Polyisocyanate composition and coating composition for paint protection film

Abstract

To provide a polyisocyanate composition capable of providing excellent quick-drying properties, good abrasion resistance, stain resistance, adhesion and extensibility.SOLUTION: There is provided a polyisocyanate composition which comprises a polyisocyanate derived from a diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate and a polyol selected from the group consisting of a polyether-based polyol having a number average molecular weight of 100 to 10000 and having an oxypropylene group, a polyester-based polyol derived from ε-caprolactone and a polycarbonate-based polyol, wherein when the number of moles of allophanate groups is defined as A, the number of moles of isocyanurate groups is defined as B and the number of moles of urethane groups is defined as C, C / (A+C) is 0.01 or more and 0.99 or less and B / (A+B+C) is 0.01 or more and 0.90 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyisocyanate composition, a coating composition, an isocyanate curing agent composition for a paint protection film, a coating composition for a paint protection film, and a substrate.

Background Art

[0002] Polyisocyanate compositions can impart various functions such as high appearance, high weather resistance, and high durability to coating films, and are thus widely used as coating raw materials for construction, automobiles, plastics, information household appliances, etc.

[0003] In recent years, the need for preventing scratches on the surfaces of plastics and films has been increasing. Usually, a method of increasing the surface hardness to make it difficult to be scratched is adopted, but this method has a problem that the coating film becomes hard and cannot follow the deformation of the substrate, resulting in the destruction of the coating film. When the coating film is made flexible to prevent coating film destruction and the scratch resistance is improved, there are problems of reduced drying property due to a decrease in the glass transition temperature (Tg) of the coating film and reduced adhesion due to substrate deformation.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and when used for a coating layer of a plastic or a film, it is excellent in quick drying property and can impart good scratch resistance, stain resistance, adhesion, and stretchability. In particular, it provides a polyisocyanate composition suitable for an isocyanate curing agent composition for a PPF (hereinafter referred to as PPF), which is a paint for a paint protection film.

Means for Solving the Problems

[0006] That is, the present invention includes the following aspects. (1) At least one diisocyanate (A) selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, At least one polyol (B) selected from the group consisting of polyether polyols (B1), polyester polyols (B2), and polycarbonate polyols (B3), and a polyisocyanate derived therefrom, wherein the number average molecular weight of the polyol (B) is 100 or more and 10,000 or less, and the number average functionality of the hydroxyl groups of the polyol (B) is 2 or more and 3 or less, the polyether polyol (B1) has an oxypropylene group, the polyester polyol (B2) is derived from ε-caprolactone, the polycarbonate polyol (B3) is derived from a carbonate group-containing substance and a diol, the polyisocyanate composition contains an allophanate group, an isocyanurate group, and a urethane group. When the number of moles of the allophanate group is A, the number of moles of the isocyanurate group is B, and the number of moles of the urethane group is C, a polyisocyanate composition in which C / (A + C) is 0.01 or more and 0.99 or less, and B / (A + B + C) is 0.01 or more and 0.90 or less. (2) The polyisocyanate composition according to (1), wherein B / (A + B + C) is 0.01 or more and 0.39 or less. (3) The polyisocyanate composition according to (1), wherein B / (A + B + C) is 0.01 or more and 0.30 or less. (4) The polyisocyanate composition according to any one of (1) to (3), wherein the number average molecular weight of the polyol (B) is 100 or more and 2,000 or less. (5) The polyisocyanate composition according to any one of (1) to (4), wherein the number average molecular weight of the polyol (B) is 100 or more and 1000 or less. (6) The polyisocyanate composition according to any one of (1) to (5), wherein the polyol (B) is a polyether polyol (B1) and / or a polyester polyol (B2). (7) The polyisocyanate composition according to any one of (1) to (6), wherein the polyol (B) is a polyester polyol (B2). (8) The polyisocyanate composition according to any one of (1) to (7), wherein the number average functionality (fn) of the isocyanate groups of the polyisocyanate contained in the polyisocyanate composition is 3.0 to 8.0. (9) A coating composition using the polyisocyanate composition according to any one of (1) to (8). (10) An isocyanate curing agent composition for PPF using the polyisocyanate composition according to any one of (1) to (8). (11) A coating composition for PPF using the isocyanate curing agent composition for PPF according to (10). (12) A substrate on which a coating film is formed using the coating composition for PPF according to (11). [Advantages of the Invention]

[0007] The coating composition for PPF using the polyisocyanate composition of the above aspect is excellent in quick drying property, and can impart good scratch resistance, stain resistance, adhesion, and stretchability to the coating film. [Embodiments for Carrying Out the Invention]

[0008] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be variously modified without departing from its gist.

[0009] In addition, in this specification, "polyol" means a compound having two or more hydroxy groups (-OH) in one molecule. Further, in this specification, "polyisocyanate" means a reactant in which a plurality of monomer compounds having two or more isocyanate groups (-NCO) are bonded. Also, in this specification, unless otherwise specified, "(meth)acryl" includes methacryl and acryl, and "(meth)acrylate" includes methacrylate and acrylate.

[0010] ≪Polyisocyanate Composition≫ The polyisocyanate composition of this embodiment contains a polyisocyanate derived from a diisocyanate (A) and a polyol (B). That is, the polyisocyanate is a reaction product of the diisocyanate (A) and the polyol (B).

[0011] The diisocyanate (A) is at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

[0012] The polyol (B) is at least one polyol selected from the group consisting of polyether polyols (B1), polyester polyols (B2), and polycarbonate polyols (B3).

[0013] In addition, the polyisocyanate composition of this embodiment contains allophanate groups, isocyanurate groups, and urethane groups. In the polyisocyanate composition of this embodiment, all of these functional groups may be contained in one polyisocyanate, or the polyisocyanate composition of this embodiment may be a mixture of polyisocyanates containing at least one of these functional groups. The polyisocyanate composition of this embodiment may contain a polyisocyanate different from the reaction product of the diisocyanate (A) and the polyol (B).

[0014] When the number of moles of the allophanate group is A, the number of moles of the isocyanurate group is B, and the number of moles of the urethane group is C, C / (A + C) is 0.01 or more and 0.99 or less, and B / (A + B + C) is 0.01 or more and 0.90 or less. C / (A + C) is more preferably 0.30 or more and 0.99 or less, and B / (A + B + C) is more preferably 0.01 or more and 0.39 or less, still more preferably 0.01 or more and 0.30 or less. If it is within the above range, the stretchability will be good.

[0015] In addition, the number of moles of each of the allophanate group, the isocyanurate group, and the urethane group can be determined by C-NMR measurement as described in the examples below. 13 For each of the number of moles A, B, and C, relative values may be determined so that the molar ratios represented by C / (A + C) and B / (A + B + C) can be calculated.

[0016] Next, each component of the polyisocyanate composition of the present embodiment will be described in detail below.

[0017] <Diisocyanate (A)> Diisocyanate (A) is at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

[0018] An aliphatic diisocyanate is a compound having an acyclic saturated aliphatic group in the molecule. On the other hand, an alicyclic diisocyanate is a compound having a cyclic aliphatic group in the molecule. Among them, it is preferable to use an aliphatic diisocyanate. By using an aliphatic diisocyanate, the resulting polyisocyanate composition has a low viscosity.

[0019] Examples of the aliphatic diisocyanate include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, and methyl 2,6-diisocyanatohexanoate (lysine diisocyanate).

[0020] Examples of the alicyclic diisocyanate include 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate; hereinafter may be abbreviated as "IPDI"), 1,3-bis(isocyanatomethyl)cyclohexane (hydrogenated xylylene diisocyanate), bis(4-isocyanatocyclohexyl)methane (hydrogenated diphenylmethane diisocyanate), 1,4-diisocyanatocyclohexane, and the like.

[0021] These diisocyanates (A) may be used alone or in combination of two or more. Among them, as the diisocyanate (A), HDI, IPDI, hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane diisocyanate is preferable because they are easily available industrially. Further, HDI is particularly preferable because of its excellent weather resistance and flexibility of the coating film.

[0022] Hereinafter, aliphatic diisocyanate and alicyclic diisocyanate may be collectively referred to as diisocyanate monomer.

