JP7109284B2 - Stain-removable paint for forming coating film, and decorative sheet using the same - Google Patents

Description

The present invention relates to coatings. More specifically, the present invention relates to a coating capable of forming a coating film having excellent stain-removing properties (hereinafter sometimes referred to as a "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, storage chests, cupboards, and desks; Base material formed using wood-based materials such as plywood, laminated wood, particle board, and hardboard; using resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester or a base material formed using a metallic material such as iron or aluminum; a decorative sheet is attached to the surface of the base material to decorate it.

In recent years, attention has been focused on dirt removability 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 (eg, Patent Document 1). However, there is a problem that the decorative sheet having a stain-removing coating film formed by these techniques has insufficient bending resistance and is 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 coating material capable of forming a coating film having excellent stain removability and bending resistance, and a decorative sheet using the same. Another object of the present invention is to provide a paint which is excellent in stain-removing properties and capable of forming a coating film capable of imparting a matte design, and a matte decorative sheet using the same. . Another object of the present invention is to provide a paint that is excellent in stain removal and bending resistance and capable of forming a coating film capable of imparting a matte design, and a matte decorative sheet using the same. is 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.

That is, the present invention has (A) 100 parts by mass of (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. compound 5 to 100 parts by mass; wherein the component (A) (meth) acrylate is (A1) polyfunctional (meth) acrylate 40 to 99 mass% and (A2) 3-phenoxybenzyl (meth) acrylate or 3-phenoxybenzyl (meth)acrylate derivative 60 to 1% by mass; component (A1) polyfunctional (meth)acrylate and component (A2) 3-phenoxybenzyl (meth)acrylate or 3-phenoxybenzyl (meth) The sum with the acrylate derivative is 100% by weight; it does not contain inorganic particles; it is a paint.

A second invention according to the first invention, further comprising (C) 1 to 200 parts by mass of resin particles having an average particle diameter of 1 to 100 μm in addition to 100 parts by mass of the (meth)acrylate component (A). It's paint.

A third invention is the paint according to the first invention or the second invention, wherein the component (A2) contains 3-phenoxybenzyl (meth)acrylate.

A fourth invention is the paint according to any one of the first to third inventions, further comprising one or more selected from the group consisting of methanol and ethanol.

A fifth invention is a decorative sheet comprising a coating film formed from the paint according to any one of the first to fourth inventions.

A sixth invention has a coating film formed from the paint according to any one of the first to fourth inventions and a layer of a thermoplastic resin film in order from the side that is normally visible in actual use. a water contact angle of 25 degrees or less on the surface of the coating film; a mandrel test value of 10 mm or less; a decorative sheet.

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

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 comprises (A) (meth)acrylate; and (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 phosphoric acid group; include. In this specification, (meth)acrylate means acrylate or methacrylate. The paint of another embodiment of the present invention has at least one anionic hydrophilic group selected from the group consisting of (A) (meth)acrylate; (B) a sulfonic acid group, a carboxyl group, and a phosphoric acid group. compound; and (C) resin particles having an average particle size of 1 to 100 μm. In one preferred embodiment, the paint of the present invention contains one or more selected from the group consisting of methanol and ethanol. The component (A) includes (A1) a polyfunctional (meth)acrylate and (A2) 3-phenoxybenzyl (meth)acrylate or a 3-phenoxybenzyl (meth)acrylate derivative. The component (A) preferably consists of (A1) a polyfunctional (meth)acrylate and (A2) 3-phenoxybenzyl (meth)acrylate or a 3-phenoxybenzyl (meth)acrylate derivative. The paint of the present invention does not contain inorganic particles. Each component will be described below.

