JP7157060B2 - Stain-removable paint for forming coating film, and decorative sheet using the same - Google Patents

Description

The present invention relates to coatings. More particularly, the present invention relates to a coating capable of forming a coating film with excellent stain-removing properties (hereinafter sometimes referred to as "stain-removing coating film"), and a decorative sheet using the same.

Conventionally, home appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as decorative shelves, chests of drawers, cupboards, and desks; , Laminated wood, particle board, and base material formed from wood-based materials such as hardboard; bases formed from resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester material; or a base material made of a metallic material such as iron or aluminum, and a decorative sheet is attached to the surface of the base material to decorate it.

In recent years, attention has been focused on the stain removability of coating films as a point of product differentiation. A coating film with excellent stain removability is a coating formed using a coating containing a compound having at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphate group. Membranes have been proposed (see, for example, Patent Document 1). However, decorative sheets having stain-removing coating films formed by these techniques have insufficient bending resistance, and have the disadvantage of being difficult to apply to so-called 2D molding such as wrapping molding.

International publication WO2007/064003

An object of the present invention is to provide a paint capable of forming a paint film with excellent stain-removing properties, and a decorative sheet using the same.
A further object of the present invention is to provide a paint capable of forming a coating film having excellent stain removal properties and bending resistance and imparting a matte design, and a matte decorative sheet using the same. to do.
Another object of the present invention is to provide a paint capable of forming a coating film excellent in stain removal and scratch resistance and imparting a matte design, and a matte decorative sheet using the same. to provide.

As a result of intensive research, the inventors of the present invention have found that the above problems can be achieved with a specific paint.
[1].
(A) 100 parts by mass of polyfunctional (meth)acrylate; and
(B) 5 to 100 parts by mass of a compound having at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphate group;
Contains no inorganic particles,
Here, the (A) polyfunctional (meth)acrylate is derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the sum total of structural units derived from the polyol compound being 100% by mass. (A1) polyfunctional urethane (meth) acrylate containing 50% by mass or more of the structural unit, the total of the (A) polyfunctional (meth) acrylate is 100% by mass, in an amount of 10 to 90% by mass include,
paint.
[2].
The paint according to item [1], which further contains (C) 5 to 200 parts by mass of resin particles having an average particle diameter of 1 to 100 μm with respect to 100 parts by mass of the component (A) polyfunctional (meth)acrylate.
[3].
The paint according to item [1] or [2] above, wherein the component (A1) polyfunctional urethane (meth)acrylate has a mass average molecular weight of 3,000 to 50,000.
[4].
A decorative sheet comprising a coating film formed from the paint according to any one of [1] to [3] above.
[5].
A coating film formed from the coating material according to any one of [1] to [3] above, and a layer of a thermoplastic resin film in order from the side that is normally visible in actual use;
The water contact angle on the surface of the coating film is 15 degrees or less;
A decorative sheet having a mandrel test value of 10 mm or less.

A coating film formed from the coating material of the present invention is excellent in stain removability.
A coating film formed from the coating material of the present invention according to one aspect has excellent stain removability and bending resistance, and has a matte design. Therefore, the decorative sheet imparted with stain removability using the paint of the present invention according to this aspect has a matte design and can be applied to so-called 2D molding such as wrapping molding.
A coating film formed from the coating material of the present invention according to another aspect has excellent stain removability and scratch resistance, and has a matte design. Therefore, the decorative sheet imparted with stain removability using the paint of the present invention according to this aspect has a matte design and excellent scratch resistance.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional conceptual diagram which shows an example of the decorative sheet of this invention.

The term "film" is used herein interchangeably or interchangeably with "sheet." As used herein, the terms "film" and "sheet" are used for those that can be industrially wound into rolls. The term "plate" is used for those that cannot be industrially wound into rolls. The term "resin" is used as a term including resin mixtures containing two or more resins and resin compositions containing components other than resins. Further, in this specification, laminating a certain layer and another layer in order means directly laminating those layers, and interposing one or more layers such as an anchor coat between those layers. and lamination.
The term "greater than or equal to" regarding 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 "up to" relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol “~” relating to numerical ranges is used to mean a certain numerical value, greater than a certain numerical value and less than another numerical value, or some other numerical value. Here, another certain numerical value is assumed to be a larger numerical value than the certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%.
Other than in the examples or unless otherwise specified, all numerical values used in the specification and claims are to be understood as being modified by the term "about." Without trying to limit the application of the doctrine of equivalents to the claims, each numerical value should be interpreted in the light of significant digits and by applying conventional rounding techniques.

1. Paint The paint of the present invention has (A) a polyfunctional (meth)acrylate; and (B) at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Contains compounds. The coating material of one embodiment of the present invention includes (A) a polyfunctional (meth)acrylate; and (B) at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group. and (C) resin particles having an average particle size of 1 to 100 μm. The paint of the present invention does not contain inorganic particles.
The polyfunctional (meth)acrylate of component (A) includes a polyfunctional urethane (meth)acrylate containing structural units derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols. Usually, the polyfunctional (meth)acrylate of the component (A) is one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the sum total of structural units derived from the polyol compound being 100% by mass. (A1) polyfunctional urethane (meth)acrylate containing 50% by mass or more of structural units derived from

(A) Polyfunctional (meth)acrylate The polyfunctional (meth)acrylate of component (A) is a (meth)acrylate having two or more (meth)acryloyl groups in one molecule. Since the component (A) has two or more (meth)acryloyl groups in one molecule, it is polymerized and cured by heat and active energy rays such as ultraviolet rays and electron beams, and functions to form a coating film. .

