WO2019031116A1

WO2019031116A1 - Coating material for forming coating film with stain removability, and decorative sheet obtained using same

Info

Publication number: WO2019031116A1
Application number: PCT/JP2018/025321
Authority: WO
Inventors: 宮川　浩; 茂一伊藤
Original assignee: リケンテクノス株式会社
Priority date: 2017-08-10
Filing date: 2018-07-04
Publication date: 2019-02-14
Also published as: JP7157060B2; JPWO2019031116A1

Abstract

The present invention relates to a coating material which comprises 100 parts by mass of (A) a polyfunctional (meth)acrylate and 5-100 parts by mass of (B) 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 and which contains no inorganic particles, wherein the polyfunctional (meth)acrylate (A) includes a polyfunctional urethane (meth)acrylate (A1) in an amount of 10-90 mass% with respect to the whole polyfunctional (meth)acrylate (A), the amount of which is taken as 100 mass%. The polyfunctional urethane (meth)acrylate (A1) comprises constituent units derived from one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, in an amount of 50 mass% or more with respect to the sum of all the polyol-compound-derived constituent units, which is taken as 100 mass%. The coating material may further contain 5-200 parts by mass of resin particles (C) having an average particle diameter of 1-100 μm per 100 parts by mass of the polyfunctional (meth)acrylate (A).

Description

Paint for removing stains, and decorative sheet using the same

The present invention relates to paints. More specifically, the present invention relates to a paint capable of forming a coating film having excellent stain removability (hereinafter sometimes referred to as "stain removability coating film"), and a decorative sheet using the same.

Traditionally, household appliances such as refrigerators, washing machines, air conditioners, mobile phones and personal computers; furniture such as display cabinets, storage cabinets, cupboards and desks; or building materials such as floors, walls and bathrooms, wood, plywood Substrates formed from wood-based materials such as laminated wood, particle board and hardboard; substrates formed from resin-based materials such as polystyrene, acrylonitrile butadiene styrene copolymer resin (ABS resin), polycarbonate and polyester A decorative sheet is used by laminating a decorative sheet on the surface of a base material formed of a metal material such as iron or aluminum.

In recent years, with regard to coating films, dirt removability has attracted attention as a product differentiation point. The coating film having excellent stain removability is a coating formed using a paint 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 phosphoric acid group. Membranes have been proposed (see, for example, Patent Document 1). However, the decorative sheet having the stain removing coating film formed by these techniques has insufficient bending resistance, and has a disadvantage that it is difficult to apply to so-called 2D molding such as lapping molding.

International Publication WO2007 / 064003

An object of the present invention is to provide a paint capable of forming a coating film excellent in stain removability, and a decorative sheet using the same.
The further subject of this invention can form the coating film excellent in dirt removal property and bending resistance, and provides the paint which can give a matte design, and a matte decorative sheet using the same. It is to do.
Another further subject of the present invention is a paint capable of forming a coating film excellent in dirt removing property and scratch resistance and capable of giving a matte design, and a matte decorative sheet using the same. It is to provide.

As a result of earnest studies, the present inventor has found that the above-mentioned problems can be achieved by a specific paint.
[1].
(A) 100 parts by mass of polyfunctional (meth) acrylate;
(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 phosphoric acid group;
Does not contain inorganic particles,
Here, the above (A) polyfunctional (meth) acrylate is derived from one or more types of polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the total of structural units derived from polyol compounds being 100% by mass. (A1) multifunctional urethane (meth) acrylate containing 50% by mass or more of the constituent units in an amount of 10 to 90% by mass, based on 100% by mass of the total of (A) polyfunctional (meth) acrylates Including
paint.
[2].
The coating material according to the above [1], further comprising 5 to 200 parts by mass of (C) 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 the above [1] or [2], wherein the weight average molecular weight of the component (A1) polyfunctional urethane (meth) acrylate is 3,000 to 50,000.
[4].
A decorative sheet comprising a coating film formed from the paint according to any one of the above items [1] to [3].
[5].
A coating film formed of the coating material according to any one of the above items [1] to [3], and a thermoplastic resin film layer, in order from the side that is usually viewed in the actual use state;
The water contact angle of the surface of the above-mentioned coating film is 15 degrees or less;
The decorative sheet whose value of a mandrel test is 10 mm or less.

The coating film formed from the paint of the present invention is excellent in the dirt removability.
The coating film formed from the coating material of the present invention according to one aspect is excellent in dirt removing property and bending resistance, and has a matte design. Therefore, the decorative sheet provided 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 lapping molding.
The coating film formed from the paint of the present invention according to another aspect is excellent in the stain removability and scratch resistance and has a matte design. Therefore, the decorative sheet provided with stain removability using the paint of the present invention according to this aspect has a matte design and is excellent in scratch resistance.

It is a conceptual diagram of the cross section which shows an example of the decorative sheet of this invention.

