JP2005298722A - Polymer solution, lusterless coating material and decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer solution that gives delustering properties to the coating film matrix itself, when applied onto a substrate sheet and dried to form the coating film, and a lusterless coating material and decorative sheet using the solution. <P>SOLUTION: This polymer solution is obtained by dissolving in an organic solvent two or more kinds of polymers having a film-forming ability and little compatibility with each other. When the polymer solution is applied onto a substrate sheet and dried to form a coating film having a thickness of 0.1-100 μm, uneven patterns in random curve shapes are formed on the surface of the coating film. Lusterless coating materials are prepared, using the solution. Decorative sheets are prepared by using the lusterless coating material to form a luster adjusting layer on the substrate sheet. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer solution, a matte paint and a decorative sheet. More specifically, in the present invention, when a coating film is provided by applying and drying on a base sheet, a random curved line uneven pattern having an arithmetic average roughness of about 0.02 to 5 μm ( A polymer solution suitably used for matte paints, and a coating film obtained by using this polymer solution with a matte appearance and having a very fine surface. The present invention relates to a matte paint and a decorative sheet having a gloss adjustment layer provided using the matte paint.

Conventionally, as a decorative sheet for furniture and kitchen products, for example, a decorative sheet in which a wood pattern, etc., is printed on a metal material such as a wood material, an inorganic material, a synthetic resin material, or a steel plate. The thing of the structure bonded together with the adhesive agent is used.
The decorative sheet used for such a decorative sheet is suitable for secondary processing such as laminating, lapping, and V-cut, suitable for processing such as machinability and rupture resistance, and usage conditions. Various properties such as weather resistance, light resistance, heat resistance, water resistance, solvent resistance, surface hardness, abrasion resistance, and scratch resistance are required.
In order to satisfy such required characteristics, the base material of the decorative sheet is made of heat such as polyvinyl chloride resin, polyolefin resin, polyester resin from the viewpoint of balance of various physical and chemical properties. Plastic resin is used.
On the other hand, timber has been mainly used as a building material in the past, but since timber is inevitably restricted in use for forest protection, polyvinyl chloride resin, Thermoplastic resins such as polyolefin resins and polyester resins are used.
As the thermoplastic resin used in the decorative sheet and building material, in recent years, due to market demands, non-halogen thermoplastic resins such as polyolefin resin, polyester resin, acrylic resin, among others, In terms of physical properties, since it is similar to polyvinyl chloride resin and is inexpensive, demand for decorative sheets and building materials based on polyolefin resin or polyester resin is increasing.
Various configurations of this decorative sheet are known. For example, an acrylic resin is formed on a sheet substrate made of an olefin resin in which a thermoplastic elastomer and an inorganic filler are blended with high-density polyethylene through a pattern printing layer. A decorative sheet formed by sequentially laminating a protective sheet, a gloss adjusting layer, and a printing layer having a gloss different from that of the gloss adjusting layer is disclosed (for example, see Patent Document 1).
As described above, a decorative sheet is usually often provided with a gloss adjusting layer. In general, the gloss adjusting layer is often obtained by moderately suppressing the light reflectance, and is usually produced by applying a coating material for forming a gloss adjusting layer to which an appropriate matting agent is dispersed.
As the matting agent, a type having a property of scattering light, or a type that itself is transparent in the coating film, but forms irregularities on the surface of the protective layer to change the light reflectance of the surface. Particles are used. In the latter type, transparency is maintained, and even if the incident angle or observation angle of light is changed, there is less change in reflection of light. There is an advantage that there is little change and the rubbing trace is hard to remain. Specifically, matte particles such as hollow particles such as mica, silica, alumina, calcium carbonate, diatomaceous earth, silica sand, or shirasu balloon, and synthetic resin particles such as polystyrene resin and acrylic resin are matted. The gloss adjusting layer can be prepared by applying the additive used in the paint for forming the gloss adjusting layer according to the required gloss level. In addition, without providing a gloss adjusting layer, the above-mentioned matting agent is contained in the protective layer to impart a gloss adjusting function to the protective layer itself.
However, when such a matting agent is used, there is a problem that irregularities due to matting agent particles are formed on the surface, so that the surface roughness is large and it is difficult to obtain a fine surface. In addition, in order to impart desired matting properties, the amount of matting agent used may need to be increased, resulting in other physical properties such as scratch resistance and adhesion to adjacent layers. There was also a problem that it might decrease.
On the other hand, a coating composition is disclosed which has a ladder silicone structure and is formed by blending a silicone oligomer, silicone polymer or silicone copolymer and an organic polymer powder to give a matte coating film (for example, Patent Documents). 2). However, in this case as well, the problems pointed out above occur.
In the conventional gloss adjustment layer or protective layer with gloss adjustment function, the resin matrix itself, which is a film-forming component, has almost no matte properties, so avoid the above-mentioned problems. I can't. Accordingly, it has been desired to impart a matte function to the resin matrix itself, which is a coating film forming component, without impairing transparency (visibility of the pattern layer or the like).
JP-A-10-146933 JP 7-166133 A

  Under such circumstances, the present invention, when applied to a substrate sheet and dried to form a coating film, imparts matting properties to the coating film matrix itself and is suitable for matting paints. The polymer solution used, and a coating obtained by using this polymer solution has a matte appearance and has a very fine surface without impairing other physical properties such as scratch resistance and adhesion. An object of the present invention is to provide a matte paint that gives a film, and a decorative sheet having a gloss adjustment layer formed using the matte paint.