[0023] <Polyol (B)> The polyol (B) is at least one polyol selected from the group consisting of polyether polyol (B1), polyester polyol (B2) and polycarbonate polyol (B3). Also, two or more kinds of polyol (B) may be used in combination. For example, two or more kinds of polyester polyols (B2) having different number average molecular weights may be combined, or a polyether polyol (B1) and a polyester polyol (B2) may be combined. The polyol (B) is preferably a polyether polyol (B1) and / or a polyester polyol (B2), and more preferably a polyester polyol (B2).

[0024] The number average molecular weight of the polyol (B) is 100 or more and 10,000 or less. Preferably it is 100 or more and 3,000 or less, more preferably 100 or more and 2,000 or less, and most preferably 100 or more and 1,000 or less. If it is within this range, good scratch resistance can be imparted to the coating film. In addition, the number average molecular weight of the polyol (B) can be obtained by GPC measurement.

[0025] Also, the number average functionality (hereinafter, may be referred to as "fn") of the hydroxyl groups of the polyol (B) is 2 or more and 3 or less.

[0026] When two or more polyol components are used in combination as the polyol (B), the number average molecular weight and the number average functionality of each polyol component only need to be within the above ranges.

[0027] [Polyether polyol (B1)] The polyether polyol (B1) is a polyether polyol having an oxypropylene group. The polyether polyol having an oxypropylene group as used herein means a polyether polyol having an oxypropylene group in the molecular chain. In this case, the oxyalkylene repeating unit may contain other oxyalkylene groups, specifically, an oxyethylene group, an oxytetramethylene group, an oxycyclohexyl group, an oxystyrene group, or the like.

[0028] The oxypropylene group is a divalent group represented by -O-CH(CH3)-CH2- or -O-CH2-CH(CH3)- and has a side chain. With respect to the total molar amount of the oxyalkylene repeating unit, the content of the oxypropylene group having a side chain is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.

[0029] In addition, the number average molecular weight of the polyether polyol (B1) can be obtained by gel permeation chromatography (hereinafter, may be abbreviated as "GPC") measurement.

[0030] Specific examples of the polyether polyol (B1) include, for example, polypropylene glycol or triol, a so-called Pluronic (registered trademark) type of polypropylene glycol or triol obtained by addition polymerization of ethylene oxide to the end of polypropylene glycol, polyoxypropylene polyoxyethylene copolymer diol or triol, polyoxypropylene polyoxyethylene block polymer diol or triol, polytetramethylene glycol or triol, polyoxydimethylpropylene polyoxybutylene copolymer diol or triol, polyoxydimethylpropylene polyoxybutylene block polymer diol or triol, polyoxycyclohexane diol, and the like. Among them, as the polyether polyol (B1), since it has excellent solubility in low-polar organic solvents, polypropylene glycol or triol, or a so-called Pluronic (registered trademark) type of polypropylene glycol or triol obtained by addition polymerization of ethylene oxide to the end of polypropylene glycol is preferred. Further, among them, as the polyether polyol (B1), since it has excellent reactivity, a so-called Pluronic (registered trademark) type of polypropylene glycol or triol obtained by addition polymerization of ethylene oxide to the end of polypropylene glycol is more preferred.

[0031] These polyether polyols (B1) may be used alone or in combination of two or more.

[0032] Examples of commercially available polyether polyols (B1) include Excenol 840 (trade name, manufactured by AGC Inc., polypropylene triol, number average molecular weight 6500), Excenol 510 (trade name, manufactured by AGC Inc., polypropylene glycol, number average molecular weight 4000), Excenol 230 (trade name, manufactured by AGC Inc., polypropylene triol, number average molecular weight 3000), Excenol 2020 (trade name, manufactured by AGC Inc., polypropylene glycol, number average molecular weight 2000), Excenol 1030 (trade name, manufactured by AGC Inc., polypropylene triol, number average molecular weight 1000), Excenol 1020 (trade name, manufactured by AGC Inc., polypropylene glycol, number average molecular weight 1000), Preminol 7012 (trade name, manufactured by AGC Inc., polypropylene triol, number average molecular weight 10000), PTG1000SN (trade name, manufactured by Hodogaya Chemical Co., Ltd., polytetramethylene glycol, number average molecular weight 1000), and the like.

[0033] Examples of the method for producing the polyether polyol (B1) include a production method in which propylene oxide (and optionally a single or mixture of other alkylene oxides) is added to a polyhydric alcohol, polyhydric phenol, polyamine, alkanolamine, etc., alone or as a mixture, using a catalyst, and a production method in which a polyhydric alcohol is subjected to dehydration condensation.

[0034] The polyhydric alcohol may be a dihydric alcohol or a trihydric alcohol. Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, and the like. Examples of the trihydric alcohol include glycerin, trimethylolpropane, and the like. Examples of the polyamine include diamines such as ethylenediamine.

[0035] Examples of the catalyst include hydroxides such as lithium, sodium, and potassium; strongly basic catalysts such as alcoholates and alkylamines; metal porphyrins; composite metal cyanide complexes; complexes of a metal and a chelating agent having three or more coordination sites; and composite metal complexes such as zinc hexacyanocobaltate complexes.

[0036] Examples of other alkylene oxides include ethylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.

[0037] [Polyester polyol (B2)] The polyester polyol (B2) is derived from a dihydric or trihydric alcohol and ε-caprolactone, that is, a reaction product of a dihydric or trihydric alcohol and ε-caprolactone. ε-Caprolactone is a kind of cyclic ester and lactone, and is a seven-membered ring compound represented by the chemical formula: (CH2)5CO2. By subjecting ε-caprolactone to ring-opening polymerization, polycaprolactone, which is a polyester polymer, can be obtained.

[0038] Examples of the dihydric or trihydric alcohol include 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, hydroxypivalic acid ester of neopentyl glycol, 2-methyl-1,3-propanediol, 2,3,5-trimethylpentanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butylene diol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, 1,1,7-trimethylolheptane, 1,2,7-trimethylolheptane, and the like. These dihydric or trihydric alcohols may be used alone or in combination of two or more.

[0039] The polyester polyol (B2) may be used alone or in combination of two or more.

[0040] Examples of commercially available polyester polyols (B2) include, for example, Polyolite OD-X-2722 (trade name, manufactured by DIC Corporation, number average molecular weight 2000, number average functional group number 2), Polyolite OD-X-2542C (trade name, manufactured by DIC Corporation, number average molecular weight 850, number average functional group number 3), and the like.

[0041] Examples of the production method of the polyester polyol (B2) include, for example, a production method in which ε-caprolactone is subjected to ring-opening polymerization using a dihydric or higher and trihydric or lower alcohol.

[0042] [Polycarbonate polyol (B3)] The polycarbonate polyol (B3) is a polyol having a carbonate group and is a compound derived from a carbonate group-containing substance and a diol. Examples of the carbonate group-containing substance include carbonate compounds.

[0043] Specifically, the polycarbonate polyol (B3) is not particularly limited, but polycarbonate diol is preferred. Among them, at least two diols (hereinafter also simply referred to as "two diols") selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound are preferably copolymerized. Hereinafter, the polycarbonate diol will be described.

[0044] [Production method of polycarbonate diol] The production method of the polycarbonate diol is not particularly limited. For example, it can be obtained by subjecting one or more diols and a carbonate compound to a dealcoholization reaction, a dephenolization reaction, or the like. Alternatively, it can be obtained by subjecting a high molecular weight polycarbonate polyol to a transesterification reaction using one or more diols. There is no particular limitation on the method for carrying out the polymerization reaction between the diol and the carbonate compound, and known methods such as various methods described on pages 9 to 20 of "Polymer Reviews, Volume 9" by H. Schnell (published by Interscience Publishers, Inc., USA in 1964) can be used.

[0045] The above two types of diols are not particularly limited, and examples thereof include diols selected from the group consisting of aliphatic diols and aromatic diols. Among these, alkylene glycols having two hydroxyl groups and 2 to 20 carbon atoms are preferred. By using such diols, the weather resistance and chemical resistance of the coating film obtained using the polyisocyanate composition tend to be more excellent. Here, the "alkylene group" may have a branch and may contain an alicyclic structure. These bifunctional alcohols may be used alone or in combination of two or more.

