JP2021151778A - Transparent resin film, decorative sheet and manufacturing method of decorative sheet - Google Patents

Abstract

To provide a transparent resin film allowing confirmation of an adhesion state when laminated on a pattern layer disposed on a substrate, and in addition having flame resistance, and also to provide a decorative sheet composed of the transparent resin film.SOLUTION: A transparent resin film is for protecting a pattern layer laminated on one side of a substrate. The transparent resin film at least includes a thermoplastic resin layer and an external haze layer on a side to be laminated on the pattern layer. The transparent resin film contains a flame retardant.SELECTED DRAWING: Figure 1

Description

The present invention relates to a transparent resin film, a decorative plate made of the transparent resin film, and a method for producing the decorative plate.

In recent years, with the spread of the inkjet printing method using an inkjet printer, it is possible to handle a wide variety of small lots of decorative sheets used for building materials and decorative molded products, and complicated patterns (characters, characters, as a pattern layer). It has become possible to print numbers and figures). Further, the inkjet printing method has an advantage that the base material to be printed is not limited to a film, but can be printed on a flat plate, a base material having irregularities or curved surfaces.
However, since the pattern layer printed by the inkjet printing method is usually on the outermost surface of the base material, the surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient, and the pattern layer is protected. It was necessary to laminate a transparent resin film on the surface of the pattern layer.
As such a transparent resin film, for example, Patent Document 1 provides an overcoat in which a protective layer is provided on one surface of transparent polypropylene containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer, and an adhesive layer is provided on the other surface. Laminated films are disclosed.

However, when the conventional transparent resin film is laminated with the pattern layer provided on the base material, air is caught between the pattern layer provided on the base material and the transparent resin film. Even if there is, since the amount of change in the gloss of the surface of the transparent resin film is small, it is difficult to visually judge whether or not it is biting air, and if it is biting air, the pattern layer and transparency In some cases, a decrease in the adhesion with the resin film has become a problem.

Further, since such a transparent resin film is laminated on the surface of a building and used as a decorative board, it may be required to satisfy the requirement for obtaining non-combustibility certification, which indicates that it is hard to burn in the event of a fire. Here, the above requirements for obtaining non-combustibility certification are the total calorific value, maximum calorific value, cracks, and heat generation test in accordance with ISO5660-1 specified in Article 2, Item 9 of the Building Standards Act of Japan. It is a predetermined requirement for the generation of holes.

As a decorative sheet used for a decorative board that meets the above requirements, a base sheet, a transparent resin layer, and a surface protective layer are laminated in this order, the thickness of each layer is in a specific range, and a flame retardant is contained. A decorative sheet to be used has been proposed (see, for example, Patent Document 2).

The above-mentioned decorative sheet is also a decorative sheet having excellent nonflammability, but it has not been studied that the decorative sheet on the base material does not easily burn and spread in the event of a fire. For members that are installed on a horizontal surface such as floor decorative materials, the expansion of the area of the decorative sheet that is burning in the event of a fire is suppressed, and the fire is hard to spread and exhibits flame retardancy, which also helps to secure evacuation time. It is an important performance.

Therefore, it is desired to develop a transparent resin film having excellent weather resistance, which is difficult to spread even in a thin film portion, and which is excellent in flame retardancy.

Japanese Unexamined Patent Publication No. 2005-120255 Japanese Unexamined Patent Publication No. 2015-182379

INDUSTRIAL APPLICABILITY According to the present invention, a transparent resin film whose adhesion state can be visually confirmed when laminated on a pattern layer provided on a base material and further has flame retardancy, and a decorative board made of the transparent resin film and the like. An object of the present invention is to provide a method for producing the decorative board.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have made an external haze layer on the surface of the transparent resin film on the side to be laminated on the pattern layer of the base material, thereby providing the pattern layer of the base material. When a transparent resin film is laminated on the surface of the By excluding it, it is a transparent resin film that can easily have excellent adhesion to the pattern layer, and by further containing a flame retardant, it is a transparent resin film that also has flame retardancy. We have found that we can do this, and have completed the present invention.

The present invention is a transparent resin film for protecting a pattern layer laminated on one of the base materials, and the transparent resin film is at least a side laminated with a thermoplastic resin layer and the pattern layer. The transparent resin film is a transparent resin film having an outer haze layer and containing a flame retardant.
Further, in the transparent resin film, the haze value of the outer haze layer is preferably 4% or more and less than 100%.
A polyethylene terephthalate film having a haze value of 0.1% or less is attached to the side of the outer haze layer opposite to the thermoplastic resin layer side via pure water, and the back surface measured from the thermoplastic resin layer side is wet. The haze value of is preferably 90% or less.
The thickness of the outer haze layer is preferably 0.5 μm or more and 20 μm or less.

The transparent resin film has an uneven shape on the side opposite to the side laminated on the pattern layer, and is a haze value excluding the surface haze on the side opposite to the side laminated on the pattern layer. (1) is 70% or more, and is a haze value (2) which is a haze value excluding the surface haze on the side laminated on the pattern layer and the surface haze on the side opposite to the side laminated on the pattern layer. ) Is preferably 70% or less.
Further, the thermoplastic resin layer preferably contains a flame retardant.
The thermoplastic resin layer preferably contains a filler.
It is preferable to have a surface protective layer on the side of the thermoplastic resin layer opposite to the side laminated on the pattern layer.
Further, the surface protective layer preferably contains a flame retardant.
Further, the surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent.
Further, the flame retardant is preferably at least one selected from the group consisting of a phosphinic acid metal salt-based flame retardant, a phosphazene-based flame retardant, and a NOR-type hindered amine-based flame retardant.

The present invention is also a decorative board, which comprises, in order in the thickness direction, a base material, a pattern layer, and the transparent resin film of the present invention.
The present invention is the method for producing a decorative board of the present invention, wherein an adhesive layer is formed on the surface of the transparent resin film on the side to be laminated on the pattern layer, and the above is performed through the adhesive layer. It is also a method for manufacturing a decorative board, which comprises a step of laminating a transparent resin film and the above-mentioned pattern layer.

Since the transparent resin film of the present invention has an outer haze layer on the surface to be laminated on the pattern layer of the base material, air is caught when the transparent resin film is laminated on the surface of the pattern layer of the base material. It can be easily visually determined whether or not it is present, and by excluding those whose adhesion to the pattern layer is reduced due to biting air, those having excellent adhesion to the pattern layer are excluded. It becomes easy to do. Further, since the thermoplastic resin constituting the transparent resin film contains a flame retardant, it has excellent flame retardancy.
The decorative board of the present invention formed by laminating the transparent resin film of the present invention on the surface of the pattern layer of the base material can be easily formed in a state where air is not caught between the pattern layer and the transparent resin film. , These adhesions can be easily made excellent, and further have flame retardancy.

It is a schematic diagram which shows the cross section of a preferable example of the transparent resin film of this invention. It is a schematic diagram which shows the cross section of another preferable example of the transparent resin film of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative board of this invention. 4 (a) and 4 (b) are schematic views for explaining a method for evaluating flame retardancy.

<Transparent resin film>
First, the transparent resin film of the present invention will be described.
In the following description, the lower and upper limits of the numerical range represented by "~" mean "greater than or equal to or less than" (for example, if α to β, it is greater than or equal to α or less than β).
A preferred example of the transparent resin film of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the transparent resin film 10 of the present invention has at least a thermoplastic resin layer 11 and an outer haze layer 12.

(Thermoplastic resin layer)
The thermoplastic resin constituting the thermoplastic resin layer contains one or more of the following resins, for example, polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene), ethylene-α olefin copolymer. , Polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, olefin-based thermoplastic elastomer, or these Olefin resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene narefurate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester-based thermoplastic Polyester resin such as elastomer, polymethyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, acrylic resin such as methyl (meth) acrylate-styrene copolymer, nylon-6, nylon-66, etc. Examples thereof include polyamide-based thermoplastic resins, polyimides, polyurethanes, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polyvinyl chlorides, polystyrenes, and ionomers. Among them, polypropylene is preferably used because it has high tensile strength, excellent chemical resistance, and excellent production process.
In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

The thermoplastic resin layer may be unstretched, but may be uniaxially stretched or biaxially stretched as needed.
The thickness of the thermoplastic resin layer is not particularly limited, but the preferable lower limit is 20 μm, the preferable upper limit is 500 μm, the more preferable lower limit is 60 μm, and the more preferable upper limit is 420 μm.
If the thickness of the thermoplastic resin layer is less than 20 μm, the tensile strength may be insufficient and the surface of the pattern layer may not be protected. If it exceeds 500 μm, the transmittance of the transparent resin film of the present invention decreases. The visibility of the pattern in the pattern layer may be reduced.

The thermoplastic resin layer is not particularly limited as long as the pattern layer provided on the base material can be seen, and may be colored. In this case, a colorant may be added to the thermoplastic resin. As the colorant, pigments or dyes used in the pattern layer described later can be used.

The thermoplastic resin layer preferably has at least two layers.

When the thermoplastic resin layer has two or more layers, it may be laminated via a transparent adhesive layer or may be laminated by a thermal laminating method.
Since no adhesive is required and problems such as peeling due to deterioration of the adhesive do not occur, it is preferable that the adhesive is laminated by a thermal laminating method.
As the heat laminating method, a known method such as a melt coextrusion method using a T-die can be used.

A known adhesive may be used as the transparent adhesive layer. For example, polyurethane, acrylic, polyolefin, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber, etc. Can be mentioned. These adhesives may be used alone or in combination of two or more.
The thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 μm, more preferably about 1 to 5 μm.

After laminating two or more layers of the thermoplastic resin layer by the heat laminating method, the haze value can be adjusted by quenching.
Here, quenching means that the transparent resin film is cooled at 200 ° C./sec or higher.
Examples of the method of quenching include a method of touching a metal roll cooled to 10 ° C. or lower for several seconds immediately after being laminated by a heat laminating method.
The rate of quenching is preferably 230 ° C./sec, more preferably 250 ° C./sec.