Examples of the polyfunctional (meth)acrylate include diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2, 2′-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane and 2,2′-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane (meth)acryloyl group-containing bifunctional reaction (meth)acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate (Meth)acryloyl group-containing tetrafunctional reactive monomers such as; (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth)acryloyl group-containing octafunctional reactive monomers such as tripentaerythritol acrylate and polymers (oligomers and prepolymers) having one or more of these monomers as constituent monomers.

Examples of the polyfunctional (meth)acrylate include polyurethane (meth)acrylate, polyester (meth)acrylate, polyacrylic (meth)acrylate, epoxy (meth)acrylate, polyalkylene glycol poly(meth)acrylate, and polyether (Meth)acryloyl group-containing prepolymers or oligomers such as (meth)acrylates having two or more (meth)acryloyl groups in one molecule can be mentioned.

As the polyfunctional (meth)acrylate other than the component (A1), one or a mixture of two or more thereof can be used. In this specification, (meth)acrylate means acrylate or methacrylate.

(A1) Polyfunctional urethane (meth)acrylate The above (A1) polyfunctional urethane (meth)acrylate is a compound having a urethane structure (-NH-CO-O-) or a derivative thereof and having two or more (meth) ) A urethane (meth)acrylate having an acryloyl group and satisfying the following property (a1).

(a1) Mainly structural units derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols (usually 50% by mass per 100% by mass of total structural units derived from polyol compounds) above, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, most preferably 95% by mass or more).

The polyfunctional urethane (meth)acrylate of component (A1) typically includes a polyol compound, a compound having two or more isocyanate groups (-N=C=O) in one molecule, and a hydroxyl group-containing (meta ) manufactured using acrylates. This includes a structural unit derived from the polyol compound, a structural unit derived from the compound having two or more isocyanate groups in one molecule, and a structural unit derived from the hydroxyl group-containing (meth)acrylate.

The polyfunctional urethane (meth)acrylate of the component (A1) mainly contains structural units derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols as structural units derived from polyol compounds. By including it, the miscibility with other components is improved.

Examples of the polyester polyol include, but are not limited to, poly(ethylene adipate), poly(butylene adipate), poly(neopentyl adipate), poly(hexamethylene adipate), poly(butylene azelaate), poly(butylene sebacate), and polycaprolactone.

Examples of the polycarbonate polyol include, but are not particularly limited to, poly(butanediol carbonate), poly(hexanediol carbonate), and poly(nonanediol carbonate).

As one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, one or a mixture of two or more thereof can be used.

The polyfunctional urethane (meth)acrylate of the component (A1) is not particularly limited to polyols other than polyester polyols and polycarbonate polyols, as long as it does not contradict the purpose of the present invention. may contain.

Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; copolymers of ethylene oxide and propylene oxide; copolymer of oxide and tetrahydrofuran; copolymer of dihydric phenol compound and polyoxyalkylene glycol; and dihydric phenol compound and alkylene oxide having 2 to 4 carbon atoms (e.g., ethylene oxide, propylene oxide, -butylene oxide and 1,4-butylene oxide).

As the polyol compound other than the above polyester polyol and polycarbonate polyol, one or a mixture of two or more thereof can be used.

The compound having two or more isocyanate groups in one molecule is not particularly limited. Among them, mention may be made of compounds having two isocyanate groups.

Examples of the compound having two or more isocyanate groups in one molecule include, for example, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, tolylene Polyisocyanates such as an isocyanurate of isocyanate, an isocyanurate of hexamethylene diisocyanate, an isocyanurate of isophorone diisocyanate, and a biuret of hexamethylene diisocyanate can be mentioned.

As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used.

Examples of the hydroxyl group-containing (meth)acrylate include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ) acrylate, 6-hydroxyhexyl (meth)acrylate, and hydroxyalkyl (meth)acrylates such as 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; dipropylene glycol (meth)acrylate, polyethylene glycol mono (meth) acrylates and glycol-based (meth) acrylates such as polypropylene glycol mono (meth) acrylate; glycerin-based (meth) acrylates such as glycerin di (meth) acrylate; meth)acrylates; phosphorus atom-containing (meth)acrylates such as 2-hydroxyethyl acryloyl phosphate; esters or ester derivative (meth)acrylic acid adducts such as 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate; pentaerythritol-based (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate; and caprolactone-modified (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified dipentaerythritol penta(meth)acrylate.

As the hydroxyl group-containing (meth)acrylate, one or a mixture of two or more thereof can be used.

The number of (meth)acryloyl groups possessed by the polyfunctional urethane (meth)acrylate of component (A1) is 2 or more from the viewpoint of the scratch resistance of the resulting coating film. On the other hand, the number of (meth)acryloyl groups contained in the component (A1) is usually 12 or less, preferably 6 or less, more preferably 4 or less, still more preferably 4 or less, from the viewpoint of the bending resistance of the resulting coating film. may be 3 or less, most preferably 2.

The mass-average molecular weight of the polyfunctional urethane (meth)acrylate of component (A1) is preferably 3,000 or more, more preferably 5,000 or more, and still more preferably 6, from the viewpoint of the stain removability of the resulting coating film. ,000 or more, most preferably 7,000 or more. On the other hand, the weight average molecular weight of the polyfunctional urethane (meth)acrylate of component (A1) is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of the curability of the paint.
In one embodiment, the weight average molecular weight of the polyfunctional urethane (meth)acrylate of component (A1) is preferably 3,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less, and 5,000. 5,000 to 30,000, 6,000 to 50,000, 6,000 to 30,000, 7,000 to 50,000, or 7,000 to 30,000 may be:

In the present specification, the weight average molecular weight is a polystyrene-equivalent weight average obtained from a differential molecular weight distribution curve (hereinafter sometimes abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC). molecular weight.

