Active energy ray-curable composition, laminate, and method for producing laminate

Abstract

To provide an active energy ray-curable composition which has low viscosity even with a small content of organic solvent, and which yields a cured coating film having superior boiling water resistance and weather resistance as well as superior appearance, and to provide a laminate having a cured layer of the active energy ray-curable composition, and a method for producing the laminate.SOLUTION: An active energy ray-curable composition of the present invention includes the following components (A), (B), and (C). Component (A): a compound having one (meth)acryloyl group in one molecule. Component (B): an ester triacrylate having an isocyanuric ring structure. Component (C): a urethane (meth)acrylate having 2 to 4 (meth)acryloyl groups in one molecule (excluding compounds corresponding to the component (B)).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition, a laminate, and a method for producing the laminate.

Background Art

[0002] Polycarbonate resin is widely used as an engineering plastic with excellent transparency, moldability, and impact resistance. In automotive applications, it is often used as a material for headlamp lenses, tail lamps, side cover lamps, and glazing. However, polycarbonate resin has insufficient weather resistance compared to other engineering plastics. As a method for this, a method of applying a coating agent to form a coating film with excellent weather resistance is known. In addition, steel plates used for building exteriors and automotive exteriors are also coated with a coating agent having durability and weather resistance on the surface for the purpose of preventing rust, preventing damage, and maintaining the appearance of commercial materials. Furthermore, these coating agents are also required to have boiling water resistance, that is, the ability to withstand hot water when formed into a coating film.

[0003] Such coating agents contain organic solvents in order to have a viscosity suitable for coating. From the perspective of environmental load, a high-solid type with a reduced content of organic solvents or a solvent-free type without organic solvents, which can obtain a viscosity suitable for coating, is desired and has been under investigation (for example, Patent Documents 1-3 below).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] As a result of intensive studies by the present inventors, although it is possible to reduce the viscosity without a solvent in the composition of the coating agent described in Patent Documents 1 to 3 above, it does not satisfy the boiling water resistance and weather resistance required for coating agents used for automobile exterior finishes, building material steel plate exterior finishes, etc.

[0006] An object of the present invention is to provide an active energy ray-curable composition that has a low viscosity even with a low content of an organic solvent, has boiling water resistance and weather resistance when formed into a cured coating film, and also has excellent appearance, and to provide a laminate having a cured layer of the active energy ray-curable composition and a method for producing the laminate.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that the above problems can be solved by using a composition containing a compound having one (meth)acryloyl group in one molecule, an ester triacrylate having an isocyanuric ring structure, and a urethane (meth)acrylate having 2 to 4 (meth)acryloyl groups in one molecule, and thus completed the present invention.

[0008] That is, the present invention provides the following inventions. [1] An active energy ray-curable composition containing the following components (A), (B), and (C). Component (A): A compound having one (meth)acryloyl group in one molecule Component (B): An ester triacrylate having an isocyanuric ring structure Component (C): A urethane (meth)acrylate having 2 to 4 (meth)acryloyl groups in one molecule (excluding compounds corresponding to the above component (B)) [2] The active energy ray-curable composition according to [1], wherein the component (A) contains a compound (A-1) represented by the following formula (1).

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

[10] A laminate having a cured layer of the active energy ray-curable composition according to any one of [1] to [9].

[11] A method for producing a laminate, comprising: step 1 of applying the active energy ray-curable composition according to any one of [1] to [9] onto a substrate to obtain a coating film; and step 2 of irradiating the coating film with active energy rays to cure part or all of the coating film.

[12] The method for producing a laminate according to

[11] , wherein after step 2, steps 1 and 2 are repeated at least once in this order. [Advantages of the Invention]

[0009] The active energy ray-curable composition of the present invention has a low viscosity even when the content of the organic solvent is low, has excellent boiling water resistance and weather resistance when formed into a cured coating film, and also has excellent appearance. Therefore, the active energy ray-curable composition of the present invention can be suitably used as a hard coat agent for resin materials in applications such as automotive applications and building material applications, and is particularly suitable for automotive exterior applications and automotive glazing applications.

Embodiments for Carrying Out the Invention

[0010] <Active energy ray-curable composition> The active energy ray-curable composition of the present invention (hereinafter, the "active energy ray-curable composition of the present invention" may be simply referred to as the "composition") contains at least three components of the following components (A), (B), and (C). Component (A): A compound having one (meth)acryloyl group in one molecule Component (B): An ester triacrylate having an isocyanuric ring structure Component (C): A urethane (meth)acrylate having 2 to 4 (meth)acryloyl groups in one molecule (however, compounds corresponding to the above component (B) are excluded) The above-mentioned "(meth)acryloyl group" may be a "(meth)acryloyloxy group". Note that the above "(meth)acryloyl group" includes both an "acryloyl group" and a "methacryloyl group". The same applies to the "(meth)acryloyloxy group".

[0011] In addition to the above components (A), (B), and (C), the composition may contain, as optional components, a compound (D) containing 5 or more (meth)acryloyl groups in one molecule (hereinafter referred to as component (D)) or a compound having a reactive group other than components (A) to (D) (hereinafter referred to as component (E)). Further, the composition may have other components described later.

[0012] The viscosity of the composition is preferably low from the viewpoints of paintability and leveling property. In the measurement using an E-type viscometer, it is preferably 1000 mPa·sec or less, more preferably 500 mPa·sec or less, still more preferably 200 mPa·sec or less, and particularly preferably 100 mPa·sec or less. It is desirable to achieve the above viscosity without substantially containing an organic solvent.

[0013] [Component (A)] When the composition contains a monofunctional (meth)acrylate compound having one (meth)acryloyl group in one molecule as component (A), the viscosity can be lowered, the paintability is improved, and the boiling water resistance and weather resistance of the coating film are improved. Component (A) may be used alone as one kind of compound, or two or more kinds may be used in combination.

[0014] As component (A), it is preferable to include a compound (A-1) represented by the following formula (1). By including such a compound containing one (meth)acryloyl group and an alkylene oxide, the weather resistance of the coating film is not lowered, and the viscosity of the composition can be made particularly low. [Chemical formula] [R1 is a methyl group or a hydrogen atom, R2 is an ethylene group, a propylene group, or a butylene group, R3 is an alkyl group having 1 to 5 carbon atoms which may have a substituent, and n is an integer of 1 to 5] In the case where there are a plurality of R2 in formula (1), they may be the same or different.

[0015] R3 in the above formula (1) may be linear or branched, but linear is preferred. As R2, an ethylene group is particularly preferred. As R3, a methyl group and an ethyl group are particularly preferred. From the viewpoints of paintability, lowering the viscosity of the coating liquid, and weather resistance, n is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 2 from the viewpoints of volatility and skin irritation.

[0016] (A-1) specific examples include methoxyethyl acrylate, ethyl carbitol acrylate, methoxy triethylene glycol acrylate, polyglycidyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate (ethylene glycol unit number is 5 - 12), polyethylene glycol monoethyl ether (meth) acrylate (ethylene glycol unit number is 5 - 12), etc. of (poly) ethylene glycol (meth) acrylates; propylene glycol monomethyl ether (meth) acrylate, propylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol monoethyl ether (meth) acrylate, tetrapropylene glycol monomethyl ether (meth) acrylate, tetrapropylene glycol monoethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate (propylene glycol unit number is 5 - 9), polypropylene glycol monoethyl ether (meth) acrylate (propylene glycol unit number is 5 - 9), etc. of (poly) propylene glycol (meth) acrylates; and the like.Among them, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, and triethylene glycol monoethyl ether (meth)acrylate are preferable from the viewpoints of paintability, reduction in the viscosity of the coating liquid, and weather resistance. More preferably, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, and diethylene glycol monoethyl ether (meth)acrylate are used. Particularly preferably, diethylene glycol monomethyl ether (meth)acrylate and diethylene glycol monoethyl ether (meth)acrylate are used.

[0017] Component (A) preferably contains a compound (A-2) having an alicyclic structure. By including such a compound containing an alicyclic structure and a (meth)acryloyl group, the weather resistance of the coating film can be maintained without being reduced, and the viscosity of the composition can be made particularly low.

[0018] Examples of the alicyclic structure in (A-2) include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, and bicyclic alkyl groups having 8 to 12 carbon atoms such as isobornyl group. In addition to the alicyclic structure, it may also have a linear or branched alkyl group having 1 to 8 carbon atoms.

[0019] Specific examples of (A-2) include 4-t-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalate, dicyclopentanyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 1-adamantyl (meth)acrylate, γ-butyrolactone (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, mevalonic acid lactone (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, phenyl glycidyl ether (meth)acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl (meth)acrylate, cyclohexane spiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, etc. Among them, from the viewpoints of reducing the viscosity of the coating liquid, weather resistance and boiling water resistance, cyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate are preferred, and more preferably, 4-t-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate.

[0020] (Component (A) may be a compound other than (A-1) and (A-2), or (A-1) or (A-2) may be used in combination with these other compounds. Such compounds include, for example, compounds having an alkyl group with 1 to 22 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isoamyl (meth)acrylate, stearyl (meth)acrylate; compounds having an aromatic group such as phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate; compounds having an ether bond such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate; compounds having a hydroxyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy(meth)acrylate (e.g., trade name "Placcel" manufactured by Daicel Chemical Industries, Ltd.), polycarbonate-modified hydroxy(meth)acrylate.)

