JP2022148524A - Active energy ray-curable composition, cured product, and laminate - Google Patents

Abstract

To provide an active energy ray-curable composition that can form a cured product having excellent wear resistance and substrate adhesion and also less prone to cracking during molding, and a cured product of the composition, and a laminate including the cured product.SOLUTION: An active energy ray-curable composition comprises at least a resin A and a resin B. The resin A is a radical polymerizable double bond equivalent of 501-10000 g/mol. The resin B has a radical polymerizable double bond equivalent of 200-500 g/mol.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition, a cured product of the active energy ray-curable composition, and a laminate having a layer comprising the cured product.

For surface protection and decoration of resin molded materials such as automobile interior and exterior parts, electronic devices, miscellaneous goods, and building material parts, a method is known in which the surface is hard-coated or a film is adhered. As the decorating method, an insert method, a thermal lamination method, a transfer method, and the like are known. Further, as a hard coat layer, generally, a curable composition containing a compound having a radically polymerizable group and a photopolymerization initiator is cured by radical polymerization. However, when a hard coat layer is used to protect the surface, the wear resistance and scratch resistance are improved, but the elongation during molding is deteriorated, which may not be suitable for decorative applications. Another issue is the adhesion between the substrate and the hard coat layer so that the hard coat layer does not peel off during processing.

Patent Document 1 uses an insert film for an in-mold label, Cited Document 2 uses a hard coating agent for decorative molding, Cited Document 3 uses a decorative sheet for automotive interiors, and Cited Document 4 uses a thermal transfer printer. A decorative hard coat film printed directly on the hard coat layer by a thermal transfer printing method is described.

Japanese Patent Application Laid-Open No. 2005-288720 JP 2016-180082 A JP 2019-189043 A JP 2011-110903 A

The hard coat layer described in Patent Document 1 is excellent in wear resistance, but does not necessarily satisfy the elongation property during molding processing, and it is difficult to follow the surface shape of the molding material. Cracks may occur. The hard coating agent described in Patent Document 2 is also excellent in wear resistance, but does not necessarily satisfy elongation and adhesion to the substrate. The sheet described in Patent Document 3 cannot sufficiently satisfy the wear resistance of the surface protective layer, and the hard coat film described in Patent Document 4 cannot ensure elongation.
INDUSTRIAL APPLICABILITY The present invention provides an active energy ray capable of forming a hard coat layer that has excellent wear resistance and chemical resistance, elongation during molding (suppresses the occurrence of cracks), and excellent adhesion to substrates. An object of the present invention is to provide a laminate having a curable composition, a cured product of the active energy ray-curable composition, and a layer comprising the cured product.

The present invention has the following aspects.
That is, the above objects of the present invention can be solved by means of the following [1] to [10].
[1] An active energy ray-curable composition containing resin A and resin B, wherein resin A has a radically polymerizable double bond equivalent of 501 to 10000 g/mol, and resin B has a radically polymerizable double bond equivalent of An active energy ray-curable composition of 200 to 500 g/mol.
[2] The active energy ray-curable composition according to [1], wherein the resin A has a hydroxyl value of 5 to 115 mgKOH/g.
[3] [1] or [2], wherein the hydroxyl value of the resin B is 116 to 270 mgKOH/g
The active energy ray-curable composition according to .
[4] The active energy ray-curable composition according to any one of “1” to [3], wherein the nonvolatile content of the active energy ray-curable composition has a radically polymerizable double bond equivalent of 300 to 1000 g/mol. sex composition.
[5] The active energy ray-curable composition according to any one of [1] to [4], which contains a leveling agent.
[6] The active energy ray-curable composition according to any one of [1] to [5], which contains an ultraviolet absorber.
[7] A cured product of the active energy ray-curable composition according to any one of [1] to [6].
[8] The cured product of [7] having an elongation of 15% or more in a tensile test at 140°C.
[9] A laminate having the cured product of [7] or [8] on a substrate.
[10] The laminate of [9] having a transmittance of 80% or less at a wavelength of 360 nm.

In this specification, "(meth)acryl" is a generic term for "acryl" and "methacryl",
"(Meth)acrylate" is a generic term for "acrylate" and "methacrylate". "
(Meth)acryloyl group" is a generic term for "acryloyl group" and "methacryloyl group" and is represented by CH ₂ =C(R ¹ )-C(=O)- (R ¹ is a hydrogen atom or a methyl group) is the base. Moreover, "monofunctional" means having one radically polymerizable double bond. "Polyfunctional" means having two or more radically polymerizable double bonds, for example, "bifunctional"
means having two radically polymerizable double bonds.

<Active energy ray-curable composition>
The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing at least resin A and resin B, and resin A has a radically polymerizable double bond equivalent of 501 to 10,000.
g/mol, and the radically polymerizable double bond equivalent of resin B is 200 to 500 g/mol. By combining resin A and resin B, it is possible not only to achieve both wear resistance of the cured product and workability during stretching, but also
It has excellent quick-drying properties in the drying process before curing by active energy rays, and can improve workability and exhibit anti-blocking properties.

<Resin A>
The radical polymerizable double bond equivalent in resin A is usually 501 to 10000 g/mol
, preferably 510 to 6000 g/mol, more preferably 530 to 2500 g/mol
, more preferably in the range of 550 to 1200 g/mol. By using it in the said range, the elongation property at the time of molding processing when forming the cured film (hard-coat layer) which is a hardened|cured material becomes favorable. Further, the radically polymerizable double bond equivalent is obtained, for example, by reacting the resin composition with a mixed solution of sodium bromide and potassium bromate, mixing a potassium iodide solution with a sodium thiosulfate solution using a starch solution as an indicator. It can be measured by the method specified in

The hydroxyl value of Resin A is usually 5 to 115 mgKOH/g, preferably 10 to 11
0 mgKOH/g, more preferably 25 to 107 mgKOH/g, more preferably 50
~105 mg KOH/g. By using it in this range, the compatibility with the resin B is improved, and the appearance of the cured product is good. Moreover, the hydroxyl value can be measured, for example, by reacting the resin composition with excess acetic anhydride in pyridine and titrating liberated acetic acid with potassium hydroxide.