GPC measurement was performed using a high-performance liquid chromatography system "HLC-8320" (trade name) manufactured by Tosoh Corporation (a system including a degasser, a liquid pump, an autosampler, a column oven and an RI (differential refractive index) detector). Using; GPC column Shodex GPC column "KF-806L" (trade name) two, "KF-802" (trade name) and "KF-801" (trade name) each one total Four tubes are connected in order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side and used; as a mobile phase; flow rate of 1.0 ml/min, column temperature of 40° C., sample concentration of 1 mg/ml, and sample injection volume of 100 microliters. The amount of elution in each retention volume can be obtained from the amount detected by the RI detector assuming that the refractive index of the sample to be measured does not depend on the molecular weight. In addition, the calibration curve from the retention volume to the polystyrene equivalent molecular weight was obtained using standard polystyrene "EasiCal PS-1" (trade name) of Agilent Technology Co., Ltd. (Molecular weights of Plain A: 6375000, 573000, 117000, 31500, 3480; Plain B molecular weights 2517000, 270600, 71800, 10750, 705). As an analysis program, Tosoh Corporation's "TOSOH HLC-8320GPC EcoSEC" (trade name) can be used. For the theory and measurement of GPC, reference books such as "Size Exclusion Chromatography, High Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Edition, December 10, 1991" by Kyoritsu Shuppan Co., Ltd. can be referred to.

The polyfunctional (meth)acrylate of component (A) includes the polyfunctional urethane (meth)acrylate of component (A1). The polyfunctional (meth)acrylate of the component (A) preferably contains 10 to 90% by mass of the polyfunctional urethane (meth)acrylate of the component (A1) based on the sum of the component (A) being 100% by mass, More preferably, it is present in an amount of 15-85% by weight, even more preferably 15-75% by weight.
The amount of the component (A1) in the component (A) is such that when the paint of the present invention is used for a decorative sheet for so-called 2D molding such as wrapping molding, the resulting coating film has stain removability and scratch resistance. , and from the viewpoint of bending resistance, it may be preferably 50 to 85% by mass, more preferably 60 to 75% by mass. In one embodiment, this amount may be 50-75% by weight, or 60-85% by weight.
In addition, when the paint of the present invention is used for a decorative sheet for so-called 1D molding such as flat bonding molding, the amount of the above component (A1) in the above component (A) is such that the stain removal property of the resulting coating film, From the viewpoint of bending resistance and scratch resistance, the content is preferably 10 to 40% by mass, more preferably 15 to 25% by mass. In one embodiment, this amount may be 10-25% by weight, or 15-40% by weight.

(B) compound having an anionic hydrophilic group The component (B) compound having an anionic hydrophilic group is at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphate group. is a compound having Component (B) is typically a compound described as compound (I) in International Publication WO2007/064003. The above compound (I) is described in detail in International Publication WO2007/064003, which is incorporated herein by reference as it is. The compound (I) is a compound represented by the following general formula (1).

[X]s[M ₁ ]L[M ₂ ]m (1)
In formula (1), s represents 1 or 2. L represents 1 or 2; m represents 0 or 1; M ₁ and M ₂ represent hydrogen ions, ammonium ions, alkali metal ions, or alkaline earth metal ions. M ₁ and M ₂ may be the same or different. X represents one selected from hydrophilic group-containing moieties represented by the following general formulas (1-1) to (1-4).

In formulas (1-1) to (1-4), J and J' represent H or _CH3 . J and J' may be the same or different. n represents 0 or 1; R and R' are aliphatic hydrocarbon groups having 1 to 600 carbon atoms, preferably 2 to 100 carbon atoms, more preferably 2 to 20 carbon atoms. The aliphatic hydrocarbon group may be linear or branched, and may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. R and R' may be the same or different. The aliphatic hydrocarbon group may have any substituent. In that case, the total number of carbon atoms including the substituents should be within the above range.

Among these, the compound having an anionic hydrophilic group of component (B) has a hydrophilic group-containing moiety represented by the above general formula (1-1) from the viewpoint of the stain removability of the resulting coating film. A compound represented by the general formula (1) is preferred.

The compounding amount of the compound having an anionic hydrophilic group of the component (B) is usually based on 100 parts by mass of the polyfunctional (meth)acrylate of the component (A), from the viewpoint of the stain removability of the resulting coating film. It is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. On the other hand, the amount of the compound having an anionic hydrophilic group of component (B) is usually 100 parts by mass or less, preferably 70 parts by mass or less, from the viewpoint of the curability of the coating material and the scratch resistance of the resulting coating film. It is more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less.
The amount of the compound having an anionic hydrophilic group of component (B) is usually 5 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 70 parts by mass or less, and 5 parts by mass or more and 60 parts by mass or less. , 5 parts by mass to 50 parts by mass, 10 parts by mass to 100 parts by mass, 10 parts by mass to 70 parts by mass, 10 parts by mass to 60 parts by mass, 10 parts by mass to 50 parts by mass, 20 parts by mass or more 100 parts by mass or less, 20 to 70 parts by mass, 20 to 60 parts by mass, 20 to 50 parts by mass, 30 to 100 parts by mass, 30 to 70 parts by mass, It may be 30 parts by mass or more and 60 parts by mass or less, or 30 parts by mass or more and 50 parts by mass or less.

(C) Resin particles having an average particle size of 1 to 100 μm A certain embodiment of the paint of the present invention contains the above component (C) resin particles having an average particle size of 1 to 100 μm. The above component (C) functions to give the coating film a matte design.