(A) (meth)acrylate;
The component (A) (meth)acrylate is a compound having one or more (meth)acryloyl groups in one molecule. The component (A) functions to form a coating film by being polymerized and cured by heat or active energy rays such as ultraviolet rays and electron beams. The component (A) includes (A1) a polyfunctional (meth)acrylate and (A2) 3-phenoxybenzyl (meth)acrylate or a 3-phenoxybenzyl (meth)acrylate derivative. The component (A) preferably consists of (A1) a polyfunctional (meth)acrylate and (A2) 3-phenoxybenzyl (meth)acrylate or a 3-phenoxybenzyl (meth)acrylate derivative.

(A1) Polyfunctional (meth)acrylate:
The component (A1) is a (meth)acrylate having two or more (meth)acryloyl groups in one molecule. The above component (A1) functions to improve the curability of the paint and improve the solvent resistance and scratch resistance.

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, Bifunctional reactions containing (meth)acryloyl groups such as 2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane (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 octaacrylate monomers; and polymers (oligomers and prepolymers) containing at least one of these constituent monomers and having two or more (meth)acryloyl groups in one molecule.

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.

One or a mixture of two or more thereof can be used as the component (A1).

(A2) 3-phenoxybenzyl (meth)acrylate or 3-phenoxybenzyl (meth)acrylate derivative:
The component (A2) is 3-phenoxybenzyl (meth)acrylate or a 3-phenoxybenzyl (meth)acrylate derivative. The component (A2) functions to improve the bending resistance. The 3-phenoxybenzyl (meth)acrylate is a compound represented by the following general formula (1-1).

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

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

In formula (1-2), _R1 represents hydrogen or a methyl group. R ₂ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The hydrocarbon group may be linear or branched. The hydrocarbon group may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. s is an integer from 1 to 4, preferably 1; When s is an integer of 2-4, R ₂ may be the same or different. R ₃ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The hydrocarbon group may be linear or branched. The hydrocarbon group may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. t is an integer from 1 to 5, preferably 1 or 2; When t is an integer of 2-5, R ₃ may be the same or different. R ₂ and R ₃ may be the same or different.

Among these, 3-phenoxybenzyl (meth)acrylate is preferable as the component (A2), and 3-phenoxybenzyl acrylate is more preferable. One or a mixture of two or more thereof can be used as the component (A2).

The mass ratio of the component (A1) and the component (A2) in the component (A) is determined based on the sum of the component (A1) and the component (A2) being 100% by mass. From the viewpoint of scratch resistance and stain removability, the component (A1) is usually 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, most preferably It is 65% by mass or more. The above component (A2) is usually 60% by mass or less, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and most preferably 35% by mass or less. On the other hand, from the viewpoint of bending resistance, the component (A2) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 12% by mass or more. The component (A1) is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 88% by mass or less.

The component (A) may contain (meth)acrylates other than the component (A1) and the component (A2) as long as the object of the present invention is not compromised. The other (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and octyl (meth)acrylate. Alkyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, and hydroxyl group-containing (meth)acrylates such as caprolactone (meth)acrylate; and compounds having one (meth)acryloyl group in one molecule. One or more of these can be used as the other (meth)acrylates.

(B) a compound having an anionic hydrophilic group:
The component (B) compound having an anionic hydrophilic group is 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. The above component (B) functions to improve the stain removability. 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 above compound (I) is a compound represented by the following general formula (2).

(Chemical 2)
[X]s[M1]L[ _M2 ]m ( ₂ )

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 groups represented by the following general formulas (2-1) to (2-4).

In formulas (2-1) to (2-4), 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. The aliphatic hydrocarbon group may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group. The above aliphatic hydrocarbon group may have any substituent. In this case, the total number of carbon atoms including substituents should be within the above range. R and R' may be the same or different.

As the component (B), among these, a compound represented by the above general formula (2) having a hydrophilic group represented by the above general formula (2-1) is preferable from the viewpoint of stain removability.

The amount of component (B) to be blended is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, from the viewpoint of stain removability with respect to 100 parts by mass of component (A). More preferably, it is 30 parts by mass or more. On the other hand, from the viewpoint of the curability and scratch resistance of the paint, it is usually 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.