[0046] The above diols are not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2'-bis(4-hydroxycyclohexyl)-propane, p-xylylene diol, p-tetrachloroxylylene diol, 1,4-dimethylolcyclohexane, bishydroxymethyltetrahydrofuran, di(2-hydroxyethyl)dimethylhydantoin, diethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, 2,6'-dihydroxyethyl hexyl ether, 2,4'-dihydroxyethyl butyl ether, 2,5'-dihydroxyethyl pentyl ether, 2,3'-dihydroxy-2',2'-dimethyl ethyl propyl ether, thioglycol, and the like.

[0047] Among these, diols having 2 to 11 carbon atoms are preferred, and diols having 3 to 6 carbon atoms are more preferred. Further, as the combination of diols, a combination of a diol having 5 carbon atoms and a diol having 6 carbon atoms, a combination of two or more isomers of a diol having 4 carbon atoms, or a combination of a diol having 4 carbon atoms and a diol having 6 carbon atoms is more preferred. By using such two kinds of diols, the stretchability, heat resistance, and water resistance (hydrolysis resistance) of the coating film obtained using the polyisocyanate composition tend to be more excellent. Such diols are not particularly limited, but specifically, one or more combinations selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2-methyl-1,3-propanediol are preferred, and a combination of 1,6-hexanediol and 1,5-pentanediol, a combination of 1,6-hexanediol and 1,4-butanediol, and a combination of 1,4-butanediol and 2-methyl-1,3-propanediol are more preferred.

[0048] The carbonate compound used for producing the polycarbonate diol is not particularly limited, and examples thereof include compounds selected from alkylene carbonate, dialkyl carbonate, diaryl carbonate, and phosgene. Such carbonate compounds are not particularly limited, and specifically, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, and the like can be mentioned. Among these, diethyl carbonate is preferred in terms of ease of production.

[0049] <Method for Producing Polyisocyanate Composition> In the production of the polyisocyanate composition of the present embodiment, it is preferable to use at least HDI as a raw material.

[0050] In the method for producing the polyisocyanate composition of the present embodiment, for example, the isocyanuration reaction, allophanatization reaction, and urethanization reaction can be carried out sequentially or some of them can be carried out in parallel. The polyisocyanate composition is obtained by carrying out these reactions in the presence of an excess of a diisocyanate monomer and a polyol (B) (at least one selected from the group consisting of a polyether polyol (B1), a polyester polyol (B2), and a polycarbonate polyol (B3)), and removing the unreacted diisocyanate monomer after the reaction is completed. Further, a polyisocyanate composition can also be obtained by mixing those obtained by carrying out the above three reactions separately.

[0051] Furthermore, in the method for producing the polyisocyanate composition of the present embodiment, alcohols such as alkyl monoalcohol and alkyl diol can also be used in combination as auxiliary raw materials. Here, when using an alcohol, as described above, it is necessary to use it so that the molar ratio of allophanate group / isocyanurate group and the molar ratio of urethane group / isocyanurate group in the polyisocyanate composition of the present embodiment are within the above ranges.

[0052] Alternatively, the polyisocyanate composition of the present embodiment is obtained, for example, by subjecting a diisocyanate to an isocyanuration reaction and an allophanatization reaction, and then subjecting the obtained reaction product and a polyol (B) (at least one selected from the group consisting of a polyether polyol (B1), a polyester polyol (B2), and a polycarbonate polyol (B3)) to a urethanization reaction. At this time, the molar ratio of the isocyanate group in the reaction product to the hydroxyl group of the polyol (B) is preferably 2 / 1 or more and 40 / 1 or less, more preferably 3 / 1 or more and 30 / 1 or less, and even more preferably 4 / 1 or more and 20 / 1 or less.

[0053] Next, each of the isocyanuration reaction, allophanatization reaction, and urethanization reaction will be described in detail below.

[0054] [Isocyanuration Reaction] When an isocyanurate group-containing polyisocyanate is derived from a diisocyanate monomer, an isocyanuration reaction catalyst is usually used. As the isocyanuration reaction catalyst, those having basicity are preferred. Examples of such isocyanuration reaction catalysts include those shown in the following 1) to 7). 1) Hydroxide or organic weak acid salt of tetraalkylammonium; 2) Hydroxide or organic weak acid salt of hydroxyalkylammonium; 3) Metal salt of alkylcarboxylic acid; 4) Metal alcoholates such as sodium and potassium; 5) Aminosilyl group-containing compounds such as hexamethyldisilazane; 6) Mannich bases; 7) Combined use of tertiary amines and epoxy compounds.

[0055] Examples of tetraalkylammonium include tetramethylammonium and tetraethylammonium. Examples of organic weak acids include acetic acid and capric acid. Examples of hydroxyalkylammonium include trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium. Examples of alkylcarboxylic acids include acetic acid, caproic acid, octylic acid, and myristic acid. Examples of metals constituting the metal salt include tin, zinc, lead, sodium, and potassium.

[0056] Among them, as the isocyanuration reaction catalyst, from the viewpoint of catalyst efficiency, the above 1), 2), 3), 4) or 5) is preferred, and the organic weak acid salt of 1) is more preferred.

[0057] The addition amount of the isocyanuration reaction catalyst is preferably 10 ppm or more and 1000 ppm or less, more preferably 10 ppm or more and 500 ppm or less, and even more preferably 10 ppm or more and 100 ppm or less, based on the mass of the charged diisocyanate.

[0058] The lower limit value of the isocyanuration reaction temperature is preferably 50 °C, more preferably 54 °C, still more preferably 57 °C, and particularly preferably 60 °C. On the other hand, the upper limit value of the isocyanuration reaction temperature is preferably 120 °C, more preferably 100 °C, still more preferably 90 °C, and particularly preferably 80 °C. That is, the isocyanuration reaction temperature is preferably 50 °C or higher and 120 °C or lower, more preferably 54 °C or higher and 100 °C or lower, still more preferably 57 °C or higher and 90 °C or lower, and particularly preferably 60 °C or higher and 80 °C or lower. When the isocyanuration reaction temperature is equal to or lower than the above upper limit value, characteristic changes such as coloring can be more effectively prevented.

[0059] [Allophanatization reaction] The allophanate group-containing polyisocyanate is obtained by adding an alcohol to a diisocyanate and using an allophanatization reaction catalyst. As the alcohol to be used, it may contain an ether group, an ester group, or a carbonyl group in the molecule, but a monoalcohol composed of a saturated hydrocarbon group and a hydroxyl group is preferred, and a branched monoalcohol is more preferred. Examples of such monoalcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, and the like. Among them, as the monoalcohol, isobutanol, 1-butanol, isoamyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol or 1,3,5-trimethylcyclohexanol is preferred because of its particularly excellent solubility in low-polarity organic solvents. Also, 1-propanol, isobutanol, 1-butanol, isoamyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-hexyl alcohol or 3,3,5-trimethyl-1-hexanol is preferred because the viscosity becomes lower. Further, isobutanol, 2-hexanol, 2-octanol, 2-ethyl-1-hexanol or 3,3,5-trimethyl-1-hexanol is more preferred because of its very excellent solubility in low-polarity organic solvents.

[0060] The addition amount of alcohol is not limited to the following, but an addition amount such that the molar ratio of the isocyanate group of diisocyanate to the hydroxyl group of alcohol is 10 / 1 or more and 1000 / 1 or less is preferable, and an addition amount such that the molar ratio is 100 / 1 or more and 1000 / 1 or less is more preferable. By the molar ratio of the isocyanate group of diisocyanate to the hydroxyl group of alcohol being equal to or higher than the above lower limit value, it is possible to secure a more appropriate number of the average number of isocyanate groups in the obtained polyisocyanate.

[0061] The allophanatization reaction catalyst is not limited to the following, and examples thereof include alkyl carboxylates such as tin, lead, zinc, bismuth, zirconium, and zirconyl. Examples of the alkyl carboxylate of tin (organotin compound) include tin 2-ethylhexanoate and dibutyltin dilaurate. Examples of the alkyl carboxylate of lead (organic lead compound) include lead 2-ethylhexanoate. Examples of the alkyl carboxylate of zinc (organic zinc compound) include zinc 2-ethylhexanoate. Examples of the alkyl carboxylate of bismuth include bismuth 2-ethylhexanoate. Examples of the alkyl carboxylate of zirconium include zirconium 2-ethylhexanoate. Examples of the alkyl carboxylate of zirconyl include zirconyl 2-ethylhexanoate.