The resin particles of component (C) are not particularly limited, but examples include silicone resins, styrene resins, acrylic resins, fluorine resins, polycarbonate resins, ethylene resins, urethane resins, and amino compounds. and resin particles such as cured resins with formaldehyde. Among these, particles of silicon-based resin, acrylic-based resin, urethane-based resin, and fluorine-based resin are preferable from the viewpoint of low specific gravity, lubricity, dispersibility, and solvent resistance. Moreover, from the viewpoint of improving the light diffusibility and facilitating the imparting of a matte design, a true spherical shape is preferable. These resin particles may also have reactive functional groups such as carbon-carbon double bonds, (meth)acryloyl groups, and isocyanate groups on their surfaces. Thereby, the scratch resistance of the coating film obtained can be improved. As the resin particles of component (C), one or a mixture of two or more of these can be used.
The acrylic resin or urethane resin used as the resin particles of the component (C) is selected depending on the presence or absence of solubility in an organic solvent, or depending on the presence or absence of a particle shape with an average particle size within the specific range. It is distinguished from the polyfunctional (meth)acrylate of (A) or the polyfunctional urethane (meth)acrylate of component (A1) above.

The average particle size of the resin particles of component (C) may be usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of imparting a matte design. On the other hand, the average particle size of the resin particles of the component (C) is usually 100 nm or less, preferably 60 nm or less, more preferably 30 μm, from the viewpoint of preventing the coating film from becoming cloudy and deteriorating the design. It may be 20 μm or less, more preferably 20 μm or less.
The average particle diameter of the resin particles of component (C) is usually 1 μm or more and 100 nm or less, preferably 1 μm or more and 60 nm or less, 1 μm or more and 30 μm or less, 1 μm or more and 20 μm or less, 2 μm or more and 100 nm or less, 2 μm or more and 60 nm or less, 2 μm or more. 30 μm or less, 2 μm or more and 20 μm or less, 3 μm or more and 100 nm or less, 3 μm or more and 60 nm or less, 3 μm or more and 30 μm or less, 3 μm or more and 20 μm or less, 4 μm or more and 100 nm or less, 4 μm or more and 60 μm or less, 4 μm or more and 30 μm or less, or 4 μm or more and 20 μm or less. you can

In the present specification, the average particle size of the resin particles refers to the smaller particle size in the particle size distribution curve measured using a laser diffraction/scattering particle size analyzer “MT3200II” (trade name) manufactured by Nikkiso Co., Ltd. It is a particle diameter at which the accumulation from is 50% by mass.

The amount of the resin particles of the component (C) is usually 5 parts by mass with respect to 100 parts by mass of the polyfunctional (meth)acrylate of the component (A), although it depends on the level of the matte design to be imparted. Above, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more. On the other hand, the amount of the resin particles of the component (C) is usually 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass, from the viewpoint of the scratch resistance and bending resistance of the resulting coating film. parts or less, more preferably 80 parts by mass or less, and most preferably 70 parts by mass or less.
The amount of the resin particles of component (C) is usually 5 parts by mass to 200 parts by mass, preferably 5 parts by mass to 150 parts by mass, 5 parts by mass to 100 parts by mass, and 5 parts by mass to 80 parts by mass. parts or less, 5 to 70 parts by mass, 20 to 200 parts by mass, 20 to 150 parts by mass, 20 to 100 parts by mass, 20 to 80 parts by mass, 20 parts by mass 30 to 150 parts by mass, 30 to 100 parts by mass, 30 to 80 parts by mass, 30 to 70 parts by mass 40 parts by mass to 200 parts by mass, 40 parts by mass to 150 parts by mass, 40 parts by mass to 100 parts by mass, 40 parts by mass to 80 parts by mass, or 40 parts by mass to 70 parts by mass, good.

As the resin particles of component (C), it is preferable to use two or more kinds of resin particles having different average particle sizes. A good matte design can be obtained (the 60-degree gloss value is lowered) even if the blending amount of the component (C) is small.

When two types of resin particles having different average particle sizes are used as the component (C), the ratio of the average particle size C1 of the large average particle size to the average particle size C2 of the small average particle size (C1/C2) may preferably be between 1.2 and 10, more preferably between 1.5 and 4. In one embodiment, this ratio may be 1.2-4, 1.5-10.
The ratio (Ca/Cb) (mass ratio) of the amount Ca with a large average particle size to the amount Cb with a small average particle size is preferably 0.1 to 6, more preferably 0.3 to 2, More preferably, it may be 0.4 to 1.5. In one embodiment, the ratio is 0.1-2, 0.1-1.5, 0.3-6, 0.3-1.5, 0.4-6, or 0.4-2. It's okay.

The paint of the present invention does not contain inorganic particles.
In general, inorganic particles such as silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; metal fluoride particles such as magnesium fluoride and sodium fluoride; metal sulfide particles; metal nitride particles; is useful. On the other hand, the interaction between the inorganic particles and the resin component such as the above component (A) is weak, which causes insufficient scratch resistance and bending resistance of the resulting coating film.
Therefore, in the present invention, by using resin particles instead of inorganic particles as particles for imparting a matte design, it is possible to maintain good scratch resistance and bending resistance of the coating film.

Here, "free of" inorganic particles means not containing any significant amount of inorganic particles. In the field of coatings for coating film formation, a significant amount of inorganic particles is usually about 1 part by mass or more per 100 parts by mass of component (A) from the viewpoint of imparting a matte design. Therefore, "not containing" inorganic particles means that the amount of inorganic particles is usually 0 parts by mass or more and less than 1 part by mass, preferably 0.5 parts by mass or less, more preferably 100 parts by mass of the component (A). is 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and most preferably 0.01 parts by mass or less.

