JP2001260301A - Decorative sheet and decorative material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem of blushing or a crack on a surface of a winding state decorative sheet when the decorative sheet is manufactured by using a heat curable resin to improve a heat resistance and a depression resistance of the surface of the sheet. SOLUTION: The winding state decorative sheet 1 is manufactured by the steps of coating an inorganic fiber base material 11 such as a glass cloth or the like with a colored opaque crosslinking type resin in which a coloring agent or the like is added, forming an opaque semi-cured crosslinking type resin layer 12 by forming a semi-cured state by heating, forming a design layer 13 thereon to form a printing sheet 3, and further forming a transparent protective layer 14 made of a cured electron beam curable resin on the layer 13. Then, the obtained sheet 1 is heated, pressurized and adhered to an adherend 17 such as an MDF or the like via an adhesive layer 16 such as melamine resin- impregnated paper or the like, the crosslinking type resin is cured to form an opaque cured crosslinking type resin layer 12a, and a heat resistance, a scuff resistance, a depression resistance and a cigaret resistance are given to a surface of the adherend 17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is used as interior decoration of floors, walls, ceilings, etc. of buildings, surface decoration materials such as furniture and various cabinets, surface decoration of fittings, interior decoration of vehicles, and the like. The present invention relates to a decorative sheet, and more particularly to a decorative sheet used for applications requiring scratch resistance, abrasion resistance, depression resistance, and heat resistance, and a decorative material (decorative board) using the same.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for decorative surfaces such as interior decoration of buildings, furniture, cabinets, etc., a printing ink layer such as a pattern layer or a solid printing layer is provided on one side of a paper base sheet. A method of applying a thermosetting urethane resin, a melamine resin, or the like as a top coat layer to protect the ink layer, heat drying and heat curing to form a thermosetting resin layer, or ionizing radiation curing There is a method of applying an ionizable resin, irradiating ionizing radiation to cure the coating, and forming a cured ionizing radiation-curable resin layer on the surface. In particular, an ionizing radiation-curable resin layer cured using an ionizing radiation-curable resin having a high crosslinking density has excellent physical properties such as surface hardness, chemical resistance, and stain resistance.

[0003] By using a hard resin as the surface protective layer as described above, the wear resistance is certainly improved. for that reason,
In the case of a decorative material using a hard base material such as a melamine decorative board, the flexibility of the surface resin layer does not matter much, so use a hard resin on the surface as a method of improving abrasion resistance. Is an effective means. However, when using a flexible base material such as thin paper or plastic sheet as the base material, if the cross-linking density of the resin is increased, the flexibility of the resin layer will be impaired, and the surface resin layer will have an impact. This causes problems such as cracks and cracks. Therefore, when a decorative sheet is manufactured in a rolled shape, flexibility is required. Therefore, there is a limit to improve the wear resistance by increasing the crosslink density of the surface resin and forming a resin layer having high hardness. there were.

[0004] Therefore, as a method of improving abrasion resistance without lowering the flexibility of the resin layer, a method of adding an inorganic material to the resin layer has been conventionally performed. For example, JP
No. 0-232642 discloses that the average particle size used as an abrasive such as a sand blast method or a brush polishing method is 1 to 3.
50 μm silica (SiO ₂ ) and alumina (Al ₂ O ₃₎
) Is disclosed in which a surface resin layer is formed using a coating compounded with a natural glass powder having a main component of (1).
The surface protective layer formed by the above-mentioned paint had higher hardness and flexibility than conventional products, and exhibited physical properties with excellent wear resistance and scratch resistance.

[0005]

However, a decorative sheet obtained by laminating a decorative sheet having an ionizing radiation-curable resin layer on the surface thereof to a medium-density fiberboard (hereinafter abbreviated as MDF), a wood board such as a particle board, etc. Heat resistance, sinking resistance and cigarette resistance (showing resistance to ash of lit cigarettes and hot cigarettes) are still inferior to those of resin decorative boards, and improvement of these properties is desired.

When an ionizing radiation-curable resin to which an inorganic filler such as spherical alumina is added is applied to an impregnating substrate such as paper, the ionizing radiation-curable resin impregnates the paper to form a paper. On the surface, the amount of ionizing radiation-curable resin holding a filler such as spherical alumina decreases, the spherical alumina cannot be sufficiently retained in the ionizing radiation-curable resin layer, and the wear resistance cannot be sufficiently exhibited. for that reason,
When an ionizing radiation-curable resin layer is formed on the surface using an impregnating substrate such as paper, the ionizing radiation-curable resin layer needs to be thick. However, increasing the application amount of the ionizing radiation-curable resin also increases the amount of expensive spherical alumina used, which increases the manufacturing cost. In addition, if the amount of the ionizing radiation-curable resin applied is increased, the curl of the decorative sheet becomes severe due to shrinkage that occurs when the ionizing radiation-curable resin is cured, and workability is deteriorated in post-processing of decorative paper. This leads to higher costs and is a major problem. Furthermore, a coating film formed using a coating liquid to which a hard, sharp-pointed polygonal powder is added has a poor touch feeling,
In addition, it cannot be used for an object which attaches importance to the touch by abrading an article in contact therewith.

[0007]

Means for Solving the Problems In order to solve the above problems, the configuration of a decorative sheet and a decorative material using the same is as follows. A decorative sheet comprising a base sheet made of inorganic fibers, a concealing layer made of a cured product of a crosslinked resin, a picture layer, and a transparent protective layer made of a cured ionizing radiation-curable resin laminated in this order. . Further, the concealing layer made of a cured product of the crosslinked resin is a thermosetting resin layer in a semi-cured state or an ionizing radiation-curable resin layer in a semi-cured state, and the base sheet made of the inorganic fibers is made of glass fiber. And a nonwoven fabric composed of cellulose fibers and a nonwoven fabric composed of glass fibers and a thermoplastic resin. Further, the decorative sheet is characterized in that the transparent protective layer (cured ionizing radiation-curable resin layer) contains inorganic particles. Then, using the decorative sheet, an adherend was laminated on the back surface of the decorative sheet by heating and pressing through an adhesive layer to produce a decorative material.