[0062] When the desired yield is achieved, a deactivator for the allophanatization reaction catalyst such as phosphoric acid or methyl paratoluenesulfonate can be added to stop the allophanatization reaction. The usage amount of the above allophanatization reaction catalyst is preferably 10 ppm or more and 10000 ppm or less, more preferably 10 ppm or more and 1000 ppm or less, and even more preferably 10 ppm or more and 500 ppm or less in terms of mass ratio with respect to the diisocyanate as the raw material.

[0063] The allophanatization reaction temperature is preferably 60°C or higher and 160°C or lower, more preferably 70°C or higher and 155°C or lower, still more preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 145°C or lower. When the allophanatization reaction temperature is at or below the above upper limit value, changes in properties such as coloring of the resulting polyisocyanate can be more effectively prevented.

[0064] The allophanatization reaction time is preferably 0.2 hours or more and 8 hours or less, more preferably 0.4 hours or more and 6 hours or less, still more preferably 0.6 hours or more and 4 hours or less, particularly preferably 0.8 hours or more and 3 hours or less, and most preferably 1.0 hours or more and 2 hours or less. By setting the allophanatization reaction time to be at or above the above lower limit value, a lower viscosity can be achieved, and by setting it to be at or below the above upper limit value, coloring of the polyisocyanate itself can be more suppressed.

[0065] In addition, the above isocyanurate-forming reaction catalyst can be used as an allophanatization reaction catalyst. When the allophanatization reaction is carried out using the above isocyanurate-forming reaction catalyst, an isocyanurate group-containing polyisocyanate is also simultaneously produced. Among them, from the viewpoint of improving productivity in terms of economy, it is preferable to use the above isocyanurate-forming reaction catalyst as the allophanatization reaction catalyst and carry out the allophanatization reaction and the isocyanurate-forming reaction.

[0066] [Urethanization reaction] In the method for producing the polyisocyanate composition of the present embodiment, the urethanization reaction is preferably carried out after the isocyanuration reaction and the allophanatization reaction. Specifically, the isocyanuration reaction and the allophanatization reaction are each carried out sequentially or in parallel to obtain a polyisocyanate containing an isocyanurate group and an allophanate group, and then the obtained polyisocyanate and a polyol (B) (at least one selected from the group consisting of a polyether polyol (B1), a polyester polyol (B2), and a polycarbonate polyol (B3)) are subjected to a urethanization reaction.

[0067] The lower limit of the urethanization reaction temperature is preferably 80°C, more preferably 100°C. On the other hand, the upper limit of the reaction temperature is preferably 150°C, more preferably 130°C. That is, the urethanization reaction temperature is preferably 80°C or higher and 150°C or lower, more preferably 100°C or higher and 130°C or lower.

[0068] When the polymerization reactions of the above-mentioned isocyanuration reaction, allophanatization reaction, and urethanization reaction reach the desired degree of polymerization, the polymerization reaction is stopped. The termination of the polymerization reaction is not limited to the following, but for example, it can be achieved by adding an acidic compound to the reaction solution to neutralize the polymerization reaction catalyst or by inactivating it by thermal decomposition, chemical decomposition, etc. Examples of the acidic compound include phosphoric acid, acidic phosphate ester, sulfuric acid, hydrochloric acid, sulfonic acid compounds, and the like. After the reaction is stopped, filtration is performed if necessary.

[0069] Since the reaction solution immediately after the reaction stop usually contains unreacted diisocyanate monomer, it is preferable to remove this by a thin-film evaporation can, extraction, etc. By performing such post-treatment, it is preferable to control the concentration of the diisocyanate monomer contained in the polyisocyanate composition to 1% by mass or less. The concentration of the diisocyanate monomer can be measured, for example, when the diisocyanate monomer is HDI, using the method described in the examples described later.

[0070] <Physical properties of the polyisocyanate composition> [Number average functionality (fn) with respect to isocyanate groups] The number average functionality with respect to the isocyanate groups of the polyisocyanate contained in the polyisocyanate composition of the present embodiment (hereinafter, may be referred to as "average NCO functionality") is preferably 3.0 or more, more preferably 3.0 or more and 8.0 or less, more preferably 3.0 or more and 10.0 or less, even more preferably 3.1 or more and 9.0 or less, even more preferably 3.1 or more and 8.5 or less, and particularly preferably 3.2 or more and 8.0 or less. Since the average NCO functionality is equal to or greater than the above lower limit value, the quick-drying property when forming a coating film can be further improved. On the other hand, since the average NCO functionality is equal to or less than the above upper limit value, it is possible to more effectively suppress the excessive increase in viscosity.

[0071] Note that the number average functionality of the isocyanate groups in the polyisocyanate composition (hereinafter sometimes referred to as "fn") can be calculated using the following formula as described in the examples below. In the formula, "NCO%" represents the isocyanate group content, and "Mn" represents the number average molecular weight. (Average NCO functionality) = (Mn × NCO% × 0.01) / 42

[0072] [Viscosity] The viscosity of the polyisocyanate composition of the present embodiment at 25°C is not particularly limited, but from the viewpoints of the amount of organic solvent and functionality, it is preferably 100 mPa·s or more and 100,000 mPa·s or less, more preferably 120 mPa·s or more and 80,000 mPa·s or less, and even more preferably 130 mPa·s or more and 70,000 mPa·s or less. If the viscosity is equal to or greater than the above lower limit value, a sufficiently large number of functional groups can be obtained, while if it is equal to or less than the above upper limit value, the amount of organic solvent can be reduced.

[0073] As described in the examples below, the viscosity can be the value measured at 25°C using an E-type viscometer (manufactured by Tokimec, Inc.).

[0074] [Isocyanate group content (NCO%)] The isocyanate group content (hereinafter sometimes referred to as "NCO%") of the polyisocyanate composition of the present embodiment is preferably 3.0% by mass or more and 20.0% by mass or less, more preferably 3.3% by mass or more and 19.0% by mass or less, and even more preferably 3.6% by mass or more and 18.0% by mass or less, from the viewpoint of the stretchability when forming a coating film. If NCO% is equal to or greater than the above lower limit value, the stretchability when forming a coating film is better, while if it is equal to or less than the above upper limit value, the crosslinking density does not become too high, and a coating film that is less likely to crack is formed.

[0075] The NCO% can be determined by back-titration with 1N hydrochloric acid after neutralizing the isocyanate groups with an excess of 2N amine as described in the examples below.

[0076] <Use and Application> The polyisocyanate composition of this embodiment can be used as a curing agent composition for a paint composition. The paint composition of this embodiment contains the above polyisocyanate composition as a curing agent component. The polyisocyanate composition of this embodiment is preferably used as an isocyanate curing agent composition for PPF and exhibits excellent performance as a curing agent component for a paint composition for PPF.

[0077] ≪Paint Composition for PPF≫ The paint composition for PPF of this embodiment contains the above isocyanate curing agent composition for PPF as a curing agent component. The paint composition for PPF of this embodiment preferably contains a polyol as a main agent component and the above isocyanate curing agent composition for PPF as a curing agent component. The paint composition for PPF of this embodiment may contain other main agent components in addition to the above polyol as a main agent component.

[0078] Further, the paint composition for PPF of this embodiment may contain other curing agent components in addition to the above isocyanate curing agent composition for PPF as a curing agent component. However, the paint composition for PPF of this embodiment preferably contains only the above isocyanate curing agent composition for PPF as a curing agent component.

[0079] <Polyol> The lower limit of the hydroxyl value of the polyol as the main agent component is preferably 5 mgKOH / g, more preferably 10 mgKOH / g, still more preferably 15 mgKOH / g, and particularly preferably 20 mgKOH / g. On the other hand, the upper limit of the hydroxyl value of the polyol is preferably 200 mgKOH / g, more preferably 160 mgKOH / g, still more preferably 120 mgKOH / g, and particularly preferably 80 mgKOH / g. That is, the hydroxyl value of the polyol is preferably 5 mgKOH / g or more and 200 mgKOH / g or less, more preferably 10 mgKOH / g or more and 160 mgKOH / g or less, still more preferably 15 mgKOH / g or more and 120 mgKOH / g or less, and particularly preferably 20 mgKOH / g or more and 80 mgKOH / g or less. When the hydroxyl value is within the above range, a more flexible and tougher coating film can be obtained.

