JP2017024361A - Manufacturing method of decorative sheet and manufacturing method of decorative panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a decorative sheet and a manufacturing method of a decorative panel capable of preventing its performance from deteriorating through thoroughly drying an applied resin.SOLUTION: A manufacturing method of a decorative sheet 1 includes: a laminate process of laminating a pattern layer 4, a transparent adhesive layer 5, a transparent thermoplastic resin layer 6, a first surface protective layer 7a, and a second surface protective layer 7b, in this order on a base material sheet 3 to form a laminate; and a spray process of spraying superheated steam to at least one of the first surface protective layer 7a and the second surface protective layer 7b. The first surface protective layer 7a and the second surface protective layer 7b contain at least one of a thermosetting resin and an ionizing radiation curable resin. A manufacturing method of a decorative panel 10 includes: a decorative sheet preparation process of preparing the decorative sheet 1 manufactured with the manufacturing method; and a bonding process of bonding the decorative sheet 1 on a base material 2.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet manufacturing method and a decorative material manufacturing method.

  Traditionally, natural materials that reflect local characteristics such as wood and stone are used for houses, and people's homes have a style rooted in their own culture. However, in recent years, industrialization has progressed with the development of the housing industry, and a shift from natural materials to artificial materials has been carried out. It has also been pointed out that heavy use of high-grade wood and stone may lead to deforestation and environmental problems. These situations are one factor that increases the demand for decorative sheets.

  With the expansion of demand for such decorative sheets, the performance of decorative sheets has been improved. For example, in Patent Document 1, the melted polyolefin resin is maintained at a temperature higher than the glass transition temperature and lower than the melting point for a predetermined time, thereby improving the crystallinity of the polyolefin resin and thereby improving the scratch resistance of the decorative sheet. Is disclosed. Moreover, in order to improve the adhesiveness and scratch resistance of the decorative sheet, a surface protective layer containing a thermosetting resin or an ionizing radiation curable resin may be provided.

JP 2012-166407 A

  However, when these thermosetting resins or ionizing radiation curable resins used mainly in solvent systems are applied and cured, it is necessary to sufficiently dry them. When these resins are not sufficiently dried, they cause poor curing, and as a result, performance such as hardness, chemical resistance, stain resistance, weather resistance, and transparency may be deteriorated. In particular, this drying defect is likely to occur for decorative sheets that are continuously produced at high speed.

  Then, an object of this invention is to provide the manufacturing method of the decorative sheet which can fully dry coated resin, and can suppress the fall of a performance, and the manufacturing method of a decorative material.

  In order to solve the above problems, a method for producing a decorative sheet according to the present invention includes a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, a first surface protective layer, and a second surface protective layer on a base sheet. A laminating step of laminating in this order to form a laminate, and a spraying step of spraying superheated steam on at least one of the first surface protective layer and the second surface protective layer, the first surface protective layer and the second The surface protective layer contains at least one of a thermosetting resin and an ionizing radiation curable resin.

  In this method for producing a decorative sheet, the solvent can be sufficiently dried in a short time in at least one of the first surface protective layer and the second surface protective layer by spraying superheated steam. For this reason, when at least one of the first surface protective layer and the second surface protective layer contains a thermosetting resin, it is possible to sufficiently cure the thermosetting resin by further heating. When at least one of the first surface protective layer and the second surface protective layer contains an ionizing radiation curable resin, the ionizing radiation curable resin can be sufficiently cured by further irradiating with ionizing radiation. is there. Therefore, the poor curing of the decorative sheet to be manufactured can be suppressed, and the original performance can be exhibited. As described above, the coated resin can be sufficiently dried to prevent the performance from being deteriorated.

  In the method for manufacturing a decorative sheet, the base sheet may contain a colored thermoplastic resin. In this case, since the color of the base sheet can be freely selected, the hue as the base color of the pattern layer laminated on the base sheet can be freely selected.

  In the above method for producing a decorative sheet, the transparent thermoplastic resin layer may contain a polyolefin. In this case, environmental compatibility and processability are improved, and the manufacturing cost can be reduced.

