MULTILAYER FILM AND TWO-LIQUID CURABLE COATING AGENT

Abstract

A multilayer film includes a substrate layer; a surface protective layer integrally laminated on a first surface of the substrate layer, the surface protective layer containing a polyurethane which is a reaction product of a polyol (P) having a hydroxyl value of 25 to 380 mgKOH/g and a content of fluorine atoms of 0.01 to 20% by mass and a polyisocyanate (I); and an adhesive layer integrally laminated on a second surface of the substrate layer. Also described is a two-liquid curable coating agent for forming the surface protective layer.

Claims

1. A multilayer film comprising: a substrate layer; a surface protective layer integrally laminated on a first surface of the substrate layer, the surface protective layer containing a polyurethane which is a reaction product of a polyol (P) having a hydroxyl value of 25 to 380 mgKOH/g and a content of fluorine atoms of 0.01 to 20% by mass and a polyisocyanate (I); and an adhesive layer integrally laminated on a second surface of the substrate layer.

2. The multilayer film according to claim 1, wherein the hydroxyl value of the polyol (P) is 120 to 180 mgKOH/g.

3. The multilayer film according to claim 1, wherein the polyol (P) contains a (meth)acrylic polyol.

4. The multilayer film according to claim 3, wherein the(meth)acrylic polyol is a polymer of a (meth)acryl-based monomer, the (meth)acryl-based monomer contains a fluorine-containing (meth)acryl-based monomer (a1) and a hydroxyl group-containing (meth)acryl-based monomer (a2), and a mass ratio of the fluorine-containing (meth)acryl-based monomer (a1) unit to the hydroxyl group-containing (meth)acryl-based monomer (a2) unit, [a mass of the fluorine-containing (meth)acryl-based monomer (a1) unit/a mass of the hydroxyl group-containing (meth)acryl-based monomer (a2) unit], in the (meth)acrylic polyol is 0.003 to 7.5.

5. The multilayer film according to claim 4, wherein the mass ratio of the fluorine-containing (meth)acryl-based monomer (a1) unit to the hydroxyl group-containing (meth)acryl-based monomer (a2) unit, [the mass of the fluorine-containing (meth)acryl-based monomer (a1) unit/the mass of the hydroxyl group-containing (meth)acryl-based monomer (a2) unit], in the (meth)acrylic polyol is 0.003 to 0.9.

6. The multilayer film according to claim 4, wherein the(meth)acryl-based monomer contains a siloxane bond-containing (meth)acryl-based monomer (a3).

7. The multilayer film according to claim 1, wherein the polyol (P) contains at least one kind of polyol selected from the group consisting of a polyether polyol, a polyester polyol, and a polycarbonate polyol.

8. The multilayer film according to claim 1, wherein the polyurethane is a reaction product of the polyol (P), the polyisocyanate (I), and a polythiol (T).

9. The multilayer film according to claim 1, wherein the substrate layer contains at least one of a thermoplastic resin and a thermoplastic elastomer.

10. The multilayer film according to claim 1, wherein the substrate layer contains a polyester-based polyurethane resin or a polyester-based polyurethane thermoplastic elastomer.

11. A film for protecting an automobile comprising the multilayer film according to claim 1.

12. A two-liquid curable coating agent comprising: a main agent including a polyol (P) having a hydroxyl value of 25 to 380 mgKOH/g and a content of fluorine atoms of 0.01 to 20% by mass; and a curing agent including a polyisocyanate (I).

Description

BRIEF DESCRIPTION OF DRAWINGS

[0132] FIG. 1 is a diagram for explaining a contact angle in the present invention.

DESCRIPTION OF EMBODIMENTS

[0133] Hereinafter, the present invention will be described in detail by way of Examples without being limited thereto.