[0080] Examples of the polyol include acrylic polyols, polyester polyols, polyether polyols, polyolefin-based polyols, silicon-containing polyols, fluorine-containing polyols, polycarbonate polyols, epoxy resins, alkyd polyols, etc. These polyols may be used alone or in combination of two or more. Further, as the polyol, a urethane-modified acrylic polyol, a urethane-modified polyester polyol, a urethane-modified polyether polyol, etc., which are obtained by modifying acrylic polyol, polyester polyol or polyether polyol, etc. with aliphatic diisocyanate, alicyclic diisocyanate or a polyisocyanate obtained therefrom, can also be used.

[0081] The polyol can be produced by known techniques. Hereinafter, the production methods of typical acrylic polyols, polyester polyols, and polyether polyols will be described.

[0082] [Acrylic polyols] Acrylic polyols can be obtained, for example, by a method of polymerizing only a polymerizable monomer having one or more active hydrogens in one molecule, or by a method of copolymerizing a polymerizable monomer having one or more active hydrogens in one molecule and, if necessary, another monomer copolymerizable with the polymerizable monomer.

[0083] Examples of the polymerizable monomer having one or more active hydrogens in one molecule include those shown in the following (i) to (vi). These may be used alone or in combination of two or more kinds. (i) Acrylic esters having active hydrogens such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate. (ii) Methacrylic esters having active hydrogens such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. (iii) (Meth)acrylic esters having polyvalent active hydrogens such as mono-(meth)acrylates of triols. Examples of the triol include glycerin and trimethylolpropane. (iv) Monoethers of polyether polyols and the above (meth)acrylic esters having active hydrogens. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polybutylene glycol. (v) Adducts of glycidyl (meth)acrylate and monobasic acids. Examples of the monobasic acid include acetic acid, propionic acid, and p-tert-butylbenzoic acid. (vi) Adducts obtained by ring-opening polymerization of lactones with the active hydrogens of the above (meth)acrylic esters having active hydrogens. Examples of the lactones include ε-caprolactone and γ-valerolactone.

[0084] Examples of other monomers copolymerizable with the polymerizable monomer include those shown in the following (i) to (v). These may be used alone or in combination of two or more. (i) (Meth)acrylate esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate; (ii) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid; (iii) unsaturated amides such as acrylamide, N-methylolacrylamide, diacetoneacrylamide; (iv) vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-(meth)acrylopropyltrimethoxysilane; (v) other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate.

[0085] As a specific production method of acrylic polyols, for example, the above monomers can be solution polymerized in the presence of a radical polymerization initiator such as a known peroxide or azo compound, and diluted with an organic solvent or the like as necessary to obtain acrylic polyols.

[0086] When the PPF coating composition of this embodiment contains a solvent with a high water content, the above monomers can be solution polymerized and converted into an aqueous layer or produced by a known method such as emulsion polymerization. In that case, the acidic part such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer can be neutralized with an amine or ammonia to impart water solubility or water dispersibility to the acrylic polyols.

[0087] [Polyester polyols] Polyester polyols can be obtained, for example, by subjecting a dibasic acid alone or a mixture of two or more kinds thereof and a polyhydric alcohol alone or a mixture of two or more kinds thereof to a condensation reaction. Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane, and the like.

[0088] As a specific production method of polyester polyols, for example, a condensation reaction can be carried out by mixing the above components and heating at about 160 °C or higher and 220 °C or lower. Alternatively, for example, polycaprolactones and the like obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol can also be used as polyester polyols.

[0089] [Polyether polyols] Polyether polyols can be obtained, for example, by using any of the following methods (1) to (3).

[0090] (1) A method of obtaining polyether polyols by randomly or block-adding an alkylene oxide alone or a mixture thereof to a polyhydric hydroxy compound alone or a mixture thereof using a catalyst. Examples of the catalyst include hydroxides such as lithium, sodium, and potassium, strongly basic catalysts, and composite metal cyanide complex compounds. Examples of the strongly basic catalyst include alcoholates and alkylamines. Examples of the composite metal cyanide complex compound include metal porphyrins and zinc hexacyanocobaltate complex compounds. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like.

[0091] (2) A method for obtaining polyether polyols by reacting a polyamine compound with an alkylene oxide. Examples of the polyamine compound include ethylenediamines and the like. Examples of the alkylene oxide are the same as those exemplified in (1) above.

[0092] (3) A method for obtaining so-called polymer polyols by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

[0093] Examples of the polyhydric hydroxy compound in (1) include those shown in the following (i) to (vi). (i) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.; (ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, ramnitol, etc.; (iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, ramnose, fucose, ribodesose, etc.; (iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, etc.; (v) Trisaccharides such as raffinose, gentianose, melezitose, etc.; (vi) Tetrasaccharides such as stachyose, etc.

[0094] <nco oh> In the paint composition for PPF of the present embodiment, the mixing ratio of the curing agent to the main agent can be represented by the molar ratio of the isocyanate group to the hydroxyl group (NCO / OH). The lower limit value of NCO / OH is preferably 0.1, more preferably 0.3, still more preferably 0.4, and particularly preferably 0.5. On the other hand, the upper limit value of NCO / OH is preferably 5.0, more preferably 4.0, still more preferably 3.0, and particularly preferably 2.0. That is, NCO / OH is preferably 0.1 or more and 5.0 or less, more preferably 0.3 or more and 4.0 or less, still more preferably 0.4 or more and 3.0 or less, and particularly preferably 0.5 or more and 2.0 or less. By having NCO / OH within the above range, a tougher coating layer for PPF can be formed.

[0095] <Various Additives> In addition to the main agent such as the above polyol and the isocyanate curing agent composition for PPF of the present embodiment, depending on the purpose and use, within a range that does not impair the effects of the present invention, coloring pigments, dyes, silane coupling agents for improving the adhesion of the coating film, ultraviolet absorbers, curing accelerators, light stabilizers, matting agents, coating film surface hydrophilizing agents, catalysts for curing acceleration, drying improvers, leveling agents, antioxidants, plasticizers, surfactants, and other various additives used in the art may be included.

[0096] The coloring pigment may be an inorganic pigment or an organic pigment. Examples of the inorganic pigment include carbon black and titanium oxide with good weather resistance. Examples of the organic pigment include phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone-based yellow.

[0097] Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, ureidopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and the like.

[0098] Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers.

[0099] Examples of the light stabilizer include hindered amine light stabilizers and the like. Specific commercially available products include, for example, Adeka Stab LA62, Adeka Stab LA67 (trade name, all manufactured by Adeka Argus Chemical Co., Ltd.), Tinuvin 292, Tinuvin 144, Tinuvin 123, Tinuvin 440 (trade name, all manufactured by Ciba Specialty Chemicals Inc.), Sanol LS765 (trade name, manufactured by Sankyo Lifetech Co., Ltd.), and the like.

[0100] Examples of the matting agent include ultrafine powder synthetic silica and the like. When a matting agent is used, an elegant semi-gloss, matte-finished coating layer can be formed.

[0101] Examples of the catalyst for promoting curing include, but are not limited to, metal salts, tertiary amines, and the like. Examples of the metal salt include dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt salts, and the like. Examples of the tertiary amines include triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N'-endoethylene piperazine, N,N'-dimethylpiperazine, and the like.

[0102] Examples of the drying improver include cellulose acetate butyrate (CAB), nitrocellulose (NC), and the like.

[0103] The leveling agent is not particularly limited, and examples thereof include silicone, aerosil, wax, stearate, polysiloxane, and the like.

[0104] The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, phosphoric acid esters, fatty acid esters, pyromellitic acid esters, epoxy plasticizers, polyether plasticizers, liquid rubbers, non-aromatic paraffin oils, and the like. Examples of the phthalic acid esters include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate, and the like. Examples of the phosphoric acid esters include tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-dichloropropyl phosphate, and the like. Examples of the fatty acid esters include trimellitic acid esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinoleate, and the like. Examples of the trimellitic acid esters include octyl trimellitate, isodecyl trimellitate, and the like. Examples of the pyromellitic acid ester include octyl pyromellitate and the like. Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl ester and the like. Examples of the polyether plasticizer include adipic acid ether ester, polyether and the like. Examples of the liquid rubber include liquid nitrile rubber (liquid NBR), liquid acrylic rubber, liquid polybutadiene and the like.