That is, a base sheet made of inorganic fibers such as glass fibers, carbon fibers, and ceramic fibers (hereinafter simply referred to as an inorganic fiber base) is colored with a cross-linkable resin such as a thermosetting resin or an ionizing radiation-curable resin. Apply an opaque uncured cross-linked resin to which an agent or the like has been added, and cure by heating or ionizing radiation, but stop in a semi-cured state so that the resin layer retains flexibility, and from the colored cross-linked resin An opaque hiding layer in a semi-cured state, that is, an opaque semi-cured crosslinked resin layer is formed. Next, a pattern layer is formed on the semi-cured opaque cross-linked resin layer by printing or the like, and the pattern layer is coated with an ionizing radiation-curable resin, and this is irradiated with ionizing radiation, thereby ionizing radiation. The curable resin is cured, and a transparent protective layer made of the cured ionizing radiation curable resin is formed on the surface to produce a decorative sheet.

Further, in order to further improve the abrasion resistance of the transparent protective layer on the surface, spherical particles of inorganic particles such as alumina (Al ₂ O ₃ ) or silica (SiO ₂ ) are added to the ionizing radiation-curable resin. Alternatively, a decorative sheet may be formed by forming a transparent protective layer comprising an ionizing radiation-curable resin layer containing inorganic particles on the surface. Therefore, the decorative sheet of the present invention
Using inorganic fiber base material (base sheet made of inorganic fiber),
In particular, by setting the cured product of the opaque concealing layer made of the colored cross-linked resin formed on the surface in a semi-cured state, it has flexibility and prevents blocking, so that the decorative sheet is wound. It can be made in the form of a letter.

Next, using the decorative sheet, MDF
(Medium-density fiberboard) or wood board such as particle board through heating and pressurization through an adhesive layer such as overlay paper impregnated with melamine resin, and semi-cured thermosetting resin (or ionizing radiation) for decorative sheet. The curable resin) is completely cross-linked or polymerized by heating and cured to produce a decorative plate having a cured thermosetting resin layer on the surface. The resulting decorative board has a hardened thermosetting resin layer such as a melamine resin immediately below the picture layer, so it has high hardness and excellent heat resistance. Compared to a decorative board using a decorative sheet having a resin layer formed thereon, the sheet has excellent heat resistance, scratch resistance, depression resistance, and cigarette resistance.

Further, since inorganic fibers are used for the base sheet of the decorative sheet, the decorative sheet is more heat-resistant, depressed, and resistant to heat than a conventional decorative sheet using paper as the decorative sheet. It has excellent cigarette properties. That is, the decorative sheet is excellent in compression resistance because the inorganic fiber base material is used, so that the collapse resistance is improved, and at the same time, the heat resistance and cigarette resistance due to the nonflammability of the inorganic fiber base material. Is improved.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the decorative sheet of the present invention. FIG. 2 is a schematic cross-sectional view of another embodiment of the decorative sheet of the present invention when inorganic particles are added to a transparent protective layer on the surface. FIG. 3 is a schematic sectional view of a decorative material manufactured using the decorative sheet of the present invention. FIG. 4 is an explanatory diagram for producing the decorative sheet of the present invention. FIG. 5 is an explanatory diagram for producing the decorative material of the present invention. FIG. 6 is an explanatory view when a decorative material is produced using a decorative sheet containing inorganic particles on the surface. FIG. 7 is an explanatory diagram when a decorative sheet is manufactured according to the first embodiment. FIG. 8 is an explanatory diagram when a decorative sheet is manufactured according to the second embodiment. FIG. 9 is an explanatory diagram when a decorative material is manufactured according to the third embodiment. FIG. 10 is an explanatory diagram when a decorative material is manufactured according to the fourth embodiment.

As shown in FIG. 1, the decorative sheet of the present invention is basically made of an impregnable sheet (hereinafter referred to as inorganic) made of inorganic fibers such as glass fiber, carbon fiber and ceramic fiber as a base sheet. A fibrous base material 11), an opaque semi-cured crosslinked resin layer 12 made of a thermosetting resin or an ionizing radiation-curable resin, a picture layer 13, and a transparent protective layer 14 made of a cured ionizing radiation-curable resin. Be composed.

That is, the feature of the decorative sheet of the present invention is that a thermosetting resin (or an ionizing radiation-curable resin) such as a melamine resin is applied to an impregnable inorganic fiber base material 11 such as a glass cloth.
Apply an uncured thermosetting resin to which pigments, dyes, other fillers, etc. are added, and then apply heat to crosslink or polymerize the thermosetting resin and cure it to prevent stickiness and blocking. However, in the embodiment shown in FIG. 1, the thermosetting resin is not completely cured so as to have a semi-cured state so that the decorative sheet has flexibility, and the opaque semi-cured crosslinked resin layer 12 is formed. When the thermosetting resin is completely cured, it loses flexibility, and when the decorative sheet is handled in a rolled form, the decorative sheet may have problems such as cracks and whitening. Therefore, in the present invention, the crosslinked resin such as a thermosetting resin is semi-cured and cured so as not to cause stickiness or blocking, but it is necessary to maintain flexibility and wind the decorative sheet. It can be handled in a state. In the specification of the present application, in the case of simply curing,
It includes both semi-cured and fully cured.

Next, a pattern layer 13 is provided on the opaque semi-cured crosslinked resin layer 12 by printing or the like, and an uncured ionizing radiation-curable resin is applied thereon, and ionizing radiation is immediately applied. Irradiation to cure the ionizing radiation curable resin,
Transparent protective layer 1 made of cured ionizing radiation curable resin
4 to form a flexible decorative sheet 1. Therefore, the decorative sheet of the present invention uses a resin having a high hardness such as a thermosetting resin, but since the crosslinked resin layer is in a semi-cured state, it has flexibility and is produced in a roll-up form. be able to. When forming the opaque semi-cured crosslinked resin layer 12 at the time of producing the decorative sheet, it can be formed in the same manner as a thermosetting resin using a colored ionizing radiation curable resin.

Further, as another embodiment of the decorative sheet of the present invention, as shown in FIG. 2, in order to further improve the heat resistance, scratch resistance, depression resistance and cigarette resistance of the surface, the surface of the decorative sheet is transparent. In the ionizing radiation curable resin forming the protective layer 14,
Inorganic particles 15 such as spherical alumina (Al ₂ O ₃ ) and silica (SiO ₂ ) are added to form a transparent protective layer 14 made of a cured ionizing radiation-curable resin containing the inorganic particles 15 on the surface. The decorative sheet 1 may be used.