The thermoplastic resin layer preferably contains a flame retardant.
The flame retardant reduces flammability by forming char during combustion, capturing radicals in the combustion gas, and the like.
When the thermoplastic resin layer has at least two layers, it is effective to include a flame retardant in the upper layer (the layer on the side opposite to the side laminated on the base material) to improve the flame retardancy.

The flame retardants include phosphinic acid metal salt flame retardants, phosphazen flame retardants, NOR type hindered amine flame retardants, halogen flame retardants, antimon flame retardants, metal hydroxide flame retardants, and phosphoric acid ester flame retardants. And so on. Among them, selected from the group consisting of phosphinic acid metal salt-based flame retardants, phosphazen-based flame retardants, and NOR-type hindered amine-based flame retardants from the viewpoint of the environment or the point that the amount of addition can be suppressed and the transparency of the layer containing the flame retardant can be maintained. It is preferable that it is at least one kind, which has a property of trapping radicals generated from organic substances during combustion and making it difficult to continue combustion, and in a horizontal combustibility test, a metal phosphinic acid salt in terms of the effect of suppressing the spread of combustion. NOR type hindered amine flame retardants are preferably contained at least one selected from the group consisting of flame retardants and phosphazen flame retardants, and have the effect of reducing the calorific value in the heat generation test of ISO5660-1. preferable.

Examples of the phosphinic acid metal salt-based flame retardant include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphine, zinc bisdiphenylphosphinate, zinc bismethylethylphosphine, and zinc bisdiphenylphosphine. , Titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate.
Commercially available products of the above phosphinic acid metal salt flame retardant include Clariant Japan's product names "EXOLITE OP-930", "EXOLITE OP-935", "EXOLITE OP-1230", "EXOLITE OP-1240", and "EXOLITE". OP-1312 ”and the like.

Examples of the phosphazene-based flame retardant include phenoxyphosphazene and (poly) tolyloxyphosphazene (eg, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, _{Cyclic and / or chain C 1-6} alkyl C _6-20 such as p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xsilyloxyphosphazene, etc. Aryloxyphosphazene and (poly) phenoxytriloxyphosphazene (eg, phenoxyo-tolyloxyphosphazene, phenoxym-tolyloxyphosphazene, phenoxyp-tolyloxyphosphazene, phenoxyo, m-tolyloxyphosphazene, phenoxyo, p- Circular and / Alternatively, chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxyphosphazene and the like can be exemplified, preferably cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _{6-. 20} aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or chain triloxyphosphazene, cyclic and / or chain phenoxytrilphenoxyphosphazene, etc.) Be done.
Further, a compound having a cross-linked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a cross-linked structure of 2,2- (4,4'-diphenylene) isopropyrine group, 4,4'-. Examples thereof include compounds having a cross-linked structure of 4,4'-diphenylene groups, compounds having a cross-linked structure of oxydiphenylene groups, compounds having a cross-linked structure of 4,4'-thiodiphenylene groups, and the like.

Examples of the NOR-type hindered amine-based flame retardant include 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecilaminopiperidin; bis (1-octyloxy-2,2,6,6-tetra). Methylpiperidin-4-yl) sebacate; 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -S-Triazine; Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 4,4'-Hexamethylenebis (Amino-2,2,6,6-Tetra) Methylpiperidin) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6--) end-capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine. Tetramethylpiperidin-4-yl) butylamino] -s-Triazine and an oligomeric compound; 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) , 2-Chloro-4,6-bis (dibutylamino) -s-triazine-terminated 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-) 4-yl) Butyamino] -an oligomeric compound that is a condensing product with s-triazine; 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)- 6-Chloro-s-triazine; peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, N, N' -Reaction product with ethane-1,2-diylbis (1,3-propanediamine) (N, N', N'''-tris {2,4-bis [(1-cyclohexyloxy-2,2,2) 6,6-Tetramethylpiperidin-4-yl) n-butylamino] -s-triazine-6-yl} -3,3'-ethylenediiminodipropylamine); bis (1-undecanoxy-2,2,2) 6,6-Tetramethylpiperidin-4-yl) carbonate; 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one; bis (1-stearyloxy-2,2,6,6) −Tetramethylpiperidin-4-yl) carbonate and the like can be mentioned. Examples of commercially available NOR-type hindered amine flame retardants include Flamestab NOR116FF manufactured by BASF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, TINUVIN PA123, and LA-81 manufactured by ADEKA CORPORATION.

The flame retardant may be used alone or in combination of two or more.

The content of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, with the total mass of the thermoplastic resin layers as 100% by mass. Further, 20% by mass or less is preferable, and 15% by mass or less is more preferable. When the lower limit of the content of the flame retardant is in the above range, the flame retardancy of the transparent resin film is further improved. Further, when the upper limit of the content of the flame retardant is within the above range, the transparency of the transparent resin film is further maintained.

The thermoplastic resin layer may contain a filler. The filler is not particularly limited as long as the transparency of the thermoplastic resin layer is not impaired, and a filler having an average particle size equal to or less than the wavelength of visible light is used in that the sharpness of the transparent resin film is further improved. preferable. Examples of the filler include inorganic fillers such as silica, calcium carbonate, talc, and clay.

The filler is preferably contained in at least one of the thermoplastic resin layers, and is preferably contained in the same layer as the layer containing the flame retardant. That is, it is preferable that at least one of the thermoplastic resin layers contains a flame retardant and a filler.

When at least one of the thermoplastic resin layers contains a flame retardant, the thermoplastic resin layer preferably further contains an inorganic filler having a polar group on the surface. When the thermoplastic resin layer containing the flame retardant contains an inorganic filler having a polar group on the surface, the sharpness and flame retardancy of the transparent resin film are further improved. It is considered that this is because the polar portion of the flame retardant is attracted to the polar group on the surface of the inorganic filler having a polar group, and the presence of the flame retardant on the surface improves the dispersibility. As the inorganic filler having a polar group on the surface, a hydrophilic inorganic filler can be used, and examples thereof include an inorganic filler having a hydroxyl group such as a silanol group on the surface, and more specifically, hydrophilic silica is used. Can be done.

The silica used as the filler may be either a natural product or a synthetic product, and may be either crystalline or amorphous. Further, the synthetic amorphous silica may be prepared by either a wet method or a dry method. The synthetic wet method silica prepared by the wet method is not particularly limited, and examples thereof include a sedimentation method and a gel method. Synthetic dry method prepared by the dry method The method for preparing silica is not particularly limited, and examples thereof include a combustion method and an arc method. The silica is preferably silica having a small average particle size from the viewpoint of further improving the sharpness of the transparent resin film, and more preferably fumed silica or hydrophilic fumed silica obtained by a combustion method.

The BET specific surface area of the filler such as hydrophilic fumed silica ^{is preferably 50 m 2} / g or more, more preferably 130 m ² / g or more, and further preferably ^{200 m 2 / g or more.} Since the lower limit of the BET specific surface area of the filler is within the above range, the average particle size is small and the amount of silanol increases in the case of hydrophilic fumed silica. Therefore, the thermoplastic resin layer is made transparent by adding the filler. The decrease in property is further suppressed, the dispersibility of the flame retardant is further improved, and the sharpness and flame retardancy of the transparent resin film are further improved. Further, when the lower limit of the BET specific surface area of the filler is within the above range, the flame retardancy of the transparent resin film is improved, and the content of the flame retardant can be reduced.

In the present specification, the BET specific surface area is the BET specific surface area measured by the nitrogen adsorption method by the measuring method based on DIN66131.

As the hydrophilic fumed silica used as the filler, a commercially available product can be used. Examples of such commercially available products include AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, and AEROSIL 380 manufactured by Japan Aerosil Co., Ltd.

When the thermoplastic resin layer contains a flame retardant and a filler, the content of the filler in the thermoplastic resin layer is 50 parts by mass or more, assuming that the content of the flame retardant in the thermoplastic fat layer is 100 parts by mass. Is preferable, 100 parts by mass or more is more preferable, and 200 parts by mass or more is further preferable. When the lower limit of the content of the filler in the thermoplastic resin layer is within the above range, the sharpness of the transparent resin film is further improved. The content of the filler in the thermoplastic resin layer is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

The thermoplastic resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, ultraviolet (UV) treatment, and flame treatment within a range not deviating from the gist of the present invention. ..
Various additives such as a matting agent, a foaming agent, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component (for example, rubber) are added to the thermoplastic resin layer. May be included.

The surface of the thermoplastic resin layer on the side where the outer haze layer is provided (hereinafter, also referred to as the back surface) and the surface on the opposite side (hereinafter, also referred to as the front surface) may be a smooth surface and have an uneven shape. May be.
When the surface is a smooth surface, the pattern layer laminated on one surface of the base material can be projected more clearly.
The smooth surface means a surface having a center line average roughness Ra of 2.0 μm or less as defined in JIS B 0601 (1982).
The "surface" means the outermost surface of the transparent resin film (the side opposite to the side laminated on the pattern layer), and when the transparent resin film has a surface protective layer described later, the surface protective layer is used. It means the outermost surface on the holding side.

Further, since the surface has an uneven shape, the transparent resin film of the present invention can be given a design feeling, and the design of the decorative board using the transparent resin film of the present invention is further improved. be able to.
Further, the depth of the uneven shape to be formed is not particularly limited, but for example, it may be appropriately adjusted so that the center line average roughness Ra defined in JIS B 0601 (1982) is within the range of 5 to 20 μm. preferable.

The uneven shape preferably has a maximum height Rz of 20 μm or more and 200 μm or less as defined by JIS B 0601 (2001).
By having the above-mentioned uneven shape, the transparent resin film of the present invention can more preferably improve the design.
On the other hand, if the maximum height Rz is less than 20 μm, the design may not be sufficiently imparted, and if it exceeds 200 μm, the shapeability of the uneven shape may decrease.
The maximum height Rz is preferably 50 μm or more and 180 μm or less, and more preferably 70 μm or more and 150 μm or less.
In this specification, the center line average roughness Ra defined in JIS B 0601 (1982) and the maximum height Rz defined in JIS B 0601 (2001) are the surface roughness measuring instruments (“SURFCOM”). -FLEX-50A ", manufactured by Tokyo Seimitsu Co., Ltd.), and can be obtained by measuring under the following conditions.
(Measurement condition)
Number of measurements: n = 5 (arbitrary 5 points)
Calculation standard: JIS'01
Measurement type: Roughness measurement Evaluation length: 12.5 mm
Cut-off value: 2.5 mm
Measurement speed: 0.60 mm / s
Filter type: Gaussian shape removal: Straight line λs value: 8.0 μm
In the case of a wood grain conduit or a hairline tone with a directional uneven shape, the flow direction and its vertical direction are measured, and the one with a large numerical value is defined as the maximum height (Rz).
At that time, the measurement location is selected and measured with an uneven shape.