The weight average molecular weight of resin A should be appropriately selected according to the application of the curable composition, preferably 1000 to 200000, more preferably 5000 to 100000, still more preferably 8000 to 80000, particularly preferably 10000. ~60000. By using it in this range, the adhesion to the base material can be improved, and the elongation during molding can be improved. In addition, the viscosity of the composition can be easily controlled within an appropriate range, and excellent coatability can be achieved. The weight average molecular weight (Mw) of the resin can be determined by gel permeation chromatography (GPC) as a converted value based on polystyrene standards. Specific measurement conditions are shown in Examples below.

The content of the resin A in the active energy ray-curable composition cannot be generalized because it varies depending on the application and the required properties of the cured film. %, more preferably 35 to 90% by mass, still more preferably 45 to 85% by mass, and particularly preferably 60 to 80% by mass. By using it within this range, it is possible to ensure good elongation during molding and good adhesion to the substrate while ensuring abrasion resistance.
In applications where elongation is particularly important, the range is preferably 60 to 99% by mass, more preferably 65 to 90% by mass, and even more preferably 70 to 85% by mass.
The non-volatile content is the total mass of components other than the solvent, such as an organic solvent. The non-volatile content of the active energy ray-curable composition can be measured by a conventionally known method. Measured by change in weight.

<Resin B>
The radically polymerizable double bond equivalent weight of Resin B is usually in the range of 200-500 g/mol, preferably 215-450 g/mol, more preferably 225-400 g/mol, and still more preferably 230-370 g/mol. By using it in this range, abrasion resistance and chemical resistance when forming a cured film (hard coat layer), which is a cured product, are improved.

(B) The hydroxyl value of the resin is usually 116 to 270 mgKOH/g, preferably 1
25 to 260 mgKOH/g, more preferably 140 to 250 mgKOH/g, more preferably 150 to 245 mgKOH/g. By using it in this range, the adhesiveness with the base material becomes good.

The weight average molecular weight of resin B should be appropriately selected depending on the application of the curable composition, preferably 1000 to 200000, more preferably 5000 to 100000, still more preferably 8000 to 80000, particularly preferably 10000. ~60000. By using it in this range, the abrasion resistance can be improved and the adhesion to the substrate can be improved. In addition, the viscosity of the composition can be easily controlled within an appropriate range, and excellent coatability can be achieved.

The content of the resin B in the active energy ray-curable composition cannot be generalized because it varies depending on the application and required properties of the cured film, but is preferably 5 to 95 masses relative to the nonvolatile content. %, more preferably 1 to 75 mass %, still more preferably 5 to 60 mass %, particularly preferably 9 to 50 mass %, most preferably 14 to 35 mass %. By using it in this range, good abrasion resistance, chemical resistance, and adhesion to the substrate can be obtained.
In applications where elongation is particularly important, the range is preferably from 1 to 40% by mass, more preferably from 3 to 25% by mass, and even more preferably from 5 to 20% by mass.

Resins such as (meth)acrylic resins, polyester resins, and urethane resins can be used as the resin A and the resin B that satisfy the above conditions. A (meth)acrylic resin is preferable from the viewpoint that it is easy to form a hard coat layer having suitable properties.

A method for introducing a radically polymerizable double bond into a (meth)acrylic resin includes a method of reacting an acrylic resin having an epoxy group with a compound having a double bond and a carboxyl group (
Method 1), a method of reacting a compound having a double bond and an epoxy group with an acrylic resin having a carboxyl group (method 2), a method of reacting a compound having a double bond and a carboxyl group with an acrylic resin having a hydroxyl group (method 3), a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having a carboxyl group (Method 4), and a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having an isocyanate group (Method 5). ,
A method of reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (Method 6). Also, the above methods may be used in combination. In addition, the monomer which has a radically polymerizable double bond may be called a vinyl monomer below.

Examples of the vinyl monomer having an epoxy group used for obtaining the acrylic resin having an epoxy group in Method 1 include glycidyl (meth)acrylate, 3,
4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like. Among these, glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may use only 1 type, and may combine 2 or more types.

Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerol di(meth)acrylate and succinic anhydride, pentaerythritol tri Adducts of (meth)acrylate and succinic anhydride, adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride, and the like. Among these, (meth)acrylic acid and adducts of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. In addition, the compound which has a double bond and a carboxyl group may use only 1 type, and may combine 2 or more types.

Examples of the vinyl monomer having a carboxyl group used to obtain the acrylic resin having a carboxyl group in Method 2 include (meth)acrylic acid, carboxyethyl (meth)acrylate, polybasic acid-modified (meth)acrylate, and the like. is mentioned. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may use only 1 type, and may combine 2 or more types.

In Method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and the like. Among these, glycidyl (meth)acrylate is preferred. These may use only 1 type, and may combine 2 or more types.

Examples of the vinyl monomer having a hydroxyl group used for obtaining the acrylic resin having a hydroxyl group in Method 3 include 2-hydroxyethyl (meth)acrylate, 4
- hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate and the like. These may use only 1 type, and may combine 2 or more types.

In Method 3, the compound having a double bond and a carboxyl group may be the same compound as in Method 1.

In Method 4, the same acrylic resin as used in Method 2 can be used as the acrylic resin having a carboxyl group.

In method 4, the compound having a double bond and a hydroxyl group may be, for example, 2
-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate and the like. These may use only 1 type, and may combine 2 or more types.

In Method 5, the vinyl monomer having an isocyanate group used for obtaining the acrylic resin having an isocyanate group includes, for example, isocyanatoethyl (meth)acrylate.

In Method 5, the compound having a double bond and a hydroxyl group may be, for example, the same compounds as those listed in Method 4 above.

In method 6, the same compound as in method 3 can be used as the acrylic resin having a hydroxyl group.

In method 6, the compound having a double bond and an isocyanate group is
Examples thereof include isocyanatoethyl (meth)acrylate. These may use only 1 type, and may combine 2 or more types.

Among the above methods, method 1 or method 2 is preferable because a hydroxyl group can be introduced at the same time. Moreover, method 1 is more preferable because the reaction can be easily controlled. In method 1, the double bond is introduced by ring-opening/addition reaction between the epoxy group of the acrylic resin having the epoxy group and the carboxyl group of the compound having the double bond and the carboxyl group.