Next, as shown in FIG. 3, the decorative sheet 1 of the present invention is formed by attaching a thermosetting resin such as a melamine resin, a diallyl phthalate resin, or a phenol resin to a wooden board such as an MDF or a particle board as the adherend 17. Is applied via an adhesive layer 16 such as overlay paper impregnated with
A (decorative board) is prepared, and the opaque semi-cured cross-linkable resin layer 12 of the decorative sheet 1 is completely cross-linked or heated by heating and pressurizing and bonding the decorative sheet 1 and the adherend 17. After being cured by polymerization, an opaque cured cross-linked resin layer 12a, a picture layer 13 and a transparent protective layer 14 are formed on the surface of the adherend 17 (wood board).
This is for imparting heat resistance, abrasion resistance, abrasion resistance, depression resistance, seagullette resistance, and the like to the surface of the (decorative board).

Hereinafter, the decorative sheet of the present invention and a method for producing a decorative material using the same will be described. First, a thermosetting resin such as a melamine resin, or an ionizing radiation-curable resin as a crosslinkable resin, and an uncured crosslinkable resin which is colored by adding a pigment, a dye, and other fillers to the crosslinkable resin. A resin composition is prepared. Next, as shown in FIG. 4A, a glass cloth or a nonwoven fabric made of glass fiber, ceramic fiber, carbon fiber, or the like is used as the inorganic fiber base material 11. The colored uncured crosslinkable resin composition is coated by a known method, and immediately cured by heating to cure the uncured crosslinkable resin so that the uncured crosslinkable resin does not have stickiness or blocking. However, a semi-cured state without being completely cured so that flexibility and easy adhesion are not lost, and a colored opaque semi-cured crosslinked resin layer 12 is formed on the inorganic fiber base material 11. . Generally, a white opaque layer to which titanium oxide or the like is added is formed as the opaque colored layer so that a picture layer can be easily formed by the next printing.

Next, on the opaque semi-cured crosslinked resin layer 12 of the inorganic fiber base material 11, as shown in FIG.
A printed layer 3 is formed by forming a picture layer 13 such as a grain pattern by gravure printing or the like. Next, as shown in FIG. 4 (c), an ionizing radiation-curable resin fat is applied to the pattern layer 13 side of the printing sheet 3 to apply an uncured ionizing radiation-curable resin layer 1.
4a is formed and immediately irradiated with ionizing radiation such as an electron beam or an ultraviolet ray to cross-link and cure the ionizing radiation-curable resin, and as shown in FIG. The decorative sheet 1 is produced by forming a transparent protective layer 14 made of a resin layer. By forming the transparent protective layer 14 made of the cured ionizing radiation curable resin layer, the pattern layer does not peel off from the inorganic fiber base material 11, and the surface of the decorative sheet has scratch resistance, abrasion resistance, Chemical resistance and the like are provided. The obtained decorative sheet 1 is flexible since the opaque cross-linked resin layer coated on the inorganic fiber base material 11 is in a semi-cured state, and can be handled in a wound state without blocking. .

The decorative sheet of the present invention is used for producing a decorative material (for example, a decorative plate) by adhering to an adherend such as a wooden board. A method for producing the decorative material will be described. As described above, as shown in FIG. 5A, an opaque semi-cured crosslinked resin layer 12 and a picture layer 13 are formed on an inorganic fiber base material 11 to produce a print sheet 3. Next, as shown in FIG. 5B, a transparent protective layer 14 made of a transparent ionizing radiation curable resin is formed on the pattern layer 13 of the printing sheet 3 to produce the decorative sheet 1.

Next, as shown in FIG.
7, the decorative sheet 1 is bonded to a wood board such as an MDF (medium density fiberboard) or a particle board via an adhesive layer 16 such as overlay paper impregnated with a melamine resin by a hot press method or the like. Is prepared. The decorative sheet 1 is stacked on the adherend 17 via the adhesive layer 16 and heated and pressed to be laminated on the inorganic fiber base material 11 (partially impregnated in the inorganic fiber base material 11 and The opaque semi-cured crosslinker-type resin layer 12 is crosslinked and cured,
As shown in FIG. 5C, an opaque cured cross-linking agent type resin layer 12a is formed, and a part of the cross-linking type resin penetrates the inorganic fiber base material 11, and the inorganic fiber base material 11 is hardened cross-linking agent. The mold resin is impregnated. Further, the melamine resin of the overlay paper impregnated with the melamine resin used as the adhesive layer 16 penetrates into the inorganic fiber base material 11 by applying heat and pressure to the lower layer of the inorganic fiber base material 11 (the adhesive layer 1).
On the 6th side), a cured melamine resin impregnated layer is also formed.

Therefore, the surface of the decorative material 2 is composed of an opaque cured cross-linking resin layer 12a, a picture layer 13, and a cured ionizing radiation-curable resin on an inorganic fiber base material 11 containing the cured cross-linking resin. The transparent protective layer 14 is laminated. Therefore, the obtained decorative material 2 is a cured cross-linking agent type resin layer 12a having excellent heat resistance and depression resistance on an inorganic fiber substrate 11 having excellent heat resistance and depression resistance as a substrate.
Is formed thereon, and a picture layer 13 and a transparent protective layer 14 made of a cured ionizing radiation-curable resin are formed thereon, so that it is excellent in heat resistance, depression resistance, scratch resistance, and cigarette resistance. Becomes

In order to further improve the heat resistance, scratch resistance, depression resistance and cigarette resistance of the surface of the decorative material, another embodiment of the decorative sheet of the present invention is to form a transparent protective layer 14 on the surface. Inorganic particles 15 such as spherical alumina (Al ₂ O ₃ ) or silica (SiO ₂ ) are added to the ionizing radiation-curable resin to form a transparent protective layer 14 containing the inorganic particles 15 on the surface. The decorative sheet 1 may be used. Hereinafter, a decorative sheet having a transparent protective layer 14 containing inorganic particles 15 formed on its surface and a decorative material using the same will be described.

First, similarly to the above, as shown in FIG. 6A, an opaque semi-cured crosslinked resin layer 12 and a picture layer 13 are formed on an inorganic fiber base material 11 such as glass cloth, and a printing sheet is formed. 3 is manufactured. Next, spherical alumina, amorphous silica, or the like is added to the ionizing radiation-curable resin to prepare a coating liquid containing inorganic particles, and using this coating liquid, the pattern layer of the printing sheet 3 is formed. 13, an uncured ionizing radiation-curable resin layer 14 a containing inorganic particles 15 is formed as shown in FIG.