The method of forming the uneven shape on the surface of the thermoplastic resin layer is not particularly limited, and examples thereof include a method of embossing with heat and a method of transferring the uneven shape to the thermoplastic resin layer by a shaping sheet.
Examples of the heat embossing include a method of embossing with a well-known single-wafer or rotary embossing machine.
Examples of the embossed pattern include sand grain, hairline, satin finish, wood grain conduit groove, stone plate surface unevenness, cloth surface texture, and many-line groove.
Also. The temperature at the time of embossing is not particularly limited, but a temperature at which the so-called embossing return at which the uneven pattern disappears during heat pressure bonding is reduced is preferable, and for example, the sheet temperature is 120 ° C. to 160 ° C., 1.0 to 4.0 MPa. The uneven pattern may be transferred.

When the transparent resin film is embossed, it may be after the surface protective layer described later is formed or before the surface protective layer is formed.
For example, as a specific embodiment, 1) a thermoplastic resin layer may be formed, a surface protective layer may be formed, and finally embossing may be performed. Further, as another specific embodiment, 2) the thermoplastic resin layer may be formed, then embossed, and finally the surface protective layer may be formed. Further, as yet another specific embodiment, 3) the thermoplastic resin layer may be formed and embossed at the same time, and then the surface protective layer may be finally formed.

(Surface protective layer)
As shown in FIG. 2, the transparent resin film 10 of the present invention has a surface protective layer 14 on the surface of the thermoplastic resin layer 11 opposite to the outer haze layer 12 via a surface protective layer primer layer 13. May be provided.
By having the above surface protective layer, the durability (scratch resistance, stain resistance, weather resistance, etc.) of the transparent resin film of the present invention becomes more excellent, and the surface protection of the pattern layer becomes possible more preferably. It is possible to suitably prevent deterioration of the design due to scratches on the transparent resin film itself of the present invention.
The surface protective layer may have a single layer structure, or may have a plurality of layer structures made of the same or different materials.

The surface protective layer is not particularly limited, and examples thereof include those made of a crosslinked cured product of a two-component curable resin and an ionization radiation curable resin composition, and the crosslinked cured product is preferably transparent. As long as it is transparent, it may be translucent or colored as long as the pattern layer described later can be visually recognized.

Examples of the two-component curable resin include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin.
Examples of the ionizing radiation curable resin composition include oligomers having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule (hereinafter, so-called prepolymers, macromonomers and the like are also included) and / or in the molecule. A monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle having an energy capable of polymerizing or cross-linking a molecule, and usually, an electron beam (EB) or an ultraviolet ray (UV) is generally used.

Examples of the oligomer or monomer include compounds having a radically polymerizable unsaturated group such as a (meth) acryloyl group, a (meth) acryloyloxy group, and a cationically polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers can be used alone or in admixture of a plurality of types. In addition, in this specification, the said (meth) acryloyl group means an acryloyl group or a methacryloyl group.

Examples of the oligomer having a radically polymerizable unsaturated group in the molecule include oligomers such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. Can be preferably used, and urethane (meth) acrylate oligomers are more preferable. As the molecular weight, a molecular weight of about 2.5 to 100,000 is usually used.

Further, as the monomer having a radically polymerizable unsaturated group in the molecule, for example, a polyfunctional monomer is preferable, and a polyfunctional (meth) acrylate is more preferable.
Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane. Ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate {5-functional (meth) acrylate}, dipentaerythritol hexa (meth) acrylate {six-functional (meth) acrylate} And so on. Here, the polyfunctional monomer means a monomer having a plurality of radically polymerizable unsaturated groups.

In the present invention, it is more preferable that the above-mentioned ionized radiation curable resin composition contains an ionized radiation curable resin component composed of a urethane acrylate oligomer and a polyfunctional monomer, and the ionized radiation curable resin component includes a urethane acrylate oligomer / polyfunctional monomer. It is particularly preferable that the monomer (mass ratio) is 6/4 to 9/1. Within this mass ratio range, scratch resistance can be made more excellent.
If necessary, in addition to the ionizing radiation curable resin component, a monofunctional monomer may be appropriately used within a range not contrary to the object of the present invention.
Examples of the monofunctional monomer include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

When the ionizing radiation curable resin composition is crosslinked with ultraviolet rays, it is preferable to add a photopolymerization initiator to the ionizing radiation curable resin composition.
When the ionizing radiation curable resin composition is a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoins, and benzoin methyl ethers are used alone or in combination as the photopolymerization initiator. Can be used.
When the ionizing radiation curable resin composition is a resin system having a cationically polymerizable unsaturated group, the photopolymerization initiator includes an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, and a benzoin. Sulfonic acid esters and the like can be used alone or as a mixture. The amount of these photopolymerization initiators added is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin component.

If necessary, various additives may be further added to the ionizing radiation curable resin composition. Examples of these additives include urethane resin, polyvinyl acetal resin, polyester resin, polyolefin resin, styrene resin, polyamide resin, polycarbonate resin, acetal resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, and acrylic resin. , Thermoplastic resins such as cellulose resins, lubricants such as silicone resins, waxes and fluororesins, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amine radical traps, silica, acrylic beads, mica, etc. It is a colorant such as a gloss, a tactile adjuster, a dye, and a pigment.

As the electron beam source of ionizing radiation, for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamistron type, and high frequency type are used. It can be used to irradiate electrons with an energy of 70 to 1000 keV. The irradiation dose of the electron beam is preferably, for example, about 1 to 10 mad.
As the ultraviolet source of the ionized radiation, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, or a metal halide lamp can be used, and the wavelength of the ultraviolet rays is usually 190 to 380 nm. The wavelength range is mainly used.

The surface protective layer preferably contains a flame retardant.
As the flame retardant, the one described in the thermoplastic resin layer can be appropriately selected and used, and is selected from the group consisting of a phosphinic acid metal salt-based flame retardant, a phosphazene-based flame retardant, and a NOR-type hindered amine-based flame retardant. It is preferably at least one kind, and a NOR type hindered amine flame retardant is more preferable. By adding a flame retardant to the surface protective layer, char flammability can be reduced because char formation, radical scavenging ability in combustion gas, and the like are exhibited against heat applied from the surface during combustion.
Regarding the content of the flame retardant in the surface protective layer, the lower limit of the content of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, assuming that the total mass of the surface protective layer is 100%. The upper limit of the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less.

The surface protective layer preferably contains the flame retardant and the filler from the viewpoint of improving the flame retardancy while maintaining the transparency.
As the filler, those described in the thermoplastic resin layer can be appropriately selected and used, and silica is preferable, and fumed silica is more preferable in consideration of the dispersibility of the flame retardant, and the fumed silica is more preferable. Among the silicas, hydrophilic fumed silica is more preferable.

The surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent. When the surface protective layer contains an antibacterial agent and an antiviral agent, the transparent resin film can be imparted with antibacterial and antiviral properties.
Further, when the sex surface protective layer contains an anti-allergen agent, the transparent resin film can be imparted with anti-allergen properties.

The antibacterial agents and antiviral agents can be generally classified into organic and inorganic agents.
Examples of organic antibacterial agents and antiviral agents include quaternary ammonium salt type, quaternary phosphonium salt type, pyridine type, pyrithione type, benzimidazole type, organic iodine type, isothiazoline type, anion type, ether type and the like. be.
Examples of the inorganic antibacterial agent and antiviral agent include those in which metal ions such as silver, copper and zinc are supported on zeolite, apatite, zirconia, glass, molybdenum oxide and the like.
The antibacterial agent and the antiviral agent may be used alone or in combination of two or more.

Among the above organic antibacterial agents and antiviral agents, benzimidazole compounds or anionic compounds that maintain the particle shape are preferably used.
The above-mentioned "maintaining the particle shape" means that it exists in the state of particles without being dissolved in the ionizing radiation curable resin composition which is the curable resin of the surface protective layer. Therefore, in the process of forming the surface protective layer, the particles of the benzimidazole compound or the particles of the anionic compound are likely to emerge, and the particles of the benzimidazole compound or the anionic compound are on the outermost surface side of the surface protective layer. Particles can be easily unevenly distributed.
Then, by unevenly distributing the particles of the benzimidazole compound or the particles of the anionic compound on the outermost surface side of the surface protective layer, an antibacterial agent or an antiviral agent necessary for obtaining predetermined antibacterial and antiviral properties. Since the amount of the virus added can be suppressed, it is possible to easily suppress the deterioration of the scratch resistance of the surface protective layer.

As the anionic antibacterial agent and antiviral agent, for example, those containing a styrene resin, a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound are preferable.
Further, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one of the structures of styrene, Na sulfonic acid, acrylic acid, maleic acid, and fumaric acid, and may include all the structures. More preferred. This is because there are two types of viruses with and without envelope, and it is considered that the structures of antibacterial agents and antiviral agents that can effectively inhibit the activity of each type are different.
Therefore, for example, if the effect of only influenza virus, which is a non-enveloped virus, is expected, only the styrene polymer derivative compound may be contained, and among them, the effect may be sufficiently obtained if only the styrene resin alone is contained.

As the inorganic antibacterial agent and antiviral agent, silver antibacterial agents and antiviral agents are preferable from the viewpoint of non-biotoxicity and excellent safety, among which phosphate-based glass-silver-supporting compounds, silver zeolite compounds, and silver zeolite compounds, and The molybdenum oxide silver double salt compound is more preferable because it exhibits antibacterial and antiviral properties even in a small amount and can suppress the addition amount.
The average particle size of the inorganic antibacterial agent or antiviral agent is preferably 0.1 to 10 μm, for example.
With the average particle size, the antibacterial agent and the antiviral agent can be preferably dispersed, and the antibacterial and antiviral properties can be suitably imparted without causing unevenness.