[0021] (The content of component (A) is, for example, 10 to 75% by mass, preferably 15 to 65% by mass, more preferably 20 to 55% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 10 to 75% by mass, preferably 15 to 65% by mass, more preferably 20 to 55% by mass, based on 100% by mass of the total of components (A) to (C). When the content of component (A) is within the above range, the viscosity can be lowered, the paintability is improved, and the boiling water resistance and weather resistance of the coating film are improved.)

[0022] Among them, as the component (A), it is preferable to use (A-1) and (A-2) in combination. When used in combination, the content of (A-1) is, for example, 2.5 to 52.5% by mass, preferably 5 to 50% by mass, more preferably 10 to 47.5% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 2.5 to 52.5% by mass, preferably 5 to 50% by mass, more preferably 10 to 47.5% by mass, based on 100% by mass of the total of components (A) to (C). When the content of the component (A-1) is within the above range, the viscosity can be lowered, and the boiling water resistance and weather resistance of the coating film are improved.

[0023] When used in combination, the content of (A-2) is, for example, 2.5 to 52.5% by mass, preferably 5 to 50% by mass, more preferably 10 to 47.5% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 2.5 to 52.5% by mass, preferably 5 to 50% by mass, more preferably 10 to 47.5% by mass, based on 100% by mass of the total of components (A) to (C). When the content of the component (A-2) is within the above range, the viscosity can be lowered, and the boiling water resistance and weather resistance of the coating film are improved.

[0024] When used in combination, (A-1) / (A-2) is, for example, 20 / 80 to 80 / 20, preferably 40 / 60 to 60 / 40. When the ratio is within the above range, the viscosity can be lowered, and the boiling water resistance and weather resistance of the coating film are improved.

[0025] [Component (B)] As the ester triacrylate having an isocyanuric ring structure which is the component (B), for example, the compound represented by the following formula (B-1) can be mentioned. By including such an ester triacrylate, the boiling water resistance and weather resistance of the coating film are improved. The component (B) may be used alone as one kind of compound, or may be used in combination of two or more kinds. [Chemical formula] [R 4 ~R 6is an alkylene group having 2 to 17 carbon atoms which may each independently have a substituent, and R 7 ~R 9 are each independently a hydrogen atom or a methyl group.]

[0026] R in formula (B-1) 4 ~R 6 may be linear or branched, but linear is preferred. For example, alkylene groups having 3 to 12 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, octylene groups are preferred.

[0027] Examples of component (B) include bis(2-acryloyloxyethyl)hydroxyethyl isocyanurate, tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., trade names Aronix M-313, Aronix M-315, manufactured by Shin-Nakamura Chemical Co., Ltd., trade names NK Ester A9300, A9300S, manufactured by Arkema, SR368, SR368NS), bis(2-acryloyloxypropyl)hydroxyethyl isocyanurate, tris(2-acryloyloxypropyl) isocyanurate, tris(2-acryloyloxyethyl) isocyanurate modified with one molecule of caprolactone (manufactured by Toagosei Co., Ltd., trade name Aronix M-325), tris(2-acryloyloxyethyl) isocyanurate modified with three molecules of caprolactone (manufactured by Toagosei Co., Ltd., trade name Aronix M-327), and the like.

[0028] The content of component (B) is, for example, 5 to 85% by mass, preferably 10 to 70% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, based on 100% by mass of the total of components (A) to (C), it is, for example, 5 to 85% by mass, preferably 7.5 to 77.5% by mass, more preferably 10 to 70% by mass. When the content of component (B) is within the above range, the boiling water resistance and weather resistance of the coating film are particularly improved.

[0029] [Component (C)] (C) component is a urethane (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule, excluding the compound corresponding to the (B) component. In the present invention, by including the (C) component having a urethane bond together with the (B) component, the weather resistance when forming a coating film is further improved. The (C) component may be used alone as one kind of compound, or may be used in combination of two or more kinds.

[0030] (C) component preferably contains a compound (C-1) represented by the following formula (2). By containing (C-1), the weather resistance when forming a coating film is particularly improved.

Chemical formula

[0031] That is, in (C-1), the bonds of Z 1 and Z 2 mean the following allophanate bond of (i) or (ii). Among them, in (C-1), having the isocyanuric ring structure of (i) is particularly preferable from the viewpoints of weather resistance and boiling water resistance.

Chemical formula

[0032] Therefore, (C-1) is particularly preferably a compound (C-1’) represented by the following formula (2’).

Chemical formula

[0033] L 1 ~L 3 The alkylene group having 2 to 17 carbon atoms which may have substituents of L 4 ~L 6 may be linear or branched, but a linear one is preferred. For example, alkylene groups having 3 to 12 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, octylene groups are preferred. The alkylene group having 1 to 5 carbon atoms which may have substituents of L

[0034] (C-1) is particularly preferably a compound represented by the following formula from the viewpoints of weather resistance and boiling water resistance.

Chemical formula

[0035] Such (C-1) can be produced by modifying an isocyanate compound with 2-hydroxyethyl acrylate (HEA) or the like as in UA-1 and UA-2 in Synthesis Example 1-2 in the examples described later. Examples of the above isocyanate compound include a triisocyanate compound represented by the following formula (5-3).

[0036] Component (C) preferably contains a compound (C-2) represented by the following formula (3-1), (3-2), (3-3), (3-4), or (4-1). By containing (C-2), the viscosity of the coating liquid decreases, the coatability and leveling property improve, and when formed into a coating film, the weather resistance particularly improves.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0037] L in formula (3-1) 7 ~L 9 may be linear or branched, similar to L 1 ~L 3 but linear is preferred. For example, alkylene groups having 3 to 12 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, and octylene groups are preferred. Also, L 10 ~L 12 may be linear or branched, similar to L 4 ~L 6 but linear is preferred. For example, alkylene groups having 1 to 4 carbon atoms such as methylene, ethylene, and propylene groups are preferred.

[0038] R in formula (3-1) 24 ~R 26 may be linear or branched, but linear is preferred. For example, alkylene groups having 3 to 12 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, and octylene groups are preferred. Also, n1 to n3 are preferably integers from 2 to 8. When there are multiple R 24 ~R 26 they may be the same or different from each other.

[0039] As the compound represented by formula (3-1), the following compounds are particularly preferred (m in the formula is each independently an integer from 1 to 10). [Chemical formula]

[0040] R in formula (3-2) 30 ~R 32 may be linear or branched, but is preferably linear, such as an alkylene group having 3 to 8 carbon atoms such as a propylene, butylene, heptylene, hexylene, heptylene, octylene group, R A -(O-CO-(CH2)5) n - or R A -(O-(CH2)4) n - is preferred. Also, X 1 and X 2 may be linear or branched, but is preferably linear, and an alkylene group having 3 to 12 carbon atoms such as a propylene, butylene, heptylene, hexylene, heptylene, octylene group is preferred. R A is preferably an alkylene group having 2 to 4 carbon atoms. n is preferably an integer of 1 to 4, and more preferably 1 to 2.

[0041] R in formula (3-3) 37 ~R 40 may be linear or branched, but is preferably linear, such as an alkylene group having 3 to 8 carbon atoms such as a propylene, butylene, heptylene, hexylene, heptylene, octylene group, R A -(O-CO-(CH2)5) n - or R A -(O-(CH2)4) n - is preferred. Also, X 3 ~X 8 may be linear or branched, but is preferably linear, and an alkylene group having 3 to 12 carbon atoms such as a propylene, butylene, heptylene, hexylene, heptylene, octylene group is preferred. R A is preferably an alkylene group having 2 to 4 carbon atoms. n is preferably an integer of 1 to 4, and more preferably 1 to 2.

[0042] R in formula (3-4) 45 ~R 50may be linear or branched, but linear is preferred. For example, alkylene groups having 3 to 8 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, octylene groups, R A -(O-CO-(CH2)5) n - or R A -(O-(CH2)4) n - is preferred. Also, X 9 ~ X 12 may be linear or branched, but linear is preferred. For example, alkylene groups having 3 to 12 carbon atoms such as propylene, butylene, heptylene, hexylene, heptylene, octylene groups are preferred. R A is preferably an alkylene group having 2 to 4 carbon atoms. n is preferably an integer of 1 to 4, more preferably 1 to 2.

[0043] X in formula (4-1) 13 X 14 and X 15 are preferably such that at least one is a polycaprolactone group or a polycarbonate group. In addition, when there are a plurality of X 15 and A 4 they may be the same or different from each other.

[0044] Such (C-2) can be produced by modifying a polyisocyanate compound with 2-hydroxyethyl acrylate (HEA), a polycaprolactone compound, and a polycarbonate compound as in UA-3 to UA-12 in Synthesis Examples 3-12 in the examples described later. As the above polyisocyanate compound, "Basonat (registered trademark) HA 3000" manufactured by BASF, "Burnock DN-902S" manufactured by DIC, "Desmodur I", "Desmodur H", "Desmodur W", "Cosmonate NBDI", "Takenate 600" manufactured by Sumika Covestro Urethane Co., Ltd. etc. can be used.

[0045] As A3 and A4 in formula (4-1), from the viewpoints of weather resistance and boiling water resistance, the groups represented by the above formulas (*1) and (*2) are preferred. Also, X 13 X14 Regarding this, when n4 > 0, an alkylene group having 1 to 5 carbon atoms is preferable. When n4 = 0, a group obtained by removing two terminal hydroxyl groups from polycaprolactone diol or a group obtained by removing two terminal hydroxyl groups from polycarbonate diol is preferable. X 15 Regarding this, it is a group obtained by removing two hydrogen atoms from a compound selected from the group consisting of a diol compound having a linear or branched alkylene group, polycaprolactone diol, polyether diol, and polycarbonate diol. Among them, Y 1 is preferably a group obtained by removing two hydrogen atoms from a compound selected from the group consisting of polycaprolactone and polycarbonate diol.