From the viewpoint of improving the curability by active energy rays, the paint of the present invention further contains a compound having two or more isocyanate groups (-N=C=O) in one molecule and/or a photopolymerization initiator. preferably included.

The compound having two or more isocyanate groups in one molecule includes, for example, methylenebis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, tri Polyisocyanates such as methylolpropane adducts, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, isophorone diisocyanate isocyanurate, hexamethylene diisocyanate biuret; and blocked isocyanates of the above polyisocyanates A urethane cross-linking agent and the like can be mentioned. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used. In addition, a catalyst such as dibutyltin dilaurate, dibutyltin diethylhexoate, or the like may be added at the time of cross-linking, if necessary.

The amount of the compound having two or more isocyanate groups in one molecule is, for 100 parts by mass of the component (A), the adhesion between the coating film and the substrate, and the surface hardness of the coating film. , usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less. On the other hand, the amount of the compound having two or more isocyanate groups in one molecule is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.5 parts by mass or more, from the viewpoint of reliably obtaining the effect of use. may be 1 part by mass or more, more preferably 2 parts by mass or more.
In one embodiment, the amount of the compound having two or more isocyanate groups in one molecule is usually 0.1 parts by mass or more and 30 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less. 0.1 to 10 parts by mass, 0.5 to 30 parts by mass, 0.5 to 20 parts by mass, 0.5 to 10 parts by mass, 1 to 30 parts by mass parts by mass or less, 1 part by mass or more and 20 parts by mass or less, 1 part by mass or more and 10 parts by mass or less, 2 parts by mass or more and 30 parts by mass or less, 2 parts by mass or more and 20 parts by mass or less, or 2 parts by mass or more and 10 parts by mass or less. you can

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; Acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone; -anthraquinone compounds such as amyl anthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; alkylphenone compounds such as acetophenone dimethyl ketal; triazine compounds; biimidazole compounds; fin oxide compounds; titanocene compounds; oxime ester compounds; oxime phenyl acetate compounds; hydroxyketone compounds; thiophenyl-based compounds; and aminobenzoate-based compounds. Among these, acetophenone-based compounds and thiophenyl-based compounds are preferred. As the photopolymerization initiator, one or a mixture of two or more thereof can be used.

The amount of the photopolymerization initiator is usually 10 parts by mass or less, preferably 7 parts by mass, based on 100 parts by mass of the component (A), from the viewpoint of preventing the formed coating film from becoming yellowed. It may be 5 parts by mass or less, more preferably 5 parts by mass or less. On the other hand, the blending amount of the photopolymerization initiator is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably It may be 2 parts by mass or more.
In one embodiment, the amount of the photopolymerization initiator is usually 0.1 parts by mass to 10 parts by mass, preferably 0.1 parts by mass to 7 parts by mass, and 0.1 parts by mass to 5 parts by mass. 0.5 to 10 parts by mass, 0.5 to 7 parts by mass, 0.5 to 5 parts by mass, 1 to 10 parts by mass, 1 to 7 parts by mass parts or less, 1 to 5 parts by mass, 2 to 10 parts by mass, 2 to 7 parts by mass, or 2 to 5 parts by mass.

Antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, and antioxidants may be added to the paint of the present invention as desired, as long as they do not contradict the purpose of the present invention. , weather stabilizers, light stabilizers, UV absorbers, heat stabilizers, and organic colorants.

The paint of the present invention may optionally contain a solvent in order to dilute it to a concentration that facilitates coating. The solvent is particularly limited as long as it does not react with the components (A), (B), and other optional components and does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the solvent, one or a mixture of two or more thereof can be used.

The paint of the present invention can be obtained by mixing and stirring these components.

A method for forming a coating film using the coating composition of the present invention is not particularly limited, and a known web coating method can be used. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, dip coating, spray coating, spin coating, air knife coating, and die coating.

The thickness of the coating film formed using the paint of the present invention is not particularly limited, but from the viewpoint of scratch resistance, it may be usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more. On the other hand, the thickness of the coating film is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and most preferably 15 μm or less, from the viewpoint of bending resistance.
In one embodiment, the thickness of the coating film is 1 μm to 100 μm, 1 μm to 50 μm, 1 μm to 30 μm, 1 μm to 15 μm, 2 μm to 100 μm, 2 μm to 50 μm, 2 μm to 30 μm, 2 μm to 15 μm. , 3 μm to 100 μm, 3 μm to 50 μm, 3 μm to 30 μm, or 3 μm to 15 μm.

2. Decorative Sheet The decorative sheet of the present invention is a decorative sheet having a coating film formed using the paint of the present invention. The coating film formed using the paint of the present invention is usually formed as a surface protective layer on the front side (the side that is normally visible in actual use) of the decorative sheet of the present invention. Here, the actual usage state means a state in which the decorative sheet is used for decorating and decorating the surfaces of various articles.

The decorative sheet of the present invention is not particularly limited. A decorative sheet having a print layer provided on the front side surface and a coating film formed using the paint of the present invention on the surface of the print layer can be exemplified.

The thermoplastic resin film is a layer that serves as a base material of the decorative sheet. The thermoplastic resin film is usually colored from the viewpoint of design and functions to conceal the adherend.

Examples of the thermoplastic resin film include, for example, polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins; ; Poly(meth)acrylimide resin; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene・Styrenic resins such as ethylene/ethylene/propylene/styrene copolymers; cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polyvinylidene chloride resins; fluorine-containing polyvinylidene fluoride and the like System resin; 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 laminated films obtained by laminating two or more layers of one or more of these.