[0134] [Synthesis of (meth)acryl polyol]

SYNTHETIC EXAMPLE 1

[0135] As a solvent, 233 parts by mass of methyl ethyl ketone (MEK) was charged in a reaction vessel and heated to 60 C. Next, 4.0 parts by mass of azobis-2-methylbromonitrile (ABN-E, manufactured by Japan Hydrazine Co., Inc.) as a polymerization catalyst was mixed, by stirring, to a monomer composition including 57 parts by mass of methyl methacrylate (MMA), 16.2 parts by mass of n-butyl acrylate (n-BA), 25.9 parts by mass of 2-hydroxyethyl acrylate (2-HEA), and 0.9 parts by mass of 2-(perfluorohexyl)ethyl acrylate (FAAC-6) to prepare a monomer mixed liquid. The monomer mixed liquid thus obtained was added dropwise to the solvent described above over a period of 3 hours, and the reaction was terminated after additional 3 hours. In this manner, a (meth)acryl polyol solution (solid content of 30% by mass) including a (meth)acryl polyol (hydroxyl value of 125 mgKOH/g and fluorine atom content of 0.5% by mass) was obtained.

SYNTHETIC EXAMPLES 2 TO 20

[0136] (Meth)acryl polyol solutions (solid contents of 30% by mass) including (meth)acryl polyols were obtained in the same manner as in Synthetic example 1 except that monomer compositions including, in formulation amounts indicated in Tables 1 and 2, 2-(perfluorohexyl)ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, -butyl--(3-methacryloxypropyl)polydimethylsiloxane (weight-average molecular weight (Mw) 1,000, manufactured by JNC Corp., trade name Silaplane FM-0711), methyl methacrylate, isobornyl methacrylate, and n-butyl acrylate, respectively, were used.

EXAMPLES 1 TO 22 AND COMPARATIVE EXAMPLES 1 TO 3

[0137] Two-liquid curable coating agents including main agents and curing agents described below were prepared. The main agents (solid contents of 40% by mass) were obtained by supplying, in formulation amounts indicated in Tables 3 and 4, the (meth)acryl polyols obtained in Synthetic examples 1 to 20, a polyether polyol (polytetramethylene glycol, manufactured by Mitsubishi Chemical Corp., PTMG650), a polyester polyol (polycaprolactone triol, manufactured by Daicel Corp., PLACCEL 303), a polycarbonate polyol (poly[cyclohexylene bis (methylene)/hexamethylene]carbonate diol, manufactured by UBE Industries, Ltd., ETERNACOLL (registered trademark) UM-90), a polythiol (T) (trimethylolpropane tris(3-mercaptopropionate)), as well as dibutyltin dilaurate as a curing catalyst and methyl isobutyl ketone, to a reaction vessel and mixing them together.

[0138] Note that, as for the (meth)acryl polyols obtained in Synthetic examples 1 to 20, a (meth)acryl polyol solution including each of the (meth)acryl polyols was supplied to the reaction vessel so that the (meth)acryl polyol was adjusted to the formulation amount (solid content) indicated in Tables 3 and 4. Further, a mass ratio of the fluorine-containing (meth)acryl-based monomer (a1) units with respect to the hydroxyl group-containing (meth)acryl-based monomer (a2) units, [the mass of the fluorine-containing (meth)acryl-based monomer (a1) unit/the mass of the hydroxyl group-containing (meth)acryl-based monomer (a2) unit], in each (meth)acryl polyol used in Examples 1 to 22 and Comparative example 1 to 3 is indicated in the column Mass ratio [(a1)/(a2)] in Tables 3 and 4. Further, fluorine atom contents (.sup.9.5 by mass) and hydroxyl values (mgOH/g) of the polyols (P), which include the (meth)acryl polyols obtained in Synthetic examples 1 to 20, the polyether polyol, the polyester polyol, and the polycarbonate polyol in the formulation amounts indicated in Tables 3 and 4, respectively, in Examples 1 to 22 and Comparative examples 1 to 3 are indicated in Tables 3 and 4.

[0139] Next, the curing agents including the polyisocyanate (I) (biuret modified product of hexamethylene diisocyanate, content of isocyanate groups: 23.3%, manufactured by Mitsui Chemicals, Inc., TAKENATE D165N) and methyl isobutyl ketone in formulation amounts (in terms of solid content for polyisocyanate (I)) indicated in Tables 3 and 4, respectively, were prepared. The curing agents were added to and mixed with the main agents. Subsequently, the resulting two-liquid curable coating agents were each immediately applied onto the first surface of the substrate layer (sheet including a polyurethane thermoplastic elastomer, manufactured by Nihon Matai Co., Ltd., ESMER URS) using a bar coater (No. 16). The applied two-liquid curable coating agent was then heated at 120 C. for 10 minutes to remove the solvent and perform heat curing, so that the surface protective layer (thickness of 10 m) integrally laminated on the first surface of the substrate layer was formed.