[0046] X in formula (4-1) 15 Examples of the diol compound having a linear alkylene group in this include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and the like.

[0047] X 15 Examples of the diol compound having a branched alkylene group in this include 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, tricyclodecane dimethanol, cyclohexane dimethanol, and the like

[0048] X 15 Specific examples of the polyether diol in this include polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol (PBG), polytetramethylene glycol (PTMG), or its block copolymer, its random copolymer, etc. Those having a mass average molecular weight of 2000 or less are preferable, those having a mass average molecular weight of 1000 or less are more preferable, and among them, polytetramethylene glycol is desirable.

[0049] X15Examples of the polycaprolactone diol include "Placcel 205" which is a polycaprolactone diol with a mass average molecular weight of 530, "Placcel 205BA" which is a polycaprolactone diol with a mass average molecular weight of 530 and having a carboxyl group in the side chain, "Placcel L205AL" which is a polycaprolactone diol with a mass average molecular weight of 500 and being a liquid at room temperature, "Placcel 205H" which is a polycaprolactone diol with a mass average molecular weight of 530 and having improved water resistance compared to Placcel 205, "Placcel 205U" which is a polycaprolactone diol with a mass average molecular weight of 530 and having lower viscosity and acid value compared to Placcel 205, "Placcel 208" which is a polycaprolactone diol with a mass average molecular weight of 830, "Placcel L208AL" which is a polycaprolactone diol with a mass average molecular weight of 830 and being a liquid at room temperature, "Placcel 210" which is a polycaprolactone diol with a mass average molecular weight of 1000, "Placcel 210BA" which is a polycaprolactone diol with a mass average molecular weight of 1000 and having a carboxyl group in the side chain, "Placcel 210CP" which is a polycaprolactone diol with a mass average molecular weight of 1000 and having lower acid value and improved water resistance compared to Placcel 210, "Placcel 210N" which is a polycaprolactone diol with a mass average molecular weight of 1000 and having a narrower molecular weight distribution compared to Placcel 210, "Placcel 212" which is a polycaprolactone diol with a mass average molecular weight of 1250, "Placcel L212AL" which is a polycaprolactone diol with a mass average molecular weight of 1250 and being a liquid at room temperature, "Placcel 220" which is a polycaprolactone diol with a mass average molecular weight of 2000, "Placcel 220BA" which is a polycaprolactone diol with a mass average molecular weight of 2000 and having a carboxyl group in the side chain, "Placcel 220CPB" which is a polycaprolactone diol with a mass average molecular weight of 2000 and having lower acid value and improved water resistance compared to Placcel 220, "Placcel 220N" which is a polycaprolactone diol with a mass average molecular weight of 2000 and having a narrower molecular weight distribution compared to Placcel 220, "Placcel 220NP1" which is a polycaprolactone diol with a mass average molecular weight of 2000 and having lower crystallinity compared to Placcel 220."Placcel L220AL", which is a polycaprolactone diol with a mass average molecular weight of 2,000 for a normal temperature liquid; "Placcel 230", which is a polycaprolactone diol with a mass average molecular weight of 3,000; "Placcel L230AL", which is a polycaprolactone diol with a mass average molecular weight of 3,000 for a normal temperature liquid; "Placcel 230CP", which is a polycaprolactone diol with a mass average molecular weight of 3,000 and a lower acid value and improved water resistance compared to Placcel 230; "Placcel 240", which is a polycaprolactone diol with a mass average molecular weight of 4,000; "Placcel 240CP", which is a polycaprolactone diol with a mass average molecular weight of 4,000 and a lower acid value and improved water resistance compared to Placcel 240; "Placcel 220EB", which is a polycaprolactone diol with a mass average molecular weight of 2,000 and improved hydrolysis resistance compared to Placcel 220; "Placcel 220EC", which is a polycaprolactone diol with a mass average molecular weight of 2,000 and excellent elastic recovery compared to Placcel 220EB (all are trade names, manufactured by Daicel Chemical Industries, Ltd.), etc. Among them, from the viewpoints of the weather resistance and abrasion resistance of the obtained cured film, polycaprolactone diols within the range of a mass average molecular weight of 500 to 1,500 are preferable, and those within the range of 500 to 1,000 are more preferable.

[0050] X 15 The polycarbonate diol in [X] can be synthesized by a transesterification reaction between a polyhydric alcohol having a linear alkyl structure, a branched alkyl structure, an alicyclic structure, a polyether diol structure, or a caprolactone diol structure and a carbonic acid ester. Specific examples of the polyhydric alcohol having a linear alkyl structure include ethylene glycol, 1,3 - propylene glycol, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, 1,8 - octanediol, 1,9 - nonanediol, 1,10 - decanediol, etc. Specific examples of the polyhydric alcohol having a branched alkyl structure include 3 - methyl - 1,5 - pentanediol, neopentyl glycol, 2 - ethyl - 1,3 - hexanediol, 2 - methyl - 1,8 - octanediol, etc. Examples of the polyhydric alcohol having an alicyclic structure include 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 4,4-biscyclohexanol, 1,3-adamantanediol, 1,3-cyclopentanediol, tricyclodecanedimethanol, and the like. Specific examples of the carbonate ester include ethylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, and the like.

[0051] X 15 Commercially available products can also be used as the polycarbonate diol compound in . Specifically, for example, UH-50 (manufactured by Ube Industries, Ltd.), UH-100 (manufactured by Ube Industries, Ltd.), UH-200 (manufactured by Ube Industries, Ltd.), UH-300 (manufactured by Ube Industries, Ltd.), PH-50 (manufactured by Ube Industries, Ltd.), PH-100 (manufactured by Ube Industries, Ltd.), PH-200 (manufactured by Ube Industries, Ltd.), PH-300 (manufactured by Ube Industries, Ltd.), UC-100 (manufactured by Ube Industries, Ltd.), UM-90 (manufactured by Ube Industries, Ltd.), UHC50-100 (manufactured by Ube Industries, Ltd.), UP-50 (manufactured by Ube Industries, Ltd.), UP-100 (manufactured by Ube Industries, Ltd.), UP-200 (manufactured by Ube Industries, Ltd.), BENEBiOL NL1010DB (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL2010DB (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL3010DB (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL1005B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL2005B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL NL1030B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL HS0830B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL HS0840B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL HS0840B (manufactured by Mitsubishi Chemical Corporation), BENEBiOL HS0850H (manufactured by Mitsubishi Chemical Corporation), Kuraray Polyol C-590 (manufactured by Kuraray Co., Ltd.), Kuraray Polyol C-1090 (manufactured by Kuraray Co., Ltd.), Kuraray Polyol C-2090 (manufactured by Kuraray Co., Ltd.), UHC50-100 (manufactured by Ube Industries, Ltd.) and UHC50-200 (manufactured by Ube Industries, Ltd.) obtained by modifying polycarbonate diol with caprolactone, and the like.

[0052] The number average molecular weight of this polycarbonate polyol compound is preferably in the range of 500 to 2000. When the number average molecular weight is 500 or more, the weather resistance of the cured film of the coating composition is improved. From the viewpoint of the weather resistance of the cured film of the coating composition, the polycarbonate polyol compound is preferably synthesized from a polyhydric alcohol having a linear alkyl structure or an alicyclic structure.

[0053] Also, from the viewpoint of reducing the viscosity, a compound obtained by modifying polycarbonate diol with caprolactone is preferable.

[0054] Specific examples of the compound (4-1) include aliphatic polyisocyanates such as 1,4-butanediisocyanate, 1,5-pentanediisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, caprolactone-modified hydroxymono (meth)acrylate (manufactured by Daicel Corporation: FA-2D, etc.), polycarbonate-modified hydroxymono (meth)acrylate (manufactured by Daicel Corporation: HEMAC, etc.), polyethylene glycol or polypropylene glycol-modified hydroxymono (meth)acrylate (manufactured by NOF Corporation: AE-200, AP-400, etc.), and compounds obtained by reacting the above-mentioned diol compounds having a linear alkylene group, diol compounds having a branched alkylene group, polyether diol, polycaprolactone diol, and polycarbonate diol.

[0055] The content of the component (C) is, for example, 5 to 80% by mass, preferably 7.5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 5 to 80% by mass, preferably 7.5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the total of the components (A) to (C). When the content of the component (C) is within the above range, the viscosity can be lowered, the paintability can be improved, and the weather resistance of the coating film can be improved.

[0056] Among them, as the component (C), it is preferable to use (C-1) and (C-2) in combination. When used in combination, the content of (C-1) is, for example, 3 to 60% by mass, preferably 4 to 50% by mass, more preferably 5 to 40% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 3 to 60% by mass, preferably 4 to 50% by mass, more preferably 5 to 40% by mass, based on 100% by mass of the total of components (A) to (C). Further, the ratio of (C-1) to the total of (C-1) and (C-2) is 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 70% by mass. When the content of the component (C-1) is within the above range, the viscosity can be lowered and the weather resistance of the coating film is improved.

[0057] When used in combination, the content of (C-2) is, for example, 3 to 60% by mass, preferably 4 to 50% by mass, more preferably 5 to 40% by mass, based on 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, it is, for example, 3 to 60% by mass, preferably 4 to 50% by mass, more preferably 5 to 40% by mass, based on 100% by mass of the total of components (A) to (C). When the content of the component (C-2) is within the above range, the viscosity can be lowered and the weather resistance of the coating film is improved.

