate and methacrylate. Similarly, the (meth)acrylic acid is a general term for acrylic acid and methacrylic acid, and the (meth)acrylamide is a general term for acrylamide and methacrylamide. In addition, the (meth)acrylic polymer refers to a polymer mainly containing a unit based on the (meth)acrylate, and the (meth)acrylic resin refers to a resin formed from the (meth)acrylic polymer.

[0031] The unit refers to a general term for an atomic group based on one molecule of the above-described monomer directly formed by polymerization of the monomer and an atomic group obtained by chemically converting a part of the above-described atomic group after polymerization. Note that the content (mol%) of each unit with respect to the total units contained in the polymer is found by analyzing the polymer using a nuclear magnetic resonance spectroscopy (NMR) method.

[0032] The acid value and the hydroxyl value are values measured according to the method of JIS K 0070-3 (1992).

[0033] The glass transition temperature (Tg) is the midpoint glass transition temperature of the polymer measured by a differential scanning calorimetry (DSC) method.

[0034] The softening temperature is a value measured according to the method of JIS K 7196 (1991).

[0035] The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by a gel permeation chromatography method using polystyrene as a standard substance.

[0036] The thickness of the laminate is a value measured using an eddy current film thickness meter. As the eddy current film thickness meter, for example, EDY-5000 manufactured by SANKO ELECTRONIC LABORATORY CO., LTD. or the like can be used. The thickness of each layer in the laminate can be calculated from the ratio of the thickness of each layer obtained by observing the cross section of the laminate using a scanning electron microscope equipped with an energy dispersive type X-ray analysis device and the thickness of the laminate.

[0037] The total light transmittance is a value measured using a D light source according to JIS K 7361-1: 1997.

[0038] The mass of the solid component of the composition, in the case where the composition contains a solvent, refers to the mass after the solvent has been removed from the composition. Note that, regarding components other than the solvent that make up the solid component of the composition, even if the form is liquid, it is regarded as a solid component. Note that the mass of the solid component of the composition is obtained as the mass remaining after 1 g of the composition has been heated at 130°C for 20 minutes.

[0039] The laminate of the present application (hereinafter also referred to as the present laminate) is a laminate having a base film and a transparent layer, the transparent layer being a layer formed by curing a composition containing a fluorine-containing polymer having a hydroxyl group or a carboxyl group, a non-fluorine polymer, and a curing agent having a functional group that reacts with the hydroxyl group or the carboxyl group, the fluorine-containing polymer having a hydroxyl value or an acid value of 20 mgKOH / g or more, the content of the fluorine-containing polymer in the composition being 30 mass% or less relative to the total content of the fluorine-containing polymer and the non-fluorine polymer.

[0040] The mechanism by which the present laminate having this configuration has excellent stretchability and solvent resistance is not clear, but is believed to be as follows.

[0041] That is, the laminate of the present application has a transparent layer. The composition used to form the transparent layer contains a fluorine-containing polymer having a hydroxyl value or an acid value of a prescribed value or more and a curing agent, and good solvent resistance is imparted to the transparent layer formed by curing the composition.

[0042] Furthermore, the composition also contains a non-fluorine polymer, and the content of the fluorine-containing polymer is prescribed to be a prescribed value or less relative to the total content of the fluorine-containing polymer and the non-fluorine polymer. The content of the fluorine-containing polymer is prescribed to be a prescribed value or less, and thus deterioration in the softness of the transparent layer formed by curing the composition due to the fluorine-containing polymer is suppressed. Therefore, it is believed that the transparent layer does not easily break when the present laminate is stretched, and the stretchability of the present laminate is also excellent.

[0043] First, the configuration of the present laminate will be described with reference to the drawings.

[0044] Figure 1 A schematic side view showing the layer structure of the laminate 10 (the present laminate) as an embodiment of the present application is shown. The laminate 10 has a bonding layer 12, a base film 14, and a transparent layer 16, and the layers are arranged in this order.

[0045] If the bonding layer 12 of the laminate 10 is pressure-bonded to an article for which surface protection should be performed, a laminated article in which the transparent layer 16, the base film 14, the bonding layer 12, and the article are arranged in this order is obtained. In this way, the transparent layer 16 is located at the outermost surface of the laminated article.

[0046] The laminate 10 can also have other layers as long as the gist of the present application is not violated.

[0047] Hereinafter, each member constituting the laminate will be described in detail.

[0048] The laminate has a base film.

[0049] The base film functions as a support material for supporting each layer when the laminate is manufactured.

[0050] Specific examples of the material constituting the base film include urethane resins (thermoplastic polyurethane, etc.), vinyl chloride resins, polyester resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), AAS resins (acrylonitrile-acrylate-styrene copolymers), AES resins (acrylonitrile-ethylene-propylene-diene-styrene copolymers), (meth)acrylic resins, olefin resins, and fluorine resins. Among these, the material constituting the base film preferably contains at least one selected from the group consisting of urethane resins and vinyl chloride resins, and particularly preferably urethane resins or vinyl chloride resins as such.

[0051] The thickness of the base film is preferably 10 to 500 μm, and particularly preferably 20 to 200 μm.

[0052] The base film can have a concave-convex pattern on one or both sides. The concave-convex pattern can be formed by embossing, fine line processing, chemical etching processing, or the like.

[0053] The laminate has a transparent layer.

[0054] The transparent layer is a layer formed by curing a prescribed composition.

[0055] Hereinafter, the composition used to form the transparent layer will also be referred to as composition (f).

[0056] The composition (f) contains a fluorine-containing polymer having a hydroxyl group or a carboxyl group (hereinafter also referred to as fluorine-containing polymer A).

[0057] The fluorine-containing polymer A preferably contains a fluorine-olefin-based unit (hereinafter also referred to as unit A1) and a unit having a hydroxyl group or a carboxyl group (hereinafter also referred to as unit A2).

[0058] If the above-described fluorine-containing polymer A is used, the hydroxyl group or the carboxyl group possessed by the fluorine-containing polymer A undergoes a cross-linking reaction, and a transparent layer containing a fluorine-containing polymer having a cross-linking structure is formed. Note that when the hydroxyl group or the carboxyl group undergoes a cross-linking reaction, a prescribed curing agent is allowed to react as described later.

[0059] The fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with a fluorine atom. One or more of the hydrogen atoms not substituted with a fluorine atom in the fluoroolefin can be substituted with a chlorine atom. The carbon number of the fluoroolefin is preferably 2 to 8, particularly preferably 2 to 4.