[0140] Next, an adhesive composition was obtained by mixing 100 parts by mass of an acryl-based adhesive (manufactured by Harima Chemicals Group, Inc., HARIACRON 560CH) and 0.5 parts by mass of an isocyanate-based crosslinking agent (manufactured by TOSOH Corp., Coronate (registered trademark) L-45E). Subsequently, the adhesive composition was immediately applied to the second surface of the substrate layer using a bar coater (No. 24) to obtain a coated film. This coated film was heated at 100 C. for 3 minutes to remove the solvent. After heating, a release paper was laminated on the coated film by slowly rolling a roller (weight of 10 kg) around which the release paper had been wound on the roller. The coated film was then cured at 40 C. for 3 days to form the adhesive layer (thickness of 25 m) on the second surface of the substrate layer. In this manner, the multilayer film including the substrate layer, the surface protective layer integrally laminated on the first surface of the substrate layer, and the adhesive layer integrally laminated on the second surface of the substrate layer was obtained.

[0141] Note that the term equivalent ratio described in Tables 3 and 4 refers to an equivalent ratio (isocyanate group/hydroxyl group) of isocyanate groups in the polyisocyanate (I) with respect to hydroxyl groups in the polyol (P) in Examples 1 to 7 and 9 to 22 and Comparative examples 1 to 3, while the term equivalent ratio refers to an equivalent ratio [isocyanate group/(hydroxyl group .sub.+thiol group)] of isocyanate groups in the polyisocyanate (I) with respect to hydroxyl groups in the polyol (P) and thiol groups in the polythiol (T) in Example 8.

[0142] [Evaluations]

[0143] The multilayer films produced in Examples 1 to 22 and Comparative examples 1 to 3 were evaluated in the water spot resistance, the scratch resistance, the slidability of squeegee, and the stretchability in accordance with the following procedures. The results are shown in Tables 3 and 4.

[0144] (Water Spot Resistance)

[0145] The multilayer film was horizontally disposed with the surface protective layer facing upward. Under the atmosphere at a temperature of 23 C. and a relative humidity of 50%, one drop of 2 1 water droplet was dropped on the surface protective layer of the multilayer film and a contact angel () was measured 1 second and 300 seconds after the dropping of the water droplet using a contact angle meter (manufactured by Kyowa Interface Science Co. Ltd., DM-501). A change rate (%) of the contact angle was calculated on the basis of a formula [change rate (%) of contact angle=100(contact angle after 1 secondcontact angle after 300 seconds)/(contact angle after 1 second)]. Note that the term contact angle refers to an angle at the side of a water droplet W out of angles formed by a tangential line L of the water droplet W at an end point P of the interface between the water droplet W and a surface protective layer S, and the surface of the surface protective layer S, as shown in FIG. 1.

[0146] The contact angle after 1 second (also simply referred to as initial contact angle) and the change rate of the contact angle are shown in Tables 3 and 4. As described above, it is considered that both the water repellency (initial water repelling property) and the hydrophilicity of the surface protective layer contribute to the water spot resistance of the surface protective layer. Thus, the contact angle after one second was scored in accordance with the following evaluation criteria (A) and the change rate of contact angle was scored in accordance with the following evaluation criteria (B). These scores are shown in Tables 3 and 4. Further, the total score of the score of the contact angle after one second and the score of the change rate of contact angle is shown in the column Overall evaluation of the water spot resistance in Tables 3 and 4. Note that, between the water repellency (initial water repelling property) and the hydrophilicity of the surface protective layer, the hydrophilicity is thought to contribute more to the water spot resistance of the surface protective layer. Thus, in the following evaluation criteria, the change rate of the contact angle was given the higher score than the contact angle after 1 second.