Next, as shown in FIG. 6B, the uncured ionizing radiation-curable resin layer 1 containing the inorganic particles 15 is formed.
4a, irradiating ionizing radiation 22 such as an electron beam or an ultraviolet ray to crosslink and cure the ionizing radiation-curable resin to form a transparent protective layer 14 made of a cured ionizing radiation-curable resin containing inorganic particles 15. The decorative sheet 1 is formed as shown in FIG. Obtained decorative sheet 1
Is formed on the inorganic fiber base material 11 by forming an opaque semi-cured cross-linkable resin layer 12 and a highly cross-linking ionizing radiation-curable resin layer containing inorganic particles 15 as a transparent protective layer 14 on the surface. Therefore, it is flexible and has excellent wear resistance.

The inorganic particles used in the present invention include:
Inorganic particles, either spherical or amorphous, can be used.
As the spherical particle, a true spherical shape, an elliptical spherical shape obtained by flattening a sphere, or a spherical particle having a shape similar to these and having a smooth curved surface is used. In particular, those having no projections or corners on the particle surface, that is, having no so-called cutting edge are preferable. Spherical particles, when added to a transparent protective layer (ionizing radiation-curable resin) on the surface, greatly improve the abrasion resistance of the resin layer and increase the surface sensation compared to amorphous particles of the same material. It is soft and can be used for applications that emphasize surface sensation. In addition, abrasion of the coating device during coating is reduced.

In the present invention, a spherical alumina having an average particle diameter of 5 to 50 μm can be used, but an average particle diameter of 10 to 23 μm is preferable. Particle size is 10μ
If it is less than m, the abrasion resistance of the coating film cannot be sufficiently exhibited, which is not preferable. When the particle size exceeds 23 μm,
Since the thickness of the transparent protective layer to which the spherical alumina is added needs to be further thicker than the particle diameter of 23 μm, the cost becomes high and it is economically disadvantageous. On the other hand, if the particle diameter of the spherical alumina exceeds 23 μm, the coating operation becomes difficult, and the flexibility of the coating film is impaired.

The amount of spherical alumina added to the ionizing radiation-curable resin is in the range of 5 to 50% by weight based on the cured coating film cured by irradiation with ionizing radiation. When the content of the spherical alumina in the transparent protective layer is less than 5% by weight, the wear resistance is insufficient, and the effect of adding the spherical alumina is not sufficiently exhibited. On the other hand, if the content exceeds 50% by weight, the total amount of the inorganic particles including inorganic particles such as amorphous silica added together with the spherical alumina becomes too large, and the holding power of the binder resin to the inorganic particles is increased. And the viscosity of the coating liquid increases, making coating difficult.

For this reason, as the spherical inorganic particles, α-alumina, which has a very high hardness and excellent abrasion resistance, and from which spherical particles can be obtained relatively easily, is preferred. As described in JP-A-2-55269, spherical α-alumina includes alumina hydrate, halogen compound,
Mineralizing agent or crystallizing agent such as boron compound is added to pulverized product of fused alumina or sintered alumina and heat-treated at a temperature of 1400 ° C or more for 2 hours or more. Is obtained. Such spherical alumina is available from Showa Denko KK as "Spherical Alumina AS-10, AS".
-20, AS-30, AS-40 and AS-50 "having various average particle sizes are commercially available.

The amorphous inorganic particles used in the present invention include fine particles having an average particle diameter of 2 μm or less,
A wide range of particle sizes up to 5 μm can be used,
Amorphous silica is preferred. In the present invention, even if amorphous silica is used alone, the abrasion resistance of the surface is improved, but in the case of amorphous silica, since there are particles with sharp corners,
It is not preferable when surface smoothness is required. Therefore, the use of amorphous silica mixed with the above-mentioned spherical alumina is better in terms of improving the coating suitability such as dispersibility of the alumina and adjusting the viscosity of the coating liquid.

Therefore, when the amorphous silica is mixed with spherical alumina, it is important that the particle diameter of the amorphous silica is smaller than that of the spherical alumina. As a result, the decorative sheet exhibits physical properties excellent in abrasion resistance, and has no roughness on the surface, so that a decorative sheet having good slipperiness can be obtained. Therefore, as the particle diameter of the amorphous silica, the particle diameter of the spherical alumina is 10 to 2
In the case of 3 μm, it is preferable to add two kinds of fine particles having a particle size of 10 to 15 μm and 2 μm or less. As in the case of spherical alumina, the content of the amorphous silica is 5 to 50% by weight based on the content of the ionizing radiation-curable resin in the cured coating film.
And it is necessary that the total amount of amorphous silica and spherical alumina added is 60% by weight or less.

Next, as shown in FIG. 6 (d), the decorative sheet 1 is applied to an adherend 17 such as MDF (medium density fiberboard) or particle board by an adhesive layer such as overlay paper impregnated with a melamine resin. The decorative material 2 is produced by bonding with a hot press method or the like via the base material 16. The decorative sheet 1 is stacked on the adherend 17 via the adhesive layer 16 and is heated and pressed to be laminated on the inorganic fiber base material 11 in the same manner as described above (partially, the inorganic fiber base material). 11) The opaque semi-cured cross-linked resin layer 12 is cross-linked and cured to obtain
As shown in FIG. 5, an opaque cured crosslinked resin layer 12a is formed, and the surface of the decorative material 2 is opaque cured inorganic resin base material 11 impregnated with the cured crosslinked resin. 13 and a transparent protective layer 14 made of a cured ionizing radiation-curable resin containing inorganic particles 15. Therefore, the obtained decorative material 2 is
Since a hardened ionizing radiation-curable resin layer containing inorganic particles 15 having excellent wear resistance, heat resistance and depression resistance is formed on the surface, wear resistance comparable to a melamine resin plate is obtained.
The decorative material 2 has heat resistance, depression resistance, scratch resistance, and cigarette resistance.

The ionizing radiation-curable resin used for the transparent protective layer on the surface of the decorative sheet of the present invention is obtained by dispersing inorganic particles in an uncured state, coating the particles, and then applying ionizing radiation such as electron beams or ultraviolet rays. Irradiation cures the coating film, and the physical properties of the cured coating film change depending on the crosslinking density.
That is, the higher the crosslink density, the higher the hardness of the cured coating film and the higher the abrasion resistance, but the lower the flexibility. Therefore, the crosslink density of the ionizing radiation-curable resin needs to be appropriately adjusted depending on which of abrasion resistance and flexibility is important depending on the use of the decorative sheet.