  In the method for producing a decorative sheet, the first surface protective layer contains a thermosetting resin, and the second surface protective layer contains an ionizing radiation curable resin based on the entire material constituting the second surface protective layer. You may contain 65% or more of mass ratio. In this case, the ionizing radiation curable resin can be more fully cured by irradiating with ionizing radiation. Moreover, since the 1st surface protective layer contains a thermosetting resin, the adhesiveness of a 1st surface protective layer and a transparent thermoplastic resin layer improves. As described above, the scratch resistance of the manufactured decorative sheet can be further improved.

  In the method for manufacturing the decorative sheet, the temperature of the superheated steam may be 100 ° C. or higher and 350 ° C. or lower. In this case, when the temperature of the superheated steam sprayed on the laminate is 100 ° C. or higher, the solvent can be sufficiently dried in a short time in the surface protective layer. Moreover, generation | occurrence | production of the flare to a decorative sheet by spraying the superheated steam of an excessively high temperature can be suppressed because the temperature of the superheated steam sprayed on a laminated body is 350 degrees C or less.

  Further, the present invention includes a decorative sheet preparation step of preparing a decorative sheet manufactured by any one of the above-described decorative sheet manufacturing methods, and an attaching step of bonding the decorative sheet to a base material. It can also be understood as an invention of a method for manufacturing a decorative material. According to this method for manufacturing a decorative material, the effects described above can be achieved, as in the method for manufacturing a decorative sheet.

  ADVANTAGE OF THE INVENTION According to this invention, the coated resin can fully be dried and the manufacturing method of the decorative sheet and the manufacturing method of a decorative material which can suppress the fall of performance can be provided.

It is typical sectional drawing which shows the cross-sectional structure of the decorative material manufactured with the manufacturing method which concerns on this invention.

  Hereinafter, a method for manufacturing a decorative sheet and a method for manufacturing a decorative material according to the present invention will be described in detail with reference to the drawings. In the description, the same reference numerals may be used for the same elements or elements having the same function, and redundant description is omitted.

  First, the structure of the decorative sheet and the decorative material manufactured by the manufacturing method according to the present invention will be described. FIG. 1 is a schematic cross-sectional view showing a cross-sectional configuration of a decorative material manufactured by the manufacturing method according to the present invention. As shown in FIG. 1, the decorative material 10 is configured by bonding a decorative sheet 1 to a base material 2. The decorative sheet 1 includes a base sheet 3, a pattern layer 4, a transparent adhesive layer 5, a transparent thermoplastic resin layer 6, and a surface protective layer 7, which are laminated in this order from the back side to the front side. ing.

  Although it does not specifically limit as the base material sheet 3, For example, materials, such as various resin, paper, cloth, can be used. Here, a material containing a colored thermoplastic resin is used as the base sheet 3. Examples of a method for coloring the thermoplastic resin constituting the base sheet 3 include mixing or kneading a colorant such as a pigment in the sheeting of the base sheet 3. By using the base material sheet 3 containing the colored thermoplastic resin, in the decorative material 10 formed by bonding the decorative sheet 1 to the base material 2, the base material 2 is seen through the decorative sheet 1 and is visually recognized. This can be suppressed. Moreover, since the color of the base material sheet 3 can be freely selected, the hue as the base color of the pattern layer 4 laminated on the base material sheet 3 can be freely selected. Note that a transparent thermoplastic resin may be used as the base sheet 3. In this case, it is possible to suppress the base material 2 from being seen through the decorative sheet 1 by forming the pattern layer 4 by performing colored solid printing on the base material sheet 3.

  The pattern pattern layer 4 is a layer for applying a pattern pattern to the decorative sheet 1. In the pattern layer 4, it is possible to print a pattern using a known printing method. For example, when the base sheet 3 can be prepared in a wound state, printing is performed with a roll-to-roll printing apparatus. be able to. The printing method is not particularly limited, but for example, a gravure printing method can be used in consideration of productivity and quality of a pattern.

  Any design pattern may be adopted as the design pattern applied to the design pattern layer 4 in consideration of the design as the decorative material 10. For example, various wood grain patterns may be imparted to the pattern pattern layer 4 as a wooden pattern, and cork may be imparted as a pattern pattern in addition to the wood grain. Alternatively, for example, a pattern such as marble stones may be added to the pattern layer 4 as a pattern inspired by a stone floor or joinery such as marble. In addition to these natural material pattern patterns, an artificial pattern such as a pattern or a geometric pattern may be added.