When the silver-based antibacterial agent or antiviral agent is added to the surface protective layer, the color changes depending on the surface protective layer (when the color is changed by heat or light in the state of the added paint, or after the surface protective layer is formed. The color may change due to heat or light), but in this case, it can be improved by adding an ultraviolet inhibitor, a light stabilizer, or the like in a timely manner.
For example, when a benzotriazole compound is used for the molybdenum oxide silver double salt compound, a discoloration improving effect can be expected.

The content of the antibacterial agent and the antiviral agent is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

The anti-allergen agent contains at least one of an inorganic compound and an organic compound, and may be used alone or in combination of two or more.
The antiallergen agent may be an antibacterial agent or an antiviral agent.

The inorganic compound is preferably a material that supports a metal.
As the material supporting the metal, for example, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate and magnesium phosphate is preferable, and among them, oxidation Titanium, zirconium phosphate and the like are preferable.
As the metal supported on the material supporting the metal, for example, at least one selected from the group consisting of gold, silver, platinum, zinc and copper is preferable, and among these, silver, zinc and the like are preferable.
As commercially available products, for example, "Parafine ANV-100: silver-supported inorganic compound" manufactured by Ohara Palladium Co., Ltd., "Atomy Ball TZ-R: zinc-supported on titanium oxide" manufactured by JGC Catalysts and Chemicals, etc. can be preferably used. , This anti-allergen agent acts effectively against various allergens such as mites and pollen.

The organic compound is at least one monomer selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, styrene sulfonic acid and a salt thereof. It is preferably a polymer containing components.

Examples of the water-insoluble polymer containing a phenolic hydroxyl group include "Allerbuster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Marcalinker M (trade name)" manufactured by Maruzen Petroleum Co., Ltd. as commercial products. Can be used.

Examples of the polyphenol compound supported on the inorganic solid acid include a combination of a polyphenol compound and a zirconium compound, and a commercially available product thereof is "Allelimve (trade name)" manufactured by Toa Synthetic Co., Ltd. And so on. These anti-allergen agents act effectively against various allergens such as mites and pollen.

As the styrene sulfonic acid and a salt thereof, a material as shown in Patent No. 6136433 can be used, and preferred examples thereof include a homopolymer of styrene sulfonate and a styrene sulfonate-styrene sulfonic acid co-weight. Examples thereof include coalescence, styrene sulfonate-styrene copolymer, styrene sulfonic acid-styrene copolymer and styrene sulfonate-styrene sulfonic acid-styrene ternary copolymer.

The anti-allergen agent may be a mixture of an organic compound and an inorganic compound, and examples thereof include a mixture of an anionic phenol-based material and a zinc-based material having anti-allergen properties.

Examples of the anionic phenolic material include tannin, tannic acid / sulphate, phenylsulfonic acid formaldehyde resin, noboratsk type resin sulfone compound, noboratsk type resin methanesulfonic acid, resol type resin methanesulfonic acid, and benzylated phenol. Examples thereof include sulfonic acids, thiophenol-based compounds, dihydrooxy, di-phenylsulfone-based compounds, ligant compounds, and metal chelate compounds thereof.

The zinc-based material is appropriately selected from a water-soluble zinc compound, a water-insoluble zinc compound, a zinc / metal oxide composite material, and the like, and is a composite particle of the water-insoluble zinc compound and / or the water-insoluble zinc / metal oxide. Is water-dispersed, the average particle size is 50 μm or less, and the metal oxide preferably contains at least one of titania, silica, and alumina.

The content of the anti-allergen agent is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

(Primer layer for surface protection layer)
The primer layer for the surface protection layer preferably contains a binder resin.
The primer layer for the surface protective layer is preferably transparent, and as long as it is transparent, it may be translucent or colored as long as the pattern layer is visible.
Examples of the binder resin include urethane resin, acrylic resin, acrylic-urethane resin (acrylic modified urethane resin), acrylic-urethane copolymer resin (block copolymer, etc.), cellulose resin, and urethane-cellulose resin (urethane-cellulose resin). For example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), a polyester resin, a vinyl chloride-vinyl acetate copolymer resin, and the like can be mentioned. When the urethane acrylate oligomer is blended in the ionization radiation curable resin composition of the surface protective layer described above, the urethane resin is preferable from the viewpoint of adhesion to the surface protective layer and efficiency during production.

The thickness of the primer layer for the surface protection layer is preferably 0.5 μm or more and 10 μm or less. If it is 0.5 μm or more, the adhesion between the transparent resin film of the present invention and the pattern layer described later can be suitably secured, and if it is 10 μm or less, the transparent resin film of the present invention does not become too thick and is sufficient. High transparency can be obtained, and the design of the decorative board can be preferably ensured. In addition, blocking during film formation can be suppressed.
Blocking is a phenomenon in which a transparent resin film is coated with a film-forming or adhesive primer, rolled up in a roll shape, and the films are difficult to separate from each other when the film is unwound. Further, the primer layer for the surface protection layer may contain inorganic fine particles such as silica.
Further, an additive may be added to the primer layer for the surface protection layer, if necessary. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a light stabilizer. The blending amount of the additive can be appropriately set according to the product characteristics.

(External haze layer)
The transparent resin film of the present invention has an outer haze layer.
The outer haze layer is laminated on the back surface of the thermoplastic resin layer in order to protect the surface of the pattern layer laminated on one surface of the base material described later.
In the transparent resin film of the present invention, the haze value of the outer haze layer is preferably 4% or more and less than 100%. If the haze value is less than 4%, air biting may not be visually discernible when the transparent resin film of the present invention is laminated on the surface of the pattern layer, and the adhesion may be insufficient. be. The more preferable lower limit of the haze value of the outer haze layer is 5%, and the more preferable lower limit is 6%.

The haze value of the outer haze layer is a value obtained by subtracting the haze when the back surface is wet from the haze of the entire transparent resin film.
The haze of the entire transparent resin film can be measured, for example, by irradiating light from the surface side of the outer haze layer or from the surface side of the transparent resin film and using a known haze meter.
The haze when the back surface is wet is obtained from the front surface side of the transparent resin film with PET having a haze value of 0.1% or less attached to the back surface side of the transparent resin film via pure water. It can be measured by exposing it to light and using a known haze meter. This is because the haze value obtained by removing the haze value of the outer haze layer from the transparent resin film can be calculated.

In the transparent resin film of the present invention, a polyethylene terephthalate film having a haze of 0.1% or less is attached to the side opposite to the thermoplastic resin layer side of the outer haze layer via pure water, and from the thermoplastic resin layer side. The haze value when the measured back surface is wet is preferably 90% or less.
When the haze value when the back surface is wet, measured from the thermoplastic resin layer side, exceeds 90%, the transparency of the transparent resin film of the present invention is lowered, and the visibility of the pattern layer when used as a decorative plate May be inferior to.
The more preferable upper limit of the haze value when the back surface is wet is 80%, and the more preferable upper limit is 60%.

The material constituting the outer haze layer is a material used to improve the adhesion with the pattern layer. For example, urethane resin, acrylic resin, urethane-acrylic resin, urethane-acrylic copolymer resin, etc. Examples thereof include cellulose-based resins, polyester resins, vinyl chloride-vinyl acetate copolymers, and the like.

The outer haze layer preferably has a thickness of 0.5 μm or more and 20 μm or less. If it is less than 0.5 μm, the adhesion between the base material and the transparent resin film is insufficient, while if it exceeds 20 μm, the front and back surfaces of the film come into contact with each other when the transparent resin film is made into a roll. Blocking may occur. A more preferable lower limit of the thickness of the outer haze layer is 0.8 μm, a more preferable upper limit is 15 μm, a further preferable lower limit is 1 μm, and a further preferable upper limit is 10 μm.

Examples of the method of keeping the haze value in the wet state of the back surface within the above range include a method of adjusting the amount of additives contained in the thermoplastic resin layer, a method of reducing the thickness of the thermoplastic resin layer, and the like. Conceivable.

In the outer haze layer, in order to further strengthen the adhesion with the thermoplastic resin layer, the surface of the thermoplastic resin layer on which the outer haze layer is provided may be subjected to surface treatment such as corona discharge treatment or plasma treatment. .. The method and conditions of the surface treatment may be carried out according to a known method.
Further, a primer layer may be formed between the outer haze layer and the base material layer to enhance the adhesion.
The outer haze layer may have a function as a primer layer for improving adhesion with the base material layer and the thermoplastic resin layer. As the primer layer, the same one as the above-mentioned primer layer for surface protection layer can be preferably used.

The outer haze layer may have a single layer or a plurality of layers similar to the thermoplastic resin layer on the surface opposite to the thermoplastic resin layer side.
Further, an additive may be added to the outer haze layer, if necessary. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a light stabilizer. The blending amount of the additive can be appropriately set according to the product characteristics.

(Haze value of transparent resin film)
The transparent resin film of the present invention preferably has a haze value (hereinafter, also referred to as haze value (1)) of 70% or more excluding the surface haze on the side opposite to the side laminated on the base material.
Since the transparent resin film of the present invention has such a haze, the heat absorption rate can be increased, so that the shape of the uneven shape is excellent.
Normally, the uneven shape formed by embossing or the like disappears due to heat, the passage of time, etc. However, when the haze value (1) is within a predetermined range, the disappearance of such an uneven shape is suppressed. can do.
The haze value (1) is more preferably 75% or more, and further preferably 80% or more.
In the present specification, the haze is a value measured using DIRECT READING HAZE METER (manufactured by Toyo Seiki Co., Ltd.).

The haze value (1) can be measured by the following method.
That is, a transparent resin film, pure water, and a PET film (haze value of 3% or less) are laminated in this order to prepare a sheet.
At this time, the pure water is laminated on the side of the transparent resin film having the uneven shape.
With respect to the obtained sheet, from the side of the PET film laminated on the side having the uneven shape of the transparent resin film, more specifically, the side having the uneven shape of the transparent resin film, DIRECT READING HAZE METER (Toyo Seiki Co., Ltd.) It can be obtained by measuring the haze value using (manufactured by) and excluding the haze value of the PET film, specifically, subtracting the haze value (for example, 3%) of the PET film.