As used herein, the term "film" is used interchangeably or interchangeably with "sheet". In the present specification, the terms "film" and "sheet" are used in what can be industrially rolled up. The term "plate" is used for those which can not be rolled up industrially. The term "resin" is used as a term also including a resin mixture containing two or more resins, and a resin composition containing components other than resins. Also, in the present specification, sequentially stacking one layer and another layer means directly laminating those layers, and interposing one or more other layers such as an anchor coat between the layers. Including both stacking.
The term "over" in the numerical range is used in the sense of a certain numerical value or a certain numerical value. For example, 20% or more means 20% or more than 20%. The term "or less" in relation 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 “to” relating to a numerical range is used in the meaning of a certain numerical value, more than a certain numerical value and less than another certain numerical value, or some other numerical value. Here, some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%.
Unless otherwise stated or unless otherwise specified, all numerical values used in the present specification and claims should be understood as being modified by the term "about." Without intending to limit the application of the doctrine of equivalents to the claims, each number 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) 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 the compound. The paint of an embodiment of the present invention is at least one anionic hydrophilic group selected from the group consisting of (A) polyfunctional (meth) acrylate; and (B) sulfonic acid group, carboxyl group, and 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 the component (A) includes a polyfunctional urethane (meth) acrylate including a structural unit derived from one or more types of polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols. In general, 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 total of structural units derived from polyol compounds being 100% by mass. And (A1) multifunctional urethane (meth) acrylate which contains the structural unit derived from (A1) in the quantity of 50 mass% or more.

(A) Multifunctional (Meth) Acrylate The multi-functional (meth) acrylate of the component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule. The component (A) has two or more (meth) acryloyl groups in one molecule, and thus functions to form a coating film by polymerization and curing by active energy rays such as ultraviolet rays and electron rays and heat. .

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, (Meth) acryloyl group-containing bifunctional reaction such as 2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane Monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; (Meth) acryloyl group-containing tetrafunctional reactive monomers such as tall tetra (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth) acryloyl groups such as tripentaerythritol acrylate Examples thereof include a contained octafunctional reactive monomer; and a polymer (oligomer or prepolymer) having one or more of these as a constituent monomer.

As said polyfunctional (meth) acrylate, For example, polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether Mention may be made of (meth) acryloyl group-containing prepolymers or oligomers such as (meth) acrylates and having two or more (meth) acryloyl groups in one molecule.

As polyfunctional (meth) acrylates other than the said component (A1), these 1 type (s) or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

(A1) Multifunctional Urethane (Meth) Acrylate The above (A1) multifunctional urethane (meth) acrylate is a compound having a urethane structure (—NH—CO—O—), or a derivative thereof, and it is preferable to use two or more ) An urethane (meth) acrylate having an acryloyl group and satisfying the following characteristics (a1).

(A1) The constituent unit derived from one or more types of polyol compounds selected from the group consisting of a polyester polyol and a polycarbonate polyol is mainly (usually 50% by mass with respect to 100% by mass of the constituent units derived from a polyol compound) Or more, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 95% by mass or more.

The polyfunctional urethane (meth) acrylate of the component (A1) is typically a polyol compound, a compound having two or more isocyanate groups (—N = C = O) in one molecule, and a hydroxyl group-containing (meth) ) Manufactured using acrylate. This includes a structural unit derived from the polyol compound, a structural unit derived from a 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, as a structural unit derived from a polyol compound, a structural unit derived from at least one polyol compound selected from the group consisting of a polyester polyol and a polycarbonate polyol. By including, the miscibility with other components is improved.

Examples of the polyester polyol include, but are not limited to, for example, poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene adipate) Sebacate), and polycaprolactone etc. can be mentioned.

The polycarbonate polyol is not particularly limited, and examples thereof include poly (butanediol carbonate), poly (hexanediol carbonate), and poly (nonanediol carbonate).

As 1 or more types of polyol compounds selected from the group which consists of said polyester polyol and a polycarbonate polyol, these 1 type, or 2 or more types of mixtures can be used.

The polyfunctional urethane (meth) acrylate of the component (A1) is not particularly limited, as long as it does not violate the object of the present invention, but is not particularly limited to polyester polyol and polycarbonate polyol, for example, structural units derived from polyether polyol It may be included.

Examples of the polyether polyols 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; ethylene A copolymer of an oxide and tetrahydrofuran; a copolymer of a dihydric phenol compound and a polyoxyalkylene glycol; and an alkylene oxide having a carbon number of 2 to 4 (for example, ethylene oxide, propylene oxide, 1, 2) -Butylene oxide, and copolymers with one or more of 1,4-butylene oxide etc. can be mentioned.

As polyol compounds other than the said polyester polyol and polycarbonate polyol, 1 type, or 2 or more types of mixtures of these can be used.

