JP3530103B2 - Cosmetic sheet and cosmetic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used as an interior material for a building such as a wall, a fitting such as a door, a surface material for furniture, and the like, and a decorative material obtained by attaching the decorative sheet to a substrate. In particular, the present invention relates to a decorative sheet having good surface properties such as abrasion resistance and good workability, which does not easily break when it is adhered to an adherend substrate, and a decorative material to which the decorative sheet is adhered.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used for the above-mentioned applications are usually required to have surface properties such as abrasion resistance and stain resistance. Therefore, for example, in Japanese Patent Publication No. 49-31033, After printing the pattern layer on the paper substrate, as a surface layer,
Disclosed is a decorative sheet in which an ionizing radiation-curable resin coating of an unsaturated polyester prepolymer is applied on the surface to form a coating film, and the surface resin layer is formed by crosslinking and curing the coating film with an electron beam. .

As described above, when the surface resin layer obtained by cross-linking and curing the ionizing radiation curable resin composed of a monomer, a prepolymer or the like with the ionizing radiation such as an electron beam is provided on the outermost surface of the decorative sheet. Due to the high cross-linking property, a decorative sheet having excellent surface physical properties such as abrasion resistance and stain resistance can be obtained.

[0004]

However, in the decorative sheet as described above, the cellulose molecules of the parf in the paper base material are cut along with the irradiation of ionizing radiation when the surface resin layer is crosslinked, and the cut ends are cut off. A carboxyl group or a carbonyl group is generated. As a result, the strength of the paper base material deteriorated, and the workability of the decorative sheet deteriorated. For this reason, when a decorative sheet is attached to an adherend substrate such as a wood plywood by applying pressure with a roller via an adhesive, the decorative sheet may be