[0060] As specific examples of the fluoroolefin, CF2=CF2, CF2=CFCl, CF2=CHF, CH2=CF2, CF2=CFCF3, CF2=CHCF3, CF3CH=CHF, and CF3CF=CH2 can be given. As the fluoroolefin, from the aspect of copolymerizability, CF2=CF2, CF2=CFCl, CF3CH=CHF, and CF3CF=CH2 are preferable, CF2=CF2 and CF2=CFCl are more preferable, and CF2=CFCl is particularly preferable.

[0061] Two or more kinds of the fluoroolefin can be used in combination.

[0062] From the aspect of weather resistance of the present laminate, the content of the unit A1 is preferably 20 to 70 mol%, more preferably 40 to 60 mol%, particularly preferably 45 to 55 mol% relative to the total units contained in the fluorine-containing polymer A.

[0063] The unit A2 can be a unit based on a monomer having a hydroxyl group (hereinafter also referred to as monomer A21) or a monomer having a carboxyl group (hereinafter also referred to as monomer A22), or can be a unit obtained by converting the above-mentioned functional group of the fluorine-containing polymer containing a unit having a functional group into a hydroxyl group or a carboxyl group. The unit A2 preferably has a hydroxyl group.

[0064] The hydroxyl group or the carboxyl group is a group that reacts with the curing agent described later.

[0065] The unit A2 preferably has no fluorine atom.

[0066] As the monomer A21, an allyl alcohol, and a (meth)acrylate, an allyl alcohol, and a monomer represented by the formula X 11 -Z 11 can be given.

[0067] X 11 is CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, and is preferably CH2=CHO- or CH2=CHCH2O-.

[0068] Z 11A monovalent organic group having a carbon number of 2 to 42 having a hydroxyl group. The above organic group can be linear or branched. In addition, the above organic group can be composed of a ring structure or can include a ring structure.

[0069] As the above organic group, an alkyl group having a carbon number of 2 to 6 having a hydroxyl group, an alkyl group including a ring alkylene group having a carbon number of 6 to 8 having a hydroxyl group, a polyoxyalkylene group having a hydroxyl group, an alkyl group having a carbon number of 2 to 6 to which a polyoxyalkylene group having a hydroxyl group is bonded, and an alkyl group having a ring alkylene group having a carbon number of 6 to 8 to which a polyoxyalkylene group having a hydroxyl group is bonded are preferable.

[0070] As the polyoxyalkylene group, a polyoxyalkylene group in which oxyethylene groups are predominant is preferable. As the oxyalkylene group other than the oxyethylene group, an oxypropylene group, a 1,2-oxybutylene group, a 1,4-oxybutylene group, and the like are exemplified, and an oxypropylene group is preferable. The proportion of the oxyethylene group in the polyoxyalkylene group is preferably 60 to 100 mole%, more preferably 80 to 100 mole%, and particularly preferably 100 mole% (i.e., a polyoxyethylene group).

[0071] In addition, the number of the alkylene group in the polyoxyalkylene group is preferably 4 or more, more preferably 6 to 40, and particularly preferably 8 to 24.

[0072] As specific examples of the monomer A21, CH2=CHO-CH2-cycloC6H 10 -CH2OH, CH2=CHCH2O-CH2-cycloC6H 10 -CH2OH, CH2=CHOCH2CH2OH, CH2=CHCH2OCH2CH2OH, CH2=CHOCH2CH2CH2CH2OH, CH2=CHCH2OCH2CH2CH2CH2OH, CH2=CHOCH2-cycloC6H 10 -CH2-(OCH2CH2) n OH, CH2=CHOCH2CH2(OCH2CH2) n OH, and CH2=CHCH2OCH2CH2(OCH2CH2) n OH.

[0073] Note that "-cycloC6H 10 -" indicates a cyclohexylene group, and the bonding site of (-cycloC6H 10 -) is usually 1,4. n indicates an integer of 8 to 24.

[0074] Two or more kinds of the monomer A21 can be used in combination.

[0075] As the monomer A22, a polymerizable unsaturated carboxylic acid such as (meth)acrylic acid can be given, and a monomer of the formula X 12 -Z 12 indicated by the formula X 12 is CH2=CH-, CH(CH3)=CH- or CH2=C(CH3)-, and is preferably CH2=CH- or CH2=C(CH3)-. Z 12 is a carboxyl group or a monovalent saturated hydrocarbon group having a carbon number of 1 to 12, and is preferably a carboxyl group or a carboxylalkyl group having a carbon number of 1 to 10.

[0076] As the monomer A22, a polymerizable unsaturated carboxylic acid such as (meth)acrylic acid can be given, and a monomer of the formula X n1 COOH, CH2=C(CH3)(CH2) n1 COOH, CH2=C(CH3)(CH2)

[0077] Two or more kinds of the monomer A22 can be used in combination.

[0078] The content of the unit A2 is preferably 5 to 60 mol%, more preferably 15 to 50 mol%, and particularly preferably 25 to 45 mol%, relative to the total units contained in the fluorine-containing polymer A. When the content of the unit A2 is 5 mol% or more, the solvent resistance of the present laminate is more excellent. When the content of the unit A2 is 60 mol% or less, the stretchability of the present laminate is more excellent.

[0079] The fluorine-containing polymer A preferably further contains a unit (hereinafter also referred to as unit A3) based on a monomer (hereinafter also referred to as monomer A3) having neither a hydroxyl group nor a carboxyl group. The monomer A3 is preferably a monomer having neither a hydroxyl group nor a carboxyl group, and further preferably a monomer having neither a hydroxyl group nor a carboxyl group and having no reactive group other than a hydroxyl group and a carboxyl group which reacts with the curing agent described later. In addition, the monomer A3 preferably contains no fluorine atom.

[0080] As the monomer A3, a monomer selected from the group consisting of a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, and a (meth)acrylic ester is preferred.

[0081] As the unit A3, a unit based on a monomer of the formula X 2 -Y 2 indicated by the formula X

[0082] X 2CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, from the viewpoint of excellent weather resistance of the present layer laminate, preferably CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, and particularly preferably CH2=CHO-.

[0083] Y 2 is a monovalent hydrocarbon group having 1 to 24 carbons. The monovalent hydrocarbon group can be linear or branched. In addition, the monovalent hydrocarbon group can be composed of a ring structure or can include a ring structure. Furthermore, the monovalent hydrocarbon group can be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.