The compound having two or more isocyanate groups in one molecule is not particularly limited, and, for example, one molecule such as diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis (4-cyclohexyl isocyanate) Mention may be made of compounds having two isocyanate groups therein.

Examples of the compound having two or more isocyanate groups in one molecule include a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, and a tolylene compound. Mention may be made of polyisocyanates such as isocyanurate of isocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate and biuret of hexamethylene diisocyanate.

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

The hydroxyl group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. ) Hydroxyalkyl (meth) acrylates such as acrylate, 6-hydroxyhexyl (meth) acrylate, and 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; Fatty acid-modified glycidyl (meth) acrylates such as glycidyl (meth) acrylate; phosphorus atom-containing (meth) acrylates such as 2-hydroxyethyl acryloyl phosphate; 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate and the like Esters or ester derivatives of (meth) acrylic acid adducts; pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, and ethylene oxide modified dipentaerythritol penta Pentaerythritol-based (meth) acrylates such as (meth) acrylates; and caprolactone-modified 2-hydroxyethyl (meth) acrylates Can be cited data pentaerythritol tri (meth) acrylate, and caprolactone-modified (meth) acrylates such as caprolactone-modified dipentaerythritol penta (meth) acrylate.

As said hydroxyl-containing (meth) acrylate, 1 type (s) or 2 or more types of mixtures of these can be used.

The number of (meth) acryloyl groups contained in the polyfunctional urethane (meth) acrylate of the component (A1) is two 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, further preferably from the viewpoint of bending resistance of the obtained coating May be 3 or less, most preferably 2 or less.

The mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 6 from the viewpoint of the stain removability of the resulting coating film. It may be over 1,000, most preferably over 7,000. On the other hand, the mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) may be preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of the curability of the paint.
In one embodiment, the mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) is preferably 3,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less, 5,000以上 50,000 or less, 5,000 to 30,000 or less, 6,000 to 50,000 or less, 6,000 to 30,000 or less, 7,000 to 50,000 or less, or 7,000 to 30,000 It may be the following.

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

The measurement of GPC is a system including Tosoh high performance liquid chromatography system "HLC-8320" (trade name) (a system including a degasser, a liquid feed pump, an autosampler, a column oven and an RI (differential refractive index) detector) 2 columns of GPC column "KF-806L" (trade name) of Shodex Co., Ltd. and a total of 1 each of "KF-802" (trade name) and "KF-801" (trade name) Connect four KF-806L, KF-806L, KF-802, and KF-801 in this order from the upstream side; Tetrahydrofuran for high-performance liquid chromatography by Wako Pure Chemical Industries, Ltd. (not including stabilizer) As the mobile phase; flow rate 1.0 ml / min, column temperature 40 ° C, sample concentration 1 mg / ml, and sample injection volume 00 can be carried out under the conditions of a micro liter. The elution amount in each holding volume can be determined from the detection amount of the RI detector, assuming that there is no molecular weight dependence of the refractive index of the measurement sample. In addition, the calibration curve from the retention volume to the polystyrene equivalent molecular weight is the standard polystyrene “EasiCal PS-1” (trade name) of Agilent Technology Co., Ltd. (Plain A molecular weight: 6375000, 573000, 117000, 31500, 3480; Molecular weights 2517000, 270600, 71800, 10750, 705) of Plain B can be used. The analysis program can use "TOSOH HLC-8320 GPC EcoSEC" (trade name) of Tosoh Corporation. For further information on GPC theory and measurement, reference books such as Kyoritsu Publishing Co., Ltd. “Size Exclusion Chromatography High-performance Liquid Chromatography of Polymers, author: Sadao Mori, First Edition, December 10, 1991” Can be referenced.

The polyfunctional (meth) acrylate of the component (A) contains the polyfunctional urethane (meth) acrylate of the component (A1). The polyfunctional (meth) acrylate of the component (A) is preferably 10 to 90 mass% of the polyfunctional urethane (meth) acrylate of the component (A1), wherein the total of the components (A) is 100 mass%, More preferably, it is contained in an amount of 15 to 85% by weight, even more preferably 15 to 75% by weight.
The amount of the component (A1) in the component (A) is the stain removability and scratch resistance of the coating film obtained when the paint of the present invention is used for a decorative sheet for so-called 2D molding such as lapping molding 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 to 75 wt%, or 60 to 85 wt%.
In addition, the amount of the component (A1) in the component (A) is the stain removability of the coating film obtained when the paint of the present invention is used for a decorative sheet for so-called 1D molding such as flat sticking molding. From the viewpoint of bending resistance and scratch resistance, it may be 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) 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 phosphoric acid group. A compound having The component (B) is typically a compound described as compound (I) in International Publication WO 2007/064003. The above compound (I) is described in detail in International Publication WO 2007/064003, and is incorporated herein by reference in its entirety. 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 each} represent a hydrogen ion, an ammonium ion, an alkali metal ion, or an alkaline earth metal ion. 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 ′ each represent H or CH ₃ . J and J 'may be the same or different. n represents 0 or 1; R and R 'each represents an aliphatic hydrocarbon group having 1 to 600 carbon atoms, preferably 2 to 100 carbon atoms, and more preferably 2 to 20 carbon atoms. The aliphatic hydrocarbon group may be linear or branched, and may further 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 substituent may be within the above range.

