JP7438801B2 - Active energy ray-curable resin composition and decorative sheet - Google Patents

Description

The present invention relates to active energy ray-curable resin compositions. More specifically, the present invention relates to an active energy ray-curable resin composition and a decorative sheet having a coating film formed using the same.

Traditionally, wood, Base material made of wood-based materials such as plywood, laminated wood, particle board, and hardboard; Base material made of resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or A base material made of a metal material such as iron or aluminum is used, and a decorative sheet is laminated onto the surface of the base material for decoration. The surface of the decorative sheet (the surface that is normally visible when the decorative sheet is used to decorate an adherend) is coated with a curable resin paint to provide functions such as surface hardness and scratch resistance. It is often done to form a cured coating film. As a curable resin coating, an active energy ray-curable resin composition is often used because it has excellent surface hardness and scratch resistance, takes a short time to cure, and has high productivity.

In recent years, more and more emphasis has been placed on design as a point of product differentiation. Therefore, it is possible to apply an uneven pattern to the surface of the decorative sheet by pressing it with an embossing roll, or to give it a three-dimensional shape by carving decorative grooves on the surface of the adherend to which the decorative sheet is attached. It is being done. However, in the cured coating film formed using the active energy ray-curable resin composition, defects such as whitening and cracking occur when pressed with an embossing roll, and the surface of the adherend to which the decorative sheet is attached When a three-dimensional shape is imparted to the decorative sheet, there is a problem in that defects such as whitening and cracking occur when the decorative sheet is bonded to an adherend.

JP2019-026832A

An object of the present invention is to provide an active energy ray-curable resin composition that can form a cured coating film that does not cause defects such as whitening or cracking even when an uneven pattern is applied by pressing with an embossing roll. It is in. A further object of the present invention is to form a cured coating film that has excellent surface hardness and scratch resistance, and does not cause defects such as whitening or cracking even when an uneven pattern is applied by pressing with an embossing roll. An object of the present invention is to provide an active energy ray-curable resin composition. Another further object of the present invention is to form a cured coating film that does not cause defective phenomena such as whitening and cracking even when a three-dimensional shape is imparted to the surface of the adherend to which the decorative sheet is attached. An object of the present invention is to provide an active energy ray-curable resin composition that can be used as an active energy ray-curable resin composition. Still another object of the present invention is to have a matte design, excellent stain resistance, surface hardness, and scratch resistance, and to prevent whitening or cracking even when an uneven pattern is applied by pressing with an embossing roll. An object of the present invention is to provide an active energy ray-curable resin composition that can form a cured coating film that does not cause defects.

As a result of extensive research, the inventors of the present invention have discovered that the above-mentioned problems can be achieved with a specific active energy ray-curable resin composition.

That is, aspects of the present invention are as follows.
[1].
(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass;
Component (A) active energy ray-curable resin contains (A1) epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine modified polyfunctional (meth)acrylate 5 to 45% by mass; and
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives;
An active energy ray-curable resin composition, wherein the sum of the blending ratios of the component (A1), the component (A2), and the component (A3) is 100% by mass.
[2].
(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass;
Component (A) active energy ray-curable resin contains (A1) epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine-modified polyfunctional (meth)acrylate 5 to 45% by mass;
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives; and
(A4) 1 to 20% by mass of an acrylamide compound having one or more hydroxyl groups in one molecule;
An active energy ray-curable resin composition, wherein the sum of the blending ratios of the component (A1), the component (A2), the component (A3), and the component (A4) is 100% by mass.
[3].
The active energy ray-curable resin composition according to item [2], wherein the acrylamide compound having one or more hydroxyl groups in one molecule of component (A4) contains hydroxyalkyl (meth)acrylamide.
[4].
The active energy ray-curable resin according to any one of claims 1 to 3, wherein the component (A1) epoxy-modified polyfunctional (meth)acrylate contains an addition reaction product of glycerin diglycidyl ether and (meth)acrylic acid. Composition.
[5].
The active energy according to any one of items [1] to [4], further comprising (D) resin particles in an amount of 5 to 200 parts by mass based on 100 parts by mass of the active energy ray-curable resin (A). Line curable resin composition.
[6].
Further, (D) resin particles are contained in an amount of 5 to 200 parts by mass based on 100 parts by mass of the active energy ray-curable resin (A), wherein the hydroxyl value of the component (D) resin particles is 1 to 100 mgKOH/ The active energy ray-curable resin composition according to any one of items [1] to [5], which is g.
[7].
A coating film formed using the active energy ray-curable resin composition according to any one of [1] to [6].
[8].
A decorative sheet having a coating film formed using the active energy ray-curable resin composition according to any one of [1] to [6].

The active energy ray-curable resin composition of the present invention can form a cured coating film that does not cause defects such as whitening and cracking even when an uneven pattern is applied by pressing with an embossing roll. In one embodiment, the active energy ray-curable resin composition of the present invention has excellent surface hardness and scratch resistance, and even when an uneven pattern is applied by pressing with an embossing roll, defects such as whitening and cracking occur. A cured coating film that does not occur can be formed. In one of the other embodiments, the active energy ray-curable resin composition of the present invention does not cause whitening, cracking, etc. even when a three-dimensional shape is imparted to the surface of the adherend to which the decorative sheet is attached. It is possible to form a cured coating film that does not cause defects. In yet another embodiment, the active energy ray-curable resin composition of the present invention has a matte design, has excellent stain resistance, surface hardness, and scratch resistance, and can be pressed with an embossing roll. This makes it possible to form a cured coating film that does not suffer from defects such as whitening or cracking even when an uneven pattern is applied. Therefore, the active energy ray-curable resin composition of the present invention can be suitably used for decorative sheets for decorating and decorating articles.

In this specification, the term "resin" is used to include resin mixtures containing two or more types of resins and resin compositions containing components other than resins. In this specification, the term "film" is used interchangeably or interchangeably with "sheet". In this specification, the terms "film" and "sheet" are used to refer to something that can be industrially wound into a roll. The term "plate" is used for anything that cannot be rolled up industrially. In addition, in this specification, sequentially laminating a certain layer and another layer means directly laminating those layers, and interposing one or more other layers such as an anchor coat between those layers. This includes both stacking and laminating.

As used herein, the term "greater than or equal to" in relation to a numerical range is used to mean a certain numerical value or greater than a certain numerical value. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" a numerical range is used to mean a certain value or less than a certain value. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "~" relating to a numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or a certain other numerical value. Here, the other numerical value is assumed to be larger than the certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%. Further, it is assumed that the upper and lower limits of the numerical range can be arbitrarily combined, and embodiments can be read in which the upper and lower limits of the numerical range are arbitrarily combined. For example, regarding the numerical range of a certain characteristic, "It is usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less." or "It is usually 10 to 40%, preferably 20% or less." 30%,” it can be read that the numerical range of the certain characteristic is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment. do.

Except in the examples or unless otherwise specified, all numerical values used in this specification and claims are to be understood as modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of the significant digits and by applying conventional rounding techniques.