[0084] As the monovalent hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a cycloalkylalkyl group are preferable, and an alkyl group having 2 to 12 carbons, a cycloalkyl group having 6 to 10 carbons, an aryl group having 6 to 10 carbons, an aralkyl group having 7 to 12 carbons, and a cycloalkylalkyl group having 6 to 10 carbons are particularly preferable.

[0085] As specific examples of the alkyl group, a methyl group, an ethyl group, a t-butyl group, a hexyl group, a nonyl group, a decyl group, and a dodecyl group can be given.

[0086] As specific examples of the cycloalkyl group, a cyclohexyl group can be given.

[0087] As specific examples of the aralkyl group, a benzyl group can be given.

[0088] As specific examples of the cycloalkylalkyl group, a cyclohexylmethyl group can be given.

[0089] As specific examples of the aryl group, a phenyl group and a naphthyl group can be given.

[0090] Note that the hydrogen atoms of the cycloalkyl group or the cycloalkyl group portion of the cycloalkylalkyl group, and the hydrogen atoms of the aryl group or the aryl group portion of the aralkyl group can be substituted with an alkyl group. In this case, the number of carbons of the alkyl group as the substituent is not included in the number of carbons of the cycloalkyl group, the aryl group, or the aralkyl group.

[0091] Two or more kinds of monomer A3 can be used in combination.

[0092] As specific examples of the monomer A3, an ethyl vinyl ether, a t-butyl vinyl ether, a 2-ethylhexyl vinyl ether, a cyclohexyl vinyl ether, a vinyl acetate, a vinyl pivalate, a vinyl neonaonate (HEXION, trade name "VeoVa 9"), a vinyl neodecanoate (HEXION, trade name "VeoVa 10"), a vinyl versatate, a vinyl benzoate, a vinyl t-butylbenzoate, a t-butyl (meth)acrylate, and a benzyl (meth)acrylate can be given.

[0093] The content of the unit A3 is preferably 1 to 60 mol%, more preferably 5 to 55 mol%, particularly preferably 10 to 30 mol%, relative to the total units contained in the fluorine-containing polymer A.

[0094] The fluorine-containing polymer A can contain, in addition to the above units, a unit having a reactive group other than a hydroxyl group or a carboxyl group.

[0095] As the above reactive group, for example, an epoxy group, a hydrolyzable silyl group, an amino group, and the like can be given.

[0096] In the fluorine-containing polymer A, relative to the total units contained in the fluorine-containing polymer A, it is preferable to contain the unit Al, the unit A2, and the unit A3 in the order of 20 to 70 mol%, 5 to 60 mol%, 1 to 60 mol%, more preferably 40 to 60 mol%, 15 to 50 mol%, 5 to 55 mol%, particularly preferably 45 to 55 mol%, 25 to 45 mol%, 10 to 30 mol%.

[0097] The fluorine-containing polymer A has a hydroxyl value or an acid value of 20 mgKOH / g or more, preferably 50 mgKOH / g or more, particularly preferably 150 mgKOH / g or more. The above hydroxyl value or acid value is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, particularly preferably 200 mgKOH / g or less.

[0098] The fluorine-containing polymer A can have both a hydroxyl value and an acid value, in which case, as long as either one of the hydroxyl value and the acid value is within the above range. The fluorine-containing polymer A preferably has a hydroxyl value within the above range.

[0099] The Tg of the fluorine-containing polymer A is preferably 10 to 150°C, more preferably 15 to 120°C, particularly preferably 20 to 60°C from the viewpoint of more excellent stretchability of the present layer stack.

[0100] The Mn of the fluorine-containing polymer A is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 3,000 or more. The above Mn is preferably 50,000 or less, more preferably 25,000 or less, particularly preferably 6,000 or less. By adjusting the above Mn to the above range, the stretchability and the solvent resistance of the transparent layer are more balanced and excellent.

[0101] The fluorine-containing polymer A preferably has the following specific modes.

[0102] • a fluorine-containing polymer formed from a unit Al based on CF2=CFCl, a unit A2 based on at least one monomer selected from the group consisting of a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group, and a unit A3 based on at least one monomer selected from the group consisting of a vinyl ether not having a reactive group and a vinyl ester.

[0103] • a fluorine-containing polymer formed from a unit Al based on CF2=CFCl, a unit A2 based on at least one monomer selected from the group consisting of a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group, and a unit A3 based on at least one monomer selected from the group consisting of a vinyl ether not having a reactive group and a vinyl ester, and the content of the above-mentioned units in the fluorine-containing polymer is 40 to 60 mol%, 15 to 50 mol%, and 5 to 55 mol%, respectively, in this order, relative to the total units possessed by the fluorine-containing polymer.

[0104] • a fluorine-containing polymer formed from a unit Al based on CF2=CFCl, a unit A2 based on a vinyl ether having a hydroxyl group, and a unit A3 based on a vinyl ether not having a reactive group, and the content of the above-mentioned units in the fluorine-containing polymer is 45 to 55 mol%, 25 to 45 mol%, and 10 to 30 mol%, respectively, in this order, relative to the total units possessed by the fluorine-containing polymer.

[0105] When the above-mentioned aspect is the case, the alternating copolymerization rate of the unit Al and the units other than the unit Al in the fluorine-containing polymer A is easily high, and the weather resistance of the present laminate is excellent. Furthermore, the unit A2 is uniformly disposed in the fluorine-containing polymer A, and thus the transparent layer is easily formed uniformly, and the stretchability of the present laminate is more excellent.

[0106] Two or more kinds of the fluorine-containing polymer A can be used.

[0107] The content of the fluorine-containing polymer A in the composition (f) is preferably 0.1 to 25 mass%, more preferably 0.5 to 10 mass%, and particularly preferably 1 to 4 mass%, relative to the total solid content of the composition (f), from the viewpoint of more excellent stretchability of the present laminate.

[0108] The composition (f) contains a non-fluorine polymer.

[0109] The non-fluorine polymer in the present application is a polymer substantially not containing a fluorine atom.

[0110] The non-fluorine polymer substantially not containing a fluorine atom means that the content of the fluorine atom is 0 to 1 mol%, preferably 0 to 0.1 mol%, more preferably 0 to 0.01 mol%, and particularly preferably 0 mol%, relative to the total atoms of the non-fluorine polymer.

[0111] The composition (f) preferably contains at least one selected from the group consisting of (meth)acrylic polymers, polyester polymers, polyoxyalkylene polymers, and polycarbonate polymers as the non-fluorinated polymer.