When the resin A is synthesized by Method 1, the monomer having an epoxy group in the acrylic resin having an epoxy group preferably accounts for 1% by weight or more of the total amount of the monomers constituting the acrylic resin having an epoxy group, more preferably is in the range of 2% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more. Although there is no particular upper limit, it is 25% by weight. By using it in this range, it is possible not only to improve the adhesion of the cured film to the base material, the scratch resistance, and the hardness, but also to achieve stretchability that does not cause cracks due to stress during decorative molding.

Further, when the resin A is synthesized by the method 1, the compound having a double bond and a carboxyl group is preferable as the ratio of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group. is 10 to 150 mol %, more preferably 30 to 130 mol %, still more preferably 50 to 120 mol %, and particularly preferably 100 to 110 mol %, which is an amount that allows the reaction to proceed just enough. By using it in this range, a radically polymerizable double bond can be effectively introduced.

When the resin B is synthesized by Method 1, the monomer having an epoxy group in the acrylic resin having an epoxy group preferably accounts for 26% by weight or more of the total amount of monomers constituting the acrylic resin having an epoxy group, more preferably is in the range of 30% by weight or more, more preferably 35% by weight or more, and particularly preferably 40% by weight or more. Although there is no particular upper limit, it is 99% by weight. By using it in this range, it is possible to achieve not only stretchability that does not cause cracks due to stress during decorative molding, but also improvement in scratch resistance and hardness of the cured film.

Further, when the resin B is synthesized by Method 1, the compound having a double bond and a carboxyl group is preferable as the ratio of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group. is 10 to 150 mol %, more preferably 30 to 130 mol %, still more preferably 50 to 120 mol %, and particularly preferably 100 to 110 mol %, which is an amount that allows the reaction to proceed just enough. By using it in this range, a radically polymerizable double bond can be effectively introduced.

It is also possible to introduce a hydroxyl group by a technique other than Method 1 or Method 2 above. for example,(
A method of copolymerizing a compound having a hydroxyl group as a monomer during the production of the meth)acrylic resin may be mentioned.

Examples of monomers having a hydroxyl group include hydroxyethyl (meth)acrylate,
Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxyllauryl (meth)acrylate, etc. Among these, hydroxyethyl (meth)acrylate is preferable from the viewpoint of ease of introduction and ability to efficiently adjust the hydroxyl value.

Furthermore, the (meth)acrylic resin such as the epoxy group-containing (meth)acrylic resin described above may be obtained by copolymerizing (meth)acrylates other than those described above or other vinyl monomers. The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

Monomers that can be used together as raw materials include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (
meth) acrylate, phenyl (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, octoxy ( poly)ethylene glycol (meth)acrylate, octoxy (poly)propylene glycol (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy (poly)ethylene glycol (meth)acrylate,
(Meth)acrylates such as stearoxy (poly)ethylene glycol (meth)acrylate; ethyl (meth)acrylamide, n-butyl (meth)acrylamide, i-butyl (
Acrylamides such as meth)acrylamide, t-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-dihydroxyethyl (meth)acrylamide; styrene, p-chlorostyrene , p-bromostyrene and other styrenic monomers. These may use only 1 type, and may combine 2 or more types.

The (meth)acrylic resin can be produced by a radical polymerization reaction using the raw material vinyl monomers described above. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of organic solvents used for radical polymerization include acetone and methyl ethyl ketone (M
EK) and other ketone solvents; ethanol, methanol, isopropyl alcohol (IPA)
, isobutanol and other alcohol solvents; ethylene glycol dimethyl ether, propylene glycol monomethyl ether and other ether solvents; ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate and other ester solvents; toluene and other aromatic carbonization A hydrogen solvent and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

Examples of radical polymerization initiators used for radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2'-azobisbutyronitrile, 2,2'-azobis( ,4-dimethylvaleronitrile), 2,2'-azobis (4-
azo compounds such as methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the raw material vinyl monomers.

Moreover, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the (meth)acrylic resin during the radical polymerization. Examples of chain transfer agents include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol,
Octadecanthiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercapto propionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1 ,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecylmercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thio Thiol compounds such as glycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

The amount of the chain transfer agent used is 0.1 to 2 parts per 100 parts by weight of the raw material vinyl monomer.
5 parts by weight is preferred, 0.5 to 20 parts by weight is more preferred, and 1.0 to 15 parts by weight is even more preferred.

The reaction time for radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours.
The reaction temperature is preferably 40-120°C, more preferably 50-100°C.

In order to react a compound having a double bond and a carboxyl group with a (meth)acrylic resin, a compound having a double bond and a carboxyl group is added to the (meth)acrylic resin obtained as described above. in the presence of one or more catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride and triethylamine at a temperature of usually 90 to 140° C., preferably 100 to 120° C., usually 3 to 9 It only needs to be reacted for about an hour. Here, the catalyst is used in a ratio of about 0.5 to 3 parts by weight with respect to a total of 100 parts by weight of the raw material (meth)acrylic acid ester polymer and the compound such as a compound having a double bond and a carboxyl group. It is preferable to use This reaction may be carried out continuously after the (meth)acrylic resin is produced by a polymerization reaction, and after the (meth)acrylic resin is once fractionated from the reaction system, a compound such as a compound having a double bond and a carboxyl group etc. may be added.

<Radical polymerizable double bond equivalent of active energy ray-curable composition>
The radically polymerizable double bond equivalent of the nonvolatile portion of the active energy ray-curable compound of the present invention is usually 300 to 1000 g/mol, preferably 330 to 600 g/mol, more preferably 400 to 575 g/mol, and still more preferably It ranges from 450 to 550 g/mol. By using it in this range, it is possible to achieve both wear resistance when forming a cured film (hard coat layer), which is a cured product, and stretchability during molding.

<Active energy ray-curable compounds other than resin A and resin B>
Furthermore, as the active energy ray-curable composition, an active energy ray-curable compound other than the resins described above may be used in order to improve or adjust the wear resistance and hardness of the cured film. However, when an active energy ray-curable compound other than a resin is used, an odor or tackiness may remain after the composition is applied to a substrate or an article and dried. This is caused by exudation of compounds other than the resin from the coating film after drying, and there are cases where there is concern about a decrease in workability due to increased danger to workers, blocking of articles, and the like. In addition, unreacted compounds remain in the cured product, causing bleed-out, which may cause contamination of equipment and environment in various processes, or deterioration of visibility after coating and curing. Due to these factors, depending on the application, it may be preferable to reduce the amount of the active energy ray-curable compound other than the resin used, or not to use it.