1. Active energy ray curable resin composition:
The active energy ray curable resin composition of the present invention comprises (A) an active energy ray curable resin; (B) a compound having two or more isocyanate groups in one molecule; and (C) a photopolymerization initiator; including. In one embodiment, the active energy ray-curable resin composition of the present invention further includes (D) resin particles. Each component will be explained below.

(A) Active energy ray curable resin:
The above-mentioned component (A) active energy ray-curable resin functions to form a coating film by polymerizing and curing with active energy rays such as ultraviolet rays and electron beams.

In one embodiment, the component (A) active energy ray-curable resin includes (A1) epoxy-modified polyfunctional (meth)acrylate; (A2) alkyl alcohol amine-modified polyfunctional (meth)acrylate; and (A3) ) 3-phenoxybenzyl (meth)acrylate, and one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate derivatives;

In one of the other embodiments, the component (A) active energy ray-curable resin includes (A1) epoxy-modified polyfunctional (meth)acrylate; (A2) alkyl alcohol amine-modified polyfunctional (meth)acrylate; (A3) ) 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives; and (A4) an acrylamide compound having one or more hydroxyl groups in one molecule; including.

As used herein, (meth)acrylate means acrylate or methacrylate. (Meth)acrylic acid means acrylic acid or methacrylic acid. (Meth)acryloyl group means acryloyl group or methacryloyl group.

(A1) Epoxy-modified polyfunctional (meth)acrylate:
The above component (A) active energy ray-curable resin of the present invention contains (A1) epoxy-modified polyfunctional (meth)acrylate. The above component (A1) epoxy-modified polyfunctional (meth)acrylate is a (meth)acrylate synthesized by an addition reaction between a compound having an epoxy group and (meth)acrylic acid, and has two or more polyfunctional (meth)acrylates in one molecule. It is a compound having a (meth)acryloyl group.

Since the component (A1) has two or more (meth)acryloyl groups in one molecule, it functions to be cured by active energy rays to form a coating film. The above component (A1) has a hydroxyl group produced by an addition reaction between the epoxy group of a compound having an epoxy group and (meth)acrylic acid, and the above component (B) has two or more isocyanate groups in one molecule. It reacts with a compound having It works to prevent defects such as whitening and cracking from occurring even when a three-dimensional shape is given to the surface to which the decorative sheet is attached to the body.

Examples of the above component (A1) include addition reaction products of compounds having two or more glycidyl ether groups in one molecule, such as alkyl diglycidyl ethers and alkyl triglycidyl ethers, and (meth)acrylic acid. I can do it.

Examples of the alkyl diglycidyl ether include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Hydrogenated products of glycidyl ether, neopentyl glycol diglycidyl ether, 1-4 butanediol diglycidyl ether, and 1-6 hexanediol diglycidyl ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether etc. can be given.

Examples of the alkyl triglycidyl ether include glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.

In one typical embodiment, the addition reaction product of the alkyl diglycidyl ether and (meth)acrylic acid may be a compound represented by the following general formula (1).

In formula (1), R ₁ represents hydrogen or a methyl group. R ₂ represents hydrogen or a methyl group. R ₃ is a hydrocarbon group having 1 to 100 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The hydrocarbon group R ₃ may include an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. The hydrocarbon group R ₃ may be linear or branched. Further, the hydrocarbon group R ₃ may preferably contain a hydroxyl group.

Among these, the above component (A1) is preferably an addition reaction product of alkyl diglycidyl ether and (meth)acrylic acid from the viewpoint of curability of the coating film, and an addition reaction product of glycerin diglycidyl ether and (meth)acrylic acid. An addition reaction product with is more preferred.

The number of (meth)acryloyl groups that the component (A1) has may be preferably two in one molecule from the viewpoint of the curability of the coating film and the extensibility of the coating film.

As the component (A1), one type or a mixture of two or more of these can be used.

(A2) Alkyl alcohol amine modified polyfunctional (meth)acrylate:
The above component (A) active energy ray-curable resin of the present invention contains (A2) alkyl alcohol amine-modified polyfunctional (meth)acrylate. Since the component (A2) has two or more (meth)acryloyl groups in one molecule, it functions to be cured by active energy rays to form a coating film. The above component (A2) has a hydroxyl group, and reacts with the above component (B) a compound having two or more isocyanate groups in one molecule to form a urethane bond, improving the elongation and crack resistance of the coating film. , and the bending resistance is improved, and even if an uneven pattern is applied by pressing with an embossing roll, or a three-dimensional shape is imparted to the decorative sheet lamination surface of the adherend, It works to prevent defects such as whitening and cracking from occurring. In addition, the component (A2) functions to suppress oxygen damage in the curing reaction caused by active energy ray irradiation.

Although not intending to be bound by theory, the component (A2) has an amine structure, and the radicals generated by abstracting the hydrogen of the methylene group adjacent to the nitrogen atom in the amine structure are oxygen radicals. It is thought that this method traps oxygen and suppresses oxygen damage.

The component (A2) is a compound represented by the following general formula (2).

In formula (2), R ₁ is a hydrocarbon group having 1 to 200 carbon atoms, preferably 3 to 100 carbon atoms, more preferably 12 to 60 carbon atoms, and has one or more (meth)acryloyl groups. The hydrocarbon group R ₁ may include an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. The hydrocarbon group R ₁ may be linear or branched. R ₂ is a hydrocarbon group having 1 to 200 carbon atoms, preferably 3 to 100 carbon atoms, more preferably 12 to 60 carbon atoms, and has one or more (meth)acryloyl groups. The hydrocarbon group R ₂ may include an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. The hydrocarbon group R ₂ may be linear or branched. The hydrocarbon group R ₁ and the hydrocarbon group R ₂ may be the same or different. R ₃ represents hydrogen or a methyl group. R ₄ represents hydrogen or a methyl group. R ₅ contains an aromatic ring, aliphatic cyclic group, ether group, or ester group having 60 or less carbon atoms, preferably 20 or less, more preferably 12 or less, even more preferably 6 or less, and most preferably 1 to 3 carbon atoms. It is a good hydrocarbon group.

The above component (A2) can be synthesized by reacting an alkyl alcohol amine and a polyfunctional (meth)acrylate. This reaction is fully active at room temperature and usually does not require heating or the addition of a catalyst. Further, from the viewpoint of keeping the viscosity of the reaction liquid within an appropriate range and preventing gelation, it is preferable to add a solvent to lower the apparent concentration.

The alkyl alcohol amine is a compound having one or more amino groups and one or more alcoholic hydroxyl groups in one molecule. In one typical embodiment, the alkyl alcohol amine may be a compound having one amino group and one alcoholic hydroxyl group in one molecule. In one preferred embodiment, the alkyl alcohol amine may be a compound having one amino group and one primary alcoholic hydroxyl group in one molecule. Preferred examples of the alkyl alcohol amines include compounds represented by the following general formula (2-1).

_NH2- ( _CH2 )n-OH (2-1)

In formula (2-1), n is usually a natural number of 1 to 12, preferably 1 to 6, more preferably 1 to 3, and even more preferably 2.

Examples of the compound represented by the above general formula (2-1) include methanolamine, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, and 6-amino-1-hexanol. etc. can be given.