[0112] In addition, the non-fluorinated polymer preferably has a reactive group such as a hydroxyl group or a carboxyl group, and particularly preferably has a hydroxyl group. The number of reactive groups per molecule of the non-fluorinated polymer is preferably 1 or more, and more preferably 2 or more. The upper limit of the number of the above-mentioned reactive groups is not particularly limited, and is, for example, 1,000 or less.

[0113] That is, the above-mentioned (meth)acrylic polymer is preferably a (meth)acrylic polymer having 2 or more hydroxyl groups (hereinafter also referred to as an acrylic polyol), the above-mentioned polyester polymer is preferably a polyester polyol, the above-mentioned polyoxyalkylene polymer is preferably a polyoxyalkylene polyol, and the above-mentioned polycarbonate polymer is preferably a polycarbonate polyol.

[0114] The composition (f) preferably contains at least a (meth)acrylic polymer as the non-fluorinated polymer.

[0115] The acrylic polyol as one form of the (meth)acrylic polymer is a polymer containing a unit based on a (meth)acrylate not having a hydroxyl group and a unit based on a monomer having a hydroxyl group, and is a compound having 2 or more hydroxyl groups per molecule. As specific examples of the monomer having a hydroxyl group, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, and allyl alcohol can be given. The acrylic polyol can contain a unit based on a monomer other than the above-mentioned monomers, and as the monomers, for example, (meth)acrylic acid, styrene, a-methylstyrene, vinyltoluene, (meth)acrylamide and derivatives thereof, and vinyl acetate, maleic anhydride can be given. Note that the acrylic polyol mostly has a carboxyl group, and generally has both a hydroxyl value and an acid value.

[0116] The hydroxyl value of the (meth)acrylic polymer having a hydroxyl group is preferably 1 to 200 mgKOH / g, more preferably 10 to 120 mgKOH / g, further preferably 20 to 80 mgKOH / g, and particularly preferably 30 to 50 mgKOH / g. The acid value of the (meth)acrylic polymer having a hydroxyl group is preferably 1 to 50 mgKOH / g, and particularly preferably 1 to 10 mgKOH / g.

[0117] The acid value of the (meth)acrylic polymer having a carboxyl group is preferably 1 to 200 mgKOH / g, more preferably 1 to 50 mgKOH / g, further preferably 1 to 10 mgKOH / g, and particularly preferably 1.0 to 10 mgKOH / g.

[0118] The Mn of the (meth)acrylic polymer is preferably 5,000 to 200,000, more preferably 10,000 to 90,000, particularly preferably 10,000 to 60,000.

[0119] The Mw of the (meth)acrylic polymer is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, particularly preferably 5,000 to 80,000.

[0120] The Tg of the (meth)acrylic polymer is preferably 1 to 200°C, more preferably 50 to 150°C, particularly preferably 80 to 130°C.

[0121] Two or more kinds of (meth)acrylic polymers are preferably used in combination, particularly preferably two kinds are used in combination. When two kinds of (meth)acrylic polymers are AC1 and AC2, the Tg of AC1 is preferably higher than the Tg of AC2. In addition, the Mw of AC2 is preferably higher than the Mw of AC1. That is, the physical properties of AC1 and AC2 satisfy at least one of the following relational expressions, preferably both.

[0122] • the Tg of AC1 > the Tg of AC2

[0123] • the Mw of AC1 < the Mw of AC2

[0124] From the viewpoint of the solvent resistance of the laminate, the difference between the Tg of AC1 and the Tg of AC2 is preferably 5°C or higher, more preferably 10°C or higher, particularly preferably 15°C or higher.

[0125] From the viewpoint of the stretchability of the laminate, the difference between the Mw of AC1 and the Mw of AC2 is preferably 1,000 or higher, more preferably 10,000 or higher, further preferably 30,000 or higher, particularly preferably 50,000 or higher.

[0126] Part of the (meth)acrylic polymer in the composition (f) can be a silicone-modified (meth)acrylic polymer. As the silicone-modified (meth)acrylic polymer, a silicone-modified acrylic polyol is preferable.

[0127] When the composition (f) contains a silicone-modified (meth)acrylic polymer, the surface smoothness, blocking resistance, and the like of the transparent layer formed using the composition (f) are good.

[0128] When the composition (f) contains a silicone-modified (meth)acrylic polymer, the content of the silicone-modified (meth)acrylic polymer is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, particularly preferably 0.01 to 1% by mass, relative to the total mass of the (meth)acrylic polymer in the composition (f).

[0129] The content of the (meth)acrylic polymer in the composition (f) is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, particularly preferably 85 to 96% by mass, relative to the total mass of the non-fluorinated polymer.

[0130] In the case where the composition (f) contains two (meth)acrylic polymers AC1 and AC2, the ratio of the content of AC1 to the content of AC2 (AC1 / AC2) in the total mass of the (meth)acrylic polymers is preferably 1 / 99 to 99 / 1, more preferably 60 / 40 to 95 / 5, particularly preferably 70 / 30 to 90 / 10.

[0131] Here, both AC1 and AC2 are preferably (meth)acrylic polymers which have not been modified with silicone.

[0132] The non-fluorinated polymer can be a polyester polymer, a polyoxyalkylene polymer, or a polycarbonate polymer. As described above, these polymers are preferably polymers having a hydroxyl group.

[0133] The number of hydroxyl groups of the polyester polymer, the polyoxyalkylene polymer, and the polycarbonate polymer having a hydroxyl group is preferably 2 to 4, particularly preferably 2.

[0134] As the polyester polymer having a hydroxyl group, a polyester diol having a residue of a dicarboxylic acid such as adipic acid or phthalic acid and a residue of an aliphatic diol having a carbon number of 2 to 8 can be given.

[0135] As the polycarbonate polymer having a hydroxyl group, a polycarbonate diol having a residue of an aliphatic diol having a carbon number of 4 to 12 can be given.

[0136] The non-fluorinated polymer preferably contains a polyoxyalkylene polymer.

[0137] As the polyoxyalkylene polyol which is one form of the polyoxyalkylene polymer, for example, polyoxytetramethylene glycol (PTMG), polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, poly(oxypropylene-ethylene) triol can be given.

[0138] Among them, as the polyoxyalkylene polyol, PTMG is preferable.

[0139] The Mn of the polyoxyalkylene polymer is preferably 200 to 10,000, more preferably 400 to 6,000, particularly preferably 600 to 2,000.