Among these, the compound having an anionic hydrophilic group of the component (B) has a hydrophilic group-containing portion represented by the above general formula (1-1) from the viewpoint of the stain removability of the obtained coating film. The compound represented by the said General formula (1) is preferable.

The compounding amount of the compound having an anionic hydrophilic group of the component (B) is usually from the viewpoint of the stain removing property of the obtained coating film with respect to 100 parts by mass of the polyfunctional (meth) acrylate of the component (A). 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 compounding amount of the compound having an anionic hydrophilic group of the 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 paint and the scratch resistance of the obtained coating film. More preferably, it is 60 parts by mass or less, still more preferably 50 parts by mass or less.
The compounding quantity of the compound which has an anionic hydrophilic group of the said component (B) is 5 mass parts or more and 100 mass parts or less normally, Preferably, 5 mass parts or more and 70 mass parts or less, 5 mass parts or more and 60 mass parts 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 100 parts by mass or less, 20 parts by mass to 70 parts by mass, 20 parts by mass to 60 parts by mass, 20 parts by mass to 50 parts by mass, 30 parts by mass to 100 parts by mass, 30 parts by mass to 70 parts by mass, 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 particle having an average particle diameter of 1 to 100 μm An embodiment of the paint of the present invention contains resin particles of the component (C) having an average particle diameter of 1 to 100 μm. The component (C) functions to make the coating film a matte design.

Although it does not specifically limit as a resin particle of the said component (C), For example, silicone resin, styrene resin, acrylic resin, fluorine resin, polycarbonate resin, ethylene resin, urethane resin, and amino compound And resin particles such as a cured resin of formaldehyde and the like. Among these, particles of silicone resin, acrylic resin, urethane resin and fluorine resin are preferable from the viewpoint of low specific gravity, lubricity, dispersibility and solvent resistance. Also, from the viewpoint of making the light diffusibility good and making it easy to give a matt design, a spherical one is preferable. These resin particles may have reactive functional groups such as carbon / carbon double bonds, (meth) acryloyl groups, and isocyanate groups on the surface. Thereby, the scratch resistance of the obtained coating can be improved. As a resin particle of the said component (C), these 1 type (s) or 2 or more types of mixtures can be used.
The acrylic resin or urethane resin used as the resin particle of the component (C) is the above component depending on the presence or absence of solubility in an organic solvent or the presence or absence of a particle shape having an average particle diameter within the specific range. It distinguishes from the polyfunctional (meth) acrylate of (A) or the polyfunctional urethane (meth) acrylate of the said component (A1).

The average particle diameter of the resin particle of the component (C) may be usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more from the viewpoint of giving a matte design. On the other hand, the average particle diameter 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 having cloudiness and reducing designability. Or less, more preferably 20 μm or less.
The average particle diameter of the resin particle of the component (C) is usually 1 μm to 100 nm, preferably 1 μm to 60 nm, preferably 1 μm to 30 μm, 1 μm to 20 μm, 2 μm to 100 nm, 2 μm to 60 nm, 2 μm or more 30 μm or less, 2 μm to 20 μm, 3 μm to 100 nm, 3 μm to 60 nm, 3 μm to 30 μm, 3 μm to 20 μm, 4 μm to 20 nm, 4 μm to 100 nm, 4 μm to 60 nm, 4 μm to 30 μm, or 4 μm to 20 μm You may

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

Although the compounding quantity of the resin particle of the said component (C) is based also on the level of the matte design which it is going to give with respect to 100 mass parts of polyfunctional (meth) acrylates of the said component (A), normally 5 mass parts The amount may be 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 compounding amount of the resin particle 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 scratch resistance and bending resistance of the obtained coating film. It may be at most parts, more preferably at most 80 parts, most preferably at most 70 parts.
The compounding amount of the resin particle of the component (C) is usually 5 parts by mass or more and 200 parts by mass or less, preferably 5 parts by mass or more and 150 parts by mass or less, 5 parts by mass or more and 100 parts by mass or less, 5 parts by mass or more and 80 parts 5 parts by weight or more and 70 parts by weight or less, 20 parts by weight or more and 200 parts by weight or less, 20 parts by weight or more and 150 parts by weight or less, 20 parts by weight or more and 100 parts by weight or less, 20 parts by weight or more and 80 parts by weight or less Parts to 70 parts by weight, 30 parts to 200 parts by weight, 30 parts to 150 parts by weight, 30 parts to 100 parts by weight, 30 parts to 80 parts by weight, 30 parts to 70 parts by weight 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 It may be lower.