As the alkyl alcohol amine, one type or a mixture of two or more types of these can be used.

The above polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyl groups in one molecule. Examples of the polyfunctional (meth)acrylate include diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. 1 such as glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane. Compounds with two (meth)acryloyl groups in the molecule; three in one molecule, such as glycerin propoxy tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolethane tri(meth)acrylate. Compounds with (meth)acryloyl groups; Compounds with 4 (meth)acryloyl groups in one molecule such as pentaerythritol tetra(meth)acrylate; 6 (meth)acryloyl groups in one molecule such as dipentaerythritol hexa(meth)acrylate Compounds having (meth)acryloyl groups of be able to. As the polyfunctional (meth)acrylate, one type or a mixture of two or more of these can be used.

As the component (A2), one type or a mixture of two or more of these can be used.

(A3) 3-phenoxybenzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate derivative:
The above-mentioned component (A) active energy ray-curable resin of the present invention contains one or more selected from the group consisting of (A3) 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives. . The above component (A3) improves the hardenability, elongation, crack resistance, and bending resistance of the coating film, and even when an uneven pattern is applied by pressing with an embossing roll, or as a decorative sheet for an adherend. It works to prevent defects such as whitening and cracking from occurring even when a three-dimensional shape is given to the bonding surface.

The above 3-phenoxybenzyl (meth)acrylate is a compound represented by the following general formula (3-1).

In formula (3-1), R ₁ represents hydrogen or a methyl group.

The 3-phenoxybenzyl (meth)acrylate derivative has a structure in which 1, 2, 3, or 4 hydrogen atoms of the aromatic ring of the benzyl group of the 3-phenoxybenzyl (meth)acrylate are substituted, and/or, It is a compound having a structure in which 1, 2, 3, 4, or 5 hydrogen atoms of the aromatic ring of the phenoxy group of the above-mentioned 3-phenoxybenzyl (meth)acrylate are substituted. The above 3-phenoxybenzyl (meth)acrylate derivative is typically a compound represented by the following general formula (3-2).

In formula (3-2), R ₁ represents hydrogen or a methyl group. R ₂ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The hydrocarbon group R ₂ may be linear or branched. The hydrocarbon group R ₂ may include an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. s is an integer from 1 to 4, preferably 1. When s is an integer of 2 to 4, R ₂ may be the same or different. R ₃ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The hydrocarbon group R ₃ may be linear or branched. The hydrocarbon group R ₃ may include an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. t is an integer from 1 to 5, preferably 1 or 2. When t is an integer of 2 to 5, R ₃ may be the same or different. R ₂ and R ₃ may be the same or different.

Among these, 3-phenoxybenzyl (meth)acrylate is preferred as the component (A3), and 3-phenoxybenzyl acrylate is more preferred.

As the component (A3), one type or a mixture of two or more of these can be used.

Although not intended to be bound by theory, the reason why the coating film formed using the active energy ray-curable resin composition of the present invention exhibits scratch recovery properties is considered as follows. One or more selected from the group consisting of component (A3) 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives have good properties despite being monofunctional (meth)acrylates. It has curability and can form a good cured coating film with the component (A1) epoxy-modified polyfunctional (meth)acrylate and the component (A2) alkyl alcohol amine-modified polyfunctional (meth)acrylate. On the other hand, since the component (A3) is a monofunctional (meth)acrylate, it reduces the crosslinking density of the cured coating film. In other words, a highly motile portion is introduced into the cured coating film. As a result, abrasion recovery properties are developed.

Here, the scratch recovery property means the property that scratches caused by applying external pressure to the surface of a coating film are restored without remaining after the external pressure is removed.

(A4) (meth)acrylamide compound having one or more hydroxyl groups in one molecule:
The active energy ray-curable resin component (A) of the present invention preferably further contains a (meth)acrylamide compound having one or more hydroxyl groups in one molecule. The above component (A4) has a hydroxyl group and reacts with the above component (B) a compound having two or more isocyanate groups in one molecule to form a urethane bond, improving the elongation and crack resistance of the coating film. , and the bending resistance is improved, and even if an uneven pattern is applied by pressing with an embossing roll, or a three-dimensional shape is imparted to the decorative sheet lamination surface of the adherend, It works to prevent defects such as whitening and cracking from occurring. In addition, the above component (A4) functions to improve the scratch resistance of the coating film. Furthermore, since the component (A4) has a very high reactivity with the component (B), the component (B) may remain unreacted and bleed out onto the surface of the cured coating. For example, it works to suppress blocking of film rolls (films wound into rolls).

Examples of the component (A4) include hydroxyalkyl (meth)acrylamides such as hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, and hydroxybutyl (meth)acrylamide.

In one typical embodiment, the component (A4) may be a compound represented by the following general formula (4).

In formula (4), R ₁ represents an aliphatic alkyl chain that may have an alkyl branch, a cyclic hydrocarbon group, or an ether group. R ₁ may typically be "(CH ₂ )m". Here, m is usually a natural number of 1 or more, preferably a natural number of 2 to 6, more preferably 2 to 4. R ₂ represents hydrogen or a methyl group. The number of hydroxyl groups that the component (A4) has may be preferably one. The hydroxyl group contained in the component (A4) may preferably be a primary hydroxyl group.

Among these, as the above component (A4), hydroxyalkyl (meth)acrylamide is preferable because it has less skin irritation and has excellent active energy ray curability and reaction rate with isocyanate (high reaction rate). Hydroxyethyl (meth)acrylamide is more preferred.

As the component (A4), one type or a mixture of two or more of these can be used.

The blending ratio of each component in an embodiment in which the component (A) includes the component (A1), the component (A2), and the component (A3) will be described. Here, the sum of the blending ratios of the component (A1), the component (A2), and the component (A3) is 100% by mass. The blending ratio of the component (A1) is appropriately determined from the viewpoint of reliably obtaining the effect of using the component (A1) and the extensibility of the coating film. The blending ratio of the component (A1) is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A1). It may be at least 35% by weight, most preferably at least 35% by weight. On the other hand, from the viewpoint of the elongation of the coating film, the content may be generally 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

The blending ratio of the component (A2) is determined as appropriate from the viewpoint of reliably obtaining the effect of using the component (A2) and from the viewpoint of stain resistance. The blending ratio of the component (A2) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A2). It may be % by mass or more. On the other hand, from the viewpoint of stain resistance, the content may be usually 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

The blending ratio of the component (A3) is appropriately determined from the viewpoint of reliably obtaining the effect of using the component (A3) and maintaining the crosslinking density and, ultimately, the surface hardness of the coating film within an appropriate range. The blending ratio of the component (A3) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A3). It may be % by mass or more. On the other hand, from the viewpoint of surface hardness, the content may be generally 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

In an embodiment in which the component (A) includes the component (A1), the component (A2), and the component (A3), the component (A) includes the component (A1), the component (A3), and the component (A1). It may contain active energy ray-curable resins other than (A2) and the above-mentioned component (A3)). In this case, the sum of the amounts of component (A1), component (A2), and component (A3) in component (A) is 100% by mass of the total amount of each component in component (A). The amount may be usually 80% by mass or more, preferably 85% by mass or more, and more preferably 90 to 100% by mass.