  The printing ink used for printing the design pattern in the design pattern layer 4 is not particularly limited, but an ink corresponding to the printing method can be appropriately selected. In particular, it is preferable to select in consideration of adhesion to the base sheet 3, printability, and weather resistance as the decorative material 10.

  The transparent adhesive layer 5 is provided for the purpose of strengthening the adhesion between the design pattern layer 4 and the transparent thermoplastic resin layer 6 laminated on the design pattern layer 4. By strengthening this adhesion, the decorative sheet 1 can be given bending workability that follows a curved surface or a right-angled surface.

  The transparent thermoplastic resin layer 6 is a layer for giving the decorative sheet 1 a design thickness and depth and improving the weather resistance and wear resistance of the decorative sheet 1. In the transparent thermoplastic resin layer 6, the grade and composition of the resin are selected in consideration of ease of sheeting, printability, and suitability for bending. Particularly in bending workability, it is important to select in consideration that whitening and cracking of the bent portion are less likely to occur. For example, the transparent thermoplastic resin layer 6 may contain polyolefin in order to improve environmental compatibility and processability and reduce manufacturing costs.

  The transparent adhesive layer 5 and the transparent thermoplastic resin layer 6 can be formed by extruding both simultaneously by coextrusion, for example.

  The surface protective layer 7 is provided on the transparent thermoplastic resin layer 6. The surface protective layer 7 has a multi-layer structure (two layers in this embodiment) having the first surface protective layer 7a and the second surface protective layer 7b in this order from the back surface side to the front surface side of the decorative sheet 1. Yes. The first surface protective layer 7a and the second surface protective layer 7b contain at least one of a thermosetting resin and an ionizing radiation curable resin. The ionizing radiation curable resin includes an ultraviolet curable resin that is cured by ultraviolet rays. Here, the first surface protective layer 7a contains a thermosetting resin. Further, the second surface protective layer 7b contains an ionizing radiation curable resin in a mass ratio of 65% or more based on the whole material constituting the second surface protective layer 7b in a state before being dried. “The second surface protective layer 7b contains an ionizing radiation curable resin in a mass ratio of 65% or more” means that the mass ratio of the ionizing radiation curable resin in a state before drying by spraying superheated steam is 65. % Or more. Here, when the solvent is dried by spraying superheated steam, the total mass decreases and the content (mass ratio) of the ionizing radiation curable resin relatively increases. Therefore, ionizing radiation curing in the state before drying is performed. If the mass ratio of the mold resin is 65% or more, the mass ratio of the ionizing radiation curable resin in the state after drying is also 65% or more.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Thermosetting resins such as urea co-condensation resin, silicon resin and polysiloxane resin can be mentioned. These resins can be used alone or in combination of a plurality of types in consideration of processability, productivity, hardness and the like. In addition, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like can be added to the thermosetting resin as necessary. As the curing agent, for example, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine or the like is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile or the like A radical initiator is added to the unsaturated polyester resin.

  Examples of ionizing radiation curable resins include monomers having radically polymerizable unsaturated groups such as (meth) acryloyl groups and (meth) acryloyloxy groups in the molecule, and cationic polymerizable functional groups such as epoxy groups. Mention may be made of polymers or polymers. These monomers, prepolymers or polymers are used as monomers, or a mixture of plural kinds is used. In this specification, for example, (meth) acrylate is used in the meaning of acrylate or methacrylate. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and includes ultraviolet rays and electron beams.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. be able to. As this prepolymer, those having a molecular weight of about 10,000 or less are usually used. When the molecular weight exceeds 10,000, surface properties such as scratch resistance, abrasion resistance, chemical resistance, heat resistance, and contamination resistance of the cured resin layer are deteriorated. The above acrylate and methacrylate can be shared. However, since the crosslinking curing rate with ionizing radiation is faster with acrylate, it is advantageous to use acrylate in order to cure efficiently at a high speed and in a short time.

  Examples of the prepolymer having a cationic polymerizable functional group include, for example, epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers and esters. And prepolymers such as vinyl ether resins such as vinyl ethers, cyclic ether compounds, and spiro compounds.

  As for the monomer having a radical polymerizable unsaturated group, for example, as a monofunctional monomer of a (meth) acrylate compound, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate 2- (meth) acryloyloxypropyl hydrogen terephthalate and the like.

  Examples of the polyfunctional monomer having a radically polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) a Relate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyl Examples thereof include oxyethyl phosphate.