It is preferable to use two or more types of resin particles having different average particle sizes as the resin particles of the component (C). Even when the amount of the component (C) is small, a good matte design can be obtained (the 60 degree gloss value can be lowered).

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 larger average particle size to the average particle size C2 of the smaller average particle size (C1 / C2) Is preferably 1.2 to 10, more preferably 1.5 to 4. In one embodiment, this ratio may be 1.2-4, 1.5-10.
The ratio (Ca / Cb) (mass ratio) of the compounding amount Ca of a large average particle diameter to the compounding amount Cb of a small average particle diameter 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 to 2, 0.1 to 1.5, 0.3 to 6, 0.3 to 1.5, 0.4 to 6, or 0.4 to 2. May be there.

The paint of the present invention does not contain inorganic particles.
In general, inorganic particles (eg, 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; metal particles etc.) are particularly suitable from the viewpoint of imparting a matt design to inorganic particles having a suitable particle size. Is useful. On the other hand, the interaction between the inorganic particles and the resin component such as the component (A) is weak, which causes the scratch resistance and the bending resistance of the resulting coating film to be insufficient.
Therefore, in the present invention, by using resin particles instead of inorganic particles as particles for giving a matte design, it is possible to favorably maintain the scratch resistance and bending resistance of the coating film.

Here, "does not contain" inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of paint for coating film formation, a significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of providing a matte design. Therefore, “does not contain” 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, relative to 100 parts by mass of the component (A). Can be rephrased as 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.

The paint of the present invention further comprises a compound having two or more isocyanate groups (-N = C = O) in one molecule and / or a photopolymerization initiator from the viewpoint of improving the curability by active energy rays. It is preferable to include it.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis 4-cyclohexyl isocyanate; trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, triol of isophorone diisocyanate. Methylol propane adducts, isocyanurates of tolylene diisocyanate, isocyanurates of hexamethylene diisocyanate, isocyanurates of isophorone diisocyanate, polyisocyanates such as biuret of hexamethylene diisocyanate; and block type isocyanates of the above polyisocyanates Urethane crosslinking agent etc. can be mentioned. As the compound having two or more isocyanate groups in one molecule, a mixture of one or more of them can be used. In addition, during crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethyl hexoate may be added, if necessary.

The compounding amount of the compound having two or more isocyanate groups in one molecule is from the viewpoint of the adhesion between the coating and the substrate and the surface hardness of the coating with respect to 100 parts by mass of the component (A). Usually, it may be 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 compounding 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, more preferably from the viewpoint of reliably obtaining the use effect. May be 1 part by mass or more, more preferably 2 parts by mass or more.
In one embodiment, the compounding 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 Or less, 1 to 20 parts by mass, 1 to 10 parts by mass, 2 to 30 parts by mass, 2 to 20 parts by mass, or 2 to 10 parts by mass. You may

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyl diphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethyl benzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone Acetophenone compounds; anthraquinone compounds such as methyl anthraquinone, 2-ethyl anthraquinone and 2-amyl anthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethyl thioxanthone and 2,4-diisopropyl thioxanthone; alkyls such as acetophenone dimethyl ketal Phenone compounds; triazine compounds; biimidazole compounds; acylphosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenyl acetate compounds; hydroxyketone compounds; 2-methyl-1- (4-methylthio Examples include thiophenyl compounds such as phenyl) -2-morpholinopropan-1-one; and aminobenzoate compounds. Among these, acetophenone compounds and thiophenyl compounds are preferable. As said photoinitiator, the 1 type (s) or 2 or more types of mixtures of these can be used.

The compounding amount of the photopolymerization initiator is usually 10 parts by mass or less, preferably 7 parts by mass from the viewpoint of preventing the formed coating from becoming yellowed and colored with respect to 100 parts by mass of the component (A). It may be at most parts by mass, more preferably at most 5 parts by mass. On the other hand, the compounding 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 from the viewpoint of obtaining the use effect reliably. It may be 2 parts by mass or more.
In one embodiment, the compounding amount of the photopolymerization initiator is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.1 parts by mass or more and 7 parts by mass or less, 0.1 parts by mass or more and 5 parts by mass 0.5 parts by weight or more and 10 parts by weight or less 0.5 parts by weight or more and 7 parts by weight or less 0.5 parts by weight or more and 5 parts by weight or less, 1 parts by weight or more and 10 parts by weight or less, 1 parts by weight or more and 7 parts by weight Or less, 1 to 5 parts by weight, 2 to 10 parts by weight, 2 to 7 parts by weight, or 2 to 5 parts by weight.

In the paint of the present invention, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, as long as the object of the present invention is not violated. One or two or more additives such as a weather resistant stabilizer, a light resistant stabilizer, an ultraviolet light absorber, a heat stabilizer, and an organic coloring agent can be contained.