[0058] When used in combination, (C-1) / (C-2) is, for example, 10 / 90 to 90 / 10, preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 70 / 30. When the ratio is within the above range, the viscosity can be lowered and the weather resistance of the coating film is improved.

[0059] [Component (D)] The component (D) is a polyfunctional (meth)acrylate compound containing 5 or more (meth)acryloyl groups in one molecule. When the composition contains the component (D), the boiling water resistance of the coating film is particularly improved. The component (D) may be used alone as one kind of compound, or two or more kinds may be used in combination.

[0060] As the component (D), for example, polyfunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, polypentaerythritol poly(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate; urethane (meth)acrylate obtained by reacting an isocyanate compound with a (meth)acrylate compound can be mentioned.

[0061] As the component (D), a compound represented by the following formula (5-0) is preferable.

[0062]

Chemical formula

[0063] In formula (5-0), at least 5 of R 60 ~R 65 represent CH2=CR B -COO-, or a (meth)acryloyloxy group modified with caprolactone CH2=CR B -CO(O(CH2)5C=O) y -O-, and the rest represent a hydroxyl group, or CH2=CR B -COO-, CH2=CR 8 -CO(O(CH2)5C=O) y -O-. R B represents a hydrogen atom or a methyl group. When R B is a hydrogen atom, it becomes an acryloyl group, and when R B is a methyl group, it becomes a methacryloyl group, and y is an integer of 1 or more. That is, the compound (5-0) has a pentaerythritol skeleton and is a polymerizable compound having 5 or more (meth)acryloyloxy groups in the structure. n30 represents an integer from 0 to 4, preferably an integer from 1 to 3, more preferably 1 or 2. It is particularly preferred from the viewpoints of boiling water resistance and curability that when n30 = 1, the compound (5-0) has a dipentaerythritol skeleton.

[0064] Component (D) may be a urethane (meth)acrylate. Such a urethane (meth)acrylate can be obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound.

[0065] As the (meth)acrylate compound having a hydroxyl group used in the production of urethane (meth)acrylate, a compound represented by the following formula (5-1) or (5-2) is particularly preferred. In the following formula, R 66 ~R 73 each independently represents a hydrogen atom or a methyl group.

[0066]

Chemical formula

[0067] Moreover, as the isocyanate compound used in the production of urethane (meth)acrylate, an aliphatic polyisocyanate or an alicyclic polyisocyanate having two or more isocyanate groups is preferred. Specifically, aliphatic polyisocyanates such as 1,4-butanediisocyanate, 1,5-pentanediisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, etc., or dimers or trimers thereof; alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc., or dimers or trimers thereof, etc. can be mentioned.

[0068] As the above isocyanate compound, a triisocyanate compound represented by the following formula (5-3) or a diisocyanate compound represented by the following formula (5-4) is also preferable.

[0069]

Chemical formula

[0070] In the formula, X 16 ~X 20 each independently represents an alkylene group having 2 to 17 carbon atoms, and an alkylene group having 2 to 6 carbon atoms is preferable. A plurality of Xs 16 ~X 20 in the formula may be the same as or different from each other. R 74 represents -R C -O-CO-CH=CH2, or a structure obtained by removing a hydroxyl group from the compound represented by the formula (5-1) or (5-2), and R C represents an alkylene group, and the number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 10.

[0071] When the component (D) is urethane (meth) acrylate, when a monomer or dimer of diisocyanate is used, a structure obtained by reacting with the formula (5-1) as an essential component is preferable from the viewpoint of boiling water resistance. When a trimer of diisocyanate is used, a product obtained by reacting the formula (5-3) with the formula (5-1) and the formula (5-2) as essential components is preferable from the viewpoint of boiling water resistance.

[0072] When the composition contains the component (D), the content of the entire component (D) is preferably 0.3 to 10% by mass, more preferably 0.5 to 5.0% by mass, and still more preferably 1.0 to 3.0% by mass with respect to 100% by mass of the total amount of the compounds having reactive groups contained in the composition. Similarly, with respect to 100% by mass of the total of the components (A) to (D), 0.3 to 10% by mass is preferable, 0.5 to 5.0% by mass is more preferable, and 1.0 to 3.0% by mass is still more preferable.

[0073] [Component (E)] The composition may contain a component (E) which is a compound having a reactive group other than the above components (A) to (D). By containing the component (E), the water resistance to boiling of the coating film is particularly improved while maintaining a low viscosity as a coating liquid. Examples of the component (E) include bifunctional or trifunctional (meth)acrylate compounds having no isocyanuric ring structure or urethane bond. Examples of such component (E) include (meth)acrylates having a linear hydrocarbon group such as 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate; (meth)acrylates having a branched-chain hydrocarbon group such as neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate.

[0074] As component (E) other than those described above, di(meth)acrylates of dihydric alcohols such as tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate;Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, di(meth)acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, di(meth)acrylate or tri(meth)acrylate obtained by reacting 2 to 3 moles of acrylic acid with 1 mole of tris(2-hydroxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate modified with ethylene oxide, polypropylene glycol di(meth)acrylate modified with propylene oxide, polytetramethylene glycol di(meth)acrylate modified with tetramethylene oxide, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, hydroxypivalic acid-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, tri(meth)acrylate phosphate modified with ethylene oxide, polyester (meth)acrylate compound synthesized by condensation reaction of polyhydric alcohol with (meth)acrylic acid and polyfunctional carboxylic acid, epoxy (meth)acrylate compound synthesized by addition reaction of novolac type epoxy resin with glycidyl group-containing acrylic polymer and (meth)acrylic acid, acrylate acrylate compound, etc. are mentioned.;

[0075] (E) As a component, from the viewpoint of maintaining a low viscosity as a coating liquid and having good boiling water resistance when formed into a coating film, an alkylene diacrylate having a linear alkyl structure and a branched alkyl structure is preferable. More preferably, they are linear hydrocarbon groups such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, etc. Particularly preferably, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediacrylate are preferable. From the viewpoint of skin irritation, 1,9-nonanediol di(meth)acrylate, 1,10-decanediacrylate are preferable.

[0076] When the composition contains the (E) component, the content of the entire (E) component is preferably 3.0 to 50% by mass, more preferably 5.0 to 45% by mass, and even more preferably 10.0 to 40% by mass with respect to 100% by mass of the total amount of the compounds having reactive groups contained in the composition (100% by mass of the total of components (A) to (E)). When the content is within this range, the boiling water resistance when formed into a coating film is particularly improved.

[0077] [Other Components] The composition may optionally contain other components other than the above components (A) to (E) within the range where the effects of the present invention can be obtained. Examples of other components include organic solvents, various resins, fillers, polymerization initiators, stabilizers, ultraviolet absorbers, leveling agents. Further, it may also contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow modifiers, coupling agents, dyes, rheology control agents, antioxidants, plasticizers.

[0078] The composition may or may not contain an organic solvent. In the present invention, it is preferably a solvent-free composition or contains a relatively small amount of an organic solvent. By making it solvent-free or low in solvent in this way, it is possible to reduce the environmental load by reducing the amount of volatile organic compounds (VOCs). When it contains an organic solvent, the content is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less in the total amount of the composition.

[0079] Examples of the organic solvent include ester solvents, ketone solvents, ether solvents, aliphatic solvents, aromatic solvents, and alcohol solvents. Specifically, examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, examples of the ketone solvent include acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, etc., examples of the ether solvent include tetrahydrofuran, dioxolane, etc., examples of the aliphatic solvent include hexane, cyclohexane, etc., examples of the aromatic solvent include toluene, xylene, etc., and examples of the alcohol solvent include ethanol, methanol, propanol, butanol, propylene glycol monomethyl ether, etc.

[0080] As various resins, thermosetting resins or thermoplastic resins can be used. A thermosetting resin is a resin that has the property of being able to change into a substantially insoluble and infusible state when cured by heating or by means such as radiation or a catalyst. Specific examples thereof include phenolic resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, epoxy resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, thermosetting polyimide resins, benzoxazine resins, reactive ester resins, aniline resins, cyanate ester resins, styrene-maleic anhydride (SMA) resins, and the like.

[0081] A thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resins, polypropylene resins, polystyrene resins, rubber-modified polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene (AS) resins, polymethyl methacrylate resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyethylene terephthalate resins, ethylene vinyl alcohol resins, cellulose acetate resins, ionomer resins, polyacrylonitrile resins, polyamide resins, polyacetal resins, polybutylene terephthalate resins, polylactic acid resins, polyphenylene ether resins, modified polyphenylene ether resins, polycarbonate resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluorine resins, syndiotactic polystyrene resins, cyclic polyolefin resins, and the like.

[0082] Also, a liquid organic polymer may be used for viscosity adjustment. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. For example, carboxyl group-containing polymer modifiers (Flowlen G-900, NC-500: Kyoeisha), acrylic polymers (Flowlen WK-20: Kyoeisha), amine salts of special modified phosphoric esters (HIPLAAD ED-251: Kusumoto Chemicals), modified acrylic block copolymers (DISPERBYK 2000; BYK Chemie) can be mentioned.

[0083] As the filler, for example, silica can be blended for the purpose of improving wear resistance. As the silica, there is no limitation, and known silica fine particles such as powdered silica, colloidal silica, and nanosilica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd. Also, examples of commercially available colloidal silica include methanol silica sol, IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL manufactured by Nissan Chemical Industries, Ltd.