As the active energy ray-curable compound other than resin A and resin B, conventionally known materials can be used, and for example, (meth)acrylate is a suitable material. (
The meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or a trifunctional or higher polyfunctional (meth)acrylate. (Meth)acrylates that are commercially available as curable resin materials can also be used. The (meth)acrylate may contain other components as long as the object of the present invention is not impaired.
Among these, polyfunctional (meta) with bifunctional or trifunctional or more is particularly excellent in wear resistance.
An acrylate is preferable, and a (meth)acrylate having a trifunctional or higher function is particularly preferable. As the (meth)acrylate, it is also possible to use epoxy (meth)acrylate, urethane (meth)acrylate, silicone (meth)acrylate, and the like.

Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-
Butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl ( meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate Acrylate, tricyclodecane (meth)acrylate, polyethylene glycol
Rumono (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, 2 - ethoxyethyl (meth)acrylate, benzyl (meth)acrylate,
Examples include mono(meth)acrylates such as phenoxyethyl(meth)acrylate and phenyl(meth)acrylate, and mono(meth)acrylate compounds such as adducts of phthalic anhydride and 2-hydroxyethyl(meth)acrylate.

Examples of bifunctional polyfunctional (meth)acrylates include 1,4-butanediol di(
meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate,
Alkanediol di(meth) such as tricyclodecanedimethylol di(meth)acrylate
Bisphenol-modified di(meth)acrylates such as acrylates, bisphenol A ethylene oxide-modified di(meth)acrylates, bisphenol F ethylene oxide-modified di(meth)acrylates, polyethylene glycol di(meth)acrylates, polypropylene glycol di(meth)acrylates, urethane di(meth)acrylates (meth)acrylates, epoxy di(
meth)acrylate and the like.

Trifunctional or higher polyfunctional (meth)acrylates include, for example, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra( meth)acrylate, pentaerythritol tri(meth)acrylate,
Ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, etc. Ethylene oxide modified (meth)
Acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε-
Isocyanuric acid-modified tri(meth)acrylates such as caprolactone-modified tris(acloxyethyl) isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate Urethane (meth)acrylates such as urethane prepolymers and the like are included.

<Leveling agent>
In order to improve the appearance of the cured product, a leveling agent can be added to the active energy ray-curable composition. Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. Among these, silicone-based leveling agents are more preferable from the viewpoint that they can also improve abrasion resistance, which is one of the problems of the present invention. A silicone-based leveling agent having a radically polymerizable functional group is particularly preferred because it also has the added benefit of preventing out. The silicone-based leveling agent imparts slip properties to the cured product and can achieve high abrasion resistance. A silicone-based leveling agent having a radically polymerizable functional group reacts with the active energy ray-curable composition and is incorporated into the cured product, thereby achieving long-term slip properties, abrasion resistance, and chemical resistance. Very useful.

The content of the leveling agent in the active energy ray-curable composition is
Preferably 20% by mass or less, more preferably 0.01 to 10% by mass, still more preferably 0
. It ranges from 1 to 5% by weight, particularly preferably from 0.2 to 4% by weight, most preferably from 0.3 to 3% by weight. By using it in this range, it is possible not only to improve the appearance of the cured film, but also to improve the abrasion resistance.

<Ultraviolet absorber>
In order to improve the weather resistance of the cured product, an ultraviolet absorber can be blended into the active energy ray-curable composition. From the viewpoint of heat resistance, those having a molecular weight of 500 or more are preferable. The UV absorber is derived from a triazine-based, benzophenone-based, benzotriazole-based, cyclic imino ester-based, salicylic acid ester-based, or cyanoacrylate-based compound from the viewpoint of good solubility in the composition and improvement of weather resistance. with a maximum absorption wavelength of 24
UV absorbers in the range of 0-380 nm are preferred. Among these, triazine-based and benzotriazole-based resins are more preferable, and triazine-based resins are even more preferable, from the viewpoint of particularly good ultraviolet absorption and excellent appearance when formed into a hard coat layer.

The triazine-based ultraviolet absorber is not limited to the following, but for example, 2-
[4-([2-hydroxy-3-dodecyloxypropyl]oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-
[4-([2-hydroxy-3-tridecyloxypropyl]oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (T
inuvin (registered trademark) 400 manufactured by BASF), 2-[4,6-bis (
2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), 2-(2,4-dihydroxyphenyl)- Reaction product of 4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate (Tinuvin® 405, manufactured by BASF), 2 , 4-bis"2-hydroxy-4-butoxyphenyl"-
6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin (registered trademark) 460, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazine-
2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin® 1
577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK
STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3
,5-triazine (Tinuvin (registered trademark) 479, manufactured by BASF) and the like.

Examples of benzotriazole-based UV absorbers include, but are not limited to, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H
-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzo triazole, 2-[2′-hydroxy-5′-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole,
2-[2′-hydroxy-3′-tert-butyl-5′-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-tert
-butyl-3′-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl]-5-
Chloro-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl) ) phenyl]-5-cyano-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy -
5′-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole and the like.