Specific examples of the ionizing radiation-curable resin used in the present invention include a (meth) acryloyl group,
Radiation polymerizable unsaturated group such as (meth) acryloyloxy group, cationic polymerizable functional group such as epoxy group, or monomer, prepolymer, oligomer, and / or polymer having two or more thiols as appropriate, ionization. A composition curable by radiation is used. Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and will be used in the same meaning hereinafter. Here, the ionizing radiation means one having an energy quantum capable of polymerizing or crosslinking a molecule in an electromagnetic wave or a charged particle beam, and usually an electron beam or an ultraviolet ray is used.

Examples of the prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, Examples include (meth) acrylates such as ether (meth) acrylate, polyol (meth) acrylate, and melamine (meth) acrylate, and cationic polymerization type epoxy compounds. A molecular weight of about 250 to 10,000 is usually used. As the polymer having a radical polymerizable unsaturated group, a polymer having a degree of polymerization of about 10,000 or more is used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, dipentaerythritol tetrathioglycolate, and the like.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate and the like.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, Acrylates such as butoxyethyl acrylate, butyl acrylate, methoxy butyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and methacrylic There are methacrylic esters such as lauryl acid.

Further, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, Substituted amino alcohol esters of unsaturated acids such as (N, N-dimethylamino) methyl methacrylate, 2- (N, N-didiethylamino) propyl acrylate, unsaturated carboxylic amides such as acrylamide and methacrylamide; There are compounds such as ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate.

Further, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or polythiol compounds having two or more thiol groups in the molecule,
For example, there are trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 95% by weight or less in order to impart ordinary coating suitability to the ionizing radiation-curable resin. Is preferred.

In selecting the monomer, if the flexibility of the cured product is required, the amount of the monomer may be reduced as long as the coatability is not hindered, or a monofunctional or bifunctional acrylate monomer may be used. A structure having a relatively low crosslink density is used. When the heat resistance, hardness, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not affect coating suitability, or use a trifunctional or higher functional acrylate monomer. It is preferable to use a structure having a high crosslinking density. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing a monofunctional or difunctional monomer and a trifunctional or higher functional monomer.

Examples of the above-mentioned monofunctional acrylate monomers include 2-hydroxyacrylate, 2-hexyl acrylate and phenoxyethyl acrylate. Examples of the bifunctional acrylate monomer include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. Examples of the trifunctional or higher acrylate monomer include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and the like.

In the case where the ionizing radiation-curable resin is cured by ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

As the inorganic fiber substrate 11 used in the present invention, a sheet of inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, etc. is used. That is, a nonwoven fabric or a woven fabric in which the above-mentioned inorganic fiber is formed into a sheet shape is often used. In addition, a nonwoven fabric composed of a mixture of glass fiber and cellulose fiber, or a nonwoven fabric using a glass fiber and a thermoplastic resin as a binder is often used.

In the present invention, when the decorative sheet is laminated on an adherend such as a particle board or an MDF, the surface of the adherend is concealed, and the inorganic fiber is formed so that the design layer of the decorative sheet sufficiently exhibits a design effect. A concealing layer made of a colored resin is formed on the substrate. That is, a coloring agent is prepared by adding a coloring agent to the thermosetting resin or the ionizing radiation-curing resin, and the coloring resin composition is coated on the inorganic fiber base material 11 to form a colored opaque semi-cured cross-linkable resin. The resin layer 12 is formed. Then, a pattern sheet 13 and a transparent protective layer 14 are provided on an opaque semi-cured crosslinked resin layer 12 formed on the inorganic fiber base material 11 to produce a decorative sheet, and the decorative sheet is produced in a roll-up form. The major feature is that it is made possible. That is, when a cross-linked resin such as a thermosetting resin or an ionizing radiation-curable resin is completely cured, it loses flexibility, and when the decorative sheet is handled in a rolled shape, problems such as cracks and whitening may occur in the decorative sheet. Therefore, the crosslinked resin is semi-cured so that it can be produced in a rolled state.

When a thermoplastic resin is used in place of a thermosetting resin or an ionizing radiation-curable resin, the decorative sheet can have flexibility, but a transparent protective layer made of an ionizing radiation-curable resin cured on the surface. However, sufficient abrasion resistance, depression resistance, heat resistance, and cigarette resistance cannot be obtained. Therefore, in the present invention, a cross-linkable resin, for example, a thermosetting resin such as a melamine resin, a pigment, a dye, an uncured thermosetting resin obtained by adding other fillers or the like is applied to the inorganic fiber base material 11, Next, the thermosetting resin is cured by heating to cure it without stickiness or blocking, but it is in a semi-cured state so that the flexibility is maintained, and the decorative sheet can be handled in a rolled shape It is.

The crosslinkable resin used in the present invention includes:
A thermosetting resin or an ionizing radiation curable resin is used.
As the ionizing radiation-curable resin, those used for the transparent protective layer are used, and those having a composition having a high crosslinking density and a high hardness when cured are used. Also,
The following are used as the thermosetting resin. That is,
As the thermosetting resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, polyurethane resin,
There are epoxy resin, amino alkyd resin, melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like.
If necessary, a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender, or the like may be added to these resins to be used as a paint. Usually, as a curing agent,
Organic sulfonate is unsaturated polyester resin, isocyanate is unsaturated polyester resin and polyurethane resin, amine is epoxy resin, radicals such as peroxide such as methyl ethyl ketone peroxide, azobisisobutyronitrile, etc. Agents are often used in unsaturated polyester resins.

As the isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of preventing thermal discoloration and weather resistance.
Specific examples include 2,4-tolylene diisocyanate,
Xylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, and the like. As a method for curing the thermosetting resin, heating may be performed as necessary in order to accelerate the curing reaction. For example, isocyanate-curable unsaturated polyester resin, urethane-curable polyurethane resin at 40-60 ° C for 1-5 days, polysiloxane resin at 80-150 ° C for 1-30 minutes, melamine resin 90 Heat at １６０160 ° C. for 30 seconds to 3 minutes. In the present invention, a melamine resin having excellent heat resistance and stain resistance and high hardness is suitable.

The melamine resin is a thermosetting resin obtained by addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde. Since it is transparent and has high hardness, and is excellent in coloring property, heat resistance and stain resistance, it has a wide range of uses such as decorative boards, molding materials and paints. Further, by blending an acrylic component with the melamine resin, the apparent life until the decorative sheet impregnated with the semi-cured melamine resin is adhered to an adherend such as a particle board may be extended. As the acrylic component, monomers, oligomers, polymers, and the like can be used. The addition amount is about 3 to 16% by weight.