As a result of intensive studies to achieve the above object, the present inventors have found that a polymer solution in which two or more types of incompatible polymers having a film-forming ability and a poor compatibility are dissolved in an organic solvent. Is applied to the substrate sheet and dried to provide a coating film having a thickness in a predetermined range. It has been found that a wrinkle pattern is formed on the surface, and matting properties are imparted to the matrix of the coating film itself.
Further, by using this polymer solution and optionally containing organic particles, a matte paint that can be adapted to the above-mentioned purpose can be obtained, and a matte adjusting layer using the matte paint on a substrate sheet It has been found that a decorative sheet having an appearance controlled to have a desired gloss can be obtained by providing.
The present invention has been completed based on such findings.
That is, the present invention
(1) A polymer solution obtained by dissolving two or more incompatible polymers having an ability to form a coating film in an organic solvent. A polymer solution characterized in that, when a coating film having a thickness of 1 to 100 μm is provided, a random curved surface uneven pattern is formed on the surface of the coating film;
(2) Item (1) above, wherein in the corrugation of the cross section of the random curved line irregular pattern formed on the coating film surface, there are 10 or more convex portions having a height of 0.2 to 2.3 μm in a 300 μm pitch. Polymer solution of
(3) Item (1) or (2) above, wherein there are two types of incompatible polymers, and one of them is a silicone oligomer, silicone polymer or silicone copolymer having a ladder silicone structure. Polymer solution,
(4) Another one of the incompatible polymers is a polymer solution according to the above (3), which is a methyl methacrylate comb polymer,
(5) The above (4), wherein the content ratio of the silicone oligomer, silicone polymer or silicone copolymer having a ladder silicone structure and the methyl methacrylate comb polymer is 50:50 to 90:10 by weight. The polymer solution according to Item,
(6) The polymer solution according to any one of (1) to (5) above, wherein the organic solvent is a mixture of two or more organic compounds having volatility and different boiling points,
(7) The polymer solution as described in (6) above, wherein the organic solvent is a mixed solvent of an aliphatic alcohol having an alkoxyl group in the molecule and an aliphatic / alicyclic ketone.
(8) The polymer solution according to (7) above, wherein the aliphatic alcohol having an alkoxyl group in the molecule is 1-methoxy-2-propanol, and the aliphatic / alicyclic ketone is methyl ethyl ketone,
(9) A matte paint using the polymer solution according to any one of (1) to (8) above,
(10) The matte paint according to the above (9), wherein the content of the hardly compatible polymer is 10 to 40% by weight,
(11) The matte paint as described in (9) or (10) above, containing 1 to 20% by weight of organic fine particles, and (12) a base sheet, and (9), (10) or ( A decorative sheet comprising a gloss adjusting layer formed using the matte paint according to item 11),
Is to provide.

According to the present invention, when a coating film is provided by applying and drying on a substrate sheet, the surface of the coating film has a random curved surface uneven pattern (wrinkle pattern) having an arithmetic average roughness of about 0.02 to 5 μm. Can be formed, and a polymer solution suitably used for matte paint can be provided.
Further, by using the polymer solution, a matte paint that gives a matte appearance and has a very fine surface without impairing other physical properties such as scratch resistance and adhesion. Furthermore, a decorative sheet having an appearance controlled to a desired gloss can be provided by providing a gloss adjusting layer on the base sheet using the mat paint.

First, the polymer solution of the present invention will be described.
The polymer solution of the present invention is a uniform solution obtained by dissolving two or more types of incompatible polymers having an ability to form a coating film in an organic solvent. And when this polymer solution is apply | coated and dried on a base material sheet and a coating film with a thickness of 0.1-100 micrometers is provided, a random curved surface uneven | corrugated pattern (wrinkle pattern) is formed in this coating-film surface. It is characterized by that.
Here, the two or more types of incompatible polymers indicate that the two or more types of polymers to be used do not substantially mix with each other. This can be confirmed, for example, by the following method. Can do.
Two or more polymers to be used are dissolved in methyl ethyl ketone so that the solid content is 30% by weight. At this point, each solution is completely dissolved and transparent. Next, when this transparent resin solution is mixed at the same weight, in the case of a poorly compatible polymer, a phenomenon of white turbidity is observed.
In the present invention, two or more such incompatible polymers are preferably two types of polymers, and one of the two types of polymers is a silicone polymer having a ladder silicone structure, Specifically, a silicone oligomer, a silicone polymer, or a silicone copolymer is preferable.

The silicone oligomer having the ladder silicone structure is, for example, an oligomer obtained by hydrolytic condensation of trialkoxysilane or trichlorosilane, and has a weight average molecular weight of about 500 to 5,000. This terminal is a hydroxyl group or an alkoxyl group, and is cured by heating or by the action of a base such as tert-butylamine or a metal salt such as tin octylate. Depending on the type of substituent of trialkoxysilane and trichlorosilane, the desired type and amount of alkyl group, phenyl group, acrylic group, methacryl group, vinyl group, epoxy group, hydroxyl group, carboxyl group, mercapto group, amino group, etc. Ladder silicone oligomers having chains are obtained, which can each be three-dimensionalized by a suitable curing method.
A silicone polymer having a ladder silicone structure is a monofunctional silane such as monoalkoxysilane or monochlorosilane, which is obtained by proceeding hydrolysis and condensation of trialkoxysilane or trichlorosilane to a weight average molecular weight of about 10,000 or more. Bifunctional silanes such as dialkoxysilane and dichlorosilane, tetrafunctional silanes such as tetraalkoxysilane and tetrachlorosilane can also be used in combination. When the terminal of this compound is a hydroxyl group or an alkoxyl group, it can be three-dimensionalized by heating or adding a catalyst such as an amine or a metal salt, but it can be used as it is without being three-dimensional. In this case, as in the case of the silicone oligomer, an alkyl group, a phenyl group, an acrylic group, a methacryl group, a vinyl group, an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, etc. are introduced into the side chain to crosslink during curing. Can be made three-dimensional.