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

Examples of the component (C) include silicone-based resins, styrene-based resins, acrylic-based resins, fluorine-based resins, polycarbonate-based resins, ethylene-based resins, urethane-based resins, and cured resins of amino-based compounds and formaldehyde. Resin particles can be mentioned. 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. By using one having a reactive functional group, the scratch resistance of the coating film can be improved. One or a mixture of two or more thereof can be used as the component (C).

From the viewpoint of imparting a matte design, the average particle size of component (C) may be usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. On the other hand, from the viewpoint of preventing the coating film from becoming cloudy and deteriorating the design property, it may be usually 100 μm or less, preferably 60 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less.

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

The amount of component (C) to be blended is usually 1 part by mass or more, preferably 5 parts by mass or more, although it depends on the level of the matte design to be imparted with respect to 100 parts by mass of component (A). It may be preferably 10 parts by mass or more, more preferably 15 parts by mass or more. On the other hand, from the viewpoint of scratch resistance and bending resistance, it is usually 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and most preferably 30 parts by mass or less. can be

It is preferable to use two or more kinds of resin particles having different average particle sizes as the component (C). 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. The ratio (Ca/Cb) of the compounding amount Ca with a large average particle size and the compounding amount Cb with a small average particle size is preferably 0.1 to 6, more preferably 0.3 to 2, and still more preferably 0 .4 to 1.5.

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; and metal particles; useful from that point of view. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes insufficient scratch resistance and bending resistance. Therefore, in the present invention, resin particles are used as the particles for imparting a matte design, and the scratch resistance and bending resistance are maintained satisfactorily by not containing inorganic particles.

Here, "free of" inorganic particles means not containing any significant amount of inorganic particles. In the field of film-forming paints, 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, "does not contain" inorganic particles means that the amount of inorganic particles is usually less than 1 part by mass, preferably 0.5 parts by mass or less, more preferably 0.1 part by mass, relative to 100 parts by mass of the component (A). Parts by mass, 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.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-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, from the viewpoint of reliably obtaining the effect of using a compound having two or more isocyanate groups in one molecule, usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, More preferably, it may be 2 parts by mass or more.

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 15 parts by mass or less, preferably 10 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 7 parts by mass or less, more preferably 7 parts by mass or less. On the other hand, from the viewpoint of reliably obtaining the effect of using the photopolymerization initiator, the amount 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 2 parts by mass or more. you can

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 above components (A) to (C) and other optional components, or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. not. Examples of the solvent include methanol, ethanol, 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.

From the viewpoint of stain removal, the solvent preferably contains one or more selected from the group consisting of methanol and ethanol, and a large amount of one or more selected from the group consisting of methanol and ethanol (usually 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, most preferably 70 to 100% by mass, where the sum of the amounts of all solvents is 100% by mass %.) is more preferable.

In the paint of the present invention, one or more selected from the group consisting of methanol and ethanol is preferably added to 100 parts by mass of the component (B) in an amount of preferably 50 parts by mass or more, more preferably, from the viewpoint of stain removal properties. may contain 100 parts by mass or more, more preferably 120 parts by mass or more. The upper limit of the amount of one or more selected from the group consisting of methanol and ethanol is not particularly limited, and is appropriately determined from the viewpoint of maintaining the viscosity of the paint of the present invention at a concentration that facilitates coating. The upper limit of the amount of one or more selected from the group consisting of methanol and ethanol may be usually 200 parts by mass or less, preferably 150 parts by mass or less per 100 parts by mass of component (A).