[0105] Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants and the like.

[0106] <Method for producing the coating composition for PPF> The coating composition for PPF of this embodiment is useful as a solvent-based coating composition and is obtained by the production method shown below.

[0107] When the coating composition for PPF of this embodiment is a solvent-based coating composition, for example, first, to the polyol or its solvent dilution as the main agent, if necessary, various additives are added, and then the above-mentioned curing agent composition for PPF is added as a curing agent. Then, if necessary, a solvent is further added to adjust the viscosity. Then, by stirring using manual stirring or a stirrer such as a magnetic stirrer, a solvent-based coating composition can be obtained.

[0108] In addition, the mixing order of the main agent component mainly composed of the above polyol, the curing agent component mainly composed of the isocyanate curing agent composition for PPF, and the above various additives is not particularly limited, and for example, they can be mixed in the following order. 1) Mix the curing agent component at the painting site with the main agent component in which various additives are previously mixed; 2) After mixing the main agent component and the curing agent component at the painting site, mix the various additives; 3) Mix the main agent component in which various additives are previously mixed with the curing agent component in which various additives are previously mixed at the painting site.

[0109] <Use> The paint composition for PPF of this embodiment is suitably used for forming a coating layer for PPF on the PPF surface.

[0110] ≪Coating layer for PPF≫ The coating layer for PPF of this embodiment is obtained by curing the above paint composition for PPF, exhibits high quick-drying property, and is excellent in scratch resistance, stain resistance, adhesion, and stretchability.

[0111] <Manufacturing method of coating layer for PPF> The manufacturing method of the coating layer for PPF of this embodiment is a method including a step of curing the above paint composition for PPF.

[0112] The coating layer for PPF of this embodiment can be manufactured by applying the above paint composition for PPF onto an object to be coated using a known coating method such as spray coating, air spray coating, brush coating, dip coating, roll coating, curtain flow coating, bell coating, electrostatic coating, etc., and then curing it.

[0113] There is no particular limitation on the object to be coated, and examples include molded products formed from materials such as metals (steel plates, surface-treated steel plates, etc.), plastics, woods, films, inorganic materials, etc. Also, the shapes of these molded products are not particularly limited, and for example, those with a small thickness such as films, sheets, boards, etc. may be used, or those with a large thickness such as cylinders, three-dimensional structures, etc. may be used. Also, hollow ones such as tubes may be used.

[0114] When the object to be coated is a laminate in which a base material, a primer layer, and a coating layer for PPF are laminated in this order, the manufacturing method of the coating layer for PPF of this embodiment can also be referred to as a manufacturing method of PPF. According to this method, PPF excellent in scratch resistance, stain resistance, adhesion, and stretchability can be obtained.

[0115] There is no particular limitation on specific examples of the object to be coated, and examples include base materials for architecture, automobiles, plastics, information household appliances, etc. When the object to be coated is a painted product, the object to be coated includes a substrate, a primer layer, and a coating film for painting, and the PPF coating layer of the present embodiment may be laminated as a protective coating film or film on the coating film for painting. When the PPF is a film to be adhered onto an object to be coated, the PPF having a substrate film and a coating film may be produced by applying the above PPF coating composition onto the substrate film. Examples of the substrate film include resin films such as polyurethane films and adhesive films.

Examples

[0116] Specific examples and comparative examples are shown below to explain the present embodiment in more detail. However, the present embodiment is not limited by the following examples and comparative examples as long as the gist thereof is not exceeded.

[0117] [Physical Property 1] (Molar ratio of urethane group / (allophanate group + urethane group), molar ratio of isocyanurate group / (allophanate group + isocyanurate group + urethane group)) Regarding the polyisocyanate compositions obtained in the examples and comparative examples, C-NMR measurement was performed using Biospin Avance600 (trade name) manufactured by Bruker. 13 Specific measurement conditions were as follows.

[0118] (Measurement Conditions) 13 C-NMR apparatus: AVANCE600 (manufactured by Bruker) CryoProbe (manufactured by Bruker) CryoProbe (registered trademark) CPDUL 600S3-C / H-D-05Z Resonance frequency: 150 MHz Concentration: 60 wt / vol% Shift reference: CDCl3 (77 ppm) Number of integrations: 10000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)

[0119] The integrated values of the following signals were divided by the number of carbons being measured to obtain the number of moles A, B, and C of the allophanate group, isocyanurate group, and urethane group, respectively. Isocyanurate group: (Integrated value around 148.6 ppm) ÷ 3 Urethane group: (Integrated value around 156.5 ppm) ÷ 1 Allophanate group: (Integrated value around 154 ppm) ÷ 1 The molar ratios C / (A + C) and B / (A + B + C) were calculated from the number of moles A, B, and C.

[0120] [Physical Property 2] (Average number of isocyanate groups (average NCO groups)) The average number of isocyanate groups (average NCO groups) of the polyisocyanate composition was determined by the following formula. (Average NCO groups) = (Mn × NCO% × 0.01) / 42

[0121] In the formula, "NCO%" represents the isocyanate group content, and the value obtained in "Physical Property 4" described later was used. Also, "Mn" represents the number average molecular weight, which was determined as the molecular weight based on polystyrene by performing GPC measurement under the measurement conditions shown below.

[0122] (Measurement Conditions) Apparatus: HLC - 8320GPC (TOSOH) Column: TSKgel Super H2500 × 1 (TOSOH) TSKgel Super H4000 × 1 (TOSOH) TSKgel Super H5000 × 1 (TOSOH) TSKgel Super H6000 × 1 (TOSOH) Carrier: Tetrahydrofuran Flow rate: 0.6 mL / min Sample concentration: 1.0 mass% Injection volume: 20 μL Temperature: 40°C Detection method: Differential refractometer

[0123] [Physical Property 3] (Viscosity at 25°C) The viscosity was measured at 25°C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The rotor used was (1°34’×R24) or (3°×R12). The rotation speeds were as follows.

[0124] (Rotation speed of 1°34’×R24) 100 r.p.m. (when less than 128 mPa·s) 50 r.p.m. (when 128 mPa·s or more and less than 256 mPa·s) 20 r.p.m. (when 256 mPa·s or more and less than 640 mPa·s) 10 r.p.m. (when 640 mPa·s or more and less than 1280 mPa·s) 5 r.p.m. (when 1280 mPa·s or more and less than 2560 mPa·s) 2.5 r.p.m. (when 2560 mPa·s or more and less than 5120 mPa·s) 1 r.p.m. (when 5120 mPa·s or more and less than 10240 mPa·s) 0.5 r.p.m. (when 10240 mPa·s or more and less than 20480 mPa·s)

[0125] (Rotation speed of 3°×R12) 5 r.p.m. (when 20480 mPa.s or more and less than 38000 mPa.s) 2.5 r.p.m. (when 38000 mPa·s or more and less than 75000 mPa·s) 1 r.p.m. (when 75000 mPa·s or more and less than 190000 mPa·s) 0.5 r.p.m. (when 190000 mPa·s or more and less than 380000 mPa·s)

[0126] [Physical Property 4] (Isocyanate group content (NCO%, NCO content)) The NCO% was determined by back-titration with 1N hydrochloric acid after neutralizing the isocyanate groups with an excess of 2N amine.

[0127] [Evaluation Method for PPF Paint Composition] Using each isocyanate curing agent composition for PPF, a paint composition for PPF was produced as follows and evaluated.

[0128] [Production Example 1] (Production of Paint Composition for PPF) First, an acrylic polyol (manufactured by Allnex, "Setalux 1152" (product name), resin solid content concentration 50% by mass, hydroxyl value 140 mg KOH / resin g) and each isocyanate curing agent composition for PPF were blended so that the molar equivalent ratio of the hydroxyl group to the isocyanate group was 1:1. Then, the paint viscosity was adjusted to 20 seconds with a Ford cup No. 4 using butyl acetate to obtain each paint composition for PPF.