Examples of monomers include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. In addition, among polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate.

Examples of the polymer include poly (methyl meth) acrylate, poly (ethyl meth) acrylate, poly (butyl meth) acrylate, and methyl (meth) acrylate-butyl (meth) acrylate. Coalesce, methyl (meth) acrylate-styrene copolymer, methyl (meth) acrylate-butyl (meth) acrylate- (meth)
2-hydroxyethyl acrylate copolymer, (meth)
Acrylic resins such as methyl acrylate-butyl (meth) acrylate- (meth) acrylate-2-hydroxyethyl-styrene copolymer are exemplified. In addition, the above (meth) acryl is used in the meaning of acryl or methacryl, and hereinafter (meth) is used in the same meaning.

In the present invention, a coloring agent is added to the crosslinked resin (thermosetting resin or ionizing radiation curable resin) to form a colored opaque semi-cured crosslinked resin layer. Examples of the coloring agent used in the present invention include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, carbon black, isoindolinone, banzai yellow A, quinacridone, permanent red 4R, and phthalocyanine. Organic pigments or dyes such as blue, metal pigments made of foil powder such as aluminum and brass, pearlescent pigments made of foil powder of titanium dioxide-coated mica, basic zinc carbonate and the like are used. If necessary, an inorganic filler may be added, and examples thereof include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). Addition amount is usually 5
６０60% by weight.

On the opaque semi-cured crosslinked resin layer 12 formed as a concealing layer of the inorganic fiber base material 11, a picture layer 13 is formed by printing or the like. As the picture layer, printed patterns by printing, embossed patterns by embossing,
There is an uneven pattern or the like formed by hairline processing, and a pattern layer can also be formed by filling a concave portion of the uneven pattern with a coloring ink by a known wiping method. The print pattern layer includes a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, various abstract patterns, and the like.

The ink for pattern printing varies depending on the material and form of the base material, but is generally chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene.
A vehicle comprising a single or a mixture of two or more resins such as nitrified cotton, cellulose acetate, vinyl chloride, vinyl acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, urethane resin, acrylic resin, polyester resin, etc. And an ordinary ink containing a coloring agent such as a pigment and a dye, an extender pigment, a curing agent, an additive, a solvent and the like. As the colorant, the colorant used for the bridge resin layer is used.

As the printing of the picture, a normal printing method such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, and ink jet printing can be used. Alternatively, a transfer pattern may be formed by forming a pattern once on a release sheet, and transferring the pattern printing by a transfer printing method from the transfer sheet obtained. Instead of the printed pattern, a metal layer such as aluminum, chromium, gold, silver, copper or the like may be vacuum-deposited, sputtered, or the like to form a pattern layer by forming a metal thin film entirely or partially on the substrate. The embossing is performed by heating and softening the base sheet, pressurizing and shaping with an embossing plate, and solidifying by cooling. A known sheet-fed or rotary embossing machine is used. Examples of the uneven shape include a wood grain channel groove, a stone plate surface unevenness (granite cleavage plane, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like.

In order to improve the adhesive strength between the printing ink and the ionizing radiation-curable resin layer formed as a transparent protective layer, an easy-adhesion layer may be provided on the picture layer. Acrylic resin, urethane resin, vinyl chloride, etc.
A coating solution obtained by dissolving a resin such as a vinyl acetate copolymer resin, a polyester resin, a polyurethane resin, a chlorinated polyethylene, or a chlorinated polypropylene in a solvent is used.In particular, a mixture of a two-part curable urethane resin and a butyral resin is used. Those used are preferred. A coating solution obtained by dissolving the resin in a solvent is applied by a known method and dried to form an easily adhesive layer.

The surface of the inorganic fiber substrate 11 provided with the picture layer 13 is applied to the surface of the above-mentioned ionizing radiation-curable resin or a resin composition obtained by adding inorganic particles to the ionizing radiation-curable resin, by a known method. Thus, a transparent protective layer is formed. Coating methods include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, dip coat, solid coat by silk screen coat, wire bar coat, comma coat, spray coat, float coat, Pouring coating, brush coating, spray coating and the like can be used. Among them, a gravure coat is preferable.

As the ionizing radiation irradiating device for curing the ionizing radiation curable resin, an ultraviolet irradiating device or an electron beam irradiating device is used. As the ultraviolet irradiation device, 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, a black light lamp, and a metal halide lamp is used. As the electron beam irradiator, various electron beam accelerators such as Cockloft-Wald type, Bande graph type, Resonant transformer type, Insulated core transformer type or linear type, Dynamitron type and high frequency type can be used. In the present invention, the object can be achieved by using any of an ultraviolet irradiation device and an electron beam irradiation device.

However, in the case of electron beam irradiation by an electron beam device, the ionizing radiation-curable resin can be cured instantaneously, which is suitable for mass production. Further, when a transparent protective layer is formed using an ionizing radiation-curable resin to which inorganic particles are added, since the transmission of ultraviolet rays is inhibited by the inorganic particles, electron beam irradiation is better.
Furthermore, when the above-mentioned colored ionizing radiation-curable resin is used as the cross-linkable resin, ultraviolet rays cannot be used for curing the colored resin, and therefore, it is necessary to use an electron beam having a large transmitting power.

When an electron beam irradiation device is used, an acceleration voltage of 1
00 to 1000 KeV, preferably 100 to 300 KeV
V, and the absorbed dose is usually 1 to 300 kG
about y. If the absorbed dose is less than 1 kGy,
And the irradiation dose exceeds 300 kGy
And the cured coating and substrate are yellowed or damaged
You. When using an ultraviolet irradiation device, the irradiation amount is
50-1000mJ / cm ^Two Is preferable. UV light
Irradiation dose is 50mJ / cm^Two If the amount is less than the above, the curing of the coating film is
Min, and the irradiation amount is 1000 mJ / cm.^Two Beyond
Then, the cured coating film turns yellow. Irradiation of ionizing radiation
As a method, first, the resin is irradiated with ultraviolet rays to cure the ionizing radiation-curable resin.
The fat is hardened at least to the extent that the surface is dry to the touch.
And then irradiate with an electron beam to completely cure the coating.
There is also a method.