  On the other hand, a silicone copolymer having a ladder silicone structure is composed of a ladder silicone oligomer having an acrylic group, a methacryl group, a vinyl group, an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, etc. in the side chain, an acrylate ester, a methacrylic ester. It can be obtained by copolymerization with a compound having a monovalent vinyl functional group such as an acid ester or an alkyl vinyl ester, an epoxy compound, a polyester having a carboxyl group or a hydroxyl group at the terminal, an allyl compound, a compound having an isocyanate group, or the like. In this case, the reaction between the ladder silicone oligomer and the compound having a functional group may be either addition polymerization or condensation polymerization. When the functional compound that copolymerizes with the ladder silicone is monofunctional, a linear polymer is formed and becomes solvent-soluble, but when the functional compound is polyfunctional, the resulting silicone copolymer is It becomes difficult to dissolve in the solvent. Therefore, in the present invention, the silicone copolymer is preferably a copolymer of the silicone oligomer and a monofunctional compound.

In the present invention, the silicone polymer having the ladder silicone structure may be used alone or in combination of two or more. Among the various silicone polymers, A ladder silicone acrylic polymer which is a copolymer of a silicone oligomer having a ladder silicone structure and a (meth) acrylic acid ester is preferable. Examples of the (meth) acrylic acid ester copolymerized with the silicone oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Can do.
As such a ladder silicone acrylic polymer, for example, “Sanfleure LS230” [trade name, manufactured by Showa Denko KK] can be obtained as a commercially available product.

  Another polymer to be combined with the silicone-based polymer having the ladder silicone structure is incompatible with the silicone-based polymer, has a film-forming ability, and is used in combination with the silicone-based polymer. Thus, any film can be used as long as it can form a coating film having a random curved surface irregularity pattern on the surface, which is the object of the present invention, and is not particularly limited. For example, a methyl methacrylate-based comb polymer is preferably used. it can. This methyl methacrylate-based comb polymer is a kind of graft copolymer of methyl methacrylate and other acrylic compounds. For example, “Reseda GP-301” [trade name, Toa Gosei Chemical Co., Ltd. Etc.] are available.

  In the polymer solution of the present invention, the content ratio of the silicone polymer having a ladder silicone structure and the methyl methacrylate comb polymer is not particularly limited, but is usually 50:50 to 90:10 by weight ratio. Selected by range. If both content ratio is in the said range, a random curved-surface uneven | corrugated pattern is formed in the coating-film surface formed, and matteness is provided. From the point of matteness, a preferable content rate is the range of 60: 40-85: 15 by weight ratio.

As the organic solvent used in the polymer solution of the present invention, a homogeneous polymer solution can be prepared by dissolving a plurality of incompatible polymers having volatility at room temperature. There is no particular limitation as long as it is a solvent that can form a random curved line uneven pattern on the surface when forming a coating film. The organic solvent may be a single solvent or two or more mixed solvents, but two or more mixed solvents having different boiling points, particularly two mixed solvents are preferable.
Examples of such a mixed solvent include a mixture of an aliphatic alcohol having an alkoxyl group in the molecule and an aliphatic / alicyclic ketone.

  Examples of aliphatic alcohols having an alkoxyl group in the molecule include 2-methoxyethanol, 2-ethoxyethanol, 2-n-propoxyethanol, 2-isopropoxyethanol, 2-n-butoxyethanol, 2-isobutoxyethanol. 2-sec-butoxyethanol, 2-tert-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-n-propoxy-2-propanol, 1-isopropoxy-2-propanol, 1-n-butoxy-2-propanol, 1-isobutoxy-2-propanol, 1-sec-butoxy-2-propanol, 1-tert-butoxy-2-propanol, 3-methoxy-1-propanol, 3-ethoxy- 1-propanol, 3-n-propo Si-1-propanol, 3-isopropoxy-1-propanol, 3-n-butoxy-1-propanol, 3-isobutoxy-1-propanol, 3-sec-butoxy-1-propanol, 3-tert-butoxy-1 -Propanol etc. are mentioned.

On the other hand, examples of the aliphatic / alicyclic ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.
In the case of using a mixture of two organic solvents having different boiling points, the solvent having the higher boiling point is appropriately selected from the aliphatic alcohols having an alkoxyl group in the molecule, while the one having the lower boiling point. The solvent is preferably selected from the above-mentioned aliphatic / alicyclic ketones and mixed to obtain a mixed solvent. Although there is no restriction | limiting in particular about the boiling point difference of 2 types of solvents, about 20-70 degreeC is enough.
The mixing ratio of the two kinds of solvents depends on the kind of the incompatible polymer to be used, but is usually 10:90 to 90:10, preferably 20:80 to 80:20 by weight ratio. More preferably, it is selected in the range of 30:70 to 70:30.

When a silicone polymer having a ladder silicone structure and a methyl methacrylate comb polymer are used as the poorly compatible polymer, 1-methoxy-2-propanol is preferred as the aliphatic alcohol having an alkoxyl group in the molecule. On the other hand, methyl ethyl ketone is preferred as the aliphatic / alicyclic ketones. In this case, the weight ratio of 1-methoxy-2-propanol and methyl ethyl ketone is preferably 50:50 to 90:10, more preferably 60:40 to 80:20.
The content of the incompatible polymer in the polymer solution of the present invention is usually selected in the range of 10 to 40% by weight, although it depends on the type of organic solvent used. When the content is in the above range, it is practical in terms of handleability and coating film formability.

  The polymer solution of the present invention can contain a crosslinking agent. The type of cross-linking agent varies depending on the type of cross-linking point in the polymer to be cross-linked, but in general, it is appropriately selected from cross-linking agents such as polyisocyanate compounds, epoxy compounds, metal chelate compounds, metal alkoxides and metal salts. The It is particularly preferable to crosslink using an epoxy compound or a polyisocyanate compound. Here, examples of the epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, Examples thereof include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Examples of polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate. Examples thereof include isocyanates, biuret bodies, isocyanurate bodies, and agduct bodies that are a reaction product with a low molecular active hydrogen-containing compound.