[0084] Reactive silica may be used as the silica. Examples of the reactive silica include reactive compound-modified silica. Examples of the reactive compound include reactive silane coupling agents having a hydrophobic group, compounds having a (meth)acryloyl group, compounds having a maleimide group, and compounds having a glycidyl group. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, MEK-AC-2140Z, etc. manufactured by Nissan Chemical Industries, Ltd. Also, silica modified by adding acrylic acid after modification with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, and silica modified with a product obtained by urethanizing 3-isocyanatopropyltriethoxysilane, a hydroxyl group, and a compound having a (meth)acryloyl group are also mentioned as reactive silica.

[0085] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped ones can be used. For example, as commercially available hollow silica fine particles, Silanax manufactured by Nippon Steel Mining Co., Ltd. etc. can be used. Also, the primary particle diameter is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the dispersion of the inorganic fine particles in the composition becomes sufficient, and when it is 200 nm or less, sufficient strength of the cured product can be maintained. The blending amount of silica is preferably 3 to 60% by mass in 100% by mass of the composition.

[0086] Examples of fillers other than silica include inorganic fillers and organic fillers. The filler shape is not limited, and particulate, plate-shaped, and fibrous fillers are mentioned. Examples of fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.; examples of those with excellent heat conduction include boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; examples of those with excellent conductivity include metallic fillers and / or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); examples of those with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc., and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; examples of those with a high refractive index include barium titanate, zirconium oxide, titanium oxide, etc.; examples of those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, tellurium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, their oxides, etc.; examples of those with excellent wear resistance include metals such as alumina, zirconia, magnesium oxide, etc., and their composites and oxides, etc.; examples of those with excellent conductivity include metals such as silver, copper, etc., tin oxide, indium oxide, etc.; examples of those with excellent ultraviolet shielding properties include titanium oxide, zinc oxide, etc.

[0087] Examples of inorganic fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, etc., and also carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers, etc. Examples of the above metal fibers include, for example, aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0088] Examples of the organic fiber include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as protein, polypeptide, and alginic acid.

[0089] The compounding amount of the filler is preferably 3 to 60% by mass in 100% by mass of the composition.

[0090] Since the composition is cured by active energy rays, it is preferable to use a polymerization initiator, particularly a photoinitiator. Known photoinitiators may be used. For example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used.

[0091] Specific examples of the photoinitiator include acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, diethoxyacetophenone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, and 4-benzoyl-4'-methyl-diphenyl sulfide; α-ketoester compounds such as methyl benzoylformate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of oxyphenylacetic acid, and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; oxime ester photoinitiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone and the like.

[0092] The photoinitiator may be used alone or in combination of two or more. The amount of the photoinitiator used is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, based on 100% by mass of the composition.

[0093] For the purpose of improving the weather resistance of the composition, an ultraviolet absorber may be compounded. Various compounds or substances can be used as the ultraviolet absorber. Specific examples of the ultraviolet absorber include benzotriazine-based ultraviolet absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl-hexyloxy)propyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyryloxyphenyl)-6-(2,4-bis-butyryloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate; and inorganic fine particles that absorb ultraviolet rays such as titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles.

[0094] Commercially available products can also be used as the ultraviolet absorber. Examples of commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 234, TINUVIN 326, TINUVIN 329, TINUVIN 900, TINUVIN 928, TINUVIN 360, TINUVIN 384-2, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 (manufactured by BASF); ADEKA STAB LA-46, ADEKA STAB LA-F70, ADEKA STAB LA-29, ADEKA STAB LA-31G, ADEKA STAB LA-32, ADEKA STAB LA-36 (manufactured by ADEKA); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) are available for use.

[0095] From the viewpoint of improving weather resistance, it is preferable to contain a benzotriazine-type ultraviolet absorber or an ultraviolet absorber having a (meth)acryloyl group. Preferably, TINUVIN 400, TINUVIN 405, TINUVIN 477, TINUVIN 479 (manufactured by BASF); ADEKA STAB LA-46 (manufactured by ADEKA), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) are preferred.

[0096] The amount of the ultraviolet absorber used is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the composition.

[0097] For the purpose of improving weather resistance, the composition may be blended with a hindered amine light stabilizer (HALS). As the hindered amine light stabilizer, known hindered amine light stabilizers can be used. Specifically, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxybenzylidene) malonate, tetrakis(2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, the condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, the condensate of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, etc. can be mentioned.

[0098] Hindered amine light stabilizers can also be commercially available products. Commercially available products include TINUVIN 123, TINUVIN 292, TINUVIN 152, TINUVIN 144, TINUVIN 622SF, TINUVIN 111FDL, TINUVIN 249, Adeka Stab LA-52 (manufactured by BASF above); Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-81, Adeka Stab LA-82, Adeka Stab LA-87 (manufactured by ADEKA above) are available.

[0099] From the viewpoint of improving weather resistance, TINUVIN 123, TINUVIN 152, TINUVIN 144 (manufactured by BASF above); Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-81 (manufactured by ADEKA), Adeka Stab LA-82 (manufactured by ADEKA), Adeka Stab LA-87 (manufactured by ADEKA) are preferred. More preferably, TINUVIN 123, TINUVIN 152 (manufactured by BASF above); Adeka Stab LA-63P, Adeka Stab LA-82 (manufactured by ADEKA), Adeka Stab LA-87 (manufactured by ADEKA). Even more preferably, TINUVIN 123, TINUVIN 152 (manufactured by BASF above).

[0100] The usage amount of the hindered amine light stabilizer is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 2.0% by mass based on 100% by mass of the composition.

[0101] For the purpose of enhancing the leveling property during coating or enhancing the slip property of the cured film to improve scratch resistance, various surface modifiers may be added to the composition. As the surface modifier, various additives that modify the surface physical properties and are commercially available under names such as surface conditioner, leveling agent, slip property imparting agent, antifouling property imparting agent, etc. can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specifically, silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain, and the like can be mentioned. One or more of these may be used. For the purpose of enhancing the persistence of slipperiness, those containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL 350 (manufactured by Daicel Ornex Co., Ltd.), BYK-333, BYK-377, BYK-378, BYK-UV3500, BYK-UV3505, BYK-UV3576 (manufactured by BYK-Chemie Japan Co., Ltd. above), Megafac RS-75, Megafac RS-76-E, Megafac RS-72-K, Megafac RS-76-NS, Megafac RS-90, Megafac RS-91, Megafac RS-55 (manufactured by DIC Corporation above), Optool DAC-HP (manufactured by Daikin Industries, Ltd.), ZX-058-A, ZX-201, ZX-202, ZX-212, ZX-214-A (manufactured by T&K TOKA Co., Ltd.), X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd. above), and the like.

[0102] The active energy ray-curable composition of the present invention can be suitably used as a cured film for protecting a substrate by irradiating active energy rays after being applied to at least one surface of various materials. This cured film is excellent in adhesion to the substrate and appearance, has weather resistance and abrasion resistance, has high boiling water resistance, and has excellent adhesion to various materials even in harsh environments such as high temperature and high humidity. Therefore, when used as a protective film for materials used for a long time in harsh environments such as outdoors and around automobiles, it exhibits excellent effects.

[0103] <Laminate> The laminate of the present invention has a cured layer of the above-described composition. The laminate may have one or more other layers in addition to the cured layer, and examples of the other layer include a base material layer. The base material and the manufacturing method of the laminate will be described later.

[0104] <Manufacturing Method of Laminate> The manufacturing method of the laminate of the present invention includes Step 1 of applying the above-described composition onto a base material to obtain a coating film, and Step 2 of irradiating the coating film with active energy rays to cure part or all of the coating film.

[0105] (Step 1) In Step 1, the above-described composition is applied onto a base material to obtain a coating film. The base material is not particularly limited and may be appropriately selected according to the application. Specifically, examples include plastic, wood, metal (steel, stainless steel, aluminum, etc.), metal oxide, paper, silicon, or modified silicon, etc. A base material obtained by joining different materials, or a base material on which the active energy ray curable composition of the present invention or other compositions are laminated as a primer may also be used. Among them, it has excellent adhesion to plastic base materials (resin base materials) and resin primers. As described above, resin materials have drawbacks such as low wear resistance, so they are likely to lose gloss and transparency, and are inferior in weather resistance. However, by coating plastic base materials and resin primers with the composition, these drawbacks can be improved. Therefore, plastic base materials and resin primers are preferred as the base materials of the laminate.

[0106] The plastic base material is not particularly limited as long as it is made of resin and can be selected according to the purpose. Specifically, the above-described thermosetting resin and thermoplastic resin can be used. In the case of obtaining a transparent laminate, polycarbonate resin (for example, aliphatic polycarbonate, aromatic polycarbonate, alicyclic polycarbonate, etc.), polymethyl methacrylate resin, polystyrene resin, etc. are preferably used. The plastic substrate may be made of a single resin or a mixture of multiple resins, and may be a single layer or may already have a laminated structure of two or more layers. In addition, the plastic substrate may contain known additives such as known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, and lubricants, and may be fiber-reinforced plastic (FRP).

[0107] As the resin primer, known water-soluble or water-dispersed paints, organic solvent-based or organic solvent-dispersed paints, powder paints, etc. can be used. Specifically, various types of paints such as acrylic resin-based paints, polyester resin-based paints, alkyd resin-based paints, epoxy resin-based paints, fatty acid-modified epoxy resin-based paints, silicon resin-based paints, polyurethane resin-based paints, fluoroolefin-based paints, or amine-modified epoxy resin paints can be used. The undercoat paint may be a clear paint that does not contain a pigment, an enamel-based paint that contains the pigment, or a metallic paint that contains aluminum flakes, or it may be a paint used for electrodeposition paints, midcoat paints, topcoat paints, or precoat metals used on automobile bodies.