The decorative sheet of the present invention is used for various applications after being laminated on various adherends and subjected to predetermined molding processing. As adherends, wood veneer, wood plywood, particle board, wood board such as medium density fiber board (MDF), wood board such as wood fiber board, glass, ceramics such as ceramics, AL
C (cement fired concrete), cemented ceramic materials such as calcium silicate, gypsum, etc., metals such as iron and aluminum, acrylic, polycarbonate, ethylene
Resins such as vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, polyvinyl chloride, cellulosic resin, and rubber. As a method for laminating the decorative sheet on these various adherends, a heating and pressing method is used in order to completely cure the semi-cured crosslinked resin of the decorative sheet.

[0065]

The present invention will be described below in more detail with reference to examples. (Example 1) First, as an inorganic fiber base material, glass cloth 11a (manufactured by Awa Paper Co., Ltd., glass fiber diameter: 20 μm
The following uncolored uncured melamine resin (A) was applied to one surface of the glass cloth 11a by a roll coating method using a glass cloth having a density of 0.176 kg / m ³ (FIG. 7A). As shown in FIG. 7, a colored and opaque uncured melamine resin layer 12b was formed on a glass cloth 11a.

Composition of colored uncured melamine resin (A): 80 parts by weight of uncured melamine resin (“M-700” manufactured by Nissan Chemical Co., Ltd.); 20 parts by weight of titanium white (manufactured by DuPont)

Next, as shown in FIG. 7A, the colored and opaque uncured melamine resin layer 12b is heated at 120 ° C. for 1.5 minutes to bring the melamine resin into a semi-cured state. As shown in (b), a colored opaque semi-cured melamine resin layer 12c having a coating amount of 50 g / m ² was formed on the glass cloth 11a.

Next, as shown in FIG. 7 (c), a wood grain pattern is printed on the colored opaque semi-cured melamine resin layer 12c by gravure printing to form a picture layer 13 and a printing sheet 3 is formed. Was prepared. Next, as shown in FIG. 7D, a roll coating method is performed on the pattern layer 13 of the printing sheet 3 using the following electron beam curable resin (A) (manufactured by Sanyo Chemical Industries, Ltd.). A transparent uncured electron beam-curable resin layer 14b is provided, and the electron beam 22a is immediately used with an electron beam irradiation device at an acceleration voltage of 175 keV so that the absorbed dose becomes 50 kGy (kilo-gray).
To cure the electron beam curable resin and apply 10
g / m ^2, a transparent cured electron beam curable resin layer 14c was formed to produce a decorative sheet 1 as shown in FIG. The obtained decorative sheet 1 did not have stickiness or blocking even in the wound state, and neither crack nor whitening occurred on the surface.

Composition of electron beam curable resin (A) 70 parts by weight of bisphenol A ethylene oxide-modified diacrylate 29 parts by weight of trimethylolpropane-modified triacrylate 1 part by weight of methacrylate-modified silicone at both ends

(Example 2) The same glass cloth 11a as in Example 1 was used as an inorganic fiber base material, and the following colored uncured electron beam curable resin (C) was coated on one surface of the glass cloth 11a. Fig. 8
As shown in (a), an uncured colored and opaque electron beam-curable resin layer 12e is formed on a glass cloth 11a, and immediately, using an electron beam irradiation apparatus, at an acceleration voltage of 200 keV and an absorbed dose of 10 kGy ( The electron beam curable resin is cured by irradiating an electron beam 22a so as to obtain a color opaque semi-cured electron beam curability of 50 g / m ² as shown in FIG. The resin layer 14f was formed.

Composition of colored uncured electron beam curable resin (C) 50 parts by weight of bisphenol A ethylene oxide-modified diacrylate 29 parts by weight of trimethylolpropane-modified triacrylate 1 part by weight of methacrylate-modified silicone at both ends 1 titanium 20 parts by weight (made by DuPont)

Next, as shown in FIG. 8 (c), a pattern layer 13 is formed on the colored opaque semi-cured electron beam curable resin layer 12f in the same manner as in Example 1 to form a printed sheet. 3 was produced. Further, similarly to the first embodiment, the printing sheet 3
A transparent cured electron beam curable resin layer 14c having a coating amount of 10 g / m ² is formed on the pattern layer 13 of FIG.
The decorative sheet 1 shown in FIG. The obtained decorative sheet 1 did not have stickiness or blocking even in the wound state, and neither crack nor whitening occurred on the surface.

(Example 3) As in Example 1, a glass cloth 11a was used as an inorganic fiber base material, and a colored and opaque semi-cured melamine resin layer 12c and a picture layer 13 were formed thereon. As shown in (a), a printing sheet 3 was produced. Next, as shown in FIG. 9B, similarly to Example 1, a transparent cured electron beam curable resin layer 14 c was formed on the picture layer 13 of the print sheet 3 to produce the decorative sheet 1. . Next, as shown in FIG.
melamine resin impregnated paper 16a as an adhesive layer and the decorative sheet 1 are superimposed on an MDF (medium density fiberboard) having a hot plate temperature of 150 ° C. and a pressure of 2.
Heat and pressurize under the condition of 94 Pa (Pascal) for 2 minutes,
Colored opaque semi-cured melamine resin 12 of decorative sheet 1
d and the melamine resin of the melamine resin-impregnated paper 16a are cross-linked and cured, and as shown in FIG.
A decorative sheet 1 was laminated on the surface a to prepare a decorative material 2 (decorative board).

As described above, the decorative sheet 1 and the MDF 17a
Is heated and pressurized through the melamine resin-impregnated paper 16a, whereby the colored opaque semi-cured melamine resin layer 12d of the decorative sheet 1 and the melamine resin of the melamine resin-impregnated paper 16a are crosslinked and cured to have a high hardness. Since it replaced with resin, the surface of the decorative material 2 had heat resistance and high hardness. Therefore, the obtained decorative material 2 has heat resistance,
A decorative material (decorative board) having excellent scratch resistance, depression resistance, and cigarette resistance was obtained.

(Example 4) A glass cloth 11a was used as an inorganic fiber base material, and a colored and opaque semi-cured melamine resin layer 12c and a picture layer 13 were formed on the glass cloth 11a in the same manner as in Example 1. As shown in (a), a printing sheet 3 was produced. Next, using the electron beam-curable resin (B) having the following composition, it was applied to the pattern layer 13 side of the decorative sheet 1 by a roll coating method, and as shown in FIG. A transparent uncured electron beam curable resin layer 14b containing m ² spherical alumina 15a was formed.