  As the monomer having a cationic polymerizable functional group, the above-mentioned prepolymer monomer having a cationic polymerizable functional group can be used.

  When the above ionizing radiation curable resin is cured by irradiation with ultraviolet rays, a photopolymerization initiator can be added as a sensitizer. As a photopolymerization initiator for a resin system having a radically polymerizable unsaturated group, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate can be used alone or in combination. Examples of the photopolymerization initiator for a resin system having a cationically polymerizable functional group include aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonate esters, and freeroxyxonium diallyl iodosyl salts. They can be used alone or in combination. In addition, generally the addition amount of these photoinitiators is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation-curable resins.

  As the base material 2 on which the decorative sheet 1 described above is bonded, a South Sea wood plywood, a particle board, a medium density fiber board (MDF), a normal plywood stipulated in Japanese Agricultural Standard can be used. A material containing a wood powder-added olefin resin can also be used as the substrate 2. The thickness of the substrate 2 is preferably about 3 to 25 mm.

  Then, the manufacturing method of the decorative sheet 1 and the decorative material 10 is demonstrated. First, the pattern layer 4, the transparent adhesive layer 5, the transparent thermoplastic resin layer 6, the first surface protective layer 7a containing a thermosetting resin, and the second containing an ionizing radiation curable resin on the base sheet 3. The surface protective layer 7b is laminated in this order to form a laminated body (lamination process).

  If necessary, an adhesive layer can be provided on the pattern layer 4 for the purpose of improving the adhesiveness between the pattern layer 4 and the transparent adhesive layer 5. Although the resin used for this is not specifically limited, For example, a 2 liquid hardening type urethane resin etc. can be used. The adhesive layer can be provided using, for example, a coating apparatus or a gravure printing apparatus.

  Next, superheated steam is sprayed on the laminate (a spraying step). “Superheated steam” is steam heated to 100 ° C. or higher. When superheated steam is sprayed, the solvent is sufficiently dried in the surface protective layer 7 in a short time. Thereby, since the poor curing of the surface protective layer 7 due to poor drying is suppressed, it is possible to suppress a decrease in the performance of the produced decorative sheet 1. Alternatively, the first superheated steam spraying process may be performed after the first surface protective layer 7a is stacked, and the second superheated steam spraying process may be performed after the second surface protective layer 7b is stacked.

  When superheated steam is sprayed on the laminate in the spraying process, the thermosetting resin contained in the first surface protective layer 7a is solvent-dried in a short time and cured by heat. The property is further improved.

  The temperature of superheated steam sprayed on the laminate is preferably 100 ° C. or higher and 350 ° C. or lower. When the temperature of the superheated steam is 100 ° C. or higher, the solvent is dried in a short time in the surface protective layer. Moreover, generation | occurrence | production of the flare to the decorative sheet 1 by spraying the superheated steam of excessively high temperature can be suppressed because the temperature of superheated steam is 350 degrees C or less. If the decorative sheet 1 having a strong flare is to be bonded to the base material 2, air enters the flare part and is difficult to bond, and the flare part may be broken and easily wrinkled. is there.

  Next, when the surface protective layer 7 contains an ionizing radiation curable resin, the laminate is irradiated with ionizing radiation. The ionizing radiation to be irradiated can be ultraviolet rays, electron beams or the like. When the laminate is irradiated with ionizing radiation, the ionizing radiation curable resin contained in the surface protective layer 7 is cured by the ionizing radiation, so that the scratch resistance is further improved. At this time, if the second surface protective layer 7b contains an ionizing radiation curable resin in a mass ratio of 65% or more based on the entire material constituting the second surface protective layer 7b, the second surface protective layer 7b is further cured by irradiation with ionizing radiation. Further, the scratch resistance is further improved.

  The decorative sheet 1 can be obtained through the above steps. Moreover, the decorative material 1 can be obtained by preparing the decorative sheet 1 in this way (decorative sheet preparation process), and bonding the decorative sheet 1 to the base material 2 (adhesion process).