Examples of the cyclic iminoester-based ultraviolet absorber include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4- one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1-
or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-
3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-
p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one one, 2-cyclohexyl-3,1-benzoxazin-4-one,
2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N
-phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N
-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, N-
Benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine-4
-one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylenebis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis (3,1
-benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) , 2,2′-m-phenylenebis(3,1-benzoxazin-4-one), 2,2
'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2
'-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazin-4-one)
, 2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2-nitro-p-phenylene)bis(3,1-benzo Oxazine-4
-one), 2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(1,4-cyclohexylene)bis(3,1 -benzoxazin-4-one), 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)
Benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,4,6-tri(3,1-benzoxazin-4-one-2-yl) Naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3)
-oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d;
4,5-d')bis(1,3)-oxazine-4,9-dione, 2,8-diphenyl-
4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6
-dione, 2,7-diphenyl-4H,9H-benzo(1,2-d;4,5-d')bis(1,3)-oxazine-4,6-dione, 6,6'-bis( 2-methyl-4H,3,1
-benzoxazin-4-one), 6,6′-bis(2-ethyl-4H,3,1-benzoxazin-4-one), 6,6′-bis(2-phenyl-4H,3,1 -benzoxazin-4-one), 6,6′-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-methylenebis(2-phenyl-4H,3,1 -benzoxazin-4-one), 6,6′-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-ethylenebis(2-phenyl-4H,3 ,1-benzoxazin-4-one), 6,6′-butylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-butylenebis(2-phenyl-4H,3 ,1-benzoxazin-4-one), 6,6′-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-oxybis(2-phenyl-4H,3 ,1-benzoxazin-4-one), 6,6′-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-sulfonylbis(2-phenyl-4H ,3,1-benzoxazin-4-one), 6,6′-carbonylbis(2-methyl-4H,3,1-
benzoxazin-4-one), 6,6′-carbonylbis(2-phenyl-4H,3,
1-benzoxazin-4-one), 7,7′-methylenebis(2-methyl-4H,3,
1-benzoxazin-4-one), 7,7′-methylenebis(2-phenyl-4H,3
,1-benzoxazin-4-one), 7,7′-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7′-ethylenebis(2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7′-sulfonylbis(2-methyl-4H ,3,1-benzoxazin-4-one), 7,7′-carbonylbis(2-methyl-4H,3,1-
benzoxazin-4-one), 6,7′-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7′-bis(2-phenyl-4H,3,1- Benzoxazin-4-one , 6,7′-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7′-methylenebis(2-phenyl-4H,3,1-benzo oxazin-4-one) and the like.

Benzophenone UV absorbers (benzophenone compounds) and oxybenzophenone UV absorbers (oxybenzophenone compounds) include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
- methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-
octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone,
4-benzyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone (trade name “KEMISORB111”, manufactured by Chemipro Kasei Co., Ltd.)
, 2,2′,4,4′-tetrahydroxybenzophenone (trade name “SEESORB10
6”, manufactured by Shipro Kasei Co., Ltd.), 2,2′-dihydroxy-4,4-dimethoxybenzophenone, and the like.

Examples of salicylic acid ester-based ultraviolet absorbers (salicylic acid ester-based compounds) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy-4. -methyl benzoate-
phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate,
Phenyl-2-hydroxy-3-methylbenzoate, Phenyl-2-hydroxy-4-methylbenzoate, Phenyl-2-hydroxy-5-methylbenzoate, Phenyl 2-
hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3,
5-di-tert-butyl-4-hydroxybenzoate (Tinuvin®
120, manufactured by BASF) and the like.

Cyanoacrylate UV absorbers (cyanoacrylate compounds) include, for example, alkyl-2-cyanoacrylates, cycloalkyl-2-cyanoacrylates, alkoxyalkyl-2-cyanoacrylates, alkenyl-2-cyanoacrylates, alkynyl-2 - includes cyanoacrylates and the like.
Moreover, these compounds may be used individually by 1 type, or may use 2 or more types together.

The content of the ultraviolet absorber in the active energy ray-curable composition is
Preferably 20% by mass or less, more preferably 0.01 to 15% by mass, still more preferably 0
. It ranges from 1 to 10% by weight, particularly preferably from 0.5 to 8% by weight, most preferably from 1 to 5% by weight. By using it in this range, a cured film can be effectively formed, and the weather resistance of the cured film is improved.

When used for applications that require weather resistance, it is preferable that it has good UV absorption, and a wavelength of 360
The transmittance of the laminate after forming the cured product in nm is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less, and particularly preferably 50% or less. The lower limit depends on the application, but in applications where weather resistance is strongly required, the lower the better, so 0%
is. By using it in the said range, it should be excellent in weather resistance.

<Light stabilizer>
In order to further improve the weather resistance of the cured product, a light stabilizer can be blended into the active energy ray-curable composition. The light stabilizer is not particularly limited as long as it is a hindered amine light stabilizer. Specific examples of light stabilizers include 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- Octoxy-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-methoxy-benzylidene)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 and other aminomethyl group-containing compounds, 1,2,3,4-butanetetracarboxylic acid and 1,2,
2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,
9-(2,4,8,10-tetraoxaspiro[5,5])undecane) condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-pentamethyl -
Condensation product of 4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, decanedicarboxylic acid and 2 , 2,6,6-tetramethyl-1-octoxy-4-piperidinol, the reaction product of the diester compound with 1,1-dimethylethyl hydroperoxide and octane (BA
SF, trade name Tinuvin 123), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]
methyl] (manufactured by BASF, trade name Tinuvin 144) and other amino ether group-containing compounds. Among these, amino ether group-containing compounds are preferable from the viewpoint of weather resistance of the cured product, and in particular bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1, dimethylethyl)-4-hydroxyphenyl]methyl] is particularly preferred. Moreover, these compounds may be used individually by 1 type, or may use 2 or more types together.

The content of the light stabilizer in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.01 to 15% by mass, still more preferably 0.1, based on the nonvolatile content.
to 10% by weight, particularly preferably 0.5 to 8% by weight, most preferably 1 to 5% by weight. By using it in this range, a cured film can be effectively formed, and the weather resistance of the cured film is improved.

<Photoinitiator>
A photopolymerization initiator may be added to accelerate the curability of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyldiphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3′-dimethyl-4- methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone,
4,4′-bis(diethylamino)benzophenone, pivaloine ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-chlorothioxanthone,
2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4
-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-
methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The content of photopolymerization initiation in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, and still more preferably 0.3, based on the nonvolatile content.
to 10% by weight, particularly preferably 0.5 to 8% by weight, most preferably 1 to 7% by weight. Formation of a cured film can be promoted effectively by using it in the said range.

The active energy ray-curable composition may further contain an organic solvent, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a dye, an antifoaming agent, a thickener, an anti-settling agent, and an antistatic agent. Various additives such as agents and anti-fogging agents may be added.