In the polymer solution of the present invention, various additives can be appropriately selected and used in accordance with the application within a range that does not impair the object of the present invention. These various additives will be described in the matte paint described later.
There is no restriction | limiting in particular about the kind of base material sheet | seat with which the polymer solution of this invention is apply | coated, According to a use, it selects suitably from various sheets.
This base material sheet can be roughly classified into various paper base materials, plastic sheets, metal foils, metal sheets and the like. These can be used alone, or laminated sheets of any combination of materials, such as composites of the same type of material such as paper or plastic, composites of different materials such as paper and plastic sheet, etc. It can also be used. These substrate sheets may be coated in the sense of adjusting the color, or a normal pattern may be formed in advance from a design viewpoint. Prior to coating or normal pattern formation, the surface may be smoothed or a base treatment may be applied to increase the degree of adhesion of the pattern. After coating or normal pattern formation, an adhesion improving treatment for facilitating subsequent processing may be performed.

Examples of various paper base materials include the following. That is, thin paper, kraft paper, titanium paper, and resin-impregnated paper that has been impregnated with resin in advance for the purpose of strengthening the paper can be used. In addition to these, a group of original fabrics often used in the building material field, such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw fabric in which a vinyl chloride resin layer is provided on the surface of the paper. Furthermore, the following papers used in the office field, normal printing, packaging, etc. can also be used. That is, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, or Japanese paper.
Examples of the plastic sheet include polyethylene resin, polypropylene resin, polymethylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, and ethylene-vinyl acetate copolymer. Polymerized resin, ethylene-vinyl alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 Or polyamide resin represented by nylon 66, cellulose triacetate resin, zero fan, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, etc. Sheet can be mentioned that.
As the metal foil or metal sheet, one made of a material such as aluminum, iron, stainless steel, or copper is used. Often used with plating.

When using a plastic sheet as the base sheet, for the purpose of improving the adhesion with the layer provided on the surface, if desired, at least one side of the base sheet may be physically or chemically such as an oxidation method or an unevenness method. Surface treatment can be performed. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base sheet, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.
The thickness of the base sheet is not particularly limited, and is appropriately selected within a wide range, for example, 20 μm to 10 mm, depending on the application.

The polymer solution of the present invention is applied onto the substrate sheet by, for example, spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, or the like. By drying, a coating film can be formed. And when a 0.1-100 micrometer-thick coating film is provided, as shown in the optical micrograph of FIG. 2 in below-mentioned Example 1, innumerable random curved-surface uneven | corrugated pattern is formed in the coating-film surface. . Here, the random curved line uneven pattern is an innumerable number of curved surface-like ridges in a mountain range, and crater-like depressions with a diameter of about 1 to 5 μm are scattered in the valleys between the mountain ranges. Indicates the state of And in the waveform of the cross section of the random curved line concavo-convex pattern formed on the coating film surface, there are usually 10 or more convex portions having a height of 0.2 to 2.3 μm in a 300 μm pitch. The surface roughness of the coating film is an arithmetic average roughness Ra, which is usually about 0.02 to 5 μm, and has a very fine surface. Matting property is imparted to the coating film by scattering of light.
The number of convex portions having a height of 0.2 to 2.3 μm and the arithmetic average roughness Ra are values measured according to the following method.
Measured in accordance with JIS B 0601 with a Keyence Corporation laser microscope (model name “VK-8500”), and the number of convex portions and the arithmetic average roughness Ra are calculated with the attached software. The height of the convex portion indicates the distance from the center line to the convex portion apex.

  That is, the polymer solution of the present invention can provide a coating film with matting properties without including matting agent particles. Even if a plurality of polymers contained in the polymer solution of the present invention are each used alone, a polymer solution is prepared in the same manner, and a coating film is formed under the same conditions, The random curved line pattern is not substantially formed, and therefore matte properties are not imparted. By combining two or more incompatible polymers, a random curved surface uneven pattern is formed on the coating surface for the first time, and matte properties are imparted. By optimizing conditions such as the type and ratio of the combination of the polymers and the selection of the solvent, for example, when the 60 ° gloss value in the case of using the polymer alone is 100, it is reduced to nearly 40.

Therefore, a coating film having a matte property comparable to or higher than the conventional one can be obtained by blending the particles of the known matting agent in the polymer solution of the present invention in an amount smaller than the conventional use amount. Can be obtained. In this case, since the blending amount of the matting agent can be reduced, deterioration of other physical properties such as scratch resistance and adhesion with an adjacent layer can be suppressed. In addition, by selecting the type and particle size of the matting agent, it is possible to form a coating film that has a very fine surface and is balanced with high levels of matting, scratch resistance, and adhesion. Can do.
The polymer solution of the present invention having such characteristics can be used for various applications, but is particularly suitable for matte paints.

Next, the matte paint of the present invention will be described.
The matte paint of the present invention is a paint that gives a matte coating prepared using the polymer solution of the present invention. In the matte paint, the content of the plurality of incompatible polymers is usually in the range of 10 to 40% by weight. When the content of the plurality of incompatible polymers that are coating film-forming components is in the above range, the paint has an appropriate viscosity and has good handleability and applicability. The preferred content is in the range of 15 to 35% by weight.
In the matte paint, as described in the polymer solution of the present invention described above, a random curved line uneven pattern is formed on the surface of the coating film even without adding a matting agent. Although the matte coating film itself is given a matting property, a matting agent can be blended in order to further improve the matting property.

In the present invention, organic fine particles are preferably used as the matting agent. The average particle size of the organic fine particles is preferably in the range of 1 to 15 μm, and in particular, a mixture of particles having an average particle size of about 1 to 5 μm and particles having an average particle size larger than 5 μm and about 15 μm or less. Is preferred. By using a mixture of particles having such an average particle size as a matting agent, it is possible to form a coating film having a very fine surface and having a balance between matting properties and scratch resistance. it can.
Examples of the organic fine particles include polyethylene particles, polystyrene particles, acrylic resin particles, polycarbonate particles, benzoguanamine / formaldehyde condensate particles, benzoguanamine / melamine / formaldehyde condensate particles, urea resin particles, and wax particles. be able to.