  Examples that specifically describe this embodiment will be described below. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Example 1>
Polypropylene film ("OW" manufactured by Riken Technos Co., Ltd.) is used as the base sheet, and gravure ink ("Lamister" manufactured by Toyo Ink Manufacturing Co., Ltd.) is used as a pattern layer on one side of the print using a gravure printing machine. Printed and provided. Thereafter, gravure coating was performed on the surface of the base sheet opposite to the pattern layer, so that the two-component urethane primer resin containing silica powder had a thickness of 1 μm after drying. Thereafter, as an adhesive layer, a two-component urethane resin adhesive having a polyester polyol as a main component and isophorone diisocyanate as a curing agent was applied onto the pattern layer so that the coating amount after drying was 2 g / m ² . . Thereafter, on the adhesive layer, a transparent adhesive layer (maleic acid-modified polypropylene resin) of 10 μm and a transparent thermoplastic resin layer of 80 μm mainly composed of random polypropylene (manufactured by Prime Polymer Co., Ltd.) are used as the transparent adhesive layer. Coextruded and laminated so as to be on the layer side. Then, after drying a coating liquid in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) are mixed as a first surface protective layer on the surface. The coating was formed to a thickness of about 6 μm, and the solvent was dried by spraying superheated steam at a temperature of 120 ° C. for 12 seconds. Furthermore, the thickness after drying a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) as the second surface protective layer is about 6 μm. Coating was performed to form a coating film, and superheated steam at a temperature of 120 ° C. was sprayed for 12 seconds to dry the solvent to obtain the desired decorative sheet.