[0147] Evaluation criteria (A): contact angle after 1 second

[0148] 1 point: contact angle after 1 second of 82 or more and less than 90

[0149] 2 points: contact angle after 1 second of 90 or more and less than 98

[0150] 3 points: contact angle after 1 second of 98 or more and less than 106

[0151] 4 points: contact angle after 1 second of 106 or more

[0152] Evaluation criteria (B): change rate of contact angle

[0153] 8 points: change rate of contact angle of 14% or more

[0154] 7 points: change rate of contact angle of 13% or more and less than 14%

[0155] 6 points: change rate of contact angle of 12% or more and less than 13%

[0156] 5 points: change rate of contact angle of 11% or more and less than 12%

[0157] 4 points: change rate of contact angle of 10% or more and less than 11%

[0158] 3 points: change rate of contact angle of 9% or more and less than 10%

[0159] 2 points: change rate of contact angle of 8% or more and less than 9%

[0160] 1 point: change rate of contact angle of 7% or more and less than 8%

[0161] 0 points: change rate of contact angle of less than 7%

[0162] (Scratch Resistance)

[0163] A glass plate was horizontally disposed. After removing the release paper from the adhesive layer of the multilayer film, the multilayer film was placed on the glass plate so that the adhesive layer came into contact with the glass plate. Then, a squeegee (manufactured by MIRAREED, PRO Big gum spatula) was slid in a reciprocating manner on the surface protective layer 10 times by hand while a load of 0.3 N is applied to the squeegee, and the number of scratches generated on the surface protective layer by this operation was counted.

[0164] (Slidability of Squeegee)

[0165] A glass plate was horizontally disposed. After removing the release paper from the adhesive layer of the multilayer film, the multilayer film was placed on the glass plate so that the adhesive layer came into contact with the glass plate. Then, the multilayer film was adhered to the glass plate by pressing and sliding the squeegee (manufactured by MIRAREED, PRO Big gum spatula) on the surface protective layer. Resistance feeling obtained by pressing and sliding the squeegee on the surface protective layer was evaluated in accordance with the following criteria.

[0166] A: no resistance feeling

[0167] B: slight resistance feeling

[0168] C: some resistance feeling

[0169] D: strong resistance feeling, unable to slide squeegee on surface protective layer

[0170] (Stretchability)

[0171] In accordance with JIS K 7127 (PlasticsDetermination of tensile properties), the multilayer film was cut in a shape of test piece type 2 and a stretch rate (%) of the multilayer film was measured under the condition of a tension rate of 100 mm/min using a tensile testing machine (manufactured by SHIMADZU Corp., Autograph AGS-X).

TABLE-US-00001 TABLE 1 Synthetic examples 1 2 3 4 5 6 7 Formulation Fluorine-containing 2-(Perfluorohexyl)ethyl acrylate 0.90 1.8 1.8 1.8 42.3 1.8 0 (parts by mass) (meth)acryl-based monomer (a1) Hydroxyl group-containing 2-Hydroxyethyl acrylate 25.9 25.9 5.2 48.2 0 0 25.9 (meth)acryl-based monomer (a2) 2-Hydroxyethyl methacrylate 0 0 0 34 5.8 0 0 Other (meth)acryl-based Methyl methacrylate 57 57 64 0 0 0 57 monomers (a4) Isobornyl methacrylate 0 0 0 16 51.9 64 0 n-Butyl acrylate 16.2 15.3 29 0 0 34.2 17.1 Total of monomers 100 100 100 100 100 100 100 Mass ratio [fluorine-containing(meth)acryl-based monomer (a1)/hydroxyl 0.035 0.069 0.35 0.022 7.3 0 group-containing (meth)acryacryl-based monomer (a2)]