A coloring agent for coloring the thermoplastic resin film is not particularly limited, and any coloring agent can be used. Examples of the coloring agent include titanium oxide and carbon black. As the colorant, one or a mixture of two or more of these can be used. The amount of the colorant to be blended is usually about 0.1 to 40 parts by mass based on 100 parts by mass of the base resin used in the thermoplastic resin film, depending on the type of the colorant and the desired concealing property. .

The thickness of the thermoplastic resin film is not particularly limited, but may be preferably 50 μm or more, more preferably 75 μm or more, from the viewpoint of handleability during production of the decorative sheet. On the other hand, from the viewpoint of workability when applying the decorative sheet to an article, the thickness is usually 300 μm or less, preferably 250 μm or less.
In one embodiment, the thermoplastic resin film may have a thickness of 50 μm to 300 μm, 50 μm to 250 μm, 75 μm to 300 μm, or 75 μm to 250 μm.

The printed layer is provided to impart a high degree of designability, and can be formed by printing any pattern using any ink and any printing machine.

The print layer can be applied entirely or partially on the front surface of the thermoplastic resin film directly or via an anchor coat. 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 texture or cloth patterns, tile patterns, brickwork patterns, marquetry 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, and the like 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. resins such as cellulose-based resins, butyral-based resins, polystyrene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins, and resin compositions thereof. In order to give a metallic design, aluminum, tin, titanium, indium and their oxides are applied directly or via an anchor coat on the front surface of the thermoplastic resin film entirely or Partially, it may be vapor-deposited by known methods.

The method of forming a coating film directly or via an anchor coat on the surface of the printed layer formed on the front side surface of the thermoplastic resin film using the paint of the present invention is not particularly limited. Instead, known web coating methods can be used. Examples of the above methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

In the decorative sheet, the thickness of the coating film formed using the paint of the present invention is not particularly limited, but from the viewpoint of scratch resistance, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more. good. In addition, the thickness of the coating film in the decorative sheet is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and most preferably 30 μm or less, from the viewpoint of the secondary processability and web handleability of the decorative sheet of the present invention. It may be 15 μm or less.
In one embodiment, the thickness of the coating film in the decorative sheet is 1 μm or more and 100 μm or less, 1 μm or more and 50 μm or less, 1 μm or more and 30 μm or less, 1 μm or more and 15 μm or less, 2 μm or more and 100 μm or less, 2 μm or more and 50 μm or less, 2 μm or more and 30 μm or less, 2 μm. 3 μm or more and 100 μm or less, 3 μm or more and 50 μm or less, 3 μm or more and 30 μm or less, or 3 μm or more and 15 μm or less.

The anchor coating agent for forming the anchor coat is not particularly limited, and any anchor coating agent can be used. Examples of the anchor coating agent include polyester-based, acrylic-based, polyurethane-based, acrylic-urethane-based, and polyester-urethane-based anchor coating agents. One or more of these can be used as the anchor coating agent.

The anchor coating agent may optionally contain antioxidants, weather stabilizers, light stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents, surfactants, One or two or more additives such as coloring agents, infrared shielding agents, leveling agents, thixotropic agents, and fillers may be included.

A method for forming the anchor coat using the anchor coating agent is not particularly limited, and a known web coating method can be used. Examples of the above methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

Although the thickness of the anchor coat is not particularly limited, it may generally be about 0.01 to 5 μm, preferably 0.1 to 2 μm.

The decorative sheet of the present invention is used on the surface of the thermoplastic resin film opposite to the front surface from the viewpoint of improving the adhesion to the adherend to be decorated and decorated using the decorative sheet. , directly or via an anchor coat to form a pressure-sensitive adhesive layer or an adhesive layer.

FIG. 1 is a schematic cross-sectional view showing a non-limiting example of the decorative sheet of the present invention. It has a coating film 1 formed from the coating material of the present invention, a printed layer 2, a colored thermoplastic resin film layer 3, and an adhesive layer 4 in order from the side that is normally viewed in actual use.

The water contact angle of the surface of the coating film of the decorative sheet of the present invention formed using the paint of the present invention is preferably 15 degrees or less, more preferably 14 degrees or less, and still more preferably 14 degrees or less, from the viewpoint of stain removal. It may be 13 degrees or less, even more preferably 11 degrees or less, most preferably 9 degrees or less. A lower water contact angle is preferred.

The mandrel test value of the decorative sheet of the present invention is preferably 10 mm or less, more preferably 8 mm or less, even more preferably 6 mm or less, and even more preferably 4 mm or less, from the viewpoint of the bending resistance of the coating film to be formed. It's okay. Smaller mandrel test values are preferred.

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

Measurement Method (i) Smoothness of Coating Film The coating surface of the decorative sheet was visually observed while the incident angle of the light from the fluorescent lamp was varied, and evaluated according to the following criteria.
⊚ (very good): Good with no undulations or uneven unevenness.
◯ (Good): There were a few portions with undulations and irregular unevenness.
Δ (slightly unsatisfactory): Parts with undulations and irregularities were somewhat conspicuous.
x (defective): There were undulations and irregularities on the whole.

(ii) 60 degree gloss value (mattness)
A multi-angle gloss meter "GM-268" (trade name) manufactured by Konica Minolta Co., Ltd. was used in accordance with JIS Z8741:1997 to measure the 60-degree gloss value of the coated surface of the decorative sheet.

(iii) Steel wool resistance (scratch resistance)
Place it on a JIS L0849: 2013 Gakushin-type tester so that the coating film of the decorative sheet is on the surface, and the reciprocating direction of the friction terminal and the machine direction of the decorative sheet are parallel. After attaching #0000 steel wool to the friction terminals, a load of 500 g was placed, and the surface of the test piece was rubbed back and forth 10 times under conditions of a moving distance of 60 mm and a speed of 1 reciprocation/second. The friction points were visually observed and evaluated according to the following criteria.
⊚ (very good): No scratches were observed.
○ (good): 1 to 3 scratches were found.
Δ (slightly unsatisfactory): 4 to 10 scratches were found.
x (defective): 11 or more scratches were found.