Next, the blending ratio of each component in an embodiment in which the component (A) includes the component (A1), the component (A2), the component (A3), and the component (A4) will be described. Here, the sum of the blending ratios of the component (A1), the component (A2), the component (A3), and the component (A4) is 100% by mass. The blending ratio of the component (A1) is appropriately determined from the viewpoint of reliably obtaining the effect of using the component (A1) and the extensibility of the coating film. The blending ratio of the component (A1) is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A1). It may be at least 35% by weight, most preferably at least 35% by weight. On the other hand, from the viewpoint of the elongation of the coating film, the content may be generally 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

The blending ratio of the component (A2) is determined as appropriate from the viewpoint of reliably obtaining the effect of using the component (A2) and from the viewpoint of stain resistance. The blending ratio of the component (A2) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A2). It may be % by mass or more. On the other hand, from the viewpoint of stain resistance, the content may be usually 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

The blending ratio of the component (A3) is appropriately determined from the viewpoint of reliably obtaining the effect of using the component (A3) and maintaining the crosslinking density and, ultimately, the surface hardness of the coating film within an appropriate range. The blending ratio of the component (A3) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A3). It may be % by mass or more. On the other hand, from the viewpoint of surface hardness, the content may be generally 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

The blending ratio of the component (A4) is appropriately determined from the viewpoint of reliably obtaining the effect of using the component (A4) and maintaining the crosslinking density and the surface hardness of the coating film within an appropriate range. The blending ratio of the component (A4) is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (A4). It may be % by mass or more. On the other hand, from the viewpoint of surface hardness, the content may be generally 20% by mass or less, preferably 16% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.

In an embodiment in which the component (A) includes the component (A1), the component (A2), the component (A3), and the component (A4), the component (A) includes these components (the component (A1), the above component (A2), the above component (A3), and the above component (A4)) may contain active energy ray-curable resins. In this case, the sum of the amounts of component (A1), component (A2), component (A3), and component (A4) in component (A) is the amount of each component in component (A). The total amount is 100% by mass, and the amount may be usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 97% by mass or more, and most preferably 99 to 100% by mass.

(B) Compound having two or more isocyanate groups in one molecule:
The active energy ray-curable resin composition of the present invention contains a compound having two or more isocyanate groups (-N=C=O) in one molecule of the component (B). Since the component (B) has two or more isocyanate groups in one molecule, it reacts with the hydroxyl group of the active energy ray-curable resin (A) to form a urethane bond, and the component (A) It works to harden and form a coating film. In addition, since urethane bonds are formed at this time, the elongation, crack resistance, and bending resistance of the coating film are improved. It works to prevent defects such as whitening and cracking from occurring even when a three-dimensional shape is imparted to the surface to which the decorative sheet is attached.

Examples of the above component (B) include compounds having two isocyanate groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene bis-4-cyclohexyl isocyanate, and diphenylmethane diisocyanate; A trimethylolpropane adduct of a compound having two isocyanate groups in one molecule, such as a trimethylolpropane adduct, a trimethylolpropane adduct of hexamethylene diisocyanate, and a trimethylolpropane adduct of isophorone diisocyanate, comprising: 1 Compounds having three isocyanate groups in one molecule; compounds having two isocyanate groups in one molecule, such as isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and isocyanurate of isophorone diisocyanate. A compound that is an isocyanurate and has three isocyanate groups in one molecule; A biuret form of a compound that has two isocyanate groups in one molecule, such as a biuret form of hexamethylene diisocyanate; Compounds having three isocyanate groups; and urethane crosslinking agents such as these blocked isocyanates can be mentioned.

The above component (B) is used to improve the elongation, crack resistance, and bending resistance of the coating film, and even when applying an uneven pattern by pressing with an embossing roll or applying a decorative sheet to the adherend. In order to prevent defective phenomena such as whitening and cracking even when a three-dimensional shape is imparted to the joint surface, trimethylolpropane adducts of compounds having two isocyanate groups in one molecule are used. A compound having three isocyanate groups in one molecule, an isocyanurate of a compound having two isocyanate groups in one molecule, and a compound having three isocyanate groups in one molecule and a biuret form of a compound having two isocyanate groups in one molecule, which is a compound having three isocyanate groups in one molecule; preferred are trimethylolpropane adducts of hexamethylene diisocyanate, hexamethylene More preferred are the isocyanurate form of diisocyanate and the biuret form of hexamethylene diisocyanate.

Without intending to be bound by theory, these are structurally characterized by the presence of isocyanate groups at distant positions at the end of the hexamethylene chain, and as a result, the resulting hard coat has improved elongation and The crack resistance and bending resistance are improved, and even when an uneven pattern is applied by pressing with an embossing roll, or when a three-dimensional shape is imparted to the surface to which the decorative sheet is attached to the adherend. Even if there is, it is thought that defective phenomena such as whitening and cracking will not occur. Therefore, it is thought that those having the structural feature that isocyanate groups are present at mutually distant positions at the end of the alkyl chain can be similarly preferably used.

As the component (B), one type or a mixture of two or more of these can be used. Further, if desired, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as long as it does not contradict the purpose of the present invention.

The amount of component (B) to be blended may be appropriately determined from the viewpoint of reliably obtaining the effect of its use and from the viewpoint of curability with active energy rays. The blending amount of the component (B) is usually 1 part by mass or more, preferably 3 parts by mass or more, from the viewpoint of reliably obtaining the effect of using the component (B), per 100 parts by mass of the component (A). The amount may be more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. On the other hand, from the viewpoint of curability with active energy rays, the amount may be usually 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less.

(C) Photopolymerization initiator:
The active energy ray-curable resin composition of the present invention contains the above component (C) a photopolymerization initiator. The component (C) is a compound that generates active species such as radicals when irradiated with active energy rays. Component (C) generates active species such as radicals, thereby polymerizing and curing the active energy ray-curable resin (A) and curing the coating film.

Examples of the component (C) include benzophenone compounds, benzoin compounds, acetophenone compounds, alkylphenone compounds, anthraquinone compounds, thioxanthone compounds, acylphosphine oxide compounds, biimidazole compounds, titanocene compounds, Examples include oxime ester compounds, oxime phenylacetate compounds, hydroxyketone compounds, triazine compounds, and aminobenzoate compounds.

Examples of the benzophenone compounds include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Examples include 4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal.

Examples of the acetophenone compounds include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl -propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and the like.

Examples of the alkylphenone compounds include α-hydroxyalkylphenone and acetophenone dimethyl ketal.

Examples of the anthraquinone compounds include methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone.

Examples of the thioxanthone compounds include thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

Among these, as the above-mentioned component (C), benzophenone compounds, acetophenone compounds, and alkylphenone compounds are preferable; combinations of benzophenone compounds and acetophenone compounds or alkylphenone compounds are more preferable; benzophenone compounds It is more preferable to use the compound in combination with a hydroxyacetophenone compound (acetophenone compound having a hydroxyl group) or a hydroxyalkylphenone compound (alkylphenone compound having a hydroxyl group).