TABLE-US-00002 TABLE 2 Synthetic examples 8 9 10 11 12 13 14 Formulation Fluorine-containing 2-(Perfluorohexyl)ethyl acrylate 1.8 1.8 17 26 1.8 1.8 1.8 (parts by (meth)acryl-based monomer mass) (a1) Hydroxyl group-containing 2-Hydroxyethyl acrylate 0 0 0 0 25.9 12.5 16.5 (meth)acryl-based monomer 2-Hydroxyethyl methacrylate 58 46 29 29 0 0 0 (a2) Siloxane bond-containing a-butyl-w-(3- 0 0 0 0 20 0 0 (meth)acryl-based monomer methacryloxypropyl)polydimethyl- (a3) siloxane Other (meth)acryl-based Methyl methacrylate 0 0 0 0 31.0 61.7 60 monomers (a4) Isobornyl methacrylate 17 24 35 35 0 0 0 n-Butyl acrylate 23.2 28.2 19 10 21.3 24 21.7 Total of monomers 100 100 100 100 100 100 100 Mass ratio [fluorine-containing(meth)acryl-based monomer (a1)/hydroxyl 0.031 0.039 0.586 0.897 0.069 0.14 0.11 group-containing (meth)acryl-based monomer (a2)] Synthetic examples 15 16 17 18 19 20 Formulation Fluorine-containing 2-(Perfluorohexyl)ethyl acrylate 0.20 0.10 1.8 1.8 1.8 1.8 (parts by (meth)acryl-based monomer mass) (a1) Hydroxyl group-containing 2-Hydroxyethyl acrylate 25.9 25.9 23.8 24.9 37.3 38.3 (meth)acryl-based monomer 2-Hydroxyethyl methacrylate 0 0 0 0 0 0 (a2) Siloxane bond-containing a-butyl-w-(3- 0 0 0 0 0 0 (meth)acryl-based monomer methacryloxypropyl)polydimethyl- (a3) siloxane Other (meth)acryl-based Methyl methacrylate 57.0 57.0 57.0 57.0 52.0 51.0 monomers (a4) Isobornyl methacrylate 0 0 0 0 0 0 n-Butyl acrylate 16.9 16.9 17.4 16.3 8.9 8.9 Total of monomers 100 100 100 100 100 100 Mass ratio [fluorine-containing(meth)acryl-based monomer (a1)/hydroxyl 0.008 0.004 0.076 0.072 0.048 0.047 group-containing (meth)acryl-based monomer (a2)]