Moreover, in the case of forming a cured film, an organic solvent can be used as necessary for the purpose of improving the workability when the active energy ray-curable composition is applied onto a substrate.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. , diethylene glycol diethyl ether, propylene glycol monomethyl ether,
Ether solvents such as anisole and phenetol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate; Amide solvents such as dimethylformamide, diethylformamide and N-methylpyrrolidone; cellosolve solvents such as butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred because they tend to improve workability in coating.

<Cured product (cured film)>
A cured product of the active energy ray-curable composition is obtained by applying the active energy ray-curable composition on a substrate or an article to form a coating film, drying if necessary, and then applying the active energy ray to the coating film. can be formed by irradiating A method for applying the active energy ray-curable composition is not particularly limited. For example, it can be applied by known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.

When the active energy ray-curable composition contains an organic solvent, it is preferably heated and dried in advance before the active energy ray irradiation. By drying by heating in advance, the organic solvent in the coating film can be effectively removed. The drying temperature for heat drying is preferably 30 to 200°C, more preferably 40 to 150°C, still more preferably 50 to 120°C. drying time is 0
. 01 to 30 minutes is preferred, and 0.1 to 10 minutes is more preferred.

Examples of active energy rays include ultraviolet rays, electron rays, visible rays, infrared rays, and X-rays. Among them, ultraviolet rays and electron beams are preferred, and ultraviolet rays are more preferred, from the viewpoint of curability and resin deterioration prevention. In addition, the irradiation amount of the active energy ray can be appropriately selected according to the active energy ray to be irradiated.

For example, when ultraviolet rays are used, the integrated light quantity of irradiation is preferably 20 to 5000 mJ/cm ² , more preferably 100 to 3000 mJ/cm ² and even more preferably 200 to 2000 mJ/cm ² . The illuminance is preferably 50 to 600 mW/cm ² , and 75 to 45 mW/cm 2 .
0 mW/cm ² is more preferable, and 100 to 300 mW/cm ² is even more preferable. As the light source, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, electrodeless lamp, metal halide lamp, or high-pressure mercury lamp, ultra-high-pressure mercury lamp, low-pressure mercury lamp, etc., such as an electron beam using a scanning or curtain-type electron beam acceleration path shall be used. can be done.

Moreover, when hardening by electron beam irradiation, various electron beam irradiation apparatuses can be used. The electron beam irradiation dose (Mrad) is usually 0.5 to 20 Mrad, from the viewpoint of the curability of the active energy ray-curable composition of the present invention, the flexibility of the cured product, the prevention of damage to the substrate, and the like. It is preferably 1 to 15 Mrad.

The thickness of the cured product (cured film) is preferably 0.1 to 20 μm, more preferably 0.2 to 1 μm.
0 μm, more preferably in the range of 0.3 to 7 μm. When the thickness of the cured product is within the above range, desired properties such as wear resistance can be easily achieved.
The thickness of the cured product can be determined by cross-sectional observation using an electron microscope or the like.

The elongation of the cured product is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more as an elongation percentage in a tensile test at 140°C, which will be described later. Particularly when used in applications where elongation is emphasized, the range is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more. Although the upper limit is not particularly limited, preferably 2
00%. By setting the content within this range, defects such as cracks during molding can be suppressed.

As the abrasion resistance of the cured product, the change in haze in the abrasion test described later is preferably 2.0% or less, more preferably 1.5% or less, still more preferably 1.0% or less, and particularly preferably 0.5. % or less, most preferably 0.3% or less, and the lower limit is 0.0%. By setting the thickness within this range, it is possible to prevent scratches during the processing process and prevent scratches after molding.

As the chemical resistance of the cured product, in the test described later, the change in haze is preferably 1
. 5% or less, more preferably 1.4% or less, still more preferably 1.2% or less, particularly preferably 1.1% or less, most preferably 0.7% or less, and the lower limit is 0.0% . By setting it as the said range, the chemical resistance after shaping|molding will be excellent.

<Laminate>
The laminate of the present invention (hereinafter also referred to as "this laminate") has a substrate layer and a layer composed of a cured product (cured film, hard coat layer) of an active energy ray-curable composition. The laminate further comprises a primer layer provided between the substrate layer and the cured product, and a back surface functional layer provided on the surface of the substrate layer opposite to the cured product side. It may have one or more layers selected from the group. Further, a surface functional layer may be provided on the surface of the cured product opposite to the substrate layer side as long as it does not impair the effects of the present invention.

(Base material layer)
As the base material layer, a known one can be used, and examples thereof include a resin base material, a metal base material, and a paper base material. Among these, a resin substrate is preferable from the viewpoint of workability.
The resin base material may have a single layer structure or a multilayer structure of two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layered structure of two or more layers and that each layer has its own characteristic to achieve multi-functionality.

Various resin films (sheets) can be used as the resin substrate, for example, polyester film, poly(meth)acrylate film, polyurethane film, polyolefin film, polycarbonate film, polyimide film, triacetylcellulose film, polystyrene film, polychlorinated vinyl film, polyvinyl alcohol film, nylon film and the like.

Polyester film, poly(meth)acrylate film, polyurethane film, and polyolefin film are preferable when using this laminate for surface protection and decoration of resin molding materials such as interior and exterior parts of automobiles and electronic devices. Polyester film, poly(meth)acrylate film, and polyurethane film are preferred in consideration of properties, and polyester film and poly(meth)acrylate film are particularly preferred.

The polyester film may be a non-stretched film or a stretched film, preferably a stretched film. Among them, a uniaxially stretched film or a biaxially stretched film is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness. In addition, an easily moldable type having good moldability is preferable, and examples thereof include polyester in which a copolymer such as an isophthalic acid structure is incorporated into the structure of polyethylene terephthalate.

The substrate layer may contain particles for the purpose of imparting lubricity, preventing scratching in each process, and improving anti-blocking properties, and may also contain an ultraviolet absorber to improve weather resistance. It is also possible to In addition, additives other than the above-described particles and ultraviolet absorbers can be included as necessary. Known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, dyes and pigments can be used as additives.

The thickness of the substrate layer is not particularly limited.
μm range.

In addition, the substrate layer may be subjected to corona treatment or plasma treatment in order to improve adhesion to the cured product of the active energy ray-curable composition.

(primer layer)
The primer layer is provided to provide various functions between the substrate layer and the cured product of the active energy ray-curable composition. Examples thereof include an adhesion improving layer and an antistatic layer.