[0108] The shape of the substrate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature (bend) entirely or partially. Furthermore, the hardness, thickness, etc. of the substrate are not particularly limited and can be determined arbitrarily.

[0109] The method for applying the composition is not particularly limited, and an inkjet method, a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, etc. can be used. By applying the composition onto a substrate by these methods, a coating film can be obtained. Further, when the composition is recoated after curing, from the viewpoint of the coating technique, an inkjet method and a spray method are preferable.

[0110] (Step 2) In Step 2, the coating film obtained in Step 1 is irradiated with active energy rays to cure part or all of the coating film. Since the composition contains a compound having a polymerizable unsaturated group, it can be cured by irradiation with active energy rays to form a cured film (cured layer). Note that all of the coating film may be cured by a single irradiation to form a cured film, or after curing only a part of the coating film by irradiation, the degree of curing may be gradually increased by multiple irradiations to finally form a cured film. Further, between multiple irradiations, an active energy ray-curable composition may be further applied from above.

[0111] Examples of the active energy rays include ionizing radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Among them, ultraviolet rays (UV) are preferable from the viewpoints of curability and convenience. Here, when ultraviolet rays are used as the active energy rays, examples of the apparatus for irradiating the ultraviolet rays include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium-cadmium laser, an argon laser, sunlight, an LED lamp, etc. By using these to irradiate the coated or molded composition with ultraviolet rays having a wavelength of about 180 to 400 nm, it is possible to obtain a cured film or a cured product. The irradiation amount of the ultraviolet rays is appropriately selected according to the type and amount of the photoinitiator used.

[0112] After the completion of Step 2, Steps 1 and 2 may be repeated at least once in this order. By repeating Step 1 (coating) and Step 2 (curing), the cured film can be made thicker. This method is useful when the thickness of the cured film is not sufficient with a single coating and curing, considering the balance between the coating method and the required film thickness. Since the composition has appropriate substrate erosion resistance, even when a cured film is formed on the film made of the composition after curing, the adhesion is not poor. Further, for the purpose of enhancing the adhesion, in the intermediate Step 2, the coating film may not be completely cured and may be left in a partially cured state (semi-cured). Since a part is uncured, the adhesion to the lower layer is improved. When only a part of the coating film is cured, it is possible to adjust the degree of curing by the irradiation amount of the active energy ray.

[0113] The laminate of the present invention may further have a second substrate on the substrate and the cured layer. There is no particular limitation on the material of the second substrate, and examples include wood, metal, metal oxide, plastic, paper, silicon, or modified silicon, etc., and a substrate obtained by joining different materials may also be used. The shape of the substrate is not particularly limited, and it may be any shape according to the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having a curvature on the entire surface or a part thereof. Also, there is no limitation on the hardness, thickness, etc. of the substrate.

[0114] Since the cured layer of the laminate of the present invention has high adhesion to both plastics and inorganic substances, it can be preferably used as an interlayer material for different materials. Particularly preferably, the substrate is plastic and the second substrate is an inorganic layer. Examples of the inorganic layer include quartz, sapphire, glass, optical film, ceramic material, inorganic oxide, vapor deposition film (CVD, PVD, sputtering), magnetic film, reflective film, metals such as Ni, Cu, Cr, Fe, stainless steel, paper, SOG (Spin On Glass), SOC (Spin On Carbon), plastic layers such as polyester, polycarbonate, polyimide, TFT array substrate, electrode plate of PDP, conductive substrates such as ITO and metal, insulating substrates, silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc.

[0115] In addition, since the cured layer of the present invention is excellent in workability even after the active energy ray-curable composition is cured to form a cured layer, it can be bent together with the substrate. For example, after directly applying the composition to a flat substrate to obtain a coated substrate, and then irradiating the coating film with active energy rays to form a substrate with a cured film (i.e., a laminate), bending can still be performed. Therefore, there is no need to take special consideration when applying the composition to a curved substrate, and the productivity of the bent processed material can be significantly improved. Further, the molded article of the present invention is not only extremely excellent in flexibility under heating, but also excellent in hard coat properties after thermoforming.

[0116] When performing bending, the thickness of the coating film formed by applying the composition of the present invention is preferably 0.5 to 40 μm, more preferably 3 to 35 μm, still more preferably 5 to 30 μm, and particularly preferably 10 to 25 μm. By setting the thickness to be not less than the above lower limit value, abrasion resistance and weather resistance can be sufficiently exhibited, and by setting the thickness to be not more than the above upper limit value, flexibility can be improved.

[0117] The method of bending is not particularly limited, and in addition to the bending process of directly bending the laminate, processing methods such as press molding, free blow molding, vacuum molding, pressure air molding, and twin composite molding can be mentioned. For thermoforming, 80°C or higher is preferable, and 150°C or higher is more preferable. Also, the upper limit temperature can be appropriately set to be less than the melting temperature of the substrate.

[0118] Since the laminate of the present application is excellent in weather resistance, boiling water resistance, and appearance, it can be particularly preferably used as various protective materials. For example, it can be used for building materials, housing equipment, transportation equipment such as automobiles, ships, airplanes, and railways, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fiber coating, resin glass protection, etc., and is particularly suitable for use in automotive headlamp lens applications, automotive glazing applications, automotive body exterior applications, plastic applications for building materials, and steel plate applications for building materials.

Examples

[0119] Hereinafter, the present invention will be described more specifically using examples and comparative examples, but the present invention is not limited to the following aspects. In addition, in this example, "parts" and "%" are based on mass unless otherwise specified.

[0120] (Synthesis Example 1: Synthesis of UA-1) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat (registered trademark) HA 3000" manufactured by BASF (NCO equivalent 19.5%, 213.39 parts), 2,6-di-tert-butyl-4-methylphenol (0.91 part), methoxyhydroquinone (0.09 part), and dibutyltin diacetate (0.09 part) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (116.1 parts) was added in portions over 1 hour. After the addition, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a urethane (meth) acrylate compound UA-1 having an allophanate bond was obtained.

[0121] (Synthesis Example 2: Synthesis of UA-2) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Burnock DN-902S" manufactured by DIC (NCO equivalent 23.5%, 178.72 parts), 2,6-di-tert-butyl-4-methylphenol (0.84 part), methoxyhydroquinone (0.084 part), and dibutyltin diacetate (0.084 part) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (116.1 parts) was added in portions over 1 hour. After the addition, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a urethane (meth) acrylate compound UA-2 having an isocyanurate bond was obtained.

[0122] (Synthesis Example 3: Synthesis of UA-3) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF's "Basonat® HA 3000" (NCO equivalent 19.5%, 213.39 parts), 2,6-di-tert-butyl-4-methylphenol (1.12 parts), methoxyhydroquinone (0.11 part), and dibutyltin diacetate (0.11 part) were added, and the temperature was raised to 70 °C. Placcel FA-2D (344.0 parts) was added in portions over 1 hour. After the addition, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared to obtain a urethane (meth)acrylate compound UA-3 having an allophanate bond.

[0123] (Synthesis Example 4: Synthesis of UA-4) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF's "Basonat® HA 3000" (NCO equivalent 19.5% by mass, 213.39 parts), 2,6-di-tert-butyl-4-methylphenol (0.91 part), methoxyhydroquinone (0.09 part), and dibutyltin diacetate (0.09 part) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (77.4 parts) and Daicel's "Placcel-210" (hydroxyl value: 113.4 164.90 parts) were added in portions over 1 hour. After the addition, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared to obtain a urethane (meth)acrylate compound UA-4 having an allophanate bond.

[0124] (Synthesis Example 5: Synthesis of UA-5) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent 23.5%, 178.72 parts), 2,6-di-tert-butyl-4-methylphenol (1.05 parts), methoxyhydroquinone (0.11 parts), and dibutyltin diacetate (0.11 parts) were added, and the temperature was raised to 70 °C. Placcel FA-2D (344.0 parts) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a urethane (meth)acrylate compound UA-5 having an isocyanurate bond was obtained.

[0125] (Synthesis Example 6: Synthesis of UA-6) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent 23.5%, 178.72 parts), 2,6-di-tert-butyl-4-methylphenol (0.84 parts), methoxyhydroquinone (0.084 parts), and dibutyltin diacetate (0.084 parts) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (77.4 parts) and "Placcel-210" manufactured by Daicel Corporation (hydroxyl value: 113.4 164.90 parts) were charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a urethane (meth)acrylate compound UA-6 having an isocyanurate bond was obtained.

[0126] (Synthesis Example 7: Synthesis of UA-7) Into a 1L separable flask equipped with a stirring device and an air blowing tube, "Desmodul I" (NCO equivalent 37.8%, 111.15 parts), 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged, and while stirring the liquid temperature at 60 to 70 °C, 344 g of Placcel FA-2D [manufactured by Daicel Corporation, caprolactone-modified monoacrylate] was added dropwise. After the dropping was completed, the mixture was stirred at 80 °C for 4 hours. By IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain the urethane (meth) acrylate compound UA-7.

[0127] (Synthesis Example 8: Synthesis of UA-8) Into a 1 L separable flask equipped with a stirrer and an air blowing tube, 132.08 g (1.0 mol of NCO) of 4,4'-methylenebiscyclohexyl isocyanate [“Desmodur W” manufactured by Covestro, NCO content 31.8%], 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged. While stirring the liquid temperature at 60 - 70 °C, 344 g of Placcel FA-2D [caprolactone-modified monoacrylate manufactured by Daicel Corporation] was added dropwise. After the dropping was completed, the mixture was stirred at 80 °C for 4 hours. By IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain the urethane (meth) acrylate compound UA-8.