[0140] The content of the polyoxyalkylene polymer is preferably 0.5 to 70% by mass, more preferably 1 to 30% by mass, particularly preferably 3 to 15% by mass, relative to the total mass of the non-fluorinated polymer.

[0141] Two or more kinds of non-fluorinated polymers can be used, and preferably two or more kinds are used.

[0142] The content of the non-fluoropolymer in the composition (f) is preferably 40 to 99 mass%, more preferably 55 to 95 mass%, particularly preferably 65 to 85 mass%, relative to the total solid content of the composition (f).

[0143] In the composition (f), the content of the fluoropolymer A is 30 mass% or less, preferably 10 mass% or less, particularly preferably 5 mass% or less, relative to the total content of the fluoropolymer A and the non-fluoropolymer. In addition, the above content is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, particularly preferably 1 mass% or more.

[0144] The composition (f) contains a curing agent.

[0145] The curing agent in the present application has two or more functional groups capable of reacting with a hydroxyl group or a carboxyl group in one molecule. When the curing agent reacts with the hydroxyl group or the carboxyl group possessed by the fluoropolymer A and the hydroxyl group possessed by the non-fluoropolymer as desired, the fluoropolymer A crosslinks with each other, the non-fluoropolymer crosslinks with each other, and / or the fluoropolymer A and the non-fluoropolymer crosslink with each other, thereby forming a transparent layer.

[0146] The curing agent generally has two to 30 functional groups capable of reacting with a hydroxyl group or a carboxyl group.

[0147] As a specific example of the curing agent, a compound having two or more isocyanate groups or epoxy groups in one molecule can be given.

[0148] As the curing agent, a polyisocyanate-based curing agent is preferred.

[0149] The polyisocyanate-based curing agent is a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.

[0150] As a specific example of the polyisocyanate, an alicyclic polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate, and a derivative of these polyisocyanates can be given. As a specific example of the polyisocyanate derivative, a multimer of the polyisocyanate, a modified body (an adduct, an allophanate body, a biuret body, an isocyanurate body, etc.) can be given.

[0151] As a specific example of the aliphatic polyisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine triisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, bis(2-isocyanatoethyl) 2-isocyanatoglutarate can be given.

[0152] As specific examples of the alicyclic polyisocyanate, there are mentioned alicyclic diisocyanates such as isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, hydrogenated xylene diisocyanate.

[0153] As specific examples of the aromatic polyisocyanate, there are mentioned aromatic diisocyanates such as xylene diisocyanate.

[0154] The polyisocyanate-based curing agent can be a compound in which two or more isocyanate groups possessed by the above polyisocyanate are blocked with a blocking agent.

[0155] The isocyanate group-containing composition (f) which has been blocked with a blocking agent is crosslinked by the reaction of the isocyanate group which is released from the blocking agent by heating at the time of curing, with the hydroxyl group or carboxyl group possessed by the fluorine-containing polymer A or the hydroxyl group possessed by the non-fluorine polymer.

[0156] The blocking agent is a compound having a reactive hydrogen, and as specific examples, there are mentioned alcohols, phenols, active methylene compounds, amines, imines, acid amides, lactams, oximes, pyrazoles, imidazoles, imidazolines, pyrimidines, guanidines.

[0157] The composition (f) containing the polyisocyanate-based curing agent which has been blocked has the following characteristics: the curing agent is not easily reacted with the fluorine-containing polymer A or the non-fluorine polymer at ordinary temperature, and thus has storage stability, and it is not necessary to mix the components immediately before coating to produce the composition (f).

[0158] The content of the curing agent (e.g., the polyisocyanate-based curing agent) in the composition (f) is preferably 5 to 50% by mass, more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass, relative to the total solid content of the composition (f).

[0159] The composition (f) can contain, as necessary, components other than the fluorine-containing polymer A, the non-fluorine polymer, and the curing agent (hereinafter also referred to as additives). As such components, there are mentioned, for example, curing catalysts, fillers (inorganic fillers such as silica, organic fillers such as resin beads, etc.), organosilicon compounds, colorants (dyes, organic pigments, inorganic pigments, luster pigments using metals or mica, etc.), ultraviolet absorbers, light stabilizers, matting agents, degassing agents, heat stabilizers, thickening agents, dispersants, surfactants (fluorine-based surfactants, etc.), antistatic agents, rust-preventive agents, silane coupling agents, antifouling agents, low-stain treatment agents.

[0160] The composition (f) preferably contains a curing catalyst among the above additives. The curing catalyst is a compound which promotes the formation of a crosslinked structure formed using the curing agent, and can be selected from publicly known curing catalysts depending on the type of the curing agent.

[0161] Among them, the curing catalyst is preferably a tin catalyst (tin octoate, tributyltin laurate, dibutyltin dilaurate, etc.) that promotes the reaction of isocyanate groups.

[0162] The curing catalyst can be used in combination of two or more.

[0163] In the case where the composition (f) contains a curing catalyst, the content of the curing catalyst is preferably 0.0001 to 5% by mass, particularly preferably 0.01 to 1% by mass, relative to the total solid content of the composition (f).

[0164] The composition (f) preferably contains an organic silicon compound among the above-mentioned additives.

[0165] The organic silicon compound can function as a surface modifier or an antifoaming agent.

[0166] Note that an organic silicon-modified acrylic resin is not included in the organic silicon compound.

[0167] The organic silicon compound preferably contains at least a part of a silicone oil, and the organic silicon compound can be a silicone oil.

[0168] In addition, the organic silicon compound can have a reactive group such as a hydroxyl group, and the organic silicon compound can be crosslinked with the fluorine-containing polymer A using a curing agent.

[0169] The organic silicon compound can be used in combination of two or more.

[0170] In the case where the composition (f) contains an organic silicon compound, the content of the organic silicon compound is preferably 0.005 to 10% by mass, particularly preferably 0.01 to 1% by mass, relative to the total solid content of the composition (f).

[0171] The composition (f) preferably contains a light stabilizer among the above-mentioned additives.

[0172] As specific examples of the light stabilizer, a hindered amine and a hindered phenol can be given, and a hindered amine is preferred.

[0173] In the case where the composition (f) contains a light stabilizer, the content of the light stabilizer is preferably 0.05 to 10% by mass, particularly preferably 0.5 to 5% by mass, relative to the total solid content of the composition (f).

[0174] The composition (f) preferably contains an ultraviolet absorber among the above-mentioned additives.