The paint of the present invention may optionally contain a solvent in order to dilute it to an easy-to-coat concentration. The solvent is not particularly limited as long as it does not react with the components (A), (B), and other optional components, or catalyze (reduce) the self reaction (including deterioration reaction) of these components. I will 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 said solvent, 1 type (s) or 2 or more types of mixtures of these can be used.

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

The method in particular of forming a coating film using the coating material of this invention is not restrict | limited, A well-known web application 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 may be usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more from the viewpoint of scratch resistance. On the other hand, the thickness of the coating film may be 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 is 1 to 100 μm, 1 to 50 μm, 1 to 30 μm, 1 to 15 μm, 2 to 100 μm, 2 to 50 μm, 2 to 30 μm, 2 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 coating 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 surface (the surface on the side that is usually viewed in actual use) of the decorative sheet of the present invention. Here, the actual use state refers to a state in which the decorative sheet is used for making and decorating the surface of various articles.

The decorative sheet of the present invention is not particularly limited. For example, a decorative sheet having a coating film formed using the paint of the present invention on the front surface side of a thermoplastic resin film; A printing layer may be provided on the surface which becomes the front side, and a decorative sheet having a coating film formed using the paint of the present invention on the surface of the printing layer may further be mentioned.

The said thermoplastic resin film is a layer used as the base material of a decorative sheet. The above-mentioned thermoplastic resin film is usually colored from the viewpoint of designability and works to hide the adherend.

Examples of the thermoplastic resin film include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; acrylic resins; polycarbonate resins Poly (meth) acrylimide resins; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / propylene / styrene copolymer, and styrene · Styrene-based resins such as ethylene / ethylene / propylene / styrene copolymers; Cellulose-based resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; Vinylidene fluoride resins; fluorine containing resins such as polyvinylidene fluoride; other resins such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, polyether sulfone A film can be mentioned. These films include non-oriented films, uniaxially oriented films, and biaxially oriented films. Moreover, the laminated | multilayer film which laminated | stacked two or more layers of 1 or more types of these are included.

The coloring agent in particular in the case of coloring the said thermoplastic resin film is not restrict | limited, Arbitrary coloring agents can be used. Examples of the colorant include titanium oxide and carbon black. As said coloring agent, 1 type (s) or 2 or more types of mixtures of these can be used. The compounding amount of the coloring agent is usually about 0.1 to 40 parts by mass, depending on the kind of the coloring agent and the desired hiding property, with 100 parts by mass of the base resin used for the thermoplastic resin film. .

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 at the time of producing a decorative sheet. On the other hand, it may be 300 μm or less, preferably 250 μm or less, from the viewpoint of workability at the time of attaching the decorative sheet to the article.
In one embodiment, the thickness of the thermoplastic resin film may be 50 μm to 300 μm, 50 μm to 250 μm, 75 μm to 300 μm, or 75 μm to 250 μm.

The said printing layer is provided in order to provide high designability, and can be formed by printing arbitrary patterns using arbitrary ink and arbitrary printing machines.

The print layer can be applied entirely or partially on the front side surface of the thermoplastic resin film directly or through an anchor coat. As patterns, metal patterns such as hairlines, grain patterns, stone patterns that imitate the surface of rocks such as marble, cloth patterns that imitate cloth or cloth patterns, tile patterns, brick pile 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 and the like 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. Resins, such as system resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. In order to give metallic designs, aluminum, tin, titanium, indium, oxides thereof, etc., directly or through an anchor coat, are entirely or entirely on the surface of the thermoplastic resin film. It may be partially deposited by known methods.

The method of forming a coating film directly or through an anchor coat on the surface of the printing layer formed on the front surface of the thermoplastic resin film using the paint of the present invention is particularly limited. Alternatively, known web application methods can be used. Examples of the method 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. Further, 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, from the viewpoint of the secondary processability and web handling properties 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 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 It may be 15 μm or more, 3 μm to 100 μm, 3 μm to 50 μm, 3 μm to 30 μm, or 3 μm to 15 μm.

The anchor coat agent for forming the anchor coat is not particularly limited, and any anchor coat 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. As the above-mentioned anchor coating agent, one or more of these can be used.

In the above-mentioned anchor coating agent, if necessary, an antioxidant, a weather resistant stabilizer, a light resistant stabilizer, an ultraviolet light absorber, a thermal stabilizer, an antistatic agent, a surfactant, as long as the object of the present invention is not violated One or more additives such as a colorant, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be contained.

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

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

The decorative sheet of the present invention is provided on the surface opposite to the front surface side of the above-mentioned thermoplastic resin film from the viewpoint of improving the adhesion to an adherend to be decorated or decorated using this. The pressure-sensitive adhesive layer or the adhesive layer may be formed directly or through an anchor coat.

FIG. 1 is a conceptual view of a cross section showing one non-limiting example of the decorative sheet of the present invention. The coating film 1, the printing layer 2, the layer 3 of a colored thermoplastic resin film, and the pressure-sensitive adhesive layer 4 formed from the coating material of the present invention are sequentially provided from the side that is usually viewed in actual use.