The organic fine particles may be used singly or in combination of two or more, and the content in the coating is usually selected in the range of 1 to 20% by weight. When the matting agent is within the above range, matting properties are further imparted, and other physical properties such as scratch resistance and adhesion of the coating film are good, and the coating film surface has fine texture. Can be maintained. A preferable content of the organic fine particles is 3 to 15% by weight.
In the matte paint, an appropriate amount of an inorganic matting agent can be blended within a range where the effects of the present invention are not impaired. Examples of the inorganic matting agent include particles such as silica, alumina, mica, calcium carbonate, barium sulfate, silica sand, and shirasu balloon.

In the matte paint, various additives such as an antioxidant, an ultraviolet absorber, an infrared shielding agent, a light stabilizer, an antistatic agent, a colorant, and an adhesive are optionally added as long as the effects of the present invention are not impaired. A filler other than a property improver, leveling agent, thixotropic agent, coupling agent, matting agent, plasticizer, and the like can be blended.
There is no restriction | limiting in particular as a base material to which the said mat paint is applied, For example, the same thing as the base material sheet illustrated in description of the polymer solution of the above-mentioned this invention can be mentioned.
The matting paint can be used for various purposes, but is particularly suitably used for forming a gloss adjusting layer of a decorative sheet.

Next, the decorative sheet of the present invention will be described.
The decorative sheet of the present invention is characterized by having a base sheet and a gloss adjusting layer formed thereon using the matte paint of the present invention described above, and the configuration is not particularly limited. Absent.
FIG. 1 shows a schematic sectional view of an example of the configuration of the decorative sheet of the present invention. The decorative sheet 10 has a structure in which an adhesive layer 2, a printed layer 7 (including a concealing solid layer 3 and a pattern layer 4), a protective layer 5 and a gloss adjusting layer 6 are laminated on the base sheet 1 in this order. ing.
As the substrate sheet 1, among the various substrate sheets exemplified in the description of the polymer solution of the present invention, a paper substrate and a plastic sheet can be preferably exemplified.
The decorative sheet of the present invention may be used, for example, for bonding to a metal-based material such as a wood-based material, an inorganic material, a synthetic resin-based material, a steel plate, etc. via an adhesive for the purpose of surface decoration, As such, it may be used as a flooring or a decorative panel. When used for the purpose of bonding to various materials for the purpose of surface decoration, a plastic sheet or paper substrate having a thickness of usually about 20 to 2000 μm, preferably 30 to 1000 μm is preferably used as the base sheet. Further, when used as a flooring or a decorative panel itself, a plastic sheet having a thickness of usually about 1 to 10 mm, preferably 2 to 6 mm, is preferably used as the base sheet.

Depending on the material of the base sheet 1, it is possible to provide a concealed solid layer or a pattern layer by printing directly on the base sheet 1, but when the base sheet 1 is a plastic sheet such as polyolefin resin, It is preferable to provide the adhesive layer 2. An adhesive resin can be used for the adhesive layer 2, and examples of the adhesive resin include acrylic resins, urethane resins, polyester resins, ethylene-vinyl acetate copolymer resins, and vinyl chloride-vinyl acetate. Examples of such resins include copolymer resins, among which acrylic resins and urethane resins are preferable. Although there is no restriction | limiting in particular as the thickness of an adhesive bond layer, Usually, it is about 0.1-10 micrometers.
The printing layer 7 includes a pattern layer 4 on which a pattern such as a grain pattern, a marble pattern (marble pattern, granite pattern), a natural leather surface pattern, a texture pattern, an abstract pattern, etc. is printed and a concealed solid layer 3 on which printing is performed on the entire surface. It is configured. The ink for forming the printing layer 7 depends on the material and form of the protective layer 5, but generally comprises a chlorinated polypropylene resin or polyurethane resin as a vehicle, and contains ordinary pigments and dyes as colorants. Used ink.

The pattern layer 4 can be formed by performing general printing such as gravure printing, screen printing, offset printing, letterpress printing, transfer printing, flexographic printing, and the like. The thickness of the pattern layer is usually about 0.5 to 5 μm.
Furthermore, the concealing solid layer can be provided by printing or coating a concealing printing ink or a coating agent in a solid state by a conventionally known method, for example, various printing methods or coating methods. The thickness of this concealing solid layer is usually about 1 to 20 μm.
The protective layer 5 can be appropriately selected from various plastic sheets conventionally used as a protective layer for decorative sheets. For example, a transparent resin sheet such as an acrylic resin sheet, an amorphous polyethylene terephthalate resin sheet, a polyolefin resin sheet, or an ionomer resin sheet can be used. The thickness of the protective layer 5 is usually about 20 to 150 μm.
As the acrylic resin sheet, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) propyl acrylate, poly (meth) butyl acrylate, (meth) methyl acrylate-(meth) (Butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer, etc. The sheet | seat which consists of the homopolymer or copolymer containing a meth) acrylic acid ester is mentioned.

As the non-crystalline polyethylene terephthalate resin sheet, a sheet of non-crystalline polyethylene terephthalate resin (usually referred to as A-PET) having a crystallinity of 5% or less is used. As the polyolefin resin sheet, a polyethylene resin sheet, a polypropylene resin sheet, or the like is used, and a polypropylene resin sheet is preferable, and a biaxially stretched polypropylene resin sheet is particularly preferable.
The ionomer resin used as a material for the ionomer resin sheet is generally a resin in which organic and inorganic components are bonded by covalent bonds and ionic bonds. The ionomer resin particularly preferably used in the present invention includes a resin in which the copolymer molecules are cross-linked with metal ions. In this case, the copolymer is an acrylate copolymer such as an ethylene-methacrylic acid copolymer. A polymer or the like is used. As the metal ions, for example, ions such as Na, K, Mg, Zn are used.
An ionomer resin sheet can be produced by adding an appropriate additive to the ionomer resin and forming the sheet by a known molding method. This ionomer resin sheet is excellent in scratch resistance, cigarette resistance, weather resistance, stain resistance, and the like.
These transparent resin sheets can contain an ultraviolet absorber, a light stabilizer, a colorant, a filler, a flame retardant, and the like as necessary.