[0175] As specific examples of the ultraviolet absorber, a benzophenone-based ultraviolet absorber, a cyano acrylate-based ultraviolet absorber, a triazine-based (particularly a hydroxyphenyl triazine-based) ultraviolet absorber, and a benzotriazole-based ultraviolet absorber can be given, and a hydroxyphenyl triazine-based ultraviolet absorber is preferred.

[0176] When the composition (f) contains the ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 15% by mass, particularly preferably 1 to 10% by mass, relative to the total solid content of the composition (f).

[0177] The composition (f) is preferably obtained by mixing the fluorine-containing polymer A, the non-fluorine polymer, the curing agent, and at least one of the above-described additives, as needed. In this case, the composition (f) can contain a solvent. When the composition (f) contains a solvent, the fluorine-containing polymer A and the curing agent can be dissolved in the solvent or can be dispersed. The composition (f) can also be in the form of a powder without a solvent.

[0178] The solvent is a solvent (an organic solvent having no active hydrogen, etc.) that is inactive to the components contained in the composition (f). For example, when a curing agent having an isocyanate group is contained as the curing agent, a solvent having no group such as a hydroxyl group that can react with the isocyanate group is used. In addition, when a blocked polyisocyanate-based curing agent is used, after the composition (f) is coated and dried to remove the solvent, heating is performed, and the fluorine-containing polymer A and the non-fluorine polymer are crosslinked, so a solvent having an active hydrogen such as a hydroxyl group can also be used.

[0179] When the composition (f) contains a solvent, the solvent is preferably an organic solvent.

[0180] Specific examples of the organic solvent include ketones, esters, and hydrocarbons.

[0181] Two or more kinds of organic solvents can be used in combination.

[0182] From the viewpoint of storage stability and coating efficiency of the composition of the present application, the content of the organic solvent in the composition (f) is preferably 1 to 90% by mass, particularly preferably 10 to 35% by mass, relative to the total mass of the composition (f).

[0183] Specific examples of the method for forming the transparent layer include a method in which a coating layer is obtained by coating the composition (f) on a surface on which the transparent layer is to be formed, and a coating film is obtained by curing the obtained coating layer.

[0184] Specific examples of the coating method include a method using spraying, an applicator, a die coater, a bar coater, a roll coater, a comma coater, a roller brush, a brush, and a doctor blade.

[0185] When the composition (f) contains a solvent, after the composition (f) is coated, warm drying can be performed in order to remove the solvent in the composition (f).

[0186] The curing of the coating layer can be performed by heating, for example. The heating temperature is preferably 30 to 250°C, particularly preferably 50 to 150°C.

[0187] Note that in the case where the composition (f) is a so-called powder coating, the transparent layer can be formed by electrostatic coating or the like.

[0188] The transparent layer can contain the fluorine-containing polymer A, the curing agent, the non-fluorine polymer in a state where crosslinking is not performed, and preferably in a state where crosslinking is performed.

[0189] In addition, the transparent layer can have the function of the appearance layer described later. In this case, if the transparent layer contains a colorant or the like, a transparent layer having the function of the appearance layer can be obtained.

[0190] The thickness of the transparent layer is preferably 0.5 to 200 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 20 μm.

[0191] From the viewpoint of the appearance of the article of the present tape laminate, the total light transmittance of the transparent layer is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

[0192] From the viewpoint of the adhesion to the article to which surface protection should be performed, the present laminate preferably has a bonding layer.

[0193] The bonding layer is a layer that bonds the present laminate to the article, and preferably contains a bonding resin. As specific examples of the bonding resin, adhesion resins, fusion-bonding resins, and adhesive resins can be given. The bonding layer can be formed using, for example, a bonding resin, a composition containing components that react with heat or the like to become a bonding resin. Note that hereinafter, the composition containing components that react with heat or the like to become a bonding resin is also referred to as composition (a).

[0194] In the case of a heat-fusion-bonding resin, the resin softened by heat is cooled and cured in a state where it contacts the surface of the article, and thus can be bonded to the surface thereof. In the case of a heat-crosslinking resin, the resin is heat-crosslinked in a state where it contacts the surface of the article, and thus can be bonded to the surface thereof.

[0195] As specific examples of the heat-fusion-bonding resin, partially crosslinked heat-fusion-bonding resins having a low softening temperature, and thermoplastic resins can be given. The bonding layer containing a heat-fusion-bonding resin can be formed using a heat-fusion-bonding resin, a composition (a). For example, by using a composition (a) containing a polyol and a polyisocyanate, a bonding layer containing a heat-fusion-bonding urethane resin can be formed.

[0196] From the viewpoint of the blocking resistance and the moldability of the present laminate, the softening temperature of the heat-fusion-bonding resin is preferably 20 to 100°C, and particularly preferably 25 to 90°C.

[0197] From the viewpoints of film formability and adhesiveness of the bonding layer, the Mw of the hot-melt adhesive resin is preferably from 5,000 to 150,000, and particularly preferably from 6,000 to 130,000.

[0198] As the hot-melt adhesive resin, from the viewpoint of excellent adhesiveness to the three-dimensional molded article, a urethane resin, a (meth)acrylic resin, an olefin resin, a vinyl chloride-vinyl acetate resin, a butyral resin, or the like is preferable.

[0199] The bonding resin can be a thermally crosslinkable resin containing a main agent and a curing agent. As such a thermally crosslinkable resin, a thermally crosslinkable urethane resin containing a solid polyol, a solid hydroxyl-terminated polyurethane prepolymer, and a solid polyisocyanate or a solid blocked polyisocyanate, an epoxy resin containing a solid polyepoxide and a solid epoxy resin curing agent, or the like can be given.

[0200] The hydroxyl-terminated polyurethane prepolymer is a prepolymer having a hydroxyl group obtained by reacting a polyisocyanate with an excess equivalent of a polyol.

[0201] The composition (a) can contain the above-mentioned thermally crosslinkable resin, and can contain the above-mentioned components to be the thermally crosslinkable resin.

[0202] The bonding layer can have the function of the appearance layer described later. In this case, if the bonding layer contains a colorant or the like, a bonding layer having the function of the appearance layer can be obtained.

[0203] The bonding layer can contain components other than the above-mentioned components. As specific examples of the components other than the above-mentioned components, an ultraviolet absorber, a light stabilizer, a curing catalyst, an antioxidant, a surface modifier, an anti-dripping agent, a thickening agent, an antifoaming agent, and a conductive filler can be given.

[0204] From the viewpoints of film formability and adhesiveness of the bonding layer, the thickness of the bonding layer is preferably from 1 to 1,000 μm, more preferably from 4 to 80 μm, and particularly preferably from 10 to 60 μm.