The amount of component (C) to be blended may be appropriately determined from the viewpoint of reliably curing the coating film and from the viewpoint of suppressing coloration of the coating film. From the viewpoint of reliably curing the coating film, the amount of the component (C) to be blended is usually 0.1 part by mass or more, preferably 0.5 part by mass or more, and more. Preferably, the amount may be 1 part by weight or more, more preferably 2 parts by weight or more, and most preferably 3 parts by weight or more. On the other hand, from the viewpoint of suppressing coloring of the coating film, the amount may be generally 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.

(D) Resin particles:
In one embodiment, the active energy ray-curable resin composition of the present invention may further include (D) resin particles. The above-mentioned component (D) functions to eliminate the luster of the coating film and impart a matte design.

Examples of the above component (D) include urethane resins, silicone resins, styrene resins, acrylic resins, fluorine resins, polycarbonate resins, ethylene resins, cellulose derivative resins, and amino compounds and formaldehyde. Examples include resin particles such as cured resin.

Among these, particles of urethane resin, silicone resin, acrylic resin, and fluorine resin are preferred from the viewpoint of low specific gravity, lubricity, dispersibility, and solvent resistance. From the viewpoint of preventing the hard coat from becoming cloudy, particles of urethane resin and acrylic resin are more preferable.

It is preferable to use resin particles having hydroxyl groups as the component (D). The scratch resistance of a coating film formed using the active energy ray-curable resin composition of the present invention can be improved.

Although there is no intention to be bound by theory, the reason why the scratch resistance of the coating film is improved by using resin particles having hydroxyl groups as the component (D) is that the hydroxyl groups in the component (D) and the component ( B) A compound having two or more isocyanate groups in one molecule reacts to form a urethane bond, and the component (B) reacts with the hydroxyl group of the active energy ray-curable resin (A) to form a urethane bond. By forming a bond, the component (D) chemically bonds with the component (A) via the component (B), and when the paint film is scratched, the component (D) falls off from the paint film. This is thought to be due to the fact that this is suppressed.

The hydroxyl value of component (D) is usually 1 mgKOH/g or more, preferably 3 gKOH/g or more, more preferably 4 mgKOH/g or more, still more preferably 5 mgKOH/g or more, from the viewpoint of reliably obtaining the above-mentioned effects. It's fine. On the other hand, from the viewpoint of water resistance, the amount may be generally 100 mgKOH/g or less, preferably 70 mgKOH/g or less, more preferably 50 mgKOH/g or less, still more preferably 40 mgKOH/g or less, and most preferably 30 mgKOH/g or less.

Here, the hydroxyl value of the component (D) is the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of the component (D), and is measured by potentiometric titration according to method A of JIS K1557-1:2007. . When a mixture of two or more types is used as the component (D), the hydroxyl value of the mixture may fall within the above-mentioned range. The same applies to other properties of the component (D).

The component (D) is preferably spherical from the viewpoint of efficiently imparting a matte design to the coating film.

The average particle diameter of the above component (D) is determined as appropriate from the viewpoint of efficiently imparting a matte design to the coating film, preventing the coating film from becoming cloudy, and imparting a good texture. All you have to do is decide. The average particle diameter of the component (D) is usually 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of efficiently imparting a matte design to the coating film. It's fine. On the other hand, from the viewpoint of preventing the coating film from becoming cloudy and from the viewpoint of imparting a good tactile sensation, the thickness may be generally 20 μm or less, preferably 15 μm or less, more preferably 12 μm or less, and still more preferably 10 μm or less. .

Here, the average particle diameter of the component (D) is determined by the laser diffraction/scattering method using a laser diffraction/scattering particle size analyzer. This is the particle size expressed as mass %. Examples of the laser diffraction/scattering particle size analyzer include the laser diffraction/scattering particle size analyzer "MT3200II (trade name)" manufactured by Nikkiso Co., Ltd.

As the component (D) resin particles, one type or a mixture of two or more types of these can be used.

The amount of component (D) to be blended may be appropriately determined depending on the desired level of matte design. The amount of component (D) to be blended is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably It may be 20 parts by weight or more, more preferably 25 parts by weight or more, and most preferably 30 parts by weight or more. On the other hand, from the viewpoint of crack resistance and bending resistance of the coating film, the amount may be generally 200 parts by mass or less, preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

The active energy ray-curable resin composition of the present invention may optionally contain other optional components other than the above-mentioned components (A) to (D), as long as it does not contradict the purpose of the present invention. Other optional ingredients mentioned above include, for example, antistatic agents, surfactants, leveling agents, thixotropic agents, anti-staining agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, and ultraviolet rays. Additives such as absorbers, heat stabilizers, inorganic particles, inorganic colorants, and organic colorants can be mentioned. The amount of the other optional components blended is usually 10 parts by mass or less, or about 0.1 to 10 parts by mass, based on 100 parts by mass of the component (A). As the above-mentioned other optional components, one or more of these can be used.

The active energy ray-curable resin composition of the present invention may contain a solvent, if desired, in order to dilute it to a concentration that is easy to coat. There are no particular restrictions on the above solvent as long as it does not react with the above components (A) to (D) and any other optional components or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, 2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the above-mentioned solvent, one kind or a mixture of two or more kinds thereof can be used.

The active energy ray-curable resin composition of the present invention can be obtained by mixing and stirring these components.

2. Decorative sheet:
The decorative sheet of the present invention has a coating film formed using the active energy ray-curable resin composition of the present invention. In one typical embodiment, the decorative sheet of the present invention has a coating film formed using the active energy ray-curable resin composition of the present invention on one side of a film base material. The coating film forms the surface of the decorative sheet (the surface that is normally visible when the decorative sheet is used to decorate an adherend).

Examples of the film base material include polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-propylene-styrene copolymer, styrene・Styrenic resins such as ethylene-ethylene-propylene-styrene copolymers and styrene-ethylene-butadiene-styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone can be mentioned. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes a laminated film in which two or more layers of one or more of these are laminated. Furthermore, these films may be transparent, opaque, have hiding properties, colored, or have a unique color. good.

When the film base material is one of the constituent layers of a decorative sheet, the thickness of the film base material is appropriately determined in consideration of the properties to be imparted to the decorative sheet and web handling properties. When the film base material is one of the constituent layers of a decorative sheet, the thickness of the film base material may be generally 20 μm or more, preferably 30 μm or more, from the viewpoint of web handling properties. From the viewpoint of design, the thickness may be more preferably 50 μm or more, and even more preferably 80 μm or more. On the other hand, from the viewpoint of workability when applying the decorative sheet to an article, the thickness may be generally 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less, and more preferably 250 μm or less.

When the coating film formed on the surface of the film base material is used by transferring it to another film base material, the thickness of the film base material is appropriately determined in consideration of web handling properties and economical efficiency. The thickness of the film base material is usually 20 μm or more, preferably 30 μm or more from the viewpoint of web handling when the coating film formed on the surface of the film base material is transferred to another film base material. It's good to be there. On the other hand, from the viewpoint of economy, the thickness may be generally 100 μm or less, preferably 75 μm or less.