The transparent resin film of the present invention has a haze value excluding the surface haze on the side laminated on the base material and the surface haze on the side opposite to the side laminated on the base material (hereinafter, also referred to as haze value (2)). ) Is preferably 70% or less.
By having such a haze, the transparent resin film of the present invention is excellent in design because the pattern formed in the pattern layer described later can be clearly seen.
The haze value (2) is more preferably 65% or less, and further preferably 60% or less.

The haze value (2) can be measured by the following method.
That is, a PET film (haze value of 3% or less), pure water, a transparent resin film, pure water, and a PET film (haze value of 3% or less) are laminated in this order to prepare a sheet.
With respect to the obtained sheet, from the side of the PET film laminated on the side having the uneven shape of the transparent resin film, more specifically, the side having the uneven shape of the transparent resin film, DIRECT READING HAZE METER (Toyo Seiki Co., Ltd.) The haze value is measured using (manufactured by), and the haze value of the above PET film is excluded. Specifically, each PET film (for example, 3% of each PET film haze value, 6% in total) is subtracted. Can be obtained by

(Manufacturing method of transparent resin film)
The method for producing the transparent resin film of the present invention is not particularly limited, and each layer described above is laminated via the transparent adhesive layer, the primer layer for a surface protection layer, or the like, or by a thermal lamination method. The method and the like can be mentioned.
As the heat laminating method, a known method such as a melt coextrusion method using a T-die can be used.

As for the various additives added to each layer of the transparent resin film (inorganic filler added to the primer layer and the surface protection layer, etc.), it is preferable that the various additives are vesicled. The method for vesicle-forming various additives is not particularly limited, and vesicles can be formed by a known method, and the supercritical reverse-phase evaporation method is particularly preferable.

Other examples of the vesicle treatment method include a Bangham method, an extrusion method, a hydration method, a reverse phase evaporation method, and a freeze-thaw method.
Briefly explaining such a vesicle treatment method, in the above Bangham method, chloroform or chloroform / methanol mixed solvent is put in a container such as a flask, and phospholipid is further put in and dissolved. Then, the solvent is removed using an evaporator to form a thin film composed of lipids, a dispersion liquid of additives is added, and then hydrated and dispersed with a vortex mixer to obtain vesicles.
The extrusion method is a method in which a thin-film phospholipid solution is prepared and passed through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain a vesicle.
The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining a vesicle by gently stirring and dispersing without using a mixer.
In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to form a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added. It is a method of obtaining vesicles by doing so.
The freeze-thaw method is a method of using cooling / heating as an external perturbation, and is a method of obtaining a vesicle by repeating this cooling / heating.

Hereinafter, the supercritical reverse phase evaporation method will be described in detail.
The supercritical reverse phase evaporation method is water-soluble or hydrophilic in a mixture in which a substance forming an outer film of a vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure condition above the supercritical point. This is a method in which an aqueous phase containing various additives as a sex encapsulant is added to form a capsule-shaped vesicle containing various additives as an encapsulant in a single layer film.
The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and is a temperature above the critical point or higher. Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained.
In general, vesicles are a general term for vesicles having a spherical shell-like closed membrane structure containing a liquid phase, and in particular, liposomes whose outer membrane is composed of biolipids such as phospholipids. ..

Examples of the phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin and other glycerophospholipids, and sphingomyelin. , Ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

As the substance constituting the outer membrane, a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.

Examples of the nonionic surfactant include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene-. One or two types such as polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The above can be used.

Examples of the cholesterol include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like. Can be used.

The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present invention, by forming the outer membrane into liposomes formed from phospholipids, the compatibility between the resin composition which is the main component of each layer and various additives can be improved.

<Veneer>
The transparent resin film of the present invention is used to protect the pattern layer, and has an outer haze layer on the surface to be laminated on the pattern layer of the base material, so that the surface of the pattern layer of the base material is transparent. When the resin films are laminated, it can be easily visually determined whether or not they are biting air, and it becomes easy to improve the adhesion to the pattern layer.
A decorative board, which comprises a base material, a pattern layer, and a transparent resin film of the present invention in this order in the thickness direction, is also an aspect of the present invention.

Next, a preferable example of the decorative board of the present invention will be described with reference to FIG.
In the decorative board 20 of the present invention, the pattern layer 24 is laminated on one surface of the base material 25, and the transparent resin film 10 of the present invention is laminated on the side of the pattern layer 24 opposite to the side having the base material 25. There is.
Further, it is preferable to have the adhesive layer 23 from the viewpoint of further strengthening the adhesion between the pattern layer 24 and the transparent resin film 10 of the present invention.
Hereinafter, each configuration of the decorative board of the present invention will be described.

(Base material)
The material constituting the base material is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, metal materials, and inorganic materials. Further, these composite materials may be used.
As the resin material, for example, it is preferable to contain a thermoplastic resin.
Examples of the thermoplastic resin include polyvinyl chloride resins such as polyvinyl chloride resin, polyvinyl acetate resin and polyvinyl alcohol resin, polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene- (meth) acrylic acid. Polyethylene resin such as based resin, polyester resin such as polyethylene terephthalate resin (PET resin), acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, polychloride Single or copolymer of thermoplastic resin such as vinyl resin plate, diene rubber such as styrene butadiene rubber, isoprene rubber, chloroprene rubber, non-diene rubber such as butyl rubber and ethylene propylene rubber, natural rubber, thermoplastic elastomer or These mixed resins are preferably mentioned. Of these, polyolefin resins, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, ionomers and the like are preferable. Further, the resin material may be foamed.

The above-mentioned thermoplastic resin plate and thermosetting resin plate may be used as a colorant (pigment or dye), a filler such as wood powder or calcium carbonate, a matting agent such as silica, a foaming agent, a flame retardant, a talc or the like, if necessary. Various additives such as lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be contained.

Examples of the wood-based material include various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melamy, and the core material includes veneer and wood single made from these materials. Any of board, wood plywood (including LVL), particle board, medium density fiberboard (MDF), high density fiberboard (HDF), veneer, etc., or a laminated material in which these are appropriately laminated may be used. ..
Examples of the metal material include iron, aluminum and the like.
Moreover, the said base material may contain an inorganic compound.

Further, the base material may contain the above-mentioned flame retardant. By containing a flame retardant, the flame retardancy of the base material is further improved.

When the base material has a plurality of thermoplastic resin layers, the types of resins forming the plurality of thermoplastic resin layers may be the same or different, and the thickness of the plurality of thermoplastic resin layers may be the same. May be the same or different.

In the present invention, the base material may have a hollow structure, a slit groove or a through hole may be provided in a part of the base material, or a frame-shaped material in which the above materials are combined may be used.

The thickness of the base material is not particularly limited, and is preferably 0.01 mm or more, more preferably 0.1 mm or more and 50 mm or less, for example.
The base material has a substantially plate-like shape other than a flat plate, and includes those having irregularities and curved surfaces.

(Pattern layer)
Further, the pattern layer provided on the base material is a layer that imparts decorativeness to the decorative board of the present invention made of the transparent resin film of the present invention, and is, for example, a uniformly colored concealing layer (solid). It may be a printing layer), a pattern layer formed by printing various patterns using ink and a printing machine, or a layer combining a concealing layer and a pattern layer (hereinafter, a pattern layer). ) May be.

By providing the concealing layer, when the above-mentioned base material is colored or has uneven color, it is possible to give an intended color and adjust the surface color.
In addition, by providing the above pattern layer, a stone pattern that imitates the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), a cloth pattern that imitates a cloth grain or a cloth-like pattern, a tiled pattern, or a brick It is possible to add a pattern such as a stack pattern or a combination of these to a decorative sheet such as a parquet, a patchwork, a character, a symbol, an abstract pattern, a flower pattern, a landscape, and a character. These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing plates of the individual colors that make up the pattern. Will be done.

As the ink composition used for the pattern layer, a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is used. The binder resin is not particularly limited, and examples thereof include urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin, and nitrocellulose resin. Be done. As the binder resin, any one of these can be used alone or in combination of two or more.
The colorants used include carbon black (black), iron black, titanium white, and antimony white.
Consists of inorganic pigments such as chrome yellow, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue, organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, or scaly foil pieces such as dyes, aluminum, and brass. Preferred examples thereof include metal pigments, titanium dioxide-coated mica, and pearl pigments composed of scaly foil pieces such as basic lead carbonate.

The thickness of the pattern layer is not particularly limited, and is preferably 0.1 μm or more, more preferably 0.5 μm or more and 600 μm or less, for example. When the thickness of the pattern layer is within the above range, an excellent design can be imparted to the decorative board of the present invention, and concealment can be imparted.
If you want to make the best use of the design of the base material itself, such as a veneer, which has a design property in advance, the base material itself also serves as a design layer, so it is not necessary to provide a separate design layer. ..

The transparent resin film of the present invention is used to protect the surface of the pattern layer by laminating the outer haze layer on the surface of the pattern layer laminated on one surface of the above-mentioned base material.
A decorative board characterized in that a base material, a pattern layer, and the transparent resin film of the present invention are provided in this order in the thickness direction is also one of the present inventions.

The thickness of the decorative board of the present invention is not particularly limited, and is preferably 0.05 mm or more, more preferably 1 mm or more and 50 mm or less, for example.

The decorative board of the present invention may further have a backer layer or the like, if necessary. At that time, the adherend may be provided on the back side of the transparent adhesive layer, the primer layer, the backer layer, or the like.
As the transparent adhesive layer and the primer layer, the same ones as those described in the transparent resin film described above can be preferably used.

(Backer layer)
Examples of the backer layer include a resin backer layer such as a synthetic resin backer layer and a foamed resin backer layer, a wood-based backer layer such as cork, and a non-woven fabric-based backer layer, and the bottom layer of the base material (the transparent resin film is laminated). It is preferable to have it on the side opposite to the side to be sewn.
When the base material has the backer layer, the scratch resistance and impact resistance of the decorative board can be further improved.

Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and highly heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1 , 4-Cyclohexanedimethanol, polyethylene terephthalate substituted with diethylene glycol, etc., so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate-isophthalate copolymer, Diene rubber such as amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, styrene butadiene rubber, isoprene rubber, chloroprene rubber, non-diene rubber such as butyl rubber and ethylene propylene rubber, Examples include natural rubber and thermoplastic elastomer. These resins can be used alone or in combination of two or more.

The synthetic resin backer layer may contain hollow beads.
As the type, particle size, content, etc. of the hollow beads, those described in JP-A-2014-188941 can be applied.

The synthetic resin backer layer may contain a flame retardant for the same reason as the thermoplastic resin layer and the like.
The flame retardants include phosphinic acid metal salt flame retardants, phosphazen flame retardants, NOR type hindered amine flame retardants, halogen flame retardants, antimon flame retardants, metal hydroxide flame retardants, and phosphoric acid ester flame retardants. And so on.

The thickness of the synthetic resin backer layer is not particularly limited, but is preferably 100 to 600 μm, more preferably 150 to 450 μm, for example.

Examples of the method for forming the synthetic resin backer layer include calendar molding, extrusion molding of molten resin, and the like. Of these, extrusion molding of molten resin is preferable, and for example, extrusion molding using a T-die is more preferable.

The foamed resin backer layer may be further lower than the synthetic resin backer layer (on the side opposite to the side having the uneven shape).
As the foamed resin backer layer, those described in JP-A-2014-188941 can be applied.

(Support)
The base material may be a support.
The support is not particularly limited, and various types of paper, plastic films, wood-based boards such as wood, ceramic materials, and the like can be appropriately selected depending on the intended use. Each of these materials may be used alone, or may be a laminate obtained by any combination such as a composite of papers or a composite of paper and a plastic film.

Examples of the above-mentioned papers include thin paper, kraft paper, titanium paper and the like. These paper substrates are used to enhance the interlayer strength between the fibers of the paper substrate or between other layers and the paper substrate, and to prevent fluffing, in addition to these paper substrates, acrylic resin, styrene-butadiene rubber, etc. Resins such as melamine resin and urethane resin may be added (impregnated with resin after fabrication or internally filled at the time of fabrication). For example, inter-paper reinforced paper, resin-impregnated paper, and the like.
In addition to these, various types of paper often used in the field of building materials such as linter paper, paperboard, base paper for gypsum board, and vinyl wallpaper raw fabric having a vinyl chloride resin layer on the surface of the paper can be mentioned.
Further, coated paper, art paper, sulfated paper, glassine paper, parchment paper, paraffin paper, Japanese paper and the like used in the office work field and ordinary printing, packaging and the like can also be used. Further, although distinguished from these papers, woven fabrics and non-woven fabrics of various fibers having an appearance and properties similar to paper can also be used as a base material. Examples of various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, and synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

When the support such as the above papers is a porous base material, a conventionally known thermosetting resin can be widely used in order to impregnate the porous base material with the thermosetting resin. Examples of the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, and melamine-. Examples thereof include urea cocondensation resin, silicon resin and polysiloxane resin.
The layer obtained by impregnating the papers with the thermosetting resin and further curing the paper in this way is also referred to as a thermosetting resin layer. Then, the thermosetting resin layer may finally play a role as a surface protective layer.

The method of impregnating the porous base material with the thermosetting resin is to supply the thermosetting resin from either or both of the front side and the back side of the porous base material. Can be done. This method is not particularly limited, and for example, a method of immersing a bathtub containing a thermosetting resin from the surface on which the release layer of the porous base material is formed or the opposite surface; a coater such as a kiss coater or a comma coater. A method of applying the thermosetting resin to the surface on which the release layer of the porous base material is formed, the opposite surface, or both surfaces thereof; the thermosetting resin is applied to the porous group by a spray device, a shower device, or the like. Examples thereof include a surface on which a release layer of the material is formed, a surface opposite to the surface, or a method of spraying on both surfaces thereof.

Specific examples of the resin constituting the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, phenol resins, polyvinyl alcohols, vinyl resins such as ethylene-vinyl alcohol copolymers, and polyethylene. Polyester resin such as terephthalate and polybutylene terephthalate, acrylic resin such as polymethylmethacrylate, methylpolyacrylate, ethylpolymethacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate, etc. Can be mentioned. Among these, polyolefin resins, vinyl chloride resins, polyester resins, or acrylic resins are preferable from the viewpoints of various physical properties such as weather resistance and water resistance, printability, molding processability, and price.

The support may contain the flame retardant described above. When the support contains a flame retardant, the flame retardancy of the decorative board is further improved for the same reason as the transparent resin layer. The flame retardant that can be contained is preferably the same as that of the thermoplastic resin layer or the like.

The thickness of the support is not particularly limited, but when the support is a plastic film, it is preferably 20 to 200 μm, more preferably 40 to 160 μm, and even more preferably 40 to 100 μm.
If the support is paper, the basis weight, usually preferably ^{20~150g / m 2, 30~100g / m} 2 is more preferable.

The shape of the support is not limited to a flat plate shape, and may be a special shape such as a three-dimensional shape.
On the support, one side or both sides may be subjected to an easy adhesion treatment such as a physical treatment or a chemical surface treatment in order to improve the adhesion to the layer provided on the support.

(Phenol resin impregnated paper)
The decorative board may be laminated with phenol resin impregnated paper, if necessary.
The phenol resin impregnated paper may be laminated on the surface of the porous base material opposite to the side on which the abrasion resistant layer and the release layer are formed.

The above-mentioned phenol resin impregnated paper is generally obtained ^{by impregnating kraft paper having a basis weight of about 150 to 250 g / m 2} as core paper with phenol resin so as to have an impregnation rate of about 45 to 60% and drying at about 100 to 140 ° C. It is a paper produced by making it. Commercially available products can be used for the phenol resin impregnated paper. When laminating the phenol resin impregnated paper, if necessary, the back surface of the porous substrate may be subjected to a corona discharge treatment, or the back surface primer layer may be formed by applying the above-mentioned primer layer. ..

(Sealer layer)
When an impregnating base material such as paper is used as the support, a sealer layer may be provided between the support and the pattern layer.

The sealer layer preferably contains a cured product of a thermosetting resin composition or a curable resin composition such as an ionizing radiation curable resin composition, and among them, a cured product of the thermosetting resin composition is included. Is more preferable.
The content of the cured product of the curable resin composition is preferably 50% by mass or more, and more preferably 65 to 95% by mass, based on the total solid content of the sealer layer.
Examples of the thermosetting resin composition and the ionizing radiation curable resin composition of the sealer layer are the same as those exemplified in the surface protective layer. Further, as the thermosetting resin composition, a two-component curable resin of a polyol and an isocyanate is preferable, and a two-component curable resin of an acrylic polyol and hexamethylene diisocyanate is more preferable.

The sealer layer preferably contains particles from the viewpoint of drying suitability and viscosity adjustment. The content of the particles is preferably 5 to 50% by mass, more preferably 5 to 35% by mass, based on the total solid content of the sealer layer.
The particles of the sealer layer are preferably inorganic particles, and among them, silica is preferable.
The particles preferably have an average particle size of 0.1 to 2.0 μm, more preferably 0.2 to 1.5 μm.

<Adhesion material>
The decorative board of the present invention may be used by being laminated on an adherend so that the side having the uneven shape and the opposite side are in contact with each other.
On the other hand, when an adherend having the pattern layer is used, the decorative board of the present invention can be obtained by laminating the transparent resin film on the adherend having the pattern layer.
As the pattern layer, the above-mentioned pattern layer can be preferably used.

The material of the adherend is, for example, a wood-based board such as a single wood board, a wood plywood, a particle board, an MDF (medium density fiberboard), an HDF (high density fiberboard); Boards; Cement boards such as calcium silicate board, asbestos slate board, lightweight foamed concrete board, hollow extruded cement board; Fiber cement board such as pulp cement board, asbestos cement board, wood piece cement board; Ceramic plates such as iron plate, zinc-plated steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, copper plate and other metal plates; polyolefin resin plate, acrylic resin plate, ABS plate, polycarbonate plate, polyvinyl chloride resin plate and other thermoplastic resins Plates: Thermo-curable resin plates such as phenol resin plate, urea resin plate, unsaturated polyester resin plate, polyurethane resin plate, epoxy resin plate, melamine resin plate; phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy Examples thereof include so-called FRP boards in which a resin such as a resin, a melamine resin, or a diallyl phthalate resin is impregnated and cured in a glass fiber non-woven fabric, cloth, paper, or other various fibrous base materials and cured, and these are used alone. Also, it may be used as a composite substrate in which two or more of these are laminated.
The thickness of the adherend is not particularly limited.

Further, the thermoplastic resin plate and the thermocurable resin plate may be used as a colorant (pigment or dye), a filler such as wood powder or calcium carbonate, a matting agent such as silica, a foaming agent, or a flame retardant, if necessary. , Lubricants such as talc, antioxidants, antioxidants, UV absorbers, light stabilizers and other various additives may be included.

The laminating method on the adherend is not particularly limited, and examples thereof include means for laminating via the above-mentioned primer layer and laminating via an adhesive.
The adhesive may be appropriately selected from known adhesives according to the type of the adherend and the like. For example, polyvinyl acetate, urethane, acrylic, urethane acrylic (including copolymer) polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylic nitrile rubber. , Neoprene rubber, natural rubber and the like.