(iv) Water contact angle A method of calculating from the width and height of water droplets using an automatic contact angle meter "DSA20" (trade name) of KRUSS for the coated surface of the decorative sheet (see JIS R3257: 1999). measured in

(v) Oleic acid removability (stain removability)
Oleic acid (reagent grade 1) from Wako Pure Chemical Industries, Ltd. and carbon black "FW-200" (trade name) from Orion Engineered Carbons Co., Ltd. were blended at a mass ratio of 10/1, and mixed and stirred well. to create contaminants. Next, 1 mg of the contaminant obtained above was applied to the coated surface of the decorative sheet in a circle having a diameter of 20 mm, and then washed off with tap water. The washing was carried out for 20 seconds by a method of directly applying running water at a flow rate of 1 liter/10 seconds to the above applied contaminants at a position 10 cm below the water faucet. At this time, if the stain removability is good, it can be observed that the stain is lifted and peeled off from the coating film. The locations where the contaminants were applied were visually observed and evaluated according to the following criteria.
⊚ (very good): The contaminants were completely removed and no trace of application remained.
○ (Good): Contaminants were removed, but traces of application remained slightly.
Δ (slightly unsatisfactory): Some of the contaminants were not removed and remained in the applied area.
x (defective): Most of the contaminants were not removed and remained as they were when applied to the application area.

(vi) Heat kettle resistance (heat resistance)
Pour 1.5 liters of tap water into an aluminum kettle (suitable capacity: 2 liters) "New Celet Aluminum Kettle H-2508" (trade name) from PEARL KINZOKU CO., LTD. placed directly on After 5 minutes had passed, the kettle was removed, and the portion of the decorative sheet placed directly on the kettle was visually observed and evaluated according to the following criteria.
⊚ (very good): No marks left when the kettle was directly placed.
◯ (Good): Slight traces of direct placement of the kettle remained.
(triangle|delta) (slightly unsatisfactory): The mark which the kettle was directly placed remained clearly.
x (defective): The decorative sheet was remarkably thermally deformed.

(vii) mandrel test (indicator of crack resistance and bending resistance)
According to JIS K5600-5-1:1999, a bending resistance test was performed by a cylindrical mandrel method using a sample of 100 mm in the machine direction and 50 mm in the lateral direction taken from the decorative sheet. The diameter of the mandrel with the smallest diameter among the mandrels that did not crack was obtained.

Raw Materials Used (A) Polyfunctional (meth)acrylates (A2) Polyfunctional (meth)acrylates other than polyfunctional urethane (meth)acrylates (A2-1) Dipentaerythritol hexaacrylate from Nippon Kayaku Co., Ltd. Number of hydroxyl groups per unit amount: 0.668 mol/Kg.

(A1) Polyfunctional urethane (meth)acrylate (A1-1) Multifunctional urethane (meth)acrylate “Artresin UN-1255” (trade name) manufactured by Negami Kogyo Co., Ltd. The number of (meth)acryloyl groups is two. All polyol compounds are polyester polyols. Mass average molecular weight 8000.
(A1-2) Polyfunctional urethane (meth)acrylate “REAX-2” (trade name) from Neagari Industry Co., Ltd. The number of (meth)acryloyl groups is two. All polyol compounds are polyester polyols. Mass average molecular weight 4500.
(A1-3) Polyfunctional urethane (meth)acrylate “UV3520EA” (trade name) from Nippon Synthetic Chemical Co., Ltd.; The number of (meth)acryloyl groups is two. All polyol compounds are polyester polyols. Mass average molecular weight 14,000.
(A1-4) Polyfunctional urethane (meth)acrylate “UN9000PEP” (trade name) from Neagari Industry Co., Ltd.; The number of (meth)acryloyl groups is two. All polyol compounds are polycarbonate polyols. Mass average molecular weight 5000.
(A1-5) Polyfunctional urethane (meth)acrylate “KY101” (trade name) from Neagari Industry Co., Ltd.; The number of (meth)acryloyl groups is two. All polyol compounds are polycaprolactone (polyester polyol). Mass average molecular weight 3000.
(A1-6) Polyfunctional urethane (meth)acrylate “KY103” (trade name) from Neagari Industry Co., Ltd.; The number of (meth)acryloyl groups is two. All polyol compounds are polycaprolactone (polyester polyol). Mass average molecular weight 5500.
(A1-7) Polyfunctional urethane (meth)acrylate “UN5500” (trade name) from Neagari Industry Co., Ltd. The number of (meth)acryloyl groups is nine. All polyol compounds are polycarbonate polyols. Mass average molecular weight 86,000.

(A'1) Polyfunctional urethane (meth)acrylate other than component (A1) above (A'1-1) Multifunctional urethane (meth)acrylate "Artresin UN-6300" (trade name) available from Negami Kogyo Co., Ltd. The number of (meth)acryloyl groups is two. Polyol compound is polyether polyol. Mass average molecular weight 12700.

(B) Compound Having an Anionic Hydrophilic Group (B-1) 3-sulfonylpropyl-acrylate potassium salt (compound of formula 2 below).

(B-2) A compound of Formula 3 below.

(B-3) A compound of formula 4 below.

(C) Resin particles having an average particle size of 1 to 100 μm (C-1) Resin particles “CERAFLOUR 1000” (trade name) from BYK-Chemie Japan. Average particle size 5 μm.
(C-2) Acrylic resin particles “ART PEARL SE-010T” (trade name) from Neagari Kogyo Co., Ltd.; Average particle size 10 μm.