In one typical embodiment, the film base material may be colored and have concealing properties for the purpose of decorating and decorating articles by pasting a decorative sheet thereon.

If desired, a printed layer may be provided on the front surface of the film base material in the actual use state in order to enhance the design. The printing layer is provided to provide a high degree of design, and can be formed by printing any pattern using any ink and any printing machine. Here, the actual use state refers to a state in which the decorative sheet is used to make up or decorate the surfaces of various articles. Further, the front surface in actual use refers to a surface that is normally visible in actual use.

Printing can be applied directly or via an anchor coat, either entirely or partially, on the front surface of the film base material in the actual use state. Patterns include metallic patterns such as hairlines, wood grain patterns, stone grain patterns that imitate the surface of rocks such as marble, fabric patterns that imitate cloth grain or cloth-like patterns, tiling patterns, brickwork patterns, parquet patterns, and patchwork. As the printing ink, a mixture of a binder, a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. as appropriate can be used. Examples of the binder include polyurethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides. It is possible to use resins such as resins, butyral-based resins, polystyrene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins, and resin compositions thereof. In addition, metals such as aluminum, tin, titanium, and indium, as well as oxides of these metals, are coated entirely or partially on the front surface of the film base material in actual use by a known method. It may also be vapor deposited. The formed thin film layer of metal or metal oxide provides a metallic design.

A transparent resin layer may be further formed on the surface of the printing layer. A deep design feeling can be imparted to the decorative sheet. The transparent resin layer can be formed by laminating transparent resin films or melt-extruding a transparent thermoplastic resin.

The coating film formed using the active energy ray-curable resin composition of the present invention, which the decorative sheet of the present invention has, is usually applied directly or directly onto the front surface of the film base material in the actual use state. Formed via anchor coat. In an embodiment in which the printing layer is formed on the front surface of the film base material in actual use, the printing layer is usually formed directly or via an anchor coat on the surface of the printing layer. Ru. In an embodiment in which the transparent resin layer is further formed on the surface of the printing layer, it is usually formed directly or via an anchor coat on the surface of the transparent resin layer.

The coating film formed using the active energy ray-curable resin composition of the present invention may be formed by directly coating on the surface of the constituent layers of the decorative sheet, or may be formed on the surface of the other film base material. It may be formed by forming the layer on top and then transferring it onto the surface of the constituent layers of the decorative sheet.

The method of forming a coating film using the active energy ray-curable resin composition of the present invention is not particularly limited, and any known web coating method can be used. Examples of the above methods include rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, roll brushing, spray coating, air knife coating, and die coating. Among these methods, from the viewpoint of forming a coating film with a stable film thickness, rod coating is preferable, and rod coating using a Mayer bar as the rod (hereinafter sometimes abbreviated as "Mayer bar method") is more preferable.

The coating amount (mass after curing) when forming a coating film using the active energy ray-curable resin composition of the present invention is appropriately determined in consideration of the properties and functions expected of the coating film. When forming a coating film using the active energy ray-curable resin composition of the present invention, the coating amount (mass after curing) is usually 0.5 g/m ² or more from the viewpoint of surface hardness and scratch resistance. , preferably 1 g/m ² or more, more preferably 2 g/m ² or more, even more preferably 3 g/m ² or more, most preferably 5 g/m ² or more. On the other hand, it is possible to improve the elongation, crack resistance, and bending resistance of the coating film, and even apply uneven patterns by pressing with an embossing roll, or create a three-dimensional shape on the decorative sheet laminating surface of the adherend. Even if it is applied, from the viewpoint of preventing defective phenomena such as whitening and cracking, it is usually 50 g/m ² or less, preferably 40 g/m ² or less, more preferably 30 g/m ² or less. , more preferably 20 g/m ² or less, most preferably 15 g/m ² or less.

FIG. 1 is a conceptual diagram of a cross section of one embodiment of the decorative sheet of the present invention. In order from the surface of the decorative sheet, a coating film 1 formed using the active energy ray-curable resin composition of the present invention containing resin particles as component (D), a transparent resin film layer 2, and printing. It has a layer 3 and a layer 4 of a colored resin film having concealing properties.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Measurement method (a) Tensile elongation:
In accordance with JIS K7127:1999, a test piece of type 2 (width 15 mm, total length 150 mm) was taken from the decorative sheet so that the machine direction and the tensile direction of the decorative sheet matched, and the distance between the gauge lines was measured. 50 mm, an initial distance between chucks of 100 mm, and a test speed of 10 mm/min. During the tensile test, the test piece was visually observed, and the elongation at the moment a crack occurred in the coating film of the test piece was defined as the tensile elongation of the decorative sheet. Technically, the value of the tensile elongation in test (a) above is considered to correspond to the tensile elongation of the coating film of the decorative sheet.

(b) Embossability:
After preheating the coated side of the decorative sheet to a temperature of 150°C using an infrared heater, the coated side of the decorative sheet was placed between the embossing roll and the receiving roll (temperature was not controlled). It was fed so that it would be on both sides and pressed to create an embossed pattern. Here, the above-mentioned embossing roll has a striped pattern (groove depth 50 μm, width 1 mm, pitch (groove-to-groove A spacer having a spacing of 2 mm was used. As the receiving roll, one having a silicone rubber surface was used. The embossed pattern on the coated surface of the decorative sheet was visually observed and evaluated based on the following criteria.
A: An uneven pattern was formed very well. There was a sense of edge at the corners of the unevenness of the formed unevenness pattern.
B: An uneven pattern was well formed.
C: The corners of the unevenness of the formed unevenness pattern had a rounded feel.
D1: The uneven pattern was not sufficiently formed.
D2: Whitening of the coating film was observed.
E: Cracks occurred in the coating film.

(c) Scratch resistance:
A Taber scratch tester (model number HA-201) manufactured by Tester Sangyo Co., Ltd. and a diamond needle with a curvature radius R of 25 mm at the tip of the needle were used as the scratching blade. The diamond needle was set in the needle fixing jig of the scratch tester, and a circular test piece with a radius of 6 cm taken from the decorative sheet was set in the test piece fixing jig of the scratch tester. At this time, so that the tip of the diamond needle escapes from the rotating test piece, the normal line to the test piece at the point where the tip of the diamond needle touches the test piece and the diamond needle form an angle of 22 degrees. , and a straight line connecting the point where the tip of the diamond needle touches the test piece and the center of rotation of the test piece is set so that the diamond needle makes a right angle. Next, the coated surface of the test piece was rubbed by rotating once under a predetermined load at a rotational speed of 1 rotation/60 seconds, and then visually observed to evaluate whether or not scratches were generated at the friction points. The predetermined load was changed at intervals of 0.1 N, and the maximum load at which no scratches were observed was determined as an index of scratch resistance.