Composition of Electron Beam-Curable Resin (B) 60 parts by weight of bisphenol A ethylene oxide-modified diacrylate 28 parts by weight of trimethylolpropane-modified triacrylate 1 part by weight of methacrylate-modified silicone at both ends 1 globular α-alumina (average 10 parts by weight ・ Silica fine powder (particles having an average particle size of 2 μm or less) 1 part by weight

Next, as shown in FIG. 10B, an absorbed dose of 50 kGy was applied to the transparent uncured electron beam-curable resin layer 14b at an acceleration voltage of 175 keV using an electron beam irradiation apparatus. (Kilo Gray) electron beam 2
Irradiate 2a to crosslink and cure the electron beam curable resin,
As shown in FIG. 10C, a transparent cured electron beam-curable resin layer 14c containing a spherical alumina 15a was formed to produce a decorative sheet 1. The obtained decorative sheet 1 did not have stickiness or blocking even in the wound state, and neither crack nor whitening occurred on the surface. Further, since the transparent cured electron beam-curable resin layer 14c containing the spherical alumina 15a was formed on the surface of the decorative sheet 1, the decorative sheet was excellent in abrasion resistance.

Next, as in Example 3, the melamine resin impregnated paper 16a and the decorative sheet 1 were overlaid on a 30 mm thick MDF, and the hot plate temperature was set to 1 by a hot press method.
Heating and pressurizing at 50 ° C. and a pressure of 2.94 Pa (Pascal) for 2 minutes, the cosmetic material 2 as shown in FIG.
(Decorative panel) was produced. The obtained decorative material 2 is excellent in abrasion resistance because spherical alumina is contained in the transparent cured electron beam curable resin layer 14b on the surface, and has improved heat resistance, scratch resistance, depression resistance, and cigarette resistance. It became an excellent decorative material (decorative board).

[0079]

The decorative sheet of the present invention uses an inorganic fiber base material such as glass cloth as a base sheet, and has an opaque semi-cured cross-link made of a thermosetting resin or an ionizing radiation-curable resin on one surface. Forming the cured resin layer of the mold resin, and having a transparent protective layer consisting of a pattern layer and a cured product of the cured ionizing radiation-curable resin on it, by keeping the cross-linked resin in a semi-cured state It is flexible and can be produced in rolled form without blocking. for that reason,
It can be produced using the same equipment as a conventional flexible decorative sheet, and the same productivity can be obtained. Further, the decorative sheet of the present invention is bonded to a wood board such as a medium density fiberboard (MDF) or a particle board via an adhesive layer such as melamine resin impregnated paper to make a decorative material (decorative board or the like).
When making, the semi-cured thermosetting resin (or ionizing radiation curable resin) formed on the inorganic fiber base material is completely cured by heating, and the surface of the decorative material is a melamine resin. The same heat resistance and hardness as those of a plate or the like can be obtained.

Also, since inorganic fibers are used as the base material, the organic components in the decorative sheet are significantly reduced as compared with the decorative sheet using paper as the conventional base material.
Heat resistance and depression resistance become very excellent, and furthermore, heat resistance, depression resistance and wear resistance are further improved by adding inorganic particles such as spherical alumina to the transparent protective layer on the surface. be able to. Therefore, the obtained decorative material is excellent in heat resistance, abrasion resistance, abrasion resistance, sinking resistance, and cigarette resistance (resistance to ash of lit cigarettes and hot cigarettes). That is, heat resistance, abrasion resistance, depression resistance, and a melamine resin plate having excellent cigarette resistance can be produced using a rolled decorative sheet having a performance equivalent to that of a melamine resin plate or the like. In addition, production costs can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a decorative sheet of the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the decorative sheet of the present invention when inorganic particles are added to a transparent protective layer on the surface.

FIG. 3 is a schematic sectional view of a decorative material produced using the decorative sheet of the present invention.

FIG. 4 is an explanatory diagram for producing a decorative sheet of the present invention.

FIG. 5 is an explanatory view when a decorative material is produced using the decorative sheet of the present invention.

FIG. 6 is an explanatory diagram when a decorative material is produced using a decorative sheet containing inorganic particles on the surface.

FIG. 7 is an explanatory diagram when a decorative sheet is produced according to Example 1.

FIG. 8 is an explanatory diagram when a decorative sheet is produced according to Example 2.

FIG. 9 is an explanatory diagram when a decorative material is manufactured according to the third embodiment.

FIG. 10 is an explanatory view when a decorative material is produced according to Example 4.

[Explanation of symbols]

 Reference Signs List 1 decorative sheet 2 decorative material 3 printing sheet 11 inorganic fiber base material 11a glass cloth 12 opaque semi-cured crosslinked resin layer 12a opaque cured crosslinked resin layer 12b colored opaque uncured melamine resin layer 12c colored opaque Semi-cured melamine resin layer 12d Colored and opaque cured melamine resin layer 12e Colored and opaque uncured electron beam curable resin layer 12f Colored and opaque semi-cured electron beam curable resin layer 13 Picture layer 14 Transparent protective layer 14a Transparent uncured ionizing radiation curable resin layer 14b Transparent uncured electron beam curable resin layer 14c Transparent cured electron beam curable resin layer 15 Inorganic particles 15a Spherical alumina 16 Adhesive layer 16a Melamine resin impregnated paper 17 Coated Body 17a MDF (medium density fibrous plate) 21 Heating 22 Ionizing radiation 22a Electron beam

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 4F100 AA01A AA01D AA21 AA21H AG00A AJ04A AK01A AK01B AK01D AK25 AK36 AK52 AL06 AT00A AT00E BA04 BA05 BA07 BA10A BA10D BA10E DE01D DG01A31 DG11 DG15B EH31GB01H JB12B JB13B JB14B JB14D JB16A JD01B JJ03 JK01 JK09 JK13 JK14 JK17 JL02 JL10 JN01D

Claims (5)

[Claims] A concealing layer made of a cured product of a crosslinked resin, a picture layer, and a transparent protective layer made of a cured ionizing radiation-curable resin are laminated in this order on a base material sheet made of inorganic fibers. To make a decorative sheet. 2. The concealing layer made of a cured product of the crosslinked resin is a thermosetting resin layer in a semi-cured state or an ionizing radiation-curable resin layer in a semi-cured state. Decorative sheet. 3. The non-woven fabric comprising a glass fiber and a cellulose fiber, or a non-woven fabric comprising a glass fiber and a thermoplastic resin. The decorative sheet according to the above. 4. The decorative sheet according to claim 1, wherein the transparent protective layer contains inorganic particles. 5. A decorative material, wherein an adherend is laminated on the back surface of the decorative sheet according to any one of claims 1 to 4 by heating and pressing via an adhesive layer.