(D) Other components (D-1) Compound "RV2" (trade name) having two or more isocyanate groups in one molecule from Light Chemical Industry Co., Ltd. Number of isocyanate groups per unit weight: 5.95 mol/Kg.
(D-2) BASF's acetophenone-based photopolymerization initiator (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane- 1-on) “IRGACURE 127” (trade name).
(D-3) Methanol.
(D-4) 1-methoxy-2-propanol.

Anchor coating agent (P-1) 100 parts by mass of amorphous polyester resin "Vylon 103" (trade name) from Toyobo Co., Ltd., 10 parts by mass of hydroxyphenyltriazine-based UV absorber "TINUVIN479" (trade name) from BASF, A paint obtained by mixing and stirring 3.3 parts by mass of the component (D-1), 120 parts by mass of methyl ethyl ketone, and 240 parts by mass of ethyl acetate.

Example 1
1. Preparation of paint Component (A2-1) 33 parts by mass, Component (A1-1) 67 parts by mass, Component (B-1) 37 parts by mass, Component (C-1) 30 parts by mass, Component ( C-2) 20 parts by mass, the component (D-1) 6 parts by mass, the component (D-2) 3.5 parts by mass, the component (D-3) 50 parts by mass, and the component (D-4 ) were mixed and stirred to obtain a paint.

2. Manufacture of decorative sheet (2-1) A vinyl chloride/vinyl acetate copolymer was placed on one side of a white colored polybutylene terephthalate resin film "HR (WHT)" (trade name) of RIKEN TECHNOS CORPORATION with a thickness of 250 μm. Using an ink as a medium, a 1 μm-thick wood-grain print layer was formed.

(2-2) Next, on the surface of the printed layer formed in (2-1) above, using a film Meyer bar type coating device, using the anchor coating agent (P-1), after curing An anchor coat layer was formed so as to have a thickness of 0.8 μm.

(2-3) Furthermore, on the surface of the anchor coat layer formed in (2-2) above, a film Meyer bar type coating device is used, and the paint obtained in 1 above is used, and the thickness after curing is A coating film was formed to a thickness of 5 μm to obtain a decorative sheet.

The obtained decorative sheet was subjected to the above tests (i) to (vii). Table 1 shows the results.

Examples 2-16, 6-1
A decorative sheet was prepared and its physical properties were measured and evaluated in the same manner as in Example 1, except that the formulation of the paint was changed to that shown in Table 1 or 2. The results are shown in Tables 1-2.

Examples 1 to 10, 13 to 16, and 6-1 were designed as decorative sheets for so-called 2D molding. Examples 11 and 12 were designed as decorative sheets for so-called 1D molding.

The paint of the present invention, which is a decorative sheet designed for so-called 2D molding, is excellent in stain removability, heat resistance, smoothness of the coated surface, and bending resistance.
The paint of the present invention, which is a decorative sheet designed for so-called 1D molding, is excellent in stain removability, heat resistance, smoothness of the coated surface, and scratch resistance. In addition, this decorative sheet has sufficient bending resistance for so-called 1D molding.

1: Coating film 2: Printed layer 3: Colored thermoplastic resin film layer 4: Adhesive layer

Claims (5)

(A) 100 parts by mass of polyfunctional (meth)acrylate; and
(B) 10 to 100 parts by mass of a compound having at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group;
Contains no inorganic particles,
Here, the (A) polyfunctional (meth)acrylate is derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the sum total of structural units derived from the polyol compound being 100% by mass. (A1) polyfunctional urethane (meth) acrylate containing 50% by mass or more of the structural unit, the total of the (A) polyfunctional (meth) acrylate is 100% by mass, in an amount of 10 to 90% by mass and containing (A2) polyfunctional (meth)acrylate other than (A1), the sum of (A) polyfunctional (meth)acrylate being 100% by mass, the remaining amount of (A1) (90 to 10 % by mass),
The compound (B) having at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group has the following general formula (1):
[X]s[M ₁ ]L[M ₂ ]m (1)
(Wherein, s represents 1 or 2, L represents 1 or 2, m represents 0 or 1, M ₁ and M ₂ are hydrogen ions, ammonium ions, alkali metal ions, or alkaline earth metal ions wherein M ₁ and M ₂ may be the same or different, and X is one selected from hydrophilic group-containing moieties represented by the following general formulas (1-1) to (1-4) represents:

(Wherein, J, J' represent H or CH3 _, J and J' may be the same or different, n represents 0 or 1, R, R' represent the number of carbon atoms 2 to 100 aliphatic hydrocarbon groups, and R and R' may be the same or different.))
is a compound represented by
(A2) polyfunctional (meth)acrylate other than (A1) above does not include the compound of formula (1) having a hydrophilic group-containing moiety represented by formula (1-4) above .
paint. The paint according to claim 1, further comprising (C) 5 to 200 parts by mass of resin particles having an average particle diameter of 1 to 100 µm with respect to 100 parts by mass of the component (A) polyfunctional (meth)acrylate. 3. The paint according to claim 1, wherein the component (A1) polyfunctional urethane (meth)acrylate has a mass average molecular weight of 3,000 to 50,000. A decorative sheet comprising a coating film formed from the coating material according to any one of claims 1 to 3. A coating film formed from the coating material according to any one of claims 1 to 3, and a layer of a thermoplastic resin film, in this order from the side that is normally visible in actual use;
The water contact angle on the surface of the coating film is 15 degrees or less;
A decorative sheet having a mandrel test value of 10 mm or less.

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