[0129] (Scratch Resistance) Each paint composition for PPF was applied to a glass plate so that the dry film thickness became 30 μm, and left at 80 °C for 120 minutes to cure to obtain each coating film. The scratch resistance was measured for the obtained coating film by the following method using a rubbing tester (manufactured by Taihei Rika Kogyo Co., Ltd.). The 20° gloss of the coated surface was measured in advance. A cleanser (product name Marzen Cleanser, manufactured by Marzen Cleanser Co., Ltd.) and water were mixed at a ratio of 3:2 to obtain an abrasive. Approximately 1 g of the abrasive was attached to the sponge of the rubbing tester, and a load of 200 g was applied to rub the coating film of the test plate back and forth 20 times. Then, the coated surface was washed with running water and naturally dried, and the 20° gloss of the coated surface was measured. The 20° gloss retention rate was calculated by the following formula, and the value was used as the evaluation value of scratch resistance. 20° gloss retention rate = (20° gloss after the test / 20° gloss before the test) × 100

[0130] (Scratch Resistance: Evaluation Criteria) ◎: 20° gloss retention rate is 80% or more ○: 20° gloss retention rate is 60% or more and less than 80% △: 20° gloss retention rate is 40% or more and less than 60% ×: 20° gloss retention rate is less than 40%

[0131] (Quick Drying Property) Each paint composition for PPF was applied to a polypropylene (PP) plate so that the dry film thickness became 30 μm, and left to cure for 24 hours under the conditions of 23°C and 50% RH to obtain each coating film. The quick-drying property was evaluated by measuring the gel fraction of the obtained coating film. The gel fraction was determined from the mass of the coating film that was immersed in acetone at 20°C for 24 hours, taken out, and dried at 105°C for 1 hour. Gel fraction (%) = ((mass of coating film before immersion - mass of coating film after immersion) / (mass of coating film before immersion)) × 100

[0132] (Quick-drying property: Evaluation criteria) ◎: Gel fraction is 80% by mass or more ○: Gel fraction is 70% by mass or more and less than 80% by mass △: Gel fraction is 60% by mass or more and less than 70% by mass ×: Gel fraction is less than 60% by mass

[0133] (Stain resistance) Each paint composition for PPF was applied to a polypropylene (PP) plate so that the dry film thickness became 30 μm, and left to cure for 120 minutes under the condition of 80°C to obtain each coating film. The stain resistance was evaluated by staining the obtained coating film with magic ink, wiping off the ink with ethanol after the ink dried, and visually observing the state of the coating film after wiping.

[0134] (Stain resistance: Evaluation criteria) ◎: No remaining ink. ○: Slight ink remains. △: Ink remains.

[0135] (Adhesion) Each paint composition for PPF was applied to a mild steel sheet so that the film thickness after drying would be 30 μm, and left to cure for 120 minutes under the condition of 80 °C to obtain each coating film. For the adhesion, in accordance with JIS K-5400, a cellophane tape peel adhesion test was conducted on the checkerboard pattern of the obtained coating film test piece. Using a cutter, cuts were made on the surface of the test piece to form 100 checkerboard patterns of 2 mm squares. After attaching cellophane tape to the surface, the cellophane tape was vigorously peeled off from the surface of the test piece, and the number of checkerboard patterns that did not peel off was counted. The adhesion was evaluated according to the following evaluation criteria. Note that, among the 100 checkerboard patterns, the one with a larger number of checkerboard patterns that did not peel off was evaluated as better.

[0136] (Adhesion: Evaluation Criteria) ◎: 100 / 100 ○: 80 / 100 or more and 99 / 100 or less △: 50 / 100 or more and 79 / 100 or less ×: 0 / 100 or more and 49 / 100 or less

[0137] (Elongation) Each paint composition for PPF was applied to a polypropylene (PP) plate so that the film thickness after drying would be 50 μm, and left to cure for 120 minutes under the condition of 80 °C to obtain each coating film. The elongation was measured by conducting a tensile test using the obtained coating film. The tensile test was measured at a temperature of 23 °C using a tensile tester (manufactured by Shimadzu Corporation, AGS 500G) at a tensile speed of 20 mm / min and a gripping interval of 20 mm. The elongation was evaluated according to the evaluation criteria shown below.

[0138] (Elongation: Evaluation Criteria) ◎: Coating film elongation is 100% or more ○: Coating film elongation is 50% or more and less than 100% △: Coating film elongation is 20% or more and less than 50% ×: Coating film elongation is less than 20%

[0139] (Synthesis of Polyisocyanate) [Synthesis Example 1] (Synthesis of Polyisocyanate Pa-1) The inside of a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen injection tube, and a dropping funnel was made into a nitrogen atmosphere, and 1000 g of HDI and 200 g of polyester polyol "Polylite OD-X-2542C" (trade name of DIC Corporation; derived from a trivalent alcohol and ε-caprolactone, number average molecular weight 850, number average functionality 3) were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After filtering the reaction solution, it was purified twice using a thin-film evaporator under the conditions of 160 °C and 0.2 Torr to obtain polyisocyanate Pa-1. The obtained polyisocyanate Pa-1 had a viscosity of 5000 mPa·s (25 °C), an NCO content of 9.2 mass%, fn = 3.3, and an HDI monomer concentration of 0.11 mass%.

[0140] [Synthesis Example 2] (Synthesis of polyisocyanate Pa-2) Into the same apparatus as in Synthesis Example 1, 1000 g of HDI and 200 g of polyester polyol "Polylite OD-X-2735" (trade name of DIC Corporation; derived from a trivalent alcohol and ε-caprolactone, number average molecular weight 500, number average functionality 3) were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate Pa-2. The obtained polyisocyanate Pa-2 had a viscosity of 3000 mPa·s (25 °C), an NCO content of 9.0 mass%, fn = 3.2, and an HDI monomer concentration of 0.11 mass%.

[0141] [Synthesis Example 3] (Synthesis of polyisocyanate Pa-3) Into the same apparatus as in Synthesis Example 1, 1000 g of HDI and 300 g of a polyester polyol “Polylite OD-X-2722” (trade name of DIC Corporation; derived from a dihydric alcohol and ε-caprolactone, number average molecular weight 2000, number average functionality 2) were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain a polyisocyanate Pa-3. The obtained polyisocyanate Pa-3 had a viscosity of 10000 mPa·s (25 °C), an NCO content of 4.6 mass%, fn = 2.0, and an HDI monomer concentration of 0.11 mass%.

[0142] [Synthesis Example 4] (Synthesis of Polyisocyanate Pa-4) Into the same apparatus as in Synthesis Example 1, 600 g of HDI and 30 g of a polyester polyol “Polylite OD-X-2733” (trade name of DIC Corporation; derived from a trihydric alcohol and ε-caprolactone, number average molecular weight 300, number average functionality 3) were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After cooling to 60 °C, 0.10 g of tetramethylammonium caprylate was added as an isocyanurate formation catalyst. When the conversion rate reached 50%, 0.21 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain a polyisocyanate Pa-4. The obtained polyisocyanate Pa-4 had a viscosity of 23000 mPa·s (25 °C), an NCO content of 18.0 mass%, fn = 5.5, an HDI monomer concentration of 0.2 mass%, and when NMR was measured, the molar ratio of allophanate / isocyanurate was 55 / 45.

[0143] [Synthesis Example 5] (Synthesis of Polyisocyanate Pa-5) Into the same apparatus as in Synthesis Example 1, 600 g of HDI and 12 g of 1,3-butanediol were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After cooling to 60 °C, 0.10 g of tetramethylammonium caprylate was added as an isocyanurate-forming catalyst. When the conversion reached 55%, 0.21 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate Pa-5. The obtained polyisocyanate Pa-5 had a viscosity of 8000 mPa·s (25 °C), an NCO content of 19.0 mass%, fn = 4.7, an HDI monomer concentration of 0.2 mass%, and when measured by NMR, the molar ratio of allophanate / isocyanurate was 55 / 45.

[0144] [Synthesis Example 6] (Synthesis of Polyisocyanate Pa-6) Into the same apparatus as in Synthesis Example 1, 600 g of HDI and 2 g of 2-ethyl-1-hexanol were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After cooling to 60 °C, 0.10 g of tetramethylammonium caprylate was added as an isocyanurate-forming catalyst. When the conversion reached 55%, 0.21 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate Pa-6. The obtained polyisocyanate Pa-6 had a viscosity of 1000 mPa·s (25 °C), an NCO content of 23.0 mass%, fn = 3.2, an HDI monomer concentration of 0.2 mass%, and when measured by NMR, the molar ratio of allophanate / isocyanurate was 5 / 95.