Although not intending to be bound by theory, the reason why it is preferable to include methanol or ethanol in the paint of the present invention from the viewpoint of stain removal is considered as follows. Solvents such as methanol and ethanol that are mutually soluble with water at an arbitrary mixing ratio at the molecular level have very high affinity with the hydrophilic groups of component (B). Therefore, in the step of drying after forming a wet coating film, when the solvent is volatilized from the surface of the coating film, the hydrophilic groups of the component (B) gather near the surface of the coating film as the solvent moves. . As a result, the water contact angle is efficiently reduced, and the stain removability is improved. Also, if this consideration is correct, it can be said that solvents other than methanol and ethanol, such as acetone, which are mutually soluble at the molecular level in an arbitrary mixing ratio with water, are also preferable solvents from the standpoint of stain removal. .

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, from the viewpoint of bending resistance, the thickness 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.

2. Cosmetic 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.

Examples of the decorative sheet of the present invention include, for example, a decorative sheet having a coating film formed using the paint of the present invention on the front surface of a thermoplastic resin film; the front surface of the thermoplastic resin film a decorative sheet having a printed layer provided thereon and a coating film formed by using the coating composition of the present invention on the surface of the printed layer;

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 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 resins such as polyvinylidene fluoride Resin; In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone; These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated|stacked 2 or more layers of 1 or more types of these is included.

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.

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 method include roll coating, gravure coating, reverse coating, roll brushing, spray 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. From the viewpoint of the secondary processability and web handleability of the decorative sheet of the present invention, the thickness 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.

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 method 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 provided on the side opposite to the front side of the thermoplastic resin film, from the viewpoint of improving adhesion to the adherend to be decorated and decorated using the decorative sheet of the present invention. A pressure-sensitive adhesive layer or adhesive layer may be formed on the surface directly or via an anchor coat.

FIG. 1 is a schematic cross-sectional view showing an example of the decorative sheet of the present invention. It has a coating film 1 made of 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 25 degrees or less, more preferably 18 degrees or less, and still more preferably 18 degrees or less, from the viewpoint of stain removal. It may be 14 degrees or less, most preferably 10 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 most preferably 4 mm or less, from the viewpoint of bending resistance. 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 (a) Smoothness of coating film:
The coating film surface of the decorative sheet was visually observed while the incident angle of light from a fluorescent lamp was varied, and evaluated according to the following criteria.
⊚: Good with no undulation or irregularities.
◯: There was a portion with slight undulations and irregular unevenness.
Δ: There was a portion with undulations and irregular unevenness.
x: There were undulations and irregularities on the whole.

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

(c) Steel wool resistance (scratch resistance):
Place it on a JIS L 0849: 2013 Gakushin-type tester so that the coating surface 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, and the Gakushin-type test After attaching #0000 steel wool to the friction terminal of the machine, a load of 500 g was placed, and the surface of the test piece was rubbed back and forth 10 times at 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.
A: No scratch was observed.
◯: There were 1 to 3 scratches.
Δ: There were 4 to 10 scratches.
x: There were 11 or more scratches.

(d) Water contact angle:
The coating film surface of the decorative sheet was measured using an automatic contact angle meter "DSA20 (trade name)" manufactured by KRUSS by a method of calculating from the width and height of water droplets (see JIS R 3257:1999).

(E) Dirt removability 1 (oleic acid 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.
⊚: The contaminants were completely removed, and no trace of application remained.
◯: Contaminants were removed, but traces of application remained slightly.
Δ: Some of the contaminants were not removed and remained in the applied area.
x: Many of the contaminants were not removed and remained as they were when applied to the application area.

(f) Stain removability 2 (water-based red ink removability):
Using a red water-based pigment marker “Juice Paint (trade name)” from Pilot Co., Ltd., a circle with a diameter of 20 mm was drawn on the coating surface of the decorative sheet, and the inside of the circle was filled in (hereinafter, what was drawn with the marker are referred to as “contaminants”). After conditioning for 24 hours at a temperature of 25° C. and a relative humidity of 50%, the contaminants were washed away with tap water. The washing was carried out for 20 seconds by directly applying running water at a flow rate of 1 liter/10 seconds to the contaminants at a position 10 cm below the faucet. At this time, if the dirt removability is good, the above-mentioned contaminants can be observed to float and peel off from the coating film. The locations where the contaminants were drawn were visually observed and evaluated according to the following criteria.
⊚: Contaminants were completely removed and no trace of drawing remained.
◯: Contaminants were removed, but traces of drawing remained slightly.
Δ: Part of the contaminant was not removed and remained in the drawn area.
x: Many of the contaminants were not removed and remained as they were when drawn in the drawn area.