<Manufacturing method of decorative board>
As a method for producing a decorative board of the present invention, for example, a heat melting method, a heat laminating method, a water-based adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot melt adhesive, and the above-mentioned transparent adhesive layer are formed. Examples thereof include a method of laminating the base material, the pattern layer, and the transparent resin film using an adhesive or the like.
Among them, in the method for manufacturing the decorative board, the step of forming an adhesive layer on the surface of the transparent resin film on the side to be laminated on the pattern layer, and the transparent via the adhesive layer. It is preferable to have a step of adhering the sex resin film and the pattern layer.
Such a method for producing a decorative board of the present invention is also an aspect of the present invention.
In the transparent resin film, when the uneven shape having the pattern layer on the opposite side surface to be laminated is formed, the uneven shape is formed by embossing or the like, but the embossed surface side is formed. Following the uneven shape, a slight uneven shape is formed on the surface opposite to the embossed surface (the surface on the side laminated on the pattern layer). In such a case, so-called air biting, in which air enters the uneven shape on the side laminated on the pattern layer formed on the transparent resin film, may occur, and the design may be deteriorated.
Since the method for producing a decorative board of the present invention includes a step of forming an adhesive layer on the surface of the transparent resin film on the side having the pattern layer, it also adheres to the concave-convex concave portion on the side having the pattern layer. The agent layer can be penetrated, the above-mentioned air biting can be prevented, and the deterioration of the design can be suppressed.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Example 1)
A transparent polypropylene film (thickness 60 μm) is prepared, and a two-component curable urethane resin (thickness 1 μm) using silica-added isocyanate as a curing agent is applied to one surface of the transparent polypropylene film to form a primer layer for a surface protective layer. Was formed.
A transparent polypropylene-based material containing a flame retardant (phosphinic acid metal salt-based flame retardant, product name Pekoflam STC, manufactured by Arcroma) on the other surface (the side where the primer layer for the surface protective layer is not coated) of the transparent polypropylene film. The resin (thickness 200 μm, flame retardant content 18.1% by mass) was extruded and laminated by a thermal laminating method.
At this time, the total thickness of the thermoplastic resin layer composed of the transparent polypropylene film and the flame-retardant-containing transparent polypropylene-based resin is 260 μm, and the content of the phosphinic acid metal salt-based flame-retardant in the thermoplastic resin layer is the thermoplastic resin layer. It was 14.1 mass%, where 100 mass% was taken as the mass of.
After corona treatment was applied to the surface of the flame retardant-containing transparent polypropylene resin, a two-component curable urethane resin (thickness 2 μm) using isocyanate as an external haze layer as a curing agent was applied.
After coating the coated surface of the primer layer for the surface protection layer with urethane (meth) acrylate, which is an ionizing radiation curable resin, by a gravure coating method so that the coating amount is 15 μm, an acceleration voltage of 165 keV is applied using an electron irradiation device. A surface protective layer was formed by irradiating an electron beam under the condition of 5Mrad.
Next, a heat absorption type embossing process was performed so that the surface having the surface protective layer was in contact with the embossed plate, and the uneven shape was formed to produce a transparent resin film.
Then, using a haze measuring machine, the haze value of the entire transparent resin film and the haze when the back surface was wet were measured by the method described later.
On the other hand, an HDF (thickness 3 mm) was prepared, and a pattern layer was formed on one surface of the HDF with an inkjet printer so as to have a thickness of 2 μm to prepare a base material.
A two-component curable polyester resin (thickness 50 μm) using isocyanate as a curing agent was applied to the side surface of the obtained transparent resin film opposite to the side having the uneven shape to form an adhesive layer, and the obtained transparency was obtained. The side surface of the resin film opposite to the side having the uneven shape and the surface provided with the pattern layer side of the base material were laminated via the adhesive layer. Then, a pressure of 10 kg / m ² was applied and cured in a normal temperature environment for 3 days to prepare a decorative board.

(Haze value measurement method)
As a measuring device, DIRECT HAZE METER (manufactured by Toyo Seiki Co., Ltd.) was used.
Haze value of the entire sheet: The haze value was measured by irradiating light from the surface side of the transparent resin film having the uneven shape, specifically, in Example 1, the surface protective layer having the uneven shape.
Haze value when the back surface is wet: Pure water is dropped on the surface side of the transparent resin film having the outer haze layer, and air bites the PET film (Toray Lumirer T60 50 μm thickness, haze value 0.1%). The haze value is determined by shining light from the surface side of the transparent resin film having the uneven shape, specifically, in Example 1, the surface protective layer having the uneven shape formed. It was measured.
Haze value of the external haze layer: Calculated as a value obtained by subtracting the haze value when the back surface is wet from the haze value of the entire sheet.

(Visual confirmation of air bite)
++ ・ ・ ・ Air bite can be clearly judged ＋ ・ ・ ・ Air bite can be judged by checking with oblique light － ・ ・ ・ Air bite cannot be judged

(Design at the time of close contact)
++++ ・ ・ ・ The design after laminating looks very clear ++ ・ ・ ・ The design after laminating looks slightly cloudy ＋ ・ ・ ・ The design after laminating looks cloudy ― ・ ・ ・ Most of the designs after laminating Invisible

(Flame retardance)
[Horizontal flammability test (flame retardancy: difficulty of spreading fire)]
The decorative material obtained in Examples 1 and 2 was cut into a size of 9 cm × 30 cm and used as a test piece.
As shown in FIGS. 4A and 4B, a metal rectangular base 103 is placed on a base 102 of a commercially available household heater 101 (voltage AC100V, power consumption 1200W), and the metal is installed on the base. A test piece 105 was placed in a frame 104 made of metal, and a test was conducted with a heater angle of 45 ° and a heater output of 4/5 to prevent the fire from spreading.
Specifically, the test piece was preheated for 2 minutes using the above household heater. Next, as shown in FIG. 4A, the end 106 on the heater side in the longitudinal direction of the test piece is heated with a lighter 107 for 1 minute to ignite, and then, as shown in FIG. 4B, the longitudinal direction of the test piece 105 is ignited. The fire spread to.
Next, the fire spread state was visually observed, and the fire spread distance (L1) was evaluated as follows.
[Fire spread distance (L1)]
The fire spread distance from the initial ignition, excluding the lighter's fire after igniting the test piece, was measured and used as the fire spread distance (L1), which was evaluated according to the following evaluation criteria. If it is + evaluation or higher, it is evaluated that there is no problem in actual use.
+: L1 is less than 10 cm-: L1 is 10 cm or more

(Example 2)
The flame retardant contained in the flame retardant-containing transparent polypropylene resin (thickness 200 μm) is added to the phosphazene flame retardant (Ravitor FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd., content 18.1% by mass in the flame retardant-containing transparent polypropylene resin). A transparent resin film and a decorative board were produced in the same manner as in Example 1 except that they were changed. Then, the same evaluation as in Example 1 was performed.
At this time, the total thickness of the thermoplastic resin layer composed of the transparent polypropylene film and the flame-retardant-containing transparent polypropylene-based resin is 260 μm, and the content of the phosphazen-based flame-retardant in the thermoplastic resin layer is the mass of the thermoplastic resin layer. As 100% by mass, it was 14.1% by mass.

(Example 3)
The flame retardant contained in the flame retardant-containing transparent polypropylene resin (thickness 200 μm) is contained in the phosphazene flame retardant (Ravitor FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd., content 17.5% by mass in the flame retardant-containing transparent polypropylene resin). , A transparent resin film and cosmetics in the same manner as in Example 2 except that hydrophilic fumed silica (AEROSIL 50 manufactured by Nippon Aerozil Co., Ltd., content 17.5% by mass in the flame retardant-containing transparent polypropylene resin) was used. A board was made. Then, the same evaluation as in Example 1 was performed.
At this time, the total thickness of the thermoplastic resin layer composed of the transparent polypropylene film and the flame-retardant-containing transparent polypropylene-based resin is 260 μm, and the content of the phosphazen-based flame-retardant in the thermoplastic resin layer is the mass of the thermoplastic resin layer. As 100% by mass, it was 14% by mass, and the content of the hydrophilic fumed silica was 14% by mass.

(Comparative Example 1)
A transparent resin film and a decorative board were produced in the same manner as in Example 1 except that a resin containing no flame retardant was used as the transparent polypropylene resin (thickness 200 μm). Then, the same evaluation as in Example 1 was performed.
At this time, the total thickness of the thermoplastic resin layer composed of the transparent polypropylene film and the flame retardant-containing transparent polypropylene resin was 260 μm.

In the transparent resin films obtained in Examples 1 and 2, air biting could be easily visually confirmed. In addition, the decorative boards obtained in Examples 1 and 2 containing a flame retardant showed excellent flame retardancy.
On the other hand, Comparative Example 1 containing no flame retardant did not have flame retardancy. Further, it was confirmed that the decorative board obtained in Example 3 in which fumed silica was added to the decorative board obtained in Example 2 containing a flame retardant had improved design.

(Example 4)
A transparent polypropylene film (thickness 60 μm) is prepared, and a primer is applied to one surface (the side laminated on the base material having a pattern layer) to use an external haze layer (thickness 2 μm, isocyanate as a curing agent). A two-component curable urethane resin) was formed. A transparent polypropylene resin (thickness 60 μm, flame retardant content 6.98% by mass) containing a flame retardant (phosphinic acid metal salt-based flame retardant, product name Pekoflam STC, manufactured by Arcroma) on the other surface of the transparent polypropylene film. ) Was laminated by an extrusion heat laminating method. Immediately after that, it was brought into contact with a metal roll having a temperature of 10 ° C. for 0.5 seconds and cooled (quenched) at 200 ° C./sec to obtain a thermoplastic resin layer on which an outer haze layer was formed.
The total thickness of the thermoplastic resin layer composed of the transparent polypropylene film of Example 4 and the extruded transparent polypropylene resin is 120 μm, and the content of the phosphinic acid metal salt flame retardant is 100, which is the total mass of the thermoplastic resin layers. As a mass%, it was 3.5 mass%.
Next, the surface of the thermoplastic resin layer opposite to the surface having the outer haze layer was subjected to corona treatment, and then a primer (thickness 2 μm) was applied to form a primer layer for a surface protective layer. An ionizing radiation curable resin (coating amount: 15 μm) was applied to the surface by a gravure coating method, and then an electron beam was irradiated to the surface using an electron irradiation device under the conditions of an acceleration voltage of 165 keV and 5 rad to form a surface protective layer.
Then, the side having the surface protective layer was heated by an infrared non-contact type heater and then embossed by heat pressure to obtain a transparent resin film having an uneven shape.
A group having a pattern layer formed by coating a two-component curable polyester (thickness 50 μm) on a surface of a transparent resin film having an outer haze layer to form an adhesive layer and providing an inkjet printer so as to have a thickness of 2 μm. A decorative board was prepared by laminating on a material (MDF (medium density fiberboard) thickness 3 mm).