  With respect to these transparent resin sheets, a physical or chemical surface such as an oxidation method or a concavo-convex method is provided on at least one side of the base sheet, if desired, for the purpose of improving the adhesion with the layer provided on the surface. Processing can be performed. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the concavo-convex method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected depending on the type of the base sheet, but generally, corona discharge treatment methods are preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.

  In the present invention, as the protective layer 5, instead of the transparent resin sheet, a coating layer of an ionizing radiation curable resin composition is provided, and this is irradiated with ionizing radiation and cured to provide scratch resistance. A protective layer excellent in the above may be formed. Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiation with ultraviolet rays or electron beams. Refers to a resin composition. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers and prepolymers conventionally used as ionizing radiation curable resin compositions.

As the polymerizable monomer, a (meth) acrylate polyfunctional or monofunctional monomer having a radically polymerizable unsaturated group in the molecule can be preferably exemplified, and examples of the polymerizable oligomer and prepolymer include epoxy. Preferable examples include (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates.
When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add an appropriate amount of a photopolymerization initiator.
In this ionizing radiation curable resin composition, if necessary, various additives such as an abrasion resistance improver, a weather resistance improver, a crosslinking agent, a polymerization inhibitor, an antistatic agent, an adhesion improver, a leveling agent, A thixotropic agent, a coupling agent, a plasticizer, a filler, a colorant, a solvent, an antifoaming agent, and the like can be appropriately blended.

Next, the gloss adjusting layer 6 provided on the protective layer 5 is a layer for adjusting the glossiness of the surface of the decorative sheet, and may be colorless and transparent or colored and transparent. In the present invention, the matte paint of the present invention described above is used to form the gloss adjusting layer 6. By using the matte paint of the present invention, the surface has a very fine surface, the surface glossiness is adjusted to a desired value, and the gloss having good scratch resistance and adhesion to the protective layer 5 is obtained. An adjustment layer can be formed.
The gloss adjusting layer 6 is formed on the protective layer 5 by applying the matte paint of the present invention to a dry thickness of usually 1 to 30 μm, preferably 1 to 20 μm, more preferably 2 to 15 μm. For example, it can be performed by applying and drying by spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, etc. .

The method for producing the decorative sheet of the present invention is not particularly limited as long as it is a method for obtaining the decorative sheet having the above-described configuration. For example, the following method can be used.
When a transparent resin sheet is used as the protective layer 5, first, a printed layer 7 composed of the pattern layer 4 and the concealed solid layer 3 in this order is provided on the back surface of the transparent resin sheet constituting the protective layer 5 by, for example, gravure printing. . On the other hand, after forming the adhesive layer 2 on the surface of the substrate sheet 1 by gravure coating or the like, the printed layer 7 of the transparent resin sheet is overlaid on the surface of the adhesive layer 2 and dry laminated.
Next, the matte paint of the present invention is applied to the surface of the transparent resin sheet as the protective layer 5 and dried to form the gloss adjusting layer 6, whereby the decorative sheet of the present invention can be manufactured.
When forming an ionizing radiation curable resin layer as the protective layer 5, first, the adhesive layer 2 is provided on the surface of the base sheet 1 by gravure coating or the like, and then, for example, by gravure printing or the like. A printing layer 7 is provided which is composed of the concealing solid layer 3 and the pattern layer 4 in this order. Next, an uncured resin layer is provided thereon using an ionizing radiation curable resin composition, and the protective layer 5 is formed by irradiating it with ionizing radiation and curing it.
Next, the matte paint of the present invention is applied to the surface of the protective layer 5 and dried to form the gloss adjusting layer 6, whereby the decorative sheet of the present invention can be manufactured.

In the decorative sheet of the present invention, a conventionally known adhesive layer can be formed on the outermost surface on the back side of the base sheet, if desired, for the purpose of adhering to various adherends. As the adhesive constituting the adhesive layer, both a heat-sensitive adhesive and a pressure-sensitive adhesive (pressure-sensitive adhesive) can be used. Examples of heat sensitive adhesives include acrylic, urethane, polyester, ethylene-vinyl acetate copolymer systems, vinyl chloride-vinyl acetate copolymer systems, etc., while pressure sensitive adhesives include, for example, rubber-based, acrylic Type, silicone type and the like. In addition, when using a pressure sensitive adhesive as an adhesive agent, providing the peeling sheet by which the peeling process was given to the surface on a pressure sensitive adhesive layer is performed normally. The thickness of this adhesive layer is usually in the range of 10 to 200 μm.
The decorative sheet of the present invention can be used as a surface decorative material for building materials, furniture, residential equipment, home appliances, etc. by bonding to a wood-based, inorganic-based, synthetic resin-based, metal-based material, or the like. It is suitably used as a building material such as a material or a decorative panel.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The 60 ° gloss value of the coating layer was measured using a portable gloss meter “GMX-202” manufactured by Murakami Color Research Laboratory. Moreover, the surface roughness measured the arithmetic mean roughness Ra according to the method of description text.
Reference example 1
As a poorly compatible polymer, a ladder silicone acrylic polymer [manufactured by Showa Denko KK, trade name “Sanflure LS230”] (solid content 50 wt%, diluted with butyl acetate) and methyl methacrylate (MMA) comb polymer [Toa A mixed solvent of 1: methoxy-2-propanol and methyl ethyl ketone in a weight ratio of 69:31 was used as an organic solvent, using a combination of trade name “Reseda GP301” (100% solids, powder) manufactured by Synthetic Chemical Industry Co., Ltd. Was used.
The ladder silicone acrylic polymer and the MMA comb polymer were mixed at a ratio shown in Table 1 in terms of solid content. Next, a predetermined amount of a polyisocyanate-based cross-linking agent [manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate HX”, polyisocyanate concentration of 100% by weight] was added to the resin mixture. Each homogeneous polymer solution was prepared by dissolving at a room temperature (20 ° C.) so that the solid content concentration would be 17 to 24% by weight with a methoxy-2-propanol / methyl ethyl ketone mixed solvent (weight ratio 69/31). .
Apply each of the above coating liquids to a surface of a 75 μm thick transparent / mirror surface polyethylene terephthalate (PET) film [trade name “A4300”, manufactured by Toyobo Co., Ltd.] with a bar coater so that the dry thickness is 3 μm. Then, it was naturally dried to form a coating layer, and the 60 ° gloss value of each coating layer was measured. The results are shown in Table 1.