[0205] The components that the composition (a) can contain are the same as the components that the above-mentioned bonding layer can contain. The components that the bonding resin and the bonding layer can contain can be dissolved in the composition (a) using a solvent such as water or an organic solvent, or can be dispersed.

[0206] Note that, in the case of Figure 1 In the example, the case where the layered body 10 has the bonding layer 12 is described, but the present layered body can not have the bonding layer as long as the present layered body can be attached to an article.

[0207] That is, the present layered body can have at least a base film and a transparent layer.

[0208] Although Figure 1 Although not shown in the present embodiment, the present laminate can have an appearance layer in order to improve the appearance and the like of the laminate. The appearance layer is a layer for imparting an appearance to an article. The appearance layer is preferably disposed between the bonding layer and the transparent layer.

[0209] Specifically, Figure 1 In the case where the laminate 10 of the present embodiment has an appearance layer, a configuration in which the bonding layer 12, the appearance layer, the base film 14, and the transparent layer 16 are disposed in this order can be given, and a configuration in which the bonding layer 12, the base film 14, the appearance layer, and the transparent layer 16 are disposed in this order can be given.

[0210] Note that the bonding layer, the base film, or the transparent layer can function as the appearance layer, in which case the appearance layer is not provided.

[0211] As specific examples of the appearance layer, a layer formed using a composition for forming an appearance layer, a layer formed by a printing method, and a layer formed by a metal evaporation method can be given.

[0212] As specific examples of the components included in the above-mentioned composition, a binder resin (urethane resin, (meth)acrylic resin, and the like), a colorant (dye, organic pigment, inorganic pigment, luster pigment using a metal or mica, and the like), and a solvent (water, organic solvent, and the like) can be given.

[0213] The layer formed by a printing method is formed using an ink (for example, including a binder resin, a colorant, and a solvent) suitable for each printing method such as inkjet printing, screen printing, offset printing, and flexographic printing.

[0214] The layer formed by a metal evaporation method is formed using a metal such as aluminum, indium, and tin. From the viewpoint of being easy to be affected by an electric wave and being suitable for use in automotive applications, the above-mentioned layer is preferably formed using indium.

[0215] The appearance layer can include components other than the above-mentioned components as necessary, and specifically, the components given in the composition (a) and the components given in the above-mentioned composition (f) can be given.

[0216] The thickness of the appearance layer can be appropriately set depending on the use.

[0217] The present laminate can have layers other than the above-mentioned layers, and for example, a layer for improving the adhesion between the layers and the like can be provided between the layers.

[0218] The method for producing the present laminate is not limited, and for example, a base film can be formed by casting a prescribed thermoplastic resin in a molten state on a previously formed transparent layer and then cooling and solidifying the same, to obtain the present laminate having the base film and the transparent layer.

[0219] Alternatively, the composition (f) can be applied to one surface of the base film and cured to form a transparent layer, thereby obtaining the present laminate.

[0220] Further, the present laminate can be obtained by separately producing the transparent layer and laminating it with the base film. The method of lamination is not particularly limited.

[0221] In order to protect the surface of an article to which surface protection should be performed, the present laminate can be elongated and used. The direction of elongation and the method of elongation can be appropriately selected depending on the shape of the article, the manufacturing conditions at the time of molding, and the like. The direction of elongation described above can be any direction, and the method of elongation described above can be any method. That is, the elongation of the present laminate can be performed by stretching the present laminate in a prescribed direction or all directions, or the present laminate can be appropriately heated to expand it.

[0222] The article with the laminate of the present application (hereinafter also referred to as the present molded article) is preferably obtained by attaching the present laminate to the surface to be protected of the article.

[0223] As specific examples of the article to which surface protection should be performed, the body of an automobile, a bicycle, a household appliance, a solar cell, furniture, and a building material can be given. As more specific examples, the roof, the engine hood, the front body, the door, and the trunk door of an automobile can be given.

[0224] The method of attaching the present laminate is not particularly limited, and vacuum molding (over molding), in-mold molding, in-mold transfer molding, in-mold attachment molding, over transfer molding, over attachment molding, water pressure transfer, and the like can be used.

[0225] Examples

[0226] Hereinafter, the present application will be described in detail with examples. However, the present application is not limited by these examples. Note that the compounding amounts of each component in Table 1 described later are indicated on a mass basis. Further, Examples 1 to 4 are examples, and Examples 5 and 6 are comparative examples.

[0227] <Abbreviations and details of components used>

[0228] Polymer Al solution: xylene solution (polymer concentration 50%) containing a polymer containing 50 mol%, 40 mol%, and 10 mol% of CTFE-based units, EVE-based units, and HBVE-based units, in this order, based on the total units contained in the fluorine-containing polymer (hydroxyl value: 57 mgKOH / g, acid value: none, Tg: 25°C, Mn: 20,000)

[0229] Polymer A2 solution: A 3-ethoxypropyl acetate solution (polymer concentration 70%) of a polymer containing 50 mol%, 15 mol%, 1 mol%, and 34 mol% of CTFE-based units, EVE-based units, CHVE-based units, and HBVE-based units, respectively, based on the total units contained in the fluorine-containing polymer (hydroxyl value: 171 mgKOH / g, acid value: none, Tg: 30°C, Mn: 4,500)

[0230] Note that CTFE is chlorotrifluoroethylene, EVE is ethyl vinyl ether, HBVE is 4-hydroxybutyl vinyl ether, and CHVE is cyclohexyl vinyl ether.

[0231] Non-fluorine polymer 1: LR-2697 (hydroxyl value: 41 mgKOH / g, acid value: 1.7 mgKOH / g, Tg: 119°C, Mn: 10,000, (meth)acrylic polymer, polymer concentration 56.8 mass%, trade name of Mitsubishi Chemical Corporation)

[0232] Non-fluorine polymer 2: 6FH-021 (hydroxyl value: 32 mgKOH / g, acid value: 4.3 mgKOH / g, Tg: 98°C, Mw: 60,000, (meth)acrylic polymer, polymer concentration 50.3 mass%, trade name of TAISEI FINE CHEMICAL CO, LTD.)

[0233] Non-fluorine polymer 3: Terathane 1000 (polyoxytetramethylene glycol, trade name of The LYCRA Company)

[0234] Non-fluorine polymer 4: BYK-Silclean 3700 (25 mass% solution, silicone-based surface modifier, hydroxyl group-containing silicone-modified (meth)acrylic polymer, trade name of BYK)

[0235] Silicone compound 1: DISPARLON 1933 (silicone-based defoaming agent, trade name of Nippon Gunee Co., Ltd.)