[0128] (Synthesis Example 9: Synthesis of UA-9) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, “Desmodur I” (NCO equivalent 37.8%, 111.15 parts) manufactured by Sumika Covestro Urethane Co., Ltd., 2,6-di-tert-butyl-4-methylphenol (0.84 parts), methoxyhydroquinone (0.084 parts), and dibutyltin diacetate (0.084 parts) were added. The temperature was raised to 70 °C, and 2-hydroxyethyl acrylate (116.1 parts) and “Placcel-210” (hydroxyl value: 113.4, 247.35 parts) manufactured by Daicel Corporation were charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared to obtain the urethane (meth) acrylate compound UA-9 having an isocyanurate bond.

[0129] (Synthesis Example 10: Synthesis of UA-10) In a 1 L separable flask equipped with a stirring device and an air blowing tube, 112 g (1.0 mol of NCO) of isophorone diisocyanate [“Desmodur I” manufactured by Covestro, NCO content 37.5%], 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged. While stirring at a liquid temperature of 60 to 70 °C, 58.2 g of 2-hydroxyethyl acrylate and 244.78 g of PH-100 [a polycarbonate diol synthesized from 1,6-hexanediol and 1,5-pentanediol: polycarbonate diol manufactured by Ube Industries, hydroxyl value: 114.5 mg KOH / g] were added dropwise. After completion of the dropwise addition, the mixture was stirred at 80 °C for 4 hours. By IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain the urethane acrylate compound UA-10 corresponding to compound (4).

[0130] (Synthesis Example 11: Synthesis of UA-11) In a 1 L separable flask equipped with a stirring device and an air blowing tube, 112 g (1.0 mol of NCO) of isophorone diisocyanate [“Desmodur I” manufactured by Covestro, NCO content 37.5%], 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged. While stirring at a liquid temperature of 60 to 70 °C, 58.2 g of 2-hydroxyethyl acrylate and 218.6 g of UM-90 [a polycarbonate diol synthesized from 1,6-hexanediol and 1,4-cyclohexanedimethanol: polycarbonate diol manufactured by Ube Industries, hydroxyl value: 128.3 mg KOH / g] were added dropwise. After completion of the dropwise addition, the mixture was stirred at 80 °C for 4 hours. By IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain the urethane acrylate compound UA-11 corresponding to compound (4).

[0131] (Synthesis Example 12: Synthesis of UA-12) Into a 1 L separable flask equipped with a stirring device and an air blowing tube, 112 g (1.0 mol of NCO) of isophorone diisocyanate [“Desmodur I” manufactured by Covestro, NCO content 37.5%], 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged. While stirring at a liquid temperature of 60 to 70 °C, 58.2 g of 2-hydroxyethyl acrylate and 247.79 g of Kuraray Polyol 1090S [a polycarbonate diol synthesized from a branched alkyldiol: Kuraray polycarbonate diol, hydroxyl value: 113.2 mg KOH / g] were added dropwise. After completion of the dropwise addition, the mixture was stirred at 80 °C for 4 hours. By IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain the urethane acrylate compound UA-12.

[0132] (Synthesis Example 13: Synthesis of UA-13) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, “Desmodur I” (NCO equivalent 37.8%, 111.15 parts) manufactured by Sumika Covestro Urethane Co., Ltd., 2,6-di-tert-butyl-4-methylphenol (0.84 parts), methoxyhydroquinone (0.084 parts), and dibutyltin diacetate (0.084 parts) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (116.1 parts) was added in portions over 1 hour. After the addition, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, to obtain a urethane (meth)acrylate compound UA-13 having an isocyanurate bond.

[0133] (Synthesis Example 14: Synthesis of UA-14) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF's "BASONAT® HB100" (NCO equivalent 23.5%, 178.72 parts), 2,6-di-tert-butyl-4-methylphenol (0.84 part), methoxyhydroquinone (0.084 part), and dibutyltin diacetate (0.084 part) were added. The temperature was raised to 70 °C, and 2-hydroxyethyl acrylate (116.1 parts) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a urethane (meth)acrylate compound UA-14 having an isocyanurate bond was obtained.

[0134] (Synthesis Example 15: Synthesis of UA-15) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, Sumika Covestro's "Desmodur H" (84.10 parts), 2,6-di-tert-butyl-4-methylphenol (1.39 part), methoxyhydroquinone (0.14 part), and dibutyltin diacetate (0.14 part) were added. The temperature was raised to 70 °C, and Toagosei's "Aronix M-403 (hydroxyl value 92)" (609.78 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1 indicating the isocyanate group disappeared, and a tetrafunctional or higher (meth)acrylate compound UA-15 was obtained.

[0135] (Synthesis Example 16: Synthesis of UA-16) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, DIC's "Burnock DN-902S" (178.72 parts), 2,6-di-tert-butyl-4-methylphenol (1.01 part), methoxyhydroquinone (0.10 part), and dibutyltin diacetate (0.10 part) were added. The temperature was raised to 70 °C, and Toagosei's "Aronix M-306 (hydroxyl value 157.2)" (356.87 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm -1The reaction was carried out at 80 °C until the infrared absorption spectrum disappeared to obtain a tetrafunctional or higher (meth)acrylate compound UA-16.

[0136] (Synthesis Example 17: Synthesis of UA-17) Into a 1 L separable flask equipped with a stirrer and an air blowing tube, 112 g (1.0 mol of NCO) of isophorone diisocyanate [“Desmodur I” manufactured by Covestro, NCO content 37.5%], 1.8 g of 2,6-di-tert-butyl-4-methylphenol, and 0.2 g of dibutyltin dilaurate were charged. While stirring the liquid temperature at 60 to 70 °C, 58.2 g of 2-hydroxyethyl acrylate and 255 g of UHC50-100 [a polyol obtained by modifying a polycarbonate diol synthesized from 1,6-hexanediol with polycaprolactone: polycarbonate diol manufactured by Ube Industries, Ltd., hydroxyl value: 110 mg / KOH / g] were added dropwise. After completion of the dropwise addition, the mixture was stirred at 80 °C for 4 hours, and by IR analysis, it was confirmed that the isocyanate groups had disappeared from the reaction solution, and the reaction was terminated to obtain a urethane acrylate compound UA-17 corresponding to compound (4).

[0137] (Example 1) 10 parts of isodecyl acrylate (IDA) as component (A), 85 parts of tris(2-hydroxyethyl) isocyanurate triacrylate (product name “SR368NS”, manufactured by Arkema) as component (B), 5 parts of UA-1 obtained in Synthesis Example 1 above as component (C-1), 2.0 parts of Omnirad 754 (manufactured by IGM) and 2.0 parts of Omnirad 819 (manufactured by IGM) as photoinitiators, 0.25 part of Tinuvin 123 (manufactured by BASF) as HALS, and 1.5 parts of Tinuvin 405 (manufactured by BASF) and 1.5 parts of Tinuvin 479 (manufactured by BASF) as ultraviolet absorbers were uniformly mixed to prepare the composition of Example 1. The viscosity measured with an E-type viscometer was 490 mPa·sec.

[0138] (Examples 2 to 86, Comparative Examples 1 to 8) Compositions of each example were obtained in the same manner as in Example 1, except that the compositions and solid content ratios shown in Tables 1 to 12 were changed. In the tables, the photoinitiator is omitted, but it was used in the same manner as in Example 1 for all examples. The viscosities measured with an E-type viscometer are shown in Tables 1 to 12.

[0139] [Preparation of Evaluation Samples] The composition of each example was coated on an acrylic-polyester resin-coated steel sheet substrate prepared by the following method using a bar coater, and irradiated with ultraviolet rays under the atmosphere using an ultraviolet irradiation device (manufactured by GS-YUASA Corporation, high-pressure mercury lamp) at an illuminance of 200 mW / cm 2 , and an irradiation light amount of 3000 mJ / cm 2 to obtain a laminate having a cured film with a film thickness of 40 μm. Method for producing an acrylic-polyester resin-coated steel sheet: A white polyester-isocyanate paint with a pigment mass concentration (PWC) of 60% was applied to the surface of a 2-mm-thick zinc-treated steel sheet so that the dry film thickness was 30 to 40 μm, and the paint was thermally cured at 80°C for 30 minutes.

[0140] [Evaluation of E-Type Viscosity] Using an E-type viscometer TV-25 (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured under the condition of a liquid temperature of 25°C, and the measured values are shown in Tables 1 to 6. From the viewpoint of coatability, <1000 mPa·sec was set as the passing value.

[0141] [Weather Resistance Evaluation] Using the following conditions, an accelerated weathering test (SUV test) was conducted on the evaluation samples of each example. Conditions: Irradiation (63°C·90%RH·100 mW / cm 2 ·4 hours) → Darkness (70°C·90%RH·4 hours) → Dew condensation (30°C, 98%RH·4 hours) were repeated, with a shower before and after irradiation The appearance was visually confirmed every 1 cycle (96 hours), and the maximum number of cycles in which no whitening or cracking was observed in the cured film was used as the evaluation result, and 3 cycles (288 hours) or more were considered passing. In addition, if no whitening was observed beyond 15 cycles, it was described as 15. The maximum number of cycles for each example is shown in Tables 1 to 6 as the weather resistance result.