<Example 2>
A procedure for forming the first surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the first surface protective layer, a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) has a thickness of about The coating was formed to a thickness of 6 μm, and the first surface protective layer was formed by drying the solvent by blowing hot air at a temperature of 60 ° C. for 12 seconds. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 3>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) has a thickness of about The coating was formed to a thickness of 6 μm, and the second surface protective layer was formed by drying the solvent by blowing hot air at a temperature of 60 ° C. for 12 seconds. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 4>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, an ultraviolet curable urethane acrylate resin (manufactured by DIC Graphics) and a thermosetting acrylic urethane resin (manufactured by DIC Graphics) are made to have a mass ratio of 1: 1. Apply a coating solution mixed with an isocyanate-based curing agent (manufactured by DIC Graphics Co., Ltd.) with a thickness of about 6 μm after drying to form a coating film, and spray superheated steam at a temperature of 120 ° C. for 12 seconds. Then, the solvent was dried and further irradiated with ultraviolet rays (high pressure mercury lamp, about 200 mJ / cm ² ) to form a second surface protective layer. Here, since the mixing amount of the isocyanate curing agent is slight compared with the mixing amount of the ultraviolet curable urethane acrylate resin and the thermosetting acrylic urethane resin, the ionizing radiation curable resin is not present in the second surface protective layer. In addition, it is contained in a mass ratio of about 50% based on the entire material constituting the second surface protective layer. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 5>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, an ultraviolet curable urethane acrylate resin (manufactured by DIC Graphics Co., Ltd.) and a thermosetting acrylic urethane resin (manufactured by DIC Graphics Co., Ltd.) are made to have a mass ratio of 7: 3. Apply a coating solution mixed with an isocyanate-based curing agent (manufactured by DIC Graphics Co., Ltd.) with a thickness of about 6 μm after drying to form a coating film, and spray superheated steam at a temperature of 120 ° C. for 12 seconds. Then, the solvent was dried and further irradiated with ultraviolet rays (high pressure mercury lamp, about 200 mJ / cm ² ) to form a second surface protective layer. Here, since the mixing amount of the isocyanate curing agent is slight compared with the mixing amount of the ultraviolet curable urethane acrylate resin and the thermosetting acrylic urethane resin, the ionizing radiation curable resin is not present in the second surface protective layer. In addition, about 70% by mass is contained based on the entire material constituting the second surface protective layer. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 6>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, an ultraviolet curable urethane acrylate resin (manufactured by DIC Graphics Co., Ltd.) is applied at a thickness of about 6 μm after drying to form a coating film, and superheated steam at a temperature of 120 ° C. is applied for 12 seconds. The solvent was dried by spraying, and further, ultraviolet rays (high pressure mercury lamp, about 200 mJ / cm ² ) were irradiated to form a second surface protective layer. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 7>
A decorative sheet was prepared by changing the formation procedure of the first surface protective layer and the second surface protective layer in Example 1 as follows. That is, as the first surface protective layer, an ultraviolet curable urethane acrylate resin (manufactured by DIC Graphics Co., Ltd.) is applied at a thickness of about 6 μm after drying to form a coating film, and superheated steam at a temperature of 120 ° C. is applied for 12 seconds. The solvent is dried by spraying, and a UV curable urethane acrylate resin (manufactured by DIC Graphics Co., Ltd.) is applied as a second surface protective layer with a thickness of about 6 μm after drying to form a coating film. The solvent was dried by spraying superheated water vapor at 12 ° C. for 12 seconds, and further irradiated with ultraviolet rays (high pressure mercury lamp, about 200 mJ / cm ² ) to form a first surface protective layer and a second surface protective layer. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 8>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, a coating liquid in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics Co., Ltd.) and an isocyanate curing agent are mixed is applied to a thickness of about 6 μm after drying. A coating film was formed, and the second surface protective layer was formed by spraying superheated steam at a temperature of 200 ° C. for 12 seconds to dry the solvent. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 9>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, a coating liquid in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics Co., Ltd.) and an isocyanate curing agent are mixed is applied to a thickness of about 6 μm after drying. A coating film was formed, and a second surface protective layer was formed by spraying superheated steam at a temperature of 300 ° C. for 12 seconds to dry the solvent. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Example 10>
The procedure for forming the second surface protective layer in Example 1 was changed as follows to prepare a decorative sheet. That is, as the second surface protective layer, a coating liquid in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics Co., Ltd.) and an isocyanate curing agent are mixed is applied to a thickness of about 6 μm after drying. A coating film was formed, and the second surface protective layer was formed by spraying superheated steam at a temperature of 400 ° C. for 12 seconds to dry the solvent. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Comparative Example 1>
A decorative sheet was prepared by changing the formation procedure of the first surface protective layer and the second surface protective layer in Example 1 as follows. That is, as the first surface protective layer, a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) has a thickness of about The coating is formed to a thickness of 6 μm, the solvent is dried by blowing hot air at a temperature of 60 ° C. for 12 seconds, and a thermosetting acrylic urethane resin (DIC Graphics Co., Ltd.) is used as the second surface protective layer. 1) and an isocyanate-based curing agent are mixed to form a coating film having a thickness of about 6 μm after drying, and the solvent is dried by blowing hot air at a temperature of 60 ° C. for 12 seconds. A surface protective layer and a second surface protective layer were formed. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Comparative example 2>
A decorative sheet was prepared by changing the formation procedure of the first surface protective layer and the second surface protective layer in Example 1 as follows. That is, as the first surface protective layer, a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) has a thickness of about The coating is formed to a thickness of 6 μm, the solvent is dried by blowing hot air at a temperature of 60 ° C. for 12 seconds, and a thermosetting acrylic urethane resin (DIC Graphics Co., Ltd.) is used as the second surface protective layer. And a coating solution formed by mixing an isocyanate-based curing agent with a thickness of about 6 μm after drying to form a coating film, spraying hot air at a temperature of 60 ° C. for 12 seconds to dry the solvent, The first surface protective layer and the second surface protective layer were formed in an atmosphere of 40 ° C. for 3 days. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Comparative Example 3>
A decorative sheet was prepared by changing the formation procedure of the first surface protective layer and the second surface protective layer in Example 1 as follows. That is, as the first surface protective layer, a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) and an isocyanate curing agent (manufactured by DIC Graphics) has a thickness of about The coating is formed to a thickness of 6 μm, the solvent is dried by blowing hot air at a temperature of 120 ° C. for 12 seconds, and a thermosetting acrylic urethane resin (DIC Graphics Co., Ltd.) is used as the second surface protective layer. 1) and an isocyanate curing agent are mixed to form a coating film having a thickness of about 6 μm after drying, and the solvent is dried by blowing hot air at a temperature of 120 ° C. for 12 seconds. A surface protective layer and a second surface protective layer were formed. Other than that, a decorative sheet was prepared in the same procedure as in Example 1.

<Production of cosmetic material for evaluation>
The decorative sheets prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were bonded to the surface of 3 mm thick MDF (hardwood) as a base material with an adhesive. A two-part aqueous emulsion adhesive (Rikabond (registered trademark) BA-10L / BA-11B = 100: 2.5 manufactured by Japan Coating Resin Co., Ltd.) was used as the adhesive, and the coating amount was 80 g / m ^{2 in} the wet state. I stuck together. Next, it was cured for 7 days to obtain a cosmetic material.