In one preferred embodiment, the primer layer is an adhesion improving layer. If the adhesiveness between the substrate layer and the cured product is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the substrate layer and the cured product is improved, and the laminate can be used for various purposes. Examples of components constituting the primer layer include polyester resins, acrylic resins, urethane resins, polyvinyl resins (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.).
etc.

<Application>
A cured product obtained from the active energy ray-curable composition of the present invention is excellent in abrasion resistance, substrate adhesion, and stretching processability, and therefore can be suitably used as a curable composition for a decorative film. For example, it can be effectively applied to various materials such as interior and exterior building materials, automobiles, household appliances, information electronic materials, and the like.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention. It may be a range defined by the value of the example or a combination of the values of the examples.
The measurement methods and evaluation methods used in the present invention are as follows.

(1) Weight Average Molecular Weight The weight average molecular weight of the copolymer was measured by GPC under the following conditions.
Equipment: "e2695" manufactured by Waters,
Column: "TSKgel Super H3000 + H4000 + H" manufactured by Tosoh Corporation
6000",
Detector: differential refractive index detector (RI detector/built-in),
solvent: tetrahydrofuran,
temperature: 40°C,
flow rate: 0.5 mL/min,
Injection volume: 10 μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: Polystyrene conversion

(2) Evaluation method for abrasion resistance test
, Under an atmosphere of 50% RH, Gakushin type friction tester (RT-2 manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.
00) was used to evaluate haze values before and after treatment with 1000 strokes of Kanakin No. 3 with a 300 g weight and an R contact arm.
For haze, a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) is used, and JIS K
-7136 (2000), the value obtained by subtracting the haze value before the abrasion test from the haze value after the abrasion test was evaluated as the haze change amount.

(3) Evaluation method for chemical resistance test
, Under an atmosphere of 50% RH, Gakushin type friction tester (RT-2 manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.
00), the haze value before and after the treatment of 50 reciprocations in a state in which 1 mL of methyl ethyl ketone was impregnated in a nonwoven fabric (BENCOT (registered trademark) M-3II manufactured by Asahi Kasei Corporation) was evaluated using an R contact arm.
For haze, a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) is used, and JIS K
-7136 (2000), the value obtained by subtracting the haze value before the abrasion test from the haze value after the abrasion test was evaluated as the haze change amount.

(4) Evaluation of elongation (cured product) The laminate on which the cured product of the active energy ray-curable composition was formed was cut into a width of 10 mm and tested with a Tensilon tensile tester (“MX2-500N” manufactured by Imada Co., Ltd.). using a temperature of 140°C
, tensile speed of 40 mm/min, and distance between chucks of 40 mm, and the elongation at break (elongation until cracks are visually observed) was measured to evaluate the elongation rate.
The elongation rate was calculated by dividing the length of the cured product when cracks occurred by the length before the tensile test.

(5) Measurement of transmittance at 360 nm A laminate formed of a cured product of an active energy ray-curable composition is measured using a spectrophotometer (Ratio beam spectrophotometer U-1900 manufactured by Hitachi High-Technologies Corporation). Mode: wavelength scan, wavelength: 300 to 600 nm, speed: 400, cell length: 10 mm, and the transmittance at a wavelength of 360 nm was evaluated.

(6) Adhesion evaluation method 23 ° C., 50% on the cured product side of the laminate in which the cured product of the active energy ray-curable composition was formed
18 mm wide tape (Nichiban Co., Ltd. Cellotape (registered trademark) CT
-18) was adhered, and the peeled surface was observed after being rapidly peeled off at a peeling angle of 180 degrees. In addition, when there is no peeling, it can be judged that the adhesion to the substrate is good.

(7) Evaluation of tackiness An active energy ray-curable composition was applied to the corona-treated surface of an easily moldable polyester film (thickness: 100 µm) as a base material, and dried using a bar coater. It was applied so as to have a thickness of 5 μm, and dried by heating at 80° C. for 2 minutes. After that, the coating film surface was touched with a finger. It can be judged that the tackiness is good when no trace of a finger remains.