  As is apparent from Table 1, when each of the ladder silicone acrylic polymer and the MMA comb polymer is used alone, the 60 ° gloss value is 100, but by using both in combination, 60 ° It can be seen that there is a mixing ratio with the lowest gloss value.

Example 1 Preparation of Polymer Solution (Coating Solution) In a mixed solvent consisting of 274 parts by weight of 1-methoxy-2-propanol and 122 parts by weight of methyl ethyl ketone, a ladder silicone acrylic polymer “Sanflure LS230” (supra, solid content) 50 parts by weight) and 140 parts by weight of MMA-based comb polymer “Reseda GP301” (previously, solid content: 100%, powder) were dissolved at room temperature (20 ° C.) to prepare a homogeneous polymer solution. . Next, 30 parts by weight of a polyisocyanate-based crosslinking agent [manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate HX”, polyisocyanate concentration: 100% by weight] was added thereto to prepare a coating solution.
The coating liquid is applied to the surface of a 75 μm thick transparent / mirror surface PET film “A4300” (described above) with a bar coater so that the dry thickness is 4 μm, and then naturally dried to form a coating layer. Formed.
The surface roughness of this coating layer was 0.25 μm in terms of arithmetic average roughness Ra. FIG. 2 shows an optical micrograph of the coating layer and the waveform of each cross section. In FIG. 2, (a) is an optical microscope (100 times) photograph of the coating layer, and (b), (c) and (d) are waveform diagrams of a cross section taken along line 1A-1B in (a), respectively. It is the waveform figure of a 2A-2B line cross section, and the waveform figure of a 3A-3B line cross section. In addition, the waveform diagram of each cross section was measured with a KEYENCE laser microscope (model name “VK-8500”).
As is apparent from FIG. 2, it can be seen that an infinite number of random curved stripe patterns (wrinkle patterns) are formed on the surface of the formed coating layer. In the waveform of the cross-section of the random curved line concavo-convex pattern, 22 convex portions having a height of 0.2 to 2.3 μm were present in a 300 μm pitch.

Comparative Example 1
In Example 1, without using an MMA comb polymer, the amount of ladder silicone acrylic polymer was 200 parts by weight, methyl ethyl ketone was 92 parts by weight, a polyisocyanate crosslinking agent [trade name “Coronate HX” manufactured by Nippon Polyurethane Co., Ltd., A coating liquid was prepared in the same manner as in Example 1 except that the polyisocyanate concentration was changed to 42 parts by weight. Next, using this coating solution, a coating layer having a thickness of 4 μm was formed on the PET film in the same manner as in Example 1.
The surface roughness of the coating layer was 0.031 μm in terms of arithmetic average roughness Ra. Moreover, when this coating-film layer was observed with the optical microscope, the random curved-surface uneven | corrugated pattern was not formed substantially but the coating-film surface was very flat. In FIG. 3, the optical micrograph of this coating film layer and the waveform of each cross section are shown. In FIG. 3, (a) is an optical microscope (100 times) photograph of the coating layer, and (b), (c) and (d) are waveform diagrams of a cross section taken along line 1A-1B in (a), respectively. It is the waveform figure of a 2A-2B line cross section, and the waveform figure of a 3A-3B line cross section. In addition, the waveform diagram of each cross section was measured with a KEYENCE laser microscope (model name “VK-8500”).

Comparative Example 2
In Example 1, without using a ladder silicone acrylic polymer and a polyisocyanate crosslinking agent [manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate HX”, polyisocyanate concentration 100 wt%], the amount of MMA comb polymer was 100 wt. A coating solution was prepared in the same manner as in Example 1 except that the amount was changed to 192 parts by weight of methyl ethyl ketone, and this coating solution was used in the same manner as in Example 1 to apply a coating having a thickness of 4 μm on the PET film. A film layer was formed.
The surface roughness of the coating layer was 0.053 μm in terms of arithmetic average roughness Ra. Moreover, when this coating-film layer was observed with the optical microscope, the random curved-surface uneven | corrugated pattern was not formed substantially but the coating-film surface was very flat.

Example 2 Preparation of Matte Paint In a mixed solvent consisting of 274 parts by weight of 1-methoxy-2-propanol and 122 parts by weight of methyl ethyl ketone, 140 parts by weight of ladder silicone acrylic polymer “Sanflure LS230” (supra) and MMA 30 parts by weight of the system comb polymer “Reseda GP301” (supra) was dissolved at room temperature (20 ° C.) to prepare a homogeneous polymer solution. Next, a polyisocyanate-based crosslinking agent [manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate HX”, polyisocyanate concentration 100% by weight], 30 parts by weight of organic filler [Nippon Kasei Co., Ltd., trade name “submicron filler” 20 parts by weight of an average particle size of 3 μm, polyethylene particles [trade name “WN3025” manufactured by Croda, 8 μm of an average particle size of 6 μm], and silica particles [trade name “AEROSIL R974” manufactured by Nippon Aerosil Co., Ltd.] [Diameter 12 μm] 5 parts by weight were added to prepare a matte paint.
Next, the matte paint is applied to the surface of a 75 μm thick transparent / mirror surface PET film “A4300” (described above) with a bar coater to a dry thickness of 10 μm, and then dried at 50 ° C. Thus, a coating layer was formed.
The surface roughness of this coating layer was 0.74 μm in terms of arithmetic average roughness Ra, and the 60 ° gloss value was 10.