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

The value of the mandrel test of the decorative sheet of the present invention is preferably 10 mm or less, more preferably 8 mm or less, still more preferably 6 mm or less, still more preferably 4 mm or less from the viewpoint of bending resistance of the formed coating May be there. The smaller the mandrel test value, the better.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

Measurement Method (i) Smoothness of Coating Film The coating film surface of the decorative sheet was visually observed while changing the incident angle of light of a fluorescent lamp in various ways, and was evaluated according to the following criteria.
◎ (very good): Good without wave or unevenness.
○ (Good): There were slight portions with undulations and uneven irregularities.
((Slightly poor): The portion with undulations and irregularities was slightly noticeable.
X (Defective): There were undulations and irregularities on the whole.

(Ii) 60 degree gloss value (mattiness)
According to JIS Z8741: 1997, using a multi-angle gloss meter “GM-268” (trade name) of Konica Minolta Co., Ltd., the 60 ° gloss value was measured on the coated surface of the decorative sheet.

(Iii) Steel wool resistance (scratch resistance)
Place it on the Gakushin form tester of JIS L 0849: 2013 so that the reciprocation direction of the friction terminal and the machine direction of the makeup sheet are parallel so that the coating film of the makeup sheet is on the surface, After attaching # 0000 steel wool to the friction terminal, a 500 g load was applied, and the surface of the test piece was rubbed 10 times under a condition of a movement distance of 60 mm and a speed of 1 reciprocation / second. The said friction location was visually observed and judged on the following references | standards.
((Very good): no scratch was observed.
○ (Good): There were 1 to 3 scratches.
Δ (Slightly poor): There were 4 to 10 scratches.
X (defect): there were 11 or more scratches.

(Iv) Water contact angle A method of calculating from the width and height of water droplets using the KRUSS automatic contact angle meter “DSA 20” (trade name) for the coated surface of a decorative sheet (refer to JIS R 3257: 1999) It measured by.

(V) Oleic acid removability (dirt removability)
Blending oleic acid (reagent grade 1) from Wako Pure Chemical Industries, Ltd. and carbon black “FW-200” (trade name) from Orion Engineered Carbons Co., Ltd. at a mass ratio of 10/1, and mixing well Contamination was created. Next, 1 mg of the contaminants obtained above was applied in a circular shape with a diameter of 20 mm to the coated surface of the decorative sheet, and then washed away with tap water. Washing with water was carried out for 20 seconds by a method in which a flow rate of 1 liter / 10 seconds was applied directly to the above-mentioned coated contamination at a position 10 cm below the water tap. At this time, if the stain removability is good, it can be observed that the contaminants float off from the coating. The application site of the contaminants was visually observed and evaluated according to the following criteria.
((Very good): The contaminants were completely removed and no application marks remained.
○ (Good): Contaminants were removed, but a slight coating mark remained.
Δ (Slightly poor): Some of the contaminants were not removed but remained at the application site.
X (defect): Many of the contaminants were not removed and remained as they were applied to the application site.

(Vi) Heat and kettle resistance (heat resistance)
1.5 liters of tap water is put into an aluminum kettle (suitable capacity 2 liters) “Neuceret Aluminum Kettle H-2508” (trade name) of Pearl Metal Co., Ltd., and immediately after boiling on the matte coated surface of the decorative sheet I put it directly on. After 5 minutes, the kettle was removed, and the portion of the decorative sheet directly placed on the kettle was visually observed and evaluated according to the following criteria.
((Very good): There was no trace of placing the kettle directly.
○ (Good): There were slightly left traces of placing the kettle directly.
((Slightly poor): Marks of directly placing the kettle were clearly left.
X (defect): the decorative sheet was significantly thermally deformed.

(Vii) Mandrel test (index of crack resistance and bending resistance)
According to JIS K 5600-5-1: 1999, using a sample collected from the decorative sheet so as to be 100 mm in the machine direction × 50 mm in the machine direction, a bending resistance test was conducted by the cylindrical mandrel method. The diameter of the mandrel with the smallest diameter among the non-breaking mandrels was determined.

Raw materials used (A) Multifunctional (meth) acrylate (A2) Multifunctional (meth) acrylate other than multifunctional urethane (meth) acrylate (A2-1) Dipentaerythritol hexaacrylate of Nippon Kayaku Co., Ltd. Number of hydroxyl groups per unit amount: 0.668 mol / kg.