<Evaluation items and evaluation methods>
About the cosmetics produced using the decorative sheet which concerns on Examples 1-10 and Comparative Examples 1-3, it tested and evaluated by the following evaluation item and the evaluation method. The evaluation results are shown in Table 1.

(1) Pencil scratch test The test method was performed in accordance with JIS-K5600 “Scratch hardness (pencil method)”. The evaluation criteria are as follows.
A: When the maximum hardness at which the coating film does not peel is 3H or more.
○: When the maximum hardness at which the coating film does not peel is F or more and 2H or less.
X: When the maximum hardness at which the coating film does not peel is HB or less.

(2) Steel Wool Test Commercially available steel wool (“Bonster # 0-1” manufactured by Nippon Steel Wool Co., Ltd.) was cut into 1 cm square, and this was applied to the surface of the decorative board with a load of 1 kg and scratched 20 times. The evaluation criteria are as follows.
A: No scratch on the surface of the test part and no change in gloss from the surface of the untested part.
◯: When no scratches are seen on the surface of the test area and a slight gloss change from the surface of the untested area is observed.
X: When a scratch is seen on the surface of the test part and a gloss change from the surface of the untested part is seen.

(3) Chemical resistance test The test method was performed in accordance with JAS special plywood "thinner resistance test". The evaluation criteria are as follows.
○: When peeling or whitening of the coating film is not observed.
X: When peeling and whitening of a coating film are seen.

(4) Anti-contamination test The test method was performed in accordance with JAS special plywood "contamination A test". Blue ink was used as a contaminant. The evaluation criteria are as follows.
○: When the coating film is not colored.
X: When coloring is seen in a coating film.

(5) Weather resistance test Weather resistance evaluation was performed using a metal weather manufactured by Daipura Wintes. Evaluation criteria and irradiation modes are as follows.
○: When peeling or whitening of the coating film is not observed.
X: When peeling and whitening of a coating film are seen.
Irradiation energy: 650 W / m ² (measured with a UVD-365PD irradiation meter manufactured by USHIO INC.)
Black panel temperature: 53 ° C
Humidity: 70%
Irradiation time: 20-hour dew condensation mode: 10-cycle test was conducted with rainfall for 2 minutes every hour during the irradiation mode, and a combination of the irradiation mode and the dew condensation mode as one cycle.

(6) Flare state About the decorative material produced using the decorative sheet which concerns on Examples 1-10 and Comparative Examples 1-3, the grade of flare was evaluated. The evaluation criteria are as follows.
○: When flare is not seen on the sheet.
Δ: When some flare is seen on the sheet.
X: When many flare is seen in a sheet | seat.

(7) Manufacturing time About the cosmetics produced using the decorative sheet which concerns on Examples 1-10 and Comparative Examples 1-3, the manufacturing time required for the production was evaluated. The evaluation criteria are as follows.
○: The shortest production time is less than 30 hours.
X: The shortest production time is 30 hours or more.

<Evaluation results>

  In Examples 1 to 10, all of the evaluation items regarding the surface physical properties were evaluation results of ◯ or more, and the decorative sheets sprayed with superheated steam and dried by the solvent exhibited good surface physical properties. On the other hand, in Comparative Examples 1 to 3 in which hot air was blown to dry the solvent, the evaluation results of the surface properties were relatively low. These results indicate that the solvent can be sufficiently dried by spraying superheated steam, and as a result, curing failure is suppressed and the surface physical properties are improved.

  Compared with comparative examples, compared with Comparative Example 1 in which hot air at a temperature of 60 ° C. was blown and solvent dried, Comparative Example 2 was further heated and cured after sprayed with hot air at a temperature of 60 ° C. In Comparative Example 3 where solvent drying was performed by blowing hot air at a temperature of 120 ° C., improvement in surface properties could be confirmed. This indicates that the temperature factor greatly affects the curing of the surface protective layer.

  In Example 5 in which a second surface protective layer was prepared by mixing an ultraviolet curable resin having a mass ratio of 7: 3 and a thermosetting resin, and in Example 6 in which only the ultraviolet curable resin was used, both were prepared. Example 4 in which the content (mass ratio) of the ultraviolet curable resin is relatively small, such as a pencil scratch test and a steel wool test, and Examples 1 to 3, 8 to 10 that do not contain an ultraviolet curable resin and comparison Compared with Examples 1-3, it was particularly excellent. This indicates that the ultraviolet curable resin is effective in improving the surface hardness and improving the scratch resistance.