TABLE-US-00003 TABLE 3 Examples 1 2 3 4 5 6 Formulation Polyol (Meth)acryl Synthetic example 1 100 0 0 0 50 50 of main (P) polyol Synthetic example 2 0 100 0 0 0 0 agent (parts by Synthetic example 3 0 0 100 0 0 0 mass) Synthetic example 4 0 0 0 100 0 0 Synthetic example 5 0 0 0 0 0 0 Synthetic example 6 0 0 0 0 0 0 Synthetic example 7 0 0 0 0 0 0 Mass ratio 0.035 0.069 0.35 0.022 0.035 0.035 [(a1)/(a2)] Other Polyether polyol 0 0 0 0 50 0 polyols Polyester polyol 0 0 0 0 0 50 (parts by Polycarbonate polyol 0 0 0 0 0 0 mass) Fluorine atom content of polyol (P) 0.50 1.0 1.0 1.0 0.25 0.25 (parts by mass) Hydroxyl value of polyol (P) (mgKOH/g) 125 125 25 380 147.5 335 Polythiol (T) (parts by mass) 0 0 0 0 0 0 Dibutyltin dilaurate (parts by mass) 0.01 0.01 0.01 0.01 0.01 0.01 Methyl isobutyl ketone (parts by mass) 150 150 150 150 150 150 Formulation Polyisocyanate (I) (TAKENATE D165N) (parts by mass) 39 39 8 122 47 108 of curing Methyl isobutyl ketone (parts by mass) 59 59 12 183 71 162 agent Equivalent ratio [isocyanate group/hydroxyl group] or 1 1 1 1 1 1 [isocyanate group/(hydroxyl group + thiol group)] Evaluation Water Contact angle after one second () 91.8 92.0 92.0 86.8 88.7 82.3 spot Score of contact angle after one second 2 2 2 1 1 1 resistance Change rate of contact angle (%) 13.2% 14.5% 12.0% 11.1% 14.1% 14.3% Score of change rate of contact angle 7 8 6 5 8 8 Overall evaluation (Total score) 9 10 8 6 9 9 Scratch resistance (Number of scratches) 3 3 8 3 0 0 Squeegee slidability B B B C B B Stretch rate 120% 120% 200% 100% 160% 130% Examples Compartive Examples 7 8 9 1 2 3 Formulation Polyol (Meth)acryl Synthetic example 1 50 50 0 0 0 0 of main (P) polyol Synthetic example 2 0 0 0 0 0 0 agent (parts by Synthetic example 3 0 0 0 0 0 0 mass) Synthetic example 4 0 0 0 0 0 0 Synthetic example 5 0 0 1 100 0 0 Synthetic example 5 0 0 0 0 100 0 Synthetic example 7 0 0 99 0 0 100 Mass ratio 0.035 0.035 0.016 7.3 0 [(a1)/(a2)] Other Polyether polyol 0 40 0 0 0 0 polyols Polyester polyol 0 0 0 0 0 0 (parts by Polycarbonate polyol 50 0 0 0 0 0 mass) Fluorine atom content of polyol (P) 0.25 0.25 0.25 25.0 1.0 0 (parts by mass) Hydroxyl value of polyol (P) (mgKOH/g) 125 145 124 25 0 125 Polythiol (T) (parts by mass) 0 10 0 0 0 0 Dibutyltin dilaurate (parts by mass) 0.01 0.01 0.01 0.01 0.01 0.01 Methyl isobutyl ketone (parts by mass) 150 150 150 150 150 150 Formulation Polyisocyanate (I) (TAKENATE D165N) (parts by mass) 39 56 39 8 0 39 of curing Methyl isobutyl ketone (parts by mass) 59 84 59 12 0 59 agent Equivalent ratio [isocyanate group/hydroxyl group] or 1 1.2 1 1 0 1 [isocyanate group/(hydroxyl group + thiol group)] Evaluation Water Contact angle after one second () 85.1 88.3 101.0 106.3 103.2 89.0 spot Score of contact angle after one second 1 1 3 4 3 1 resistance Change rate of contact angle (%) 13.2% 12.8% 10.0% 6.1% 7.5% 10.2% Score of change rate of contact angle 7 6 4 0 1 4 Overall evaluation (Total score) 8 7 7 4 4 5 Scratch resistance (Number of scratches) 2 0 2 10 23 11 Squeegee slidability B B B B B D Stretch rate 180% 145% 115% 230% 250% 120%