(A1) Multifunctional Urethane (Meth) Acrylate (A1-1) Multifunctional Urethane (Meth) Acrylate “Art Resin UN-1255” (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polyester polyols. Mass average molecular weight 8000.
(A1-2) Multifunctional urethane (meth) acrylate "REAX-2" (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polyester polyols. Mass average molecular weight 4500.
(A1-3) Multifunctional urethane (meth) acrylate "UV 3520 EA" (trade name) of Nippon Synthetic Chemical Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polyester polyols. Mass average molecular weight 14000.
(A1-4) Multifunctional urethane (meth) acrylate "UN 9000 PEP" (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polycarbonate polyols. Mass average molecular weight 5000.
(A1-5) Multifunctional urethane (meth) acrylate "KY101" (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polycaprolactones (polyester polyols). Mass average molecular weight 3000.
(A1-6) Multifunctional urethane (meth) acrylate "KY103" (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polycaprolactones (polyester polyols). Mass average molecular weight 5500.
(A1-7) Multifunctional urethane (meth) acrylate "UN5500" (trade name) of Negami Industrial Co., Ltd. The number 9 of (meth) acryloyl groups. All polyol compounds are polycarbonate polyols. Mass average molecular weight 86000.

(A'1) Multifunctional urethane (meth) acrylates other than the above component (A1) (A'1-1) Multifunctional urethane (meth) acrylate "Art resin UN-6300" (trade name) manufactured by Negami Co., Ltd. The number 2 of (meth) acryloyl groups. Polyol compounds are polyether polyols. Mass average molecular weight 12700.

(B) Compound having an anionic hydrophilic group (B-1) 3-sulfonylpropyl-acrylate potassium salt (compound of the following formula 2).

(B-2) A compound of the following formula 3.

(B-3) a compound of the following formula 4.

(C) Resin particles having an average particle diameter of 1 to 100 μm. (C-1) Resin particles “CERAFLOUR 1000” (trade name) of BIC Chemie Japan Ltd. Average particle size 5 μm.
(C-2) Acrylic resin particles "Art Pearl SE-010T" (trade name) of Negami Industrial 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 of Wright Chemical Industries, Ltd. Number of isocyanate groups per unit amount: 5.95 mol / kg.
(D-2) Acetophenone photopolymerization initiator (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane- of BASF AG 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 non-crystalline polyester resin "VYLON 103" (trade name) of Toyobo Co., Ltd., 10 parts by mass of hydroxyphenyl triazine ultraviolet absorber "TINUVIN 479" (trade name) of 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 33 parts by mass of the component (A2-1), 67 parts by mass of the component (A1-1), 37 parts by mass of the component (B-1), 30 parts by mass of the component (C-1), the component C-2) 20 parts by mass, 6 parts by mass of the component (D-1), 3.5 parts by mass of the component (D-2), 50 parts by mass of the component (D-3), and the component (D-4) 150 parts by mass was mixed and stirred to obtain a paint.

2. Production of decorative sheet (2-1) A vinyl chloride / vinyl acetate copolymer is formed on one side of a colored polybutylene terephthalate resin film "HR (WHT)" (trade name) with a thickness of 250 μm and white of Riken Technos Co., Ltd. A printing layer having a thickness of 1 μm was formed using an ink as a medium.

(2-2) Next, a film mayer bar type coating apparatus is used on the surface of the printing layer formed in the above (2-1), and after curing using the above anchor coating agent (P-1) The anchor coat layer was formed to have a thickness of 0.8 μm.

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

The above tests (i) to (vii) were performed on the obtained decorative sheet. The results are shown in Table 1.

Examples 2-16, 6-1
Preparation of a decorative sheet and measurement and evaluation of physical properties were conducted in the same manner as in Example 1 except that the composition of the paint was changed to those shown in Table 1 or 2. The results are shown in Tables 1 and 2.

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

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

1: Coating 2: Printing layer 3: Layer of colored thermoplastic resin film 4: Adhesive layer

Claims

(A) 100 parts by mass of polyfunctional (meth) acrylate;
(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 phosphoric acid group;
Does not contain inorganic particles,
Here, the above (A) polyfunctional (meth) acrylate is derived from one or more types of polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the total of structural units derived from polyol compounds being 100% by mass. (A1) multifunctional urethane (meth) acrylate containing 50% by mass or more of the constituent units in an amount of 10 to 90% by mass, based on 100% by mass of the total of (A) polyfunctional (meth) acrylates Including
paint.
The paint according to claim 1, further comprising 5 to 200 parts by mass of resin particles (C) having an average particle diameter of 1 to 100 μm with respect to 100 parts by mass of the component (A) polyfunctional (meth) acrylate.
The paint according to claim 1 or 2, wherein the weight average molecular weight of the component (A1) polyfunctional urethane (meth) acrylate is 3,000 to 50,000.
A decorative sheet comprising a coating film formed from the paint according to any one of claims 1 to 3.
A coating film formed of the paint according to any one of claims 1 to 3 and a layer of a thermoplastic resin film in order from the side of the side that is usually viewed in the actual use state;
The water contact angle of the surface of the above-mentioned coating film is 15 degrees or less;
The decorative sheet whose value of a mandrel test is 10 mm or less.