Comparative Example 3
In Example 2, the amount of the ladder silicone acrylic polymer was changed to 200 parts by weight, methyl ethyl ketone was changed to 92 parts by weight without using the MMA comb polymer, and the amount of the polyisocyanate crosslinking agent “Coronate HX” (described above). A matte paint was prepared in the same manner as in Example 2 except that was changed to 42 parts by weight, and a coating layer having a thickness of 10 μm was formed on the surface of the PET film.
The surface roughness of this coating layer was 0.50 μm in terms of arithmetic average roughness Ra, and the gloss value at 60 ° was 32.

Comparative Example 4
In Example 2, without using the ladder silicone acrylic polymer and the polyisocyanate crosslinking agent, the amount of the MMA comb polymer was changed to 100 parts by weight, and methyl ethyl ketone was changed to 192 parts by weight. A matte paint was prepared, and a coating layer having a thickness of 10 μm was formed on the surface of the PET film.
The surface roughness of the coating layer was 0.55 μm in terms of arithmetic average roughness Ra, and the gloss value at 60 ° was 31.

Comparative Example 5
Using a commercially available urethane matte paint [trade name “NHWP mat” manufactured by The Inktec Co., Ltd.], a coating layer having a thickness of 10 μm was formed on the surface of the PET film in the same manner as in Example 2.
The surface roughness of the coating layer was 0.60 μm in terms of arithmetic average roughness Ra, and the 60 ° gloss value was 30.

Example 3 Production of a decorative sheet A pattern layer and a concealed solid layer were printed on a gravure rotary press with a biaxially stretched polypropylene film having a thickness of 20 μm and subjected to double-sided corona treatment using an ink containing a chlorinated polypropylene resin as a vehicle. A polypropylene film (for protective layer) was produced.
On the other hand, after corona treatment was performed on one side of an unstretched polypropylene film having a thickness of 100 μm as a base sheet, a urethane adhesive was gravure coated thereon to form an adhesive layer having a thickness of 6 μm.
Next, the laminated film is laminated by laminating a polypropylene film having the printed layer on the adhesive layer so that the surface of the concealed solid layer is in contact with each other and roll laminating through a nip roll heated to 40 to 70 ° C. Obtained. The 60 ° gloss value of the surface of the polypropylene film as the protective layer in this laminated sheet was 20.
Next, the matte paint prepared in Example 2 was applied to the surface of the polypropylene film as the protective layer with a bar coater so that the dry thickness was 10 μm, and then dried at 50 ° C. to adjust the gloss. A layer was provided to prepare a decorative sheet.
The gloss adjusting layer surface of this decorative sheet had a 60 ° gloss value of 5, and the surface roughness was 1.00 μm in terms of arithmetic average roughness Ra.
Thus, although the gloss adjusting layer has excellent matting properties, the surface thereof is very fine and excellent in appearance.

When the polymer solution of the present invention is applied and dried on a substrate sheet to provide a coating film, the surface of the coating film has a random curved line uneven pattern with an arithmetic average roughness of about 0.1 to 100 μm ( A wrinkle pattern is formed, and it is suitably used for matte paint. In addition, the matte paint obtained using this polymer solution has a matte appearance and can give a coating film having a very fine surface, which is useful for forming a gloss adjustment layer in a decorative sheet. Preferably used.
Furthermore, the decorative sheet of the present invention is bonded to a wood-based, inorganic-based, synthetic resin-based, metal-based material, etc. as a surface decorative material for building materials, furniture, residential equipment, home appliances, etc. It is suitably used as a building material such as a flooring material or a decorative panel.

It is a schematic sectional drawing which shows an example of a structure of the decorative sheet of this invention. In Example 1, it is the optical microscope photograph figure of the coating-film surface formed using the polymer solution, and the wave form diagram of each cross section. In the comparative example 1, it is the optical microscope photograph figure of the coating-film surface formed using the polymer solution, and the waveform figure of each cross section.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Adhesive layer 3 Concealment solid layer 4 Picture layer 5 Protective layer 6 Gloss adjustment layer 7 Print layer 10 Cosmetic sheet

Claims (12)

  A polymer solution in which two or more incompatible polymers having an ability to form a coating film are dissolved in an organic solvent, which is applied to a substrate sheet and dried to a thickness of 0.1 to 0.1. A polymer solution characterized in that, when a 100 μm coating film is provided, a random curved stripe pattern is formed on the surface of the coating film.   2. The polymer solution according to claim 1, wherein 10 or more convex portions having a height of 0.2 to 2.3 μm are present in a 300 μm pitch in a waveform of a cross section of the random curved line uneven pattern formed on the surface of the coating film.   3. The polymer solution according to claim 1 or 2, wherein there are two types of incompatible polymers, one of which is a silicone oligomer, a silicone polymer or a silicone copolymer having a ladder silicone structure.   4. The polymer solution according to claim 3, wherein another one of the hardly compatible polymers is a methyl methacrylate-based comb polymer.   5. The polymer according to claim 4, wherein the content ratio of the silicone oligomer, the silicone polymer or the silicone copolymer having a ladder silicone structure and the methyl methacrylate-based comb polymer is 50:50 to 90:10 by weight. solution.   The polymer solution according to any one of claims 1 to 5, wherein the organic solvent is a mixture of two or more organic compounds having volatility and different boiling points.   7. The polymer solution according to claim 6, wherein the organic solvent is a mixed solvent of an aliphatic alcohol having an alkoxyl group in the molecule and an aliphatic / alicyclic ketone.   8. The polymer solution according to claim 7, wherein the aliphatic alcohol having an alkoxyl group in the molecule is 1-methoxy-2-propanol, and the aliphatic / alicyclic ketone is methyl ethyl ketone.   A matte paint comprising the polymer solution according to any one of claims 1 to 8.   The matte paint according to claim 9, wherein the content of the hardly compatible polymer is 10 to 40% by weight.   The matte paint according to claim 9 or 10, comprising 1 to 20% by weight of organic fine particles. A decorative sheet comprising a base sheet and a gloss adjusting layer formed thereon using the matte paint according to claim 9, 10 or 11.

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