  In Example 4 in which the second surface protective layer was prepared by mixing an ultraviolet curable resin having a mass ratio of 1: 1 and a thermosetting resin, an evaluation result equivalent to that in Example 1 not including the ultraviolet curable resin was obtained. It has become. This indicates that a sufficient effect cannot be obtained unless mixing is performed at a certain mass ratio or more in order to increase the scratch resistance by the ultraviolet curable tree.

  The decorative sheet according to Example 7 does not show high scratch resistance despite using an ultraviolet curable resin for the second surface protective layer. This is probably because the adhesion between the transparent thermoplastic resin and the first surface protective layer is not high. In order to improve this adhesion, it is considered preferable to use a thermosetting resin for the first surface protective layer.

  In Example 8 and Example 9 in which superheated steam was sprayed at temperatures of 200 ° C. and 300 ° C., the evaluation results were the same as those of Example 1 in which superheated steam was sprayed at a temperature of 120 ° C. in any evaluation item.

  In Example 10 in which superheated steam was sprayed at a temperature of 400 ° C., the surface physical properties were the same as those in Example 1 in which superheated steam was sprayed at a temperature of 120 ° C., but in the sheet state, it was acceptable. Some flare has occurred to some extent. This indicates that when superheated steam at a certain temperature or more is sprayed, flare is generated in the sheet due to the heat.

  Summing up these results, cosmetics with improved surface properties such as scratch resistance and chemical resistance can be obtained by spraying superheated steam onto a laminate containing a thermosetting resin or ionizing radiation curable component as a component of the surface protective layer. It turns out that it becomes possible to provide a sheet. In particular, as in Example 6, when the second surface protective layer 7b is made of only an ultraviolet curable resin, or as in Example 5, the second surface protective layer 7b is made of an ultraviolet curable resin and a thermosetting resin. It was confirmed that the scratch resistance can be further improved when the mass ratio is 7: 3. Moreover, in order to suppress the flare of a decorative sheet, it was confirmed that it is more preferable to spray superheated steam in a temperature range of 350 ° C. or lower as in Examples 1-9.

  From the above results, according to the production method of the present invention, it is possible to sufficiently reduce the performance by drying the coated resin, and excellent surface properties, the state of flare more than acceptable, And it was verified that all of the short manufacturing time can be realized.

  DESCRIPTION OF SYMBOLS 1 ... Cosmetic sheet, 2 ... Base material, 3 ... Base material sheet, 4 ... Picture pattern layer, 5 ... Transparent adhesive layer, 6 ... Transparent thermoplastic resin layer, 7 ... Surface protective layer, 7a ... 1st surface protective layer, 7b ... second surface protective layer, 10 ... decorative material.

Claims (6)

A laminating step of laminating the pattern layer, the transparent adhesive layer, the transparent thermoplastic resin layer, the first surface protective layer, and the second surface protective layer in this order on the base sheet;
A spraying step of spraying superheated steam on at least one of the first surface protective layer and the second surface protective layer, and
The method for producing a decorative sheet, wherein the first surface protective layer and the second surface protective layer contain at least one of a thermosetting resin and an ionizing radiation curable resin.   The method for manufacturing a decorative sheet according to claim 1, wherein the base sheet contains a colored thermoplastic resin.   The said transparent thermoplastic resin layer contains polyolefin, The manufacturing method of the decorative sheet of Claim 1 or 2 characterized by the above-mentioned. The first surface protective layer contains a thermosetting resin,
The said 2nd surface protective layer contains 65% or more of ionization radiation curable resins on the basis of the whole material which comprises the said 2nd surface protective layer, The any one of Claims 1-3 characterized by the above-mentioned. The manufacturing method of the decorative sheet of description.   The method for producing a decorative sheet according to any one of claims 1 to 4, wherein the temperature of the superheated steam is 100 ° C or higher and 350 ° C or lower. A decorative sheet preparation step of preparing a decorative sheet manufactured by the method of manufacturing a decorative sheet according to any one of claims 1 to 5;
An adhering step for adhering the decorative sheet to a base material, and a method for producing a cosmetic material, comprising:

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