[0142] [Evaluation of boiling water resistance] Using the following conditions, a boiling water resistance test was conducted on the evaluation samples of each example. The evaluation samples were immersed in deionized water at 95°C or higher, and a cellophane tape adhesion test was performed on the surface of the evaluation samples every 10 minutes based on JIS K 5600-5-6. The maximum time without peeling was described in Tables 1 to 6 as the result of the boiling water resistance. Those without peeling after 20 minutes of immersion were considered qualified. In addition, if no peeling was observed beyond 130 minutes, it was described as 130.

[0143]

Table 1

[0144]

Table 2

[0145]

Table 3

[0146]

Table 4

[0147]

Table 5

[0148]

Table 6

[0149]

Table 7

[0150]

Table 8

[0151]

Table 9

[0152]

Table 10

[0153]

Table 11

[0154]

Table 12

[0155] The abbreviations shown in Tables 1 to 12 respectively represent the following compounds or the compounds obtained in the above synthesis examples. IDA: Isodecyl acrylate THFA: Tetrahydrofurfuryl acrylate 2-MTA: Methoxyethyl acrylate CBA: Ethyl carbitol acrylate (ethoxyethoxyethyl acrylate) MTG: Methoxytriethylene glycol acrylate PG-MA: Polyglycidyl methacrylate CHA: Cyclohexyl acrylate IBXA: Isobornyl acrylate TBCHA: 4-tert-Butylcyclohexyl acrylate SR420NS: 3,3,5-Trimethylcyclohexanol acrylate (product name "SR420NS", manufactured by Arkema) FA-513AS: SR368NS: Isocyanurate triacrylate (product name "SR368NS", manufactured by Arkema) EO-TEMPTA: Trimethylolpropane EO-added triacrylate (Miramer M3130 manufactured by MIWON Co., Ltd.) DPHA: Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) DPCA-20: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) DPCA-60: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) Tinuvin123: HALS "Tinuvin123" (trade name, manufactured by BASF) Tinuvin292: HALS "Tinuvin292" (trade name, manufactured by BASF) Tinuvin152: HALS "Tinuvin152" (trade name, manufactured by BASF) LA-46: UV absorber "ADEKA STAB LA-46" (trade name, manufactured by ADEKA) Tinuvin405: UV absorber "Tinuvin405" (trade name, manufactured by BASF) Tinuvin479: UV absorber "Tinuvin479" (trade name, manufactured by BASF) Tinuvin477: UV absorber "Tinuvin477" (trade name, manufactured by BASF) TinuvinPS: UV absorber "TinuvinPS" (trade name, manufactured by BASF) Ruva-93: UV absorber "Ruva-93" (trade name, manufactured by Otsuka Chemical Co., Ltd.) BYK-UV3575: Reactive silicone leveling agent "BYK-UV-3575" (trade name, manufactured by BYK) BYK-333: Silicone leveling agent "BYK-333" (trade name, manufactured by BYK)

[0156] From the results of Examples 1 to 86 in Tables 1 to 11 above, it was confirmed that the cured film of the active energy ray-curable composition of the present invention is excellent in weather resistance and boiling water resistance. On the other hand, it was confirmed that Comparative Examples 1 to 8 in Table 12 are inferior in at least one of the properties.

Claims

1. An active energy ray-curable composition containing the following components (A), (B), and (C). Component (A): A compound having one (meth)acryloyl group in one molecule Component (B): An ester triacrylate having an isocyanuric ring structure Component (C): A urethane (meth)acrylate having 2 to 4 (meth)acryloyl groups in one molecule (excluding the compound corresponding to the above component (B))

2. The active energy ray-curable composition according to claim 1, wherein the component (A) contains a compound (A-1) represented by the following formula (1). 【Chemical Formula 1】 [R １ is a methyl group or a hydrogen atom, R ２ is an ethylene group, a propylene group, or a butylene group, R ３ is an alkyl group having 1 to 5 carbon atoms which may have a substituent, and n is an integer of 1 to 5]

3. The active energy ray-curable composition according to claim 1, wherein the component (A) contains a compound (A-2) having an alicyclic structure.

4. The active energy ray-curable composition according to claim 1, wherein the component (C) contains a compound (C-1) represented by the following formula (2). 【Chemical 2】 [L １ ~L ３ each independently may have a substituent and is an alkylene group having 2 to 17 carbon atoms, L ４ ~L ６ each independently may have a substituent and is an alkylene group having 1 to 5 carbon atoms. R １１ ~R １３ each independently is a hydrogen atom or a methyl group. Z １ is an oxygen atom or a nitrogen atom, Z ２ is a hydrogen atom or -C(=O)-, provided that when Z １ is an oxygen atom (-O-), Z ２ is a hydrogen atom (-H). On the other hand, when Z １ is a nitrogen atom, Z ２ is -C(=O)-, and the nitrogen atom of Z １ and -C(=O)- of Z ２ are bonded to form a ring. ]

5. The active energy ray-curable composition according to claim 1, wherein the component (C) contains a compound (C-1') represented by the following formula (2-1). [Chemical Formula 3] [L １ ~L ３ each independently may have a substituent and is an alkylene group having 2 to 17 carbon atoms, L ４ ~L ６ each independently may have a substituent and is an alkylene group having 1 to 5 carbon atoms. R １１ ~R １３ each independently is a hydrogen atom or a methyl group.]

6. The active energy ray-curable composition according to claim 1, wherein the component (C) contains a compound (C-2) represented by the following formula (3-1), (3-2), (3-3), (3-4), or (4-1). 【Chemical Formula 4】 [L ７ ~L ９ each independently represents an alkylene group having 2 to 17 carbon atoms which may have a substituent, and L １０ ~L １２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent. R ２１ ~R ２３ each independently represents a hydrogen atom or a methyl group, and R ２４ ~R ２６ each independently represents an alkylene group having 2 to 12 carbon atoms which may have a substituent. n1 to n3 are each independently an integer of 1 to 10.] 【Chemical Formula 5】 [R ２７ ~R ２９ are each independently a hydrogen atom or a methyl group. R ３０ ~R ３２ are each independently an alkylene group having 2 to 10 carbon atoms which may have a substituent or may have a substituent having a substituent, R Ａ -(O-CO-(CH ２ ) ５ ) ｎ - or R Ａ -(O-(CH ２ ) ４ ) ｎ -, and at least one is R Ａ -(O-CO-(CH ２ ) ５ ) ｎ -. R Ａ represents an alkylene group, and n represents an integer of 1 to 5. X １ and X ２ each independently represent an alkylene group having 2 to 17 carbon atoms.] 【Chemical Formula 6】 [R ３３ ~R ３６ are each independently a hydrogen atom or a methyl group. R ３７ ~R ４０ are each independently an alkylene group having 2 to 10 carbon atoms which may have a substituent, R Ａ -(O-CO-(CH ２ )) ５ )) ｎ - or R Ａ -(O-(CH ２ )) ４ )) ｎ -, where R Ａ represents an alkylene group and n represents an integer from 1 to 5. X ３ ~X ８ each independently represent an alkylene group having 2 to 17 carbon atoms which may have a substituent. A １ is a structure obtained by removing a hydroxyl group from either end of a caprolactone-modified diol. ] 【Chemical Formula 7】 [R ４１ ~R ４４ are each independently a hydrogen atom or a methyl group. R ４５ ~R ５０ are each independently an alkylene group having 2 to 10 carbon atoms which may have a substituent, R Ａ -(O-CO-(CH ２ )) ５ )) ｎ - or R Ａ -(O-(CH ２ )) ４ )) ｎ -. R Ａ represents an alkylene group, and n represents an integer of 1 to 5. X ９ ~X １２ each independently represent an alkylene group having 2 to 17 carbon atoms which may have a substituent. A ２ is a structure obtained by removing a hydroxyl group from either end of a caprolactone-modified diol.] 【Chemical 8】 [R ５１ and R ５２ are each independently a hydrogen atom or a methyl group. X １３ and X １４ each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, a group obtained by removing two terminal hydroxyl groups from polycaprolactone diol, or a group obtained by removing two terminal hydroxyl groups from polycarbonate diol. X １５ each independently represent a group obtained by removing two terminal hydrogen atoms from polycaprolactone diol or a group obtained by removing two terminal hydrogen atoms from polycarbonate diol. n4 is an integer of 1 to 10. A ３ and A ４ are each independently any of the groups represented by the following formulas (*1) to (*4).] 【Chemical Formula 9】 [* is a bond and binds to the nitrogen atom in formula (4-1).]

7. The active energy ray-curable composition according to claim 1, further containing a compound (D) containing 5 or more (meth)acryloyl groups in one molecule.

8. The active energy ray-curable composition according to claim 1, containing the component (A) in a proportion of 10 to 75% by mass, the component (B) in a proportion of 5 to 85% by mass, and the component (B) in a proportion of 5 to 80% by mass, based on the total amount of the compounds having reactive groups contained in the active energy ray-curable composition.

9. The active energy ray-curable composition according to claim 1, wherein the content of the organic solvent in the total amount of the active energy ray-curable composition is 30% by mass or less.

10. A laminate having a cured layer of the active energy ray-curable composition according to any one of claims 1 to 9.

11. A method for producing a laminate, comprising: step 1 of applying the active energy ray-curable composition according to any one of claims 1 to 9 onto a substrate to obtain a coating film; and step 2 of irradiating the coating film with active energy rays to cure part or all of the coating film.

12. The method for manufacturing a laminate according to claim 11, wherein after the step 2, the step 1 and the step 2 are repeated at least once in this order.

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