[0145] [Synthesis Example 7] (Synthesis of Polyisocyanate Pa-7) Into the same apparatus as in Synthesis Example 1, 600 g of HDI and 60 g of 2-ethyl-1-hexanol were charged, and a urethanization reaction was carried out at 90 °C for 2 hours with stirring. Then, 0.05 g of tetramethylammonium caprylate was added as an isocyanurate formation catalyst. When the conversion rate reached 40%, 0.1 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate Pa-7. The obtained polyisocyanate Pa-7 had a viscosity of 500 mPa·s (25 °C), an NCO content of 18.0 mass%, fn = 2.4, an HDI monomer concentration of 0.2 mass%, and when measured by NMR, the molar ratio of allophanate / isocyanurate was 60 / 40.

[0146] [Synthesis Example 8] (Synthesis of Polyisocyanate Pa-8) Into the same apparatus as in Synthesis Example 1, 1000 g of HDI and 100 g of polyester polyol "Polyolite OD-X-2171" (trade name of DIC Corporation; derived from a dihydric alcohol and ε-caprolactone, number average molecular weight 540, number average functionality 2) were charged, and a urethanization reaction was carried out at 90 °C for 1 hour with stirring. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate Pa-8. The obtained polyisocyanate Pa-8 had a viscosity of 7000 mPa·s (25 °C), an NCO content of 8.9 mass%, fn = 2.0, and an HDI monomer concentration of 0.11 mass%.

[0147] [Synthesis Example 9] (Synthesis of Polyisocyanate Pa-9) Into the same apparatus as in Synthesis Example 1, 100 g of Pa-7 and 70 g of a difunctional polyether polyol "Excenol 1020" (trade name of AGC Inc., containing oxypropylene groups, number average molecular weight 1000, number average functionality 2) were charged, and a urethanization reaction was carried out at 120 °C for 6 hours with stirring to obtain polyisocyanate Pa-9. The obtained polyisocyanate Pa-9 had a viscosity of 50000 mPa·s (25 °C), an NCO content of 7.1 mass%, fn = 3.8, and an HDI monomer concentration of 0.2 mass%.

[0148] [Synthesis Example 10] (Synthesis of Polyisocyanate Pa-10) Into the same apparatus as in Synthesis Example 1, 100 g of Pa-7 and 30 g of polycarbonate diol "Duranol T5650E" (trade name of Asahi Kasei Corporation, number average molecular weight 500, number average functional group number 2) were charged, and a urethanization reaction was carried out at 120 °C for 6 hours with stirring to obtain polyisocyanate Pa-10. The obtained polyisocyanate Pa-10 had a viscosity of 6000 mPa·s (25 °C), an NCO content of 10.0% by mass, fn = 2.6, and an HDI monomer concentration of 0.2% by mass.

[0149] [Synthesis Example 11] (Synthesis of Polyisocyanate Pa-11) Into the same apparatus as in Synthesis Example 1, 100 g of Pa-7 and 170 g of difunctional polyether polyol "Excenol 3020" (trade name of AGC Inc., containing oxypropylene groups, number average molecular weight 3200, number average functional group number 2) were charged, and a urethanization reaction was carried out at 120 °C for 6 hours with stirring to obtain polyisocyanate Pa-11. The obtained polyisocyanate Pa-11 had a viscosity of 80000 mPa·s (25 °C), an NCO content of 4.7% by mass, fn = 3.5, and an HDI monomer concentration of 0.2% by mass.

[0150] ><Production of Polyisocyanate Composition>[ [Production Example 1] (Production of Polyisocyanate Composition P-1) Into the same apparatus as in Synthesis Example 1, 47 g of polyisocyanate Pa-1 obtained in Synthesis Example 1 and 53 g of polyisocyanate Pa-4 obtained in Synthesis Example 4 were added. Then, mixing was carried out at 60 °C for 1 hour with stirring to obtain polyisocyanate composition P-1. The obtained polyisocyanate composition P-1 was a transparent liquid, having a viscosity of 11000 mPa·s (25 °C), an NCO content of 13.8% by mass, and fn = 4.5.

[0151] [Production Examples 2 to 19] (Production of Polyisocyanate Compositions P-2 to P-19) Except for the formulations described in Tables 1 and 2, each polyisocyanate composition was obtained in the same manner as in Production Example 1.

[0152] Also, using each of the obtained polyisocyanate compositions as an isocyanate curing agent composition for PPF, the abrasion resistance, quick drying property, stain resistance, adhesion, and stretchability were evaluated by the above method. The results are shown in Tables 3 and 4. The types of polyol (B) used in the polyisocyanate compositions represent polycaprolactone (PCL), polypropylene glycol (PPG), and polycarbonate diol (PCD), respectively. When two or more types of polyol components with different Mn values were used, the Mn values were shown by connecting them with a plus sign.

[0153]

Table 1

[0154]

Table 2

[0155]

Table 3

[0156]

Table 4

[0157] From Tables 3 and 4, the coating films obtained by curing the PPF coating compositions using the polyisocyanate compositions P-1 to P-17 (Examples 1 to 17) as the isocyanate curing agent compositions for PPF were excellent in all of abrasion resistance, quick drying property, stain resistance, adhesion, and stretchability.

[0158] On the other hand, in the coating film obtained by curing the PPF coating composition using the polyisocyanate compositions P-18 to P-19 (Comparative Examples 1 to 2) as the isocyanate curing agent composition for PPF from Table 4, none of the scratch resistance, quick drying property, stain resistance, adhesion, and stretchability were excellent.

Industrial Applicability

[0159] According to the polyisocyanate composition of the present embodiment, when used for PPF, it is possible to provide an isocyanate curing agent composition for PPF that is excellent in quick drying property and can impart good scratch resistance, stain resistance, adhesion, and stretchability to the coating layer of the PPF layer.< / nco>

Claims

1. At least one diisocyanate (A) selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates; At least one polyol (B) selected from the group consisting of polyether polyols (B1), polyester polyols (B2), and polycarbonate polyols (B3), and a polyisocyanate derived from the number average molecular weight of the polyol (B) is 100 or more and 10,000 or less, and the number average functionality of the hydroxyl groups of the polyol (B) is 2 or more and 3 or less, The polyether polyol (B1) has an oxypropylene group, The polyester polyol (B2) is derived from ε-caprolactone, The polycarbonate-based polyol (B3) is derived from a carbonate group-containing substance and a diol, When the polyisocyanate composition contains an allophanate group, an isocyanurate group, and a urethane group, and the number of moles of the allophanate group is A, the number of moles of the isocyanurate group is B, and the number of moles of the urethane group is C, A polyisocyanate composition, in which C / (A+C) is 0.01 or more and 0.99 or less, and B / (A+B+C) is 0.01 or more and 0.90 or less.

2. The polyisocyanate composition according to claim 1, wherein B / (A+B+C) is 0.01 or more and 0.39 or less.

3. The polyisocyanate composition according to claim 1, wherein B / (A+B+C) is 0.01 or more and 0.30 or less.

4. The polyisocyanate composition according to claim 1, wherein the polyol (B) has a number average molecular weight of 100 or more and 2,000 or less.

5. The polyisocyanate composition according to claim 1, wherein the polyol (B) has a number average molecular weight of 100 or more and 1,000 or less.

6. The polyisocyanate composition according to claim 1, wherein the polyol (B) is a polyether-based polyol (B1) and / or a polyester-based polyol (B2).

7. The polyisocyanate composition according to claim 1 , wherein the polyol (B) is a polyester-based polyol (B2).

8. The polyisocyanate composition according to claim 1, wherein the number average functionality (fn) of the isocyanate group of the polyisocyanate contained in the polyisocyanate composition is 3.0 to 8.

0.

9. A coating composition using the polyisocyanate composition according to any one of claims 1 to 8.

10. An isocyanate curing agent composition for paint protection films, which uses the polyisocyanate composition according to any one of claims 1 to 8.

11. A coating composition for paint protection films, which uses the isocyanate curing agent composition for paint protection films according to claim 10.

12. A substrate having a coating film formed thereon using the coating composition for paint protection film according to claim 11.

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