(g) Solvent resistance:
So that the coating surface of the decorative sheet is the surface, and the reciprocating direction of the friction terminal and the machine direction of the decorative sheet are parallel, JIS L0849: 2013 Gakushin type tester (friction tester type 2) placed. Subsequently, a stainless plate (length 10 mm, width 10 mm, thickness 1 mm) covered with four layers of gauze (medical type 1 gauze manufactured by Kawamoto Sangyo Co., Ltd.) was attached to the friction terminal of the Gakushin type tester. Set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, place a load of 500 g, soak the gauze with methyl ethyl ketone sufficiently (to the extent that it is soaked), and then move the distance of 60 mm and the speed of 1 reciprocation / second. The surface of the test piece was rubbed back and forth 20 times. The friction points were visually observed and judged according to the following criteria.
A: No change was observed in the coating film. There was no difference between the luster of the rubbed portion and the luster of the non-rubbed portion.
○: The gloss of the rubbed portion was slightly lower than the gloss of the non-rubbed portion. However, no change was observed in the smoothness of the coating film (evaluated by the method of test (a) above; hereinafter the same).
Δ: The gloss of the rubbed portion was clearly lower than that of the non-rubbed portion. However, no change was observed in the smoothness of the coating film.
x: The gloss of the rubbed portion was remarkably lower than the gloss of the non-rubbed portion. Furthermore, the smoothness of the coating film at the rubbed portion was reduced.

(H) 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)” manufactured by Pearl Metal Co., Ltd. I left it. 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.
(double-circle): The trace which the kettle was directly placed did not remain at all.
◯: A trace of direct placement of the kettle was slightly left.
Δ: Marks of direct placement of the kettle were clearly left.
x: The decorative sheet was remarkably thermally deformed.

(I) Mandrel test (indicator of crack resistance and bending resistance):
In accordance with JIS K5600-5-1:1999, a bending resistance test was performed by a cylindrical mandrel method using a sample taken from the decorative sheet so as to have a size of 100 mm in the machine direction of the decorative sheet and 50 mm in the transverse direction. The diameter of the mandrel with the smallest diameter among the mandrels that did not crack was determined.

Raw material (A1) polyfunctional (meth)acrylate used:
(A1-1) Dipentaerythritol hexaacrylate from Nippon Kayaku Co., Ltd.;
(A1-2) Polyfunctional urethane (meth)acrylate “Artresin UN-1255 (trade name)” from Neagari Kogyo Co., Ltd.; The number of (meth)acryloyl groups is two.

(A2) 3-phenoxybenzyl (meth)acrylate or 3-phenoxybenzyl (meth)acrylate derivative:
(A2-1) Kyoeisha Chemical Co., Ltd. 3-phenoxybenzyl acrylate “Light acrylate POB-A (trade name)”.

(A′) monofunctional acrylate other than component (A2) above:
(A′-1) Kyoeisha Chemical Co., Ltd. 2-hydroxy-3-phenoxypropyl acrylate “Epoxy Ester M-600A (trade name)”.
(A′-2) Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate “Light acrylate PO-A (trade name)”.

(B) a compound having an anionic hydrophilic group (B-1) 3-sulfonylpropyl-acrylate potassium salt (compound of formula 3-1 below);

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

(B-3) A compound of formula 3-3 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)” manufactured by Neagari Kogyo Co., Ltd. Average particle size 10 μm.