(Example 5)
A decorative board was produced in the same manner as in Example 4 except that the thickness of the outer haze layer was changed to 1 μm.

(Comparative Example 2)
A transparent resin film and a decorative board were produced in the same manner as in Example 4 except that the transparent polypropylene resin (60 μm) laminated by the extrusion heat laminating method did not contain a flame retardant.
The total thickness of the thermoplastic resin layer composed of the transparent polypropylene film of Comparative Example 2 and the extruded transparent polypropylene resin was 120 μm.

(Reference example 1)
A polypropylene resin (thickness 60 μm) was prepared, and a primer (thickness 2 μm, a two-component curable urethane resin using isocyanate as a curing agent) was applied to one surface to form an outer haze layer. A transparent polypropylene resin (thickness 60 μm, flame retardant content 6.98% by mass) containing a flame retardant (phosphinic acid metal salt flame retardant, product name Pekoflam STC, manufactured by Arcroma) on the other surface of the polypropylene resin. ) Was laminated by an extrusion heat laminating method. Immediately after that, it was brought into contact with a metal roll at 50 ° C. for 0.5 seconds, left in an environment of 25 ° C., and further cooled (slowly cooled) at 50 ° C./sec to form the heat of forming the outer haze layer. A plastic resin layer was obtained.
Except for the above, a decorative board was produced in the same manner as in Example 4.
The total thickness of the thermoplastic resin layer composed of the transparent polypropylene film of Reference Example 1 and the extruded transparent polypropylene resin is 120 μm, and the content of the phosphinic acid metal salt flame retardant is 100, which is the total mass of the thermoplastic resin layers. As a mass%, it was 3.5 mass%.

<Haze value>
The haze value (1) excluding the surface haze on the side opposite to the side to be laminated on the base material of the transparent resin film obtained in Examples 4 and 5, Comparative Example 2 and Reference Example 1 and the haze value (1) laminated on the base material. The haze value (2) excluding the surface haze on the side facing the surface and the surface haze on the side opposite to the side laminated on the base material was measured by the following method.

<Haze value (1)>
A sheet was prepared in which a transparent resin film, pure water, and a PET film (Toray's Lumirror T60 100 μm thickness, haze value 1.5%) were laminated in this order.
At this time, the pure water was laminated on the side of the transparent resin film having the uneven shape.
With respect to the obtained sheet, from the side of the PET film laminated on the side having the uneven shape of the transparent resin film, more specifically, the side having the uneven shape of the transparent resin film, DIRECT READING HAZE METER (Toyo Seiki Co., Ltd.) The haze value (1) was obtained by measuring the haze value of the PET film, excluding the haze value of the PET film, and specifically subtracting the haze value of 1.5% of the PET film.

<Haze value (2)>
PET film (Toray Lumirror T60 100 μm thickness, haze value 1.5%), pure water, transparent resin film, pure water, and PET film (Toray Lumirror T60 100 μm thickness, haze value 1.5%) ), A sheet laminated in this order was produced.
With respect to the obtained sheet, from the side of the PET film laminated on the side having the uneven shape of the transparent resin film, more specifically, the side having the uneven shape of the transparent resin film, DIRECT READING HAZE METER (Toyo Seiki Co., Ltd.) The haze value is measured using (manufactured by), and the haze value of the PET film is excluded. Specifically, the haze value (2) is subtracted by 1.5% for each of the haze values of the PET film and 3% in total. ) Was obtained.

(Shaping property of uneven shape)
Examples 4 and 5, the transparent resin film obtained in Comparative Example 2 and Reference Example 1, gloss value on the side where the uneven shape is formed (the side having a surface protective layer) and (G _A) was measured.
Then, the transparent resin film was immersed for 30 seconds in a 100 ° C. glycerin, cooled in cold water and measured gloss values of the irregular shape again form the side a (G _B).
The shapeability of the uneven shape was evaluated according to the following evaluation criteria. (G _A) and (G _B) and is more is close values, which means that loss uneven pattern is small.
A gloss meter (Murakami Color Technology Research Institute GMX-202 (angle 60 °) was used for the measurement of the gloss value. This measurement conforms to JIS Z8741.
_{++ :( G B) / (G} A) is 80% or more.
_{+ :( G B) / (G} A) is 60% or more and less than 80%.
_{- :( G B) / (G} A) is less than 60%.

(Creativity)
The decorative boards obtained in Examples 4 and 5, Comparative Example 2 and Reference Example 1 were visually observed and evaluated according to the following criteria.
++: The printed pattern formed on the pattern layer is clearly visible.
+: The printed pattern formed on the pattern layer appears to be slightly discolored (cloudy).
-: The printed pattern formed on the pattern layer is not clearly visible.

(Flame retardance)
The decorative boards obtained in Examples 4 and 5, Comparative Example 2 and Reference Example 1 were subjected to the above-mentioned horizontal flammability test and evaluated in the same manner.

It was confirmed that the transparent resin films obtained in Examples 4 and 5 were excellent in shaping of the uneven shape, and the decorative board obtained in Examples was also excellent in design. In addition, Example 4 containing a flame retardant showed excellent flame retardancy.
On the other hand, Comparative Example 2 containing no flame retardant did not have flame retardancy.
Further, in Reference Example 1 in which the haze value (2) exceeded 70%, the design was inferior.

(Example 6)
Transparency as in Example 1 except that 3 parts by mass of a phosphoric acid-based glass silver-supporting compound (manufactured by Koa Glass / PG-711) was added to 100 parts by weight of the ionizing radiation curable resin as an antiviral agent. A resin film and a decorative board were produced.

(Example 7)
An anionic phenol-based material having anti-allergenic properties (“EXP20530A” manufactured by DIC Corporation) is blended with an ionizing radiation curable resin at a solid content ratio of 23% by mass, and a zinc-based material having anti-allergenic properties (“DIC Corporation” A transparent resin film and a decorative board were produced in the same manner as in Example 1 except that EXP20530B ”) was blended in a solid content ratio of 23% by mass.

<Antiviral>
The transparent resin films prepared in Examples 1 and 6 were subjected to an antiviral performance test by a method based on the antiviral test method (ISO21702), and the antiviral activity value against influenza virus was evaluated. The results are shown in Table 4.
+: Antiviral activity value 2.0 or more-: Antiviral activity value less than 2.0

<Anti-allergenicity>
The transparent resin films prepared in Examples 1 and 7 were cut into small pieces, and the amount of allergen after being immersed in an aqueous mite allergen solution for 1 day was visually confirmed by a horizontal development chromatography method (mighty checker). The results are shown in Table 5.
+: A decrease in the amount of allergen was confirmed-: A decrease in the amount of allergen could not be confirmed.

From Table 4, it was confirmed that the transparent resin film obtained in Example 6 had antiviral performance.
From Table 5, it was confirmed that the transparent resin film obtained in Example 7 had anti-allergen performance.

According to the present invention, it is possible to visually confirm whether or not the pattern layer of the base material and the transparent resin film can be adhered to each other, and it is possible to provide a transparent resin film having flame retardancy. The decorative board of the present invention is suitably used for doors such as fittings and sliding doors, which are building materials for interiors, floor materials, walls, ceilings, and various decorative molded bodies.

10 Transparent resin film of the present invention 11 Thermoplastic resin layer 12 External haze layer 13 Primer layer for surface protective layer 14 Surface protective layer 20 Decorative board 23 Adhesive layer 24 Pattern layer 25 Base material 101 Household heater 102 Household heater 102 Base 103 Rectangular base 104 Metal frame 105 Test piece 106 End 107 Writer

Claims (13)

A transparent resin film for protecting the pattern layer laminated on one of the base materials.
The transparent resin film has at least a thermoplastic resin layer and an external haze layer on the side to be laminated on the pattern layer.
The transparent resin film is a transparent resin film containing a flame retardant. The transparent resin film according to claim 1, wherein the haze value of the outer haze layer is 4% or more and less than 100%. A polyethylene terephthalate film having a haze value of 0.1% or less is attached to the side of the outer haze layer opposite to the thermoplastic resin layer side via pure water, and the back surface measured from the thermoplastic resin layer side is wet. The transparent resin film according to claim 1 or 2, wherein the haze value of is 90% or less. The transparent resin film according to claim 1, 2 or 3, wherein the thickness of the outer haze layer is 0.5 μm or more and 20 μm or less. The transparent resin film has an uneven shape on the side opposite to the side laminated on the pattern layer.
The haze value (1), which is the haze value excluding the surface haze on the side opposite to the side laminated on the pattern layer, is 70% or more.
Claim 1 in which the haze value (2), which is the haze value excluding the surface haze on the side laminated on the pattern layer and the surface haze on the side opposite to the side laminated on the pattern layer, is 70% or less. The transparent resin film described. The transparent resin film according to any one of claims 1 to 5, wherein the thermoplastic resin layer contains a flame retardant. The transparent resin film according to any one of claims 1 to 6, wherein the thermoplastic resin layer contains a filler. The transparent resin film according to any one of claims 1 to 7, which has a surface protective layer on the side of the thermoplastic resin layer opposite to the side laminated on the pattern layer. The transparent resin film according to claim 8, wherein the surface protective layer contains a flame retardant. The transparent resin film according to claim 8 or 9, wherein the surface protective layer contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent. The transparent resin film according to any one of claims 1 to 10, wherein the flame retardant is at least one selected from the group consisting of a phosphinic acid metal salt-based flame retardant, a phosphazene-based flame retardant, and a NOR-type hindered amine-based flame retardant. .. A decorative board comprising a base material, a pattern layer, and a transparent resin film according to any one of claims 1 to 11 in this order in the thickness direction. The method for manufacturing a decorative board according to claim 12.
The process of forming an adhesive layer on the surface to be laminated on the pattern layer of the transparent resin film, and
A method for producing a decorative board, which comprises a step of adhering the transparent resin film and the pattern layer via the adhesive layer.

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