(d) Scratch resistance (steel wool resistance):
A test piece measuring 150 mm in length and 50 mm in width, taken with the machine direction of the decorative sheet in the longitudinal direction of the test piece, was placed in a JIS L0849:2013 Gakushin type tester ( (friction tester type 2). Next, after attaching #0000 steel wool to the friction terminal of the Gakushin type testing machine, a 250 g load was placed on the coated surface of the test piece under the conditions that the friction terminal was moving at a speed of 300 mm/min and a moving distance of 30 mm. After rubbing back and forth 5 times, the friction points were visually observed. If no scratches were observed, the rubbing was repeated 5 times back and forth, and then visual observation of the friction areas was repeated, and evaluation was made based on the following criteria.
A: No scratches were observed even after 15 reciprocations.
B: No scratches were observed after 10 reciprocations, but scratches were visible after 15 reciprocations.
C: No scratches were observed after 5 reciprocations, but scratches were visible after 10 reciprocations.
D: The scratches were visible after 5 reciprocations.

(e) Three-dimensional formability:
(E-1) Tokunaga NC Co., Ltd.'s medium density fiberboard (hereinafter referred to as "MDF") "MDF processed product (product name)" (MDF with a smooth surface) is 300 mm long, 200 mm wide, and 18 mm thick. It was cut into shapes, curved (3 to 10R), and a decorative groove was carved on the top surface to obtain an adherend. A photograph of the obtained adherend is shown in FIG.
(E-2) An adhesive "630.2 (trade name)" manufactured by KLEIBERIT was spray applied to the entire surface of the obtained adherend.
(E-3) A pedestal (size: 290 mm long, 180 mm wide, 18 mm thick, smooth surface MDF ), and place the adherend on the pedestal so that the surface opposite to the top surface is on the pedestal side, so that the vertical direction of the pedestal and the vertical direction of the adherend are aligned. Place the cut decorative sheet (450 mm in the machine direction, lateral 350 mm in direction), so that the surface opposite to the coating surface is the adhesion surface, the longitudinal direction of the adherend matches the machine direction of the decorative sheet, and the The adherend was placed so that the intersection of the diagonal lines of the vertical and horizontal surfaces of the cut decorative sheet coincided with the intersection of the diagonal lines of the vertical and horizontal surfaces of the cut decorative sheet.
(E-4) After preheating the membrane of the membrane molding machine so that the surface temperature of the membrane is 80°C, the membrane is molded under the conditions of a temperature of 110°C, a pressing time of 60 seconds, and a pressure of 0.39 MPa, and the molded product is I got it.
(E-5) The appearance of the molded product obtained above was visually observed using the naked eye (corrected visual acuity 1.0) or a magnifying glass (magnification 25 times), and evaluated according to the following criteria.
A: The decorative sheet uniformly followed the three-dimensional shape of the adherend, and the color pattern was uniformly extended.
B: The decorative sheet extended to follow the three-dimensional shape of the adherend. However, in the areas where the coating was stretched to a large extent, there were minute cracks in the coating film that were not visible to the naked eye but were noticeable when viewed using a magnifying glass.
C: The decorative sheet extended to follow the three-dimensional shape of the adherend. However, the coating film had cracks that were visible to the naked eye in the areas where it was stretched to a large extent.
D: There were parts where the decorative sheet could not follow the three-dimensional shape of the adherend.

(f) Abrasion recovery properties:
Test piece after the above test (d) abrasion resistance (steel wool resistance) test (test piece with scratches observed at the friction point. For rank A, increase the number of reciprocations until scratches are observed at the friction point. ) was visually observed in the test, and then visually observed again one hour and one day later, and evaluated using the following criteria.
A: When visually observed after 1 hour, no scratches were observed.
B: When visually observed after 1 hour, scratches could be observed, but when visually observed after 1 day, no scratches were observed.
C: Scratches were also visible when visually observed one day later.

(g) 60 degree gloss value:
The 60 degree gloss value of the coating film surface was measured in accordance with JIS Z8741:1997 using a multi-angle gloss meter "GM-268" (trade name) manufactured by Konica Minolta, Inc.

(h) Stain resistance:
A piece of absorbent cotton with a length of 10 mm, a width of 10 mm, and a thickness of 2 mm was placed on the painted surface of the decorative sheet, and a red ink for fountain pens by Pilot Co., Ltd., "Pilot Ink Red (product name)" was applied until the absorbent cotton sufficiently contained the ink. Drop it onto the absorbent cotton (usually about 1 mL) and leave it for 24 hours at a room temperature of 25°C and a relative humidity of 50%, then remove the absorbent cotton and clean the contaminated area with Lion Co., Ltd.'s dishwashing detergent. Mama Lemon (product name)" was used, and 3M's dishwashing sponge "Scotch-Brite Antibacterial Urethane Sponge Scrubber, Leaf Type/3 Layer, No Abrasive Particles (product name)" was used to wash the dishes. Afterwards, the contaminated areas were visually observed and evaluated using the following criteria.
A: Contamination was almost completely removed.
B: A slight amount of contamination remained, and the contaminated location could be identified.
C: Contamination remained and the contaminated area was reddish.
D: Significant contamination remained, and the contaminated area remained red even after washing with water.

Raw materials used (A) active energy ray curable resin:
(A1) Epoxy-modified polyfunctional (meth)acrylate:
(A1-1) Kyoeisha Chemical Co., Ltd.'s acrylic acid adduct of glycerin diglycidyl ether "Epoxy Ester 80MFA (trade name)", the number of acryloyl groups is 2 and the number of hydroxyl groups is 3.
(A1-2) Nippon Kayaku Co., Ltd.'s acrylic acid adduct of hexamethylene diol diglycidyl ether "KAYARAD R-167 (trade name)", 2 acryloyl groups, 2 hydroxyl groups.

(A2) Alkyl alcohol amine modified polyfunctional (meth)acrylate:
(A2-1) Multifunctional (meth)acrylate (glycerin propoxytriacrylate) "OTA480 (trade name)" from Daicel Allnex Corporation and 2-aminoethanol were mixed into a glass in a ratio of 2 moles of the former to 1 mole of the latter. The mixture was charged into a manufactured reaction vessel made of aluminum and reacted for 72 hours at a temperature of 23° C. with stirring to obtain an alkyl alcohol amine-modified polyfunctional (meth)acrylate having four acryloyl groups in one molecule.
(A2-2) Multifunctional (meth)acrylate (tripropylene glycol diacrylate) "TPGDA (trade name)" from Daicel Allnex Corporation and 2-aminoethanol in a ratio of 2 moles of the former to 1 mole of the latter. The mixture was charged into a glass reaction vessel and reacted with stirring at a temperature of 23° C. for 72 hours to obtain an alkyl alcohol amine-modified polyfunctional (meth)acrylate having two acryloyl groups in one molecule.

(A3) One or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives:
(A3-1) 3-phenoxybenzyl acrylate (CAS number 409325-06-0) "Light acrylate POB-A (product name)" from Kyoeisha Chemical Co., Ltd.

(A4) Acrylamide compound having one or more hydroxyl groups in one molecule:
(A4-1) Hydroxyethyl acrylamide

(B) Compound having two or more isocyanate groups in one molecule:
(B-1) "RV2 (trade name)", a compound having two or more isocyanate groups in one molecule (isocyanurate of hexamethylene diisocyanate), manufactured by Light Chemical Industry Co., Ltd.