Compounds used in Examples and Comparative Examples are as follows.
・(Meth) acrylic resin (A)
A (meth)acrylic resin produced by the method shown below.
Propylene glycol monomethyl ether (178 parts by weight), glycidyl methacrylate (20 parts by weight), methyl methacrylate (79 parts by weight), ethyl acrylate (1.0 parts by weight), and 2,2′-azobis(2,4-dimethylvaleronitrile) (0.6 parts by mass) were added and reacted at 65° C. for 3 hours. After that, further 2,2′-azobis(2,4-dimethylvaleronitrile) (0.3
parts by mass) and allowed to react for 3 hours, then propylene glycol monomethyl ether (48
parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C.
Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) are added and reacted at 110° C. for 6 hours to obtain a radically polymerizable double bond amount (acryloyl group concentration (acryloyl Introduction amount of group)) 615 g/mol of (meth)acrylic resin (A) was obtained. The weight average molecular weight was 48,800. The hydroxyl value was 91 mgKOH/g.
・(Meth) acrylic resin (B-1)
A (meth)acrylic resin produced by the method shown below.
Propylene glycol monomethyl ether (178 parts by mass), glycidyl methacrylate (40 parts by mass), methyl methacrylate (59 parts by mass), ethyl acrylate (1.0 parts by mass), and 2,2′-azobis(2,4-dimethylvaleronitrile) (0.6 parts by mass) were added and reacted at 65° C. for 3 hours. After that, further 2,2′-azobis(2,4-dimethylvaleronitrile) (0.3
parts by mass) and allowed to react for 3 hours, then propylene glycol monomethyl ether (48
parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C.
Next, acrylic acid (21 parts by mass) and triphenylphosphine (1.6 parts by mass) are added and reacted at 110° C. for 6 hours to reduce the amount of double bonds (acryloyl group concentration (acryloyl group introduction Amount)) A (meth)acrylic polymer (B-1) with 365 g/mol of side chains was obtained. The weight average molecular weight was 40,000. The hydroxyl value was 154 mgKOH/g.
・(Meth) acrylic resin (B-2)
A (meth)acrylic resin produced by the method shown below.
Propylene glycol monomethyl ether (178 parts by weight), glycidyl methacrylate (66 parts by weight), methyl methacrylate (33 parts by weight), ethyl acrylate (1.0 parts by weight), and 2,2′-azobis(2,4-dimethylvaleronitrile) (1.0 part by mass) were added and reacted at 65° C. for 3 hours.
After that, 2,2′-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, then propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol ( 0.5 parts by mass) was added and heated to 100°C.
Next, acrylic acid (34 parts by mass) and triphenylphosphine (1.6 parts by mass) are added and reacted at 110° C. for 6 hours to reduce the amount of double bonds (acryloyl group concentration (acryloyl group introduction Amount)) 266 g/mol of acrylic polymer (B-2) having radically polymerizable double bonds in side chains was obtained. The weight average molecular weight (Mw) was 31,800. The hydroxyl value was 211 mgKOH/g.
・(Meth) acrylic resin (B-3)
Propylene glycol monomethyl ether (157 parts by weight), glycidyl methacrylate (98 parts by weight), methyl methacrylate (1.0 parts by weight), ethyl acrylate (1.0 parts by weight) were placed in a flask equipped with a thermometer, stirrer and reflux condenser. ), mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2′-azobis(2,4-dimethylvaleronitrile) (1.0 parts by mass), γ-trimethoxysilylpropanethiol (Shin-Etsu Chemical Co., Ltd. 1.9 parts by mass of KBM-803 manufactured by Co., Ltd. was added and reacted at 65° C. for 3 hours.
After that, 2,2′-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, then propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol ( 0.45 parts by mass) was added and heated to 100°C.
Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) are added and reacted at 110° C. for 6 hours to obtain an unsaturated double bond amount (acryloyl equivalent (acryloyl group Amount introduced)) 216 g/mol of acrylic resin (B-3) having a radically polymerizable double bond in the side chain was obtained. The weight average molecular weight (Mw) was 17,700. The hydroxyl value was 259 mgKOH/g.
・(Meth) acrylic resin (C)
A methyl methacrylate polymer having no radically polymerizable double bond and hydroxyl group (weight average molecular weight 8000).
・(Meth)acrylate: D
Dipentaerythritol hexaacrylate (hexafunctional) (Kayarad (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.)
・Leveling agent: E
A silicone-based leveling agent having a radically polymerizable functional group (BYK-UV
3500)
・Ultraviolet absorber: F
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-
4,6-bis(4-phenylphenyl)-1,3,5-triazine (manufactured by BASF Ti
nuvin 479)
・ Light stabilizer: G
bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(
1,1, dimethylethyl)-4-hydroxyphenyl]methyl] (BASF Tin
uvin 144)
・Photopolymerization initiator: H
1-hydroxycyclohexyl phenyl ketone (OMNIRAD 184 manufactured by IGM Resins B.V.)

[Example 1]
A coating solution (active energy ray-curable composition) shown in Table 1 below was dried using a bar coater on the corona-treated surface of an easy-to-form polyester film (thickness: 100 µm) corona-treated as a substrate. It was applied to a thickness of 5 μm and dried by heating at 80° C. for 2 minutes. After that, in an air atmosphere with a high-pressure mercury lamp, the integrated light amount is 300 mJ/cm ² and the illuminance is 200 mW.
/ cm ² (high output UV device manufactured by Eye Graphics Co., Ltd. (model: US5-X1802)
-X1202) UV conveyor) was irradiated with ultraviolet rays to form a cured product (cured film) to obtain a laminate.

The obtained laminate had good abrasion resistance, chemical resistance, elongation and adhesion. The properties of this laminate are shown in Table 2 below.

[Examples 2 to 8]
A laminate having a cured film was obtained in the same manner as in Example 1, except that the coating composition of Example 1 was changed to that shown in Table 1. The obtained laminate has abrasion resistance, chemical resistance,
All of extensibility, adhesion and tackiness were good. The properties of the obtained laminate are shown in Table 2 below.

[Comparative Examples 1 to 7]
A laminate having a cured film was obtained in the same manner as in Example 1, except that the coating composition of Example 1 was changed to that shown in Table 1. As shown in Table 2 below, the obtained laminate had poor properties such as abrasion resistance and elongation. Since Comparative Example 1 does not have a radically polymerizable double bond or a hydroxyl group, it is inferior in abrasion resistance and substrate adhesion. Comparative Examples 2 and 3 used a polyfunctional (meth)acrylate instead of resin B, and therefore had poor tackiness.
Since Comparative Examples 4 and 5 did not contain resin B, their chemical resistance was insufficient. Furthermore, Comparative Example 4
Compared to Comparative Example 5, since it did not contain a silicone-based leveling agent having a radically polymerizable functional group, the scratch resistance was lowered. Since Comparative Examples 6 and 7 did not contain resin A, they were inferior in extensibility.

For the coating agents in Table 1, the coating liquid was adjusted with methyl ethyl ketone so that the non-volatile component content was 25%. The unit of each numerical value in the table is parts by mass.

Claims (10)

An active energy ray-curable composition containing resin A and resin B, wherein resin A has a radically polymerizable double bond equivalent of 501 to 10000 g/mol, and resin B has a radically polymerizable double bond equivalent of 200 to 500 g. / mol active energy ray-curable composition. 2. The active energy ray-curable composition according to claim 1, wherein the resin A has a hydroxyl value of 5 to 115 mgKOH/g. 3. The active energy ray-curable composition according to claim 1, wherein the resin B has a hydroxyl value of 116 to 270 mgKOH/g. The radically polymerizable double bond equivalent of the nonvolatile component of the active energy ray-curable composition is 30
The active energy ray-curable composition according to any one of claims 1 to 3, which is 0 to 1000 g/mol. The active energy ray-curable composition according to any one of claims 1 to 4, which contains a leveling agent. The active energy ray-curable composition according to any one of claims 1 to 5, which contains an ultraviolet absorber. A cured product of the active energy ray-curable composition according to any one of claims 1 to 6. The cured product according to claim 7, which has an elongation of 15% or more in a tensile test at 140°C. A laminate having the cured product according to claim 7 or 8 on a substrate. 10. The laminate according to claim 9, which has a transmittance of 80% or less at a wavelength of 360 nm.