[0236] Silicone compound 2: KF-96 (silicone oil, trade name of Shin-Etsu Chemical Co., Ltd.)

[0237] Curing catalyst 1: U-CAT SA102 (10-fold diluted product, trade name of San-Apro Ltd.)

[0238] Curing catalyst 2: DBTDL (1,000-fold diluted product of dibutyltin dilaurate)

[0239] Light stabilizer: Tinuvin 123 (trade name of BASF)

[0240] UV absorber: Tinuvin 477 (hydroxyphenyltriazine-based, product of BASF Corporation)

[0241] Curing agent: 24A-100 (hexamethylene diisocyanate-based curing agent, product of Asahi Kasei Corporation)

[0242] Note that the dilutions of the curing catalyst 1 and the curing catalyst 2 mean that each product is diluted with a solvent (xylene) at a prescribed ratio (mass basis).

[0243] <Examples 1 to 6>

[0244] Each component described in the component column of Table 1 was mixed to obtain the composition of each example.

[0245] Next, each composition was applied to one face of a substrate film (a film made of urethane resin having a thickness of 150 μm), dried at 25°C to remove the solvent, and then heated at 80°C for 5 minutes to crosslink and cure, thereby forming a transparent layer having a thickness of 6 μm. Thus, each laminate having a substrate film and a transparent layer in this order was obtained.

[0246] The obtained laminates were evaluated as described later. The results are shown in Table 1.

[0247] <Stretchability>

[0248] A test piece was made using each laminate. The elongation of the test piece was measured using a Tensilon universal testing machine (RTC-1250A, manufactured by A&D Company) at 23°C based on the tensile strength and elongation test according to JIS Z0237. Note that the initial grip interval of the chuck of the tensile tester was set to 100 mm, and the tensile speed was set to 100 mm / s, and the elongation until the transparent layer of the test piece broke was measured, and the elongation was calculated according to the following equation.

[0249] Elongation (%) E = (L1 - L0) / L0 x 100

[0250] E: Elongation (%)

[0251] L0: Initial interval of the chuck (mm)

[0252] L1: Interval of the chuck at the time of cutting (mm)

[0253] S: The elongation of the laminate is 200% or more.

[0254] A: The elongation of the laminate is 150% or more but less than 200%.

[0255] B: The elongation of the laminate is less than 150%.

[0256] <solvent resistance>

[0257] A drop of xylene of about 10 mm was placed on the transparent layer in each of the examples, and left to stand for 30 minutes at 23°C. Subsequently, the surface state of the transparent layer was confirmed by visual observation while standing in a constant-temperature bath at 90 ± 1°C for 1 hour. In the case where dissolved matter was confirmed on the transparent layer, the surface state after wiping by wiping was further confirmed.

[0258] S: No abnormality was observed in the transparent layer.

[0259] A: Dissolved matter was confirmed on the surface of the transparent layer, but no abnormality was observed in the transparent layer after wiping.

[0260] B: A trace of dissolution remained on the transparent layer.

[0261] <results>

[0262] The compounding (mass ratio) of the components included in the composition in each of the examples and the evaluation results of the laminate formed using the composition are shown in the following table.

[0263] In the table, the values (unit: mgKOH / g) shown in parentheses in the columns of the polymer A1 solution and the polymer A2 solution are the hydroxyl values of the fluorine-containing polymer A included in the polymer A1 solution and the polymer A2 solution, respectively.

[0264] In the table, the column of "content of fluorine-containing polymer (relative to the total polymer, mass %)" shows the content mass (mass %) of the fluorine-containing polymer A in the composition relative to the total content of the fluorine-containing polymer A and the non-fluorine-containing polymer.

[0265] [table 1]

[0266]

[0267] Note that the specification, claims, abstract, and drawings of Japanese Patent Application No. 2021-059971 filed on March 31, 2021 are hereby incorporated by reference in their entirety as the specification disclosure of the present application.

[0268] Explanation of Reference Signs

[0269] 10 laminate

[0270] 12 bonding layer

[0271] 14 substrate film

[0272] 16 transparent layer

Claims

1. A laminate having a substrate film and a transparent layer, The transparent layer is a layer formed by curing the composition, which comprises: a fluoropolymer having hydroxyl or carboxyl groups, a non-fluoropolymer, and a curing agent having functional groups that react with the hydroxyl or carboxyl groups. The fluoropolymer has a hydroxyl value or acid value of 20 mg KOH / g or higher. In the composition, the content of the fluoropolymer is less than 30% by mass relative to the total content of the fluoropolymer and the non-fluoropolymer. The composition comprises at least one (meth)acrylic polymer as a non-fluorinated polymer, and two (meth)acrylic polymers are used in combination, with a Tg difference of more than 5°C between the two (meth)acrylic polymers.

2. The laminated body according to claim 1, wherein, In the composition, the content of the fluoropolymer is less than 5% by mass relative to the total content of the fluoropolymer and the non-fluoropolymer.

3. The laminate according to claim 1 or 2, wherein, In the composition, the content of the fluoropolymer is 0.1% by mass or more relative to the total content of the fluoropolymer and the non-fluoropolymer.

4. The laminate according to claim 1 or 2, wherein, The number-average molecular weight of the fluoropolymer is below 6000.

5. The laminate according to claim 1 or 2, wherein, The hydroxyl value or acid value of the fluoropolymer is below 400 mg KOH / g.

6. The laminate according to claim 1 or 2, wherein, The fluoropolymer is a fluoropolymer containing hydroxyl groups.

7. The laminate according to claim 1 or 2, wherein, The fluoropolymer is a fluoropolymer with hydroxyl groups and a hydroxyl value of 150 mg KOH / g or higher.

8. The laminate according to claim 1 or 2, wherein, The non-fluoropolymer has hydroxyl groups.

9. The laminate according to claim 1 or 2, wherein, The composition also contains an organosilicon compound.

10. The laminate according to claim 9, wherein, The organosilicon compound is silicone oil.

11. The laminate according to claim 1 or 2, wherein, The composition also contains an ultraviolet absorber.

12. The laminate according to claim 1 or 2, wherein, The material constituting the substrate film includes at least one selected from the group consisting of urethane resin and vinyl chloride resin.

13. An article having a laminated body, comprising the laminated body as described in any one of claims 1 to 12.

Images