(C) Photopolymerization initiator:
(C-1) Acetophenone photoinitiator (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane from IGM Resins) -1-on) "Omnirad127 (product name)".
(C-2) Benzophenone from Wako Pure Chemical Industries, Ltd.

(D) Resin particles:
(D-1) Urethane resin particles "Art Pearl C-800TH (trade name)" manufactured by Negami Kogyo Co., Ltd., average particle diameter 8 μm, hydroxyl value 18 mgKOH/g.
(D-2) Sekisui Plastics Co., Ltd.'s crosslinked polybutyl methacrylate resin particles "Techpolymer BM30X-8 (trade name)", average particle diameter 8 μm, hydroxyl value 0.0 mgKOH/g.

Film base material:
(α-1) 120 μm thick polyvinyl chloride resin film “S23018Fc24458 (trade name)” manufactured by RIKEN TECHNOS Co., Ltd.

Example 1
(1) Preparation of active energy ray-curable resin composition:
40 parts by mass of the above component (A1-1), 25 parts by mass of the above component (A2-1), 30 parts by mass of the above component (A3-1), 5 parts by mass of the above component (A4-1), the above component (B-1) ) 18 parts by mass, 3 parts by mass of the above component (C-1), 3 parts by mass of the above component (C-2), 60 parts by mass of the above component (D-1), 1-methoxy-2-propanol (in the table: 100 parts by mass of 2-propanol (described as "PGM") and 100 parts by mass of 2-propanol (described as "IPA" in the table) were mixed and stirred to obtain an active energy ray-curable resin composition. Here, all components other than 1-methoxy-2-propanol and 2-propanol are values in terms of solid content.

(2) Formation of coating film:
On the hard coat formation surface of one side of the film base material (α-1), a 1 μm thick wood grain pattern printing layer is formed using an ink containing vinyl chloride/vinyl acetate copolymer as a medium, Furthermore, using a Mayer bar type coating device, using the active energy ray-curable resin composition obtained in (1) above, so that the coating amount (mass after curing) was 11.7 g/m ² , It was applied, dried, and cured by irradiation with active energy rays at a cumulative light intensity of 240 mJ/cm ² to form a cured coating film, thereby obtaining a decorative sheet.

(3) Evaluation of decorative sheet:
Table 1 shows the results of the above tests (a) to (h).

Examples 2-17
The same procedure as in Example 1 was conducted except that the formulation of the active energy ray-curable resin composition was changed as shown in Table 1 or 2. The results are shown in Table 1 or 2.

It has been found that the cured coating film formed using the active energy ray-curable resin composition of the present invention does not suffer from defects such as whitening or cracking even when an uneven pattern is applied by pressing with an embossing roll. The cured coating film formed using the preferred active energy ray-curable resin composition of the present invention will not cause whitening or cracking even if a three-dimensional shape is imparted to the decorative sheet laminating surface of the adherend. It was found that such defects did not occur. It also had excellent stain resistance, surface hardness, and scratch resistance. Furthermore, it has been found that it is possible to provide a matte design or a high gloss design as desired. Therefore, it was considered that the active energy ray-curable resin composition of the present invention can be suitably used for decorative sheets for decorating and decorating articles.

1 is a conceptual diagram of a cross section of one embodiment of a decorative sheet of the present invention. This is the adherend used for evaluation of three-dimensional molding.

1: Coating film formed using the active energy ray-curable resin composition of the present invention containing resin particles as component (D) 2: Transparent resin film layer 3: Printed layer 4: Colored Layer of resin film with hiding properties

Claims (10)

(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass; and
(D) Resin particles 5 to 200 parts by mass
Component (A) active energy ray-curable resin contains (A1) epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine modified polyfunctional (meth)acrylate 5 to 45% by mass; and
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives;
, where the sum of the blending proportions of the component (A1), the component (A2), and the component (A3) is 100% by mass,
Here, the above component (D) is an active energy ray-curable resin composition containing resin particles having a hydroxyl value of 1 to 100 mgKOH/g .
(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass; and
(D) Resin particles 5 to 200 parts by mass
Component (A) active energy ray-curable resin contains (A1) epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine-modified polyfunctional (meth)acrylate 5 to 45% by mass;
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives; and
(A4) 1 to 20% by mass of an acrylamide compound having one or more hydroxyl groups in one molecule;
, where the sum of the blending proportions of the component (A1), the component (A2), the component (A3), and the component (A4) is 100% by mass,
Here, the above component (D) is an active energy ray-curable resin composition containing resin particles having a hydroxyl value of 1 to 100 mgKOH/g .
(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass;
, where the above component (A) active energy ray-curable resin is
(A1) Epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine modified polyfunctional (meth)acrylate 5 to 45% by mass; and
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives;
, where the sum of the blending proportions of the component (A1), the component (A2), and the component (A3) is 100% by mass,
Here, the above component (A1) epoxy-modified polyfunctional (meth)acrylate includes a compound represented by the following general formula (1),
In formula (1), R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen or a methyl group, and R ₃ is a hydrocarbon group having 1 to 12 carbon atoms containing a hydroxyl group. thing.
(A) 100 parts by mass of active energy ray-curable resin;
(B) 1 to 50 parts by mass of a compound having two or more isocyanate groups in one molecule; and
(C) Photopolymerization initiator 0.1 to 20 parts by mass;
, where the above component (A) active energy ray-curable resin is
(A1) Epoxy-modified polyfunctional (meth)acrylate 10 to 60% by mass;
(A2) Alkyl alcohol amine-modified polyfunctional (meth)acrylate 5 to 45% by mass;
(A3) 5 to 45% by mass of one or more selected from the group consisting of 3-phenoxybenzyl (meth)acrylate and 3-phenoxybenzyl (meth)acrylate derivatives; and
(A4) 1 to 20% by mass of an acrylamide compound having one or more hydroxyl groups in one molecule;
, where the sum of the blending proportions of the component (A1), the component (A2), the component (A3), and the component (A4) is 100% by mass,
Here, the above component (A1) epoxy-modified polyfunctional (meth)acrylate contains a compound represented by the following general formula (1),
In formula (1), R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen or a methyl group, and R ₃ is a hydrocarbon group having 1 to 12 carbon atoms containing a hydroxyl group. thing.
The active energy ray-curable resin composition according to claim 3 , further comprising 5 to 200 parts by mass of (D) resin particles based on 100 parts by mass of the active energy ray-curable resin (A).
The active energy ray-curable resin composition according to claim 5, wherein the component (D) resin particles include resin particles having a hydroxyl value of 1 to 100 mgKOH/g.
The active energy ray-curable resin composition according to claim 2 or 4, wherein the acrylamide compound having one or more hydroxyl groups in one molecule of component (A4) contains hydroxyalkyl (meth)acrylamide.
The active energy ray-curable resin according to any one of claims 1 to 7, wherein the component (A1) epoxy-modified polyfunctional (meth)acrylate contains an addition reaction product of glycerin diglycidyl ether and (meth)acrylic acid. Composition.
A coating film formed using the active energy ray-curable resin composition according to any one of claims 1 to 8 .
A decorative sheet having a coating film formed using the active energy ray-curable resin composition according to any one of claims 1 to 8 .