(D) Other ingredients:
(D-1) Compound "RV2 (trade name)" having two or more isocyanate groups in one molecule, available from Light Chemical Industry Co., Ltd.
(D-2)) Acetophenone-based photoinitiator from BASF (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.
(D-5) ethanol.

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, the above components ( D-1) A paint obtained by mixing and stirring 3.3 parts by mass, 120 parts by mass of methyl ethyl ketone, and 240 parts by mass of ethyl acetate.

Example 1
1. Preparation of paint:
The component (A1-1) 86 parts by mass, the component (A2-1) 14 parts by mass, the component (B-1) 37 parts by mass, the component (C-2) 16 parts by mass, the component (D-1) ), 6 parts by mass of component (D-2), 68 parts by mass of component (D-3), and 14 parts by mass of component (D-4) were mixed and stirred to obtain a paint.

2. Production of decorative sheets:
(2-1) On one side of a 250 μm-thick white polybutylene terephthalate resin film “HR (WHT) (trade name)” manufactured by RIKEN TECHNOS CO., LTD. was used to form a 1 μm-thick wood-grain printed layer.

(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 (a) to (i). Table 1 shows the results.

Examples 2-15
The same procedure as in Example 1 was carried out except that the formulation of the paint was changed to that shown in Table 1 or 2. The results are shown in Table 1 or 2.

The decorative sheet on which a coating film made of the paint of the present invention was formed was excellent in stain removability. The decorative sheet on which a coating film made of the coating material of another embodiment of the present invention was formed was excellent in stain removability and had a matte design. Also, from the results of the mandrel test, it was determined that the method can be applied to so-called 2D molding such as lapping molding.

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

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

Claims (7)

(A) (meth) acrylate 100 parts by mass ;
(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; and
(D) a solvent that is mutually soluble at the molecular level with water in any mixing ratio;
including
Here, the component (A) (meth)acrylate is
(A1) polyfunctional (meth)acrylate 40 to 99% by mass and (A2) 3-phenoxybenzyl (meth)acrylate or 3-phenoxybenzyl (meth)acrylate derivative 60 to 1% by mass;
The sum of the component (A1) polyfunctional (meth)acrylate and the component (A2) 3-phenoxybenzyl (meth)acrylate or 3-phenoxybenzyl (meth)acrylate derivative is 100% by mass;
does not contain inorganic particles;
paint.
Per 100 parts by mass of the component (A) (meth)acrylate, (C) resin particles having an average particle diameter of 1 to 100 μm 1
~200 parts by weight; The paint of Claim 1.
3. The paint according to claim 1 , wherein said component (D) is a solvent mutually soluble with water at a molecular level at any mixing ratio, and contains one or more selected from the group consisting of methanol and ethanol.
The above component (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 phosphoric acid group,
The paint according to any one of claims 1 to 3, comprising a compound represented by the general formula [X]s[M1]L[M2]m:
Here, in the above general formula, s represents 1 or 2, L represents 1 or 2, m represents 0 or 1, M1 and M2 may be the same or different hydrogen ion, ammonium ion, alkali metal represents an ion or an alkaline earth metal ion, and X represents one selected from hydrophilic groups represented by the following general formulas (2-1) to (2-4):

Here, in the above general formulas (2-1) to (2-4), J and J 'may be the same or different H, or CH ₃ , n represents 0 or 1, and R and R' are aliphatic hydrocarbon groups having 1 to 600 carbon atoms which may be the same or different.
The paint according to any one of claims 1 to 4, wherein the component (A2) contains 3-phenoxybenzyl (meth)acrylate.
A decorative sheet comprising a coating film formed from the coating material according to any one of claims 1 to 5 .
A coating film formed from the coating material according to any one of claims 1 to 5 , 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 25 degrees or less;
Mandrel test value is 10 mm or less;
cosmetic sheet.

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