TABLE-US-00004 TABLE 4 Examples 10 11 12 13 14 15 16 Formulation Polyol (Meth)acryl Synthetic 99 0 0 0 0 0 0 of main (P) polyol example 2 agent (parts by Synthetic 0 100 0 0 0 0 0 mass) example 8 Synthetic 0 0 100 0 0 0 0 example 9 Synthetic 0 0 0 100 0 0 0 example 10 Synthetic 0 0 0 0 100 0 0 example 11 Synthetic 1 0 0 0 0 0 0 example 12 Synthetic 0 0 0 0 0 100 0 example 13 Synthetic 0 0 0 0 0 0 100 example 14 Synthetic 0 0 0 0 0 0 0 example 15 Synthetic 0 0 0 0 0 0 0 example 16 Synthetic 0 0 0 0 0 0 0 example 17 Synthetic 0 0 0 0 0 0 0 example 18 Synthetic 0 0 0 0 0 0 0 example 19 Synthetic 0 0 0 0 0 0 0 example 20 Mass ratio 0.069 0.031 0.039 0.586 0.897 0.14 0.11 [(a1)/(a2)] Other Polyether 0 0 0 0 0 0 0 polyols polyol (parts by Polyester 0 0 0 0 0 0 0 mass) polyol Polycarbonate 0 0 0 0 0 0 0 polyol Fluorine atom content of polyol 1.0 1.0 1.0 10.0 15.0 1.0 1.0 (P) (parts by mass) Hydroxyl value of polyol (P) 125 250 200 125 125 60 80 (mgKOH/g) Polythiol (T) (parts by mass) 0 0 0 0 0 0 0 Dibutyltin dilaurate (parts by mass) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Methyl isobutyl ketone (parts by 150 150 150 150 150 150 150 mass) Formulation Polyisocyanate (I) (TAKENATE D165N) 39 80 64 39 39 19 25 of curing (parts by mass) agent Methyl isobutyl ketone (parts by 59 120 96 59 59 29 38 mass) Equivalent ratio [isocyanate group/hydroxyl group] 1 1 1 1 1 1 1 Evaluation Water Contact angle after one second () 102.0 96.2 95.2 104.4 105.5 92.1 91.8 spot Score of contact angle after one 3 2 2 3 3 2 2 resistance second Change rate of contact angle (%) 11.0% 11.4% 12.0% 10.5% 9.6% 12.2% 13.0% Score of change rate of contact angle 5 5 6 4 3 6 7 Overall evaluation (Total score) 8 7 8 7 6 8 9 Scratch resistance (Number of scratches) 2 3 3 3 3 8 5 Squeegee slidability A C B B B B B Stretch rate 120% 105% 105% 120% 120% 160% 130% Examples 17 18 19 20 21 22 Formulation Polyol (Meth)acryl Synthetic 0 0 0 0 0 0 of main (P) polyol example 2 agent (parts by Synthetic 0 0 0 0 0 0 mass) example 8 Synthetic 0 0 0 0 0 0 example 9 Synthetic 0 0 0 0 0 0 example 10 Synthetic 0 0 0 0 0 0 example 11 Synthetic 0 0 0 0 0 0 example 12 Synthetic 0 0 0 0 0 0 example 13 Synthetic 0 0 0 0 0 0 example 14 Synthetic 100 0 0 0 0 0 example 15 Synthetic 0 100 0 0 0 0 example 16 Synthetic 0 0 100 0 0 0 example 17 Synthetic 0 0 0 100 0 0 example 18 Synthetic 0 0 0 0 100 0 example 19 Synthetic 0 0 0 0 0 100 example 20 Mass ratio 0.0080 0.0040 0.076 0.072 0.048 0.047 [(a1)/(a2)] Other Polyether 0 0 0 0 0 0 polyols polyol (parts by Polyester 0 0 0 0 0 0 mass) polyol Polycarbonate 0 0 0 0 0 0 polyol Fluorine atom content of polyol 0.10 0.050 1.0 1.0 1.0 1.0 (P) (parts by mass) Hydroxyl value of polyol (P) 125 125 115 120 180 185 (mgKOH/g) Polythiol (T) (parts by mass) 0 0 0 0 0 0 Dibutyltin dilaurate (parts by mass) 0.01 0.01 0.01 0.01 0.01 0.01 Methyl isobutyl ketone (parts by 150 150 150 150 150 150 mass) Formulation Polyisocyanate (I) (TAKENATE D165N) 39 39 36 37 56 58 of curing (parts by mass) agent Methyl isobutyl ketone (parts by 59 59 54 56 84 87 mass) Equivalent ratio [isocyanate group/hydroxyl group] 1 1 1 1 1 1 Evaluation Water Contact angle after one second () 91.5 91.0 91.2 91.8 95.2 96.0 spot Score of contact angle after one 2 2 2 2 2 2 resistance second Change rate of contact angle (%) 11.0 10.9% 13.5% 14.3% 14.1% 12.5% Score of change rate of contact angle 5 4 7 8 8 6 Overall evaluation (Total score) 7 6 9 10 10 8 Scratch resistance (Number of scratches) 4 9 4 3 3 3 Squeegee slidability B C B B B B Stretch rate 120% 120% 120% 120% 110% 110%

INDUSTRIAL APPLICABILITY

[0172] According to the present invention, it becomes possible to provide the multilayer film including the surface protective layer excellent in the water spot resistance and the scratch resistance and the two-liquid curable coating agent for forming the surface protective layer. The surface protective layer can protect an article surface from a dirt and a scratch and maintain excellent appearance of the article surface.

REFERENCE SIGNS LIST

[0173] S surface protective layer

[0174] W water droplet

[0175] L tangential line of water droplet

[0176] P end point of interface between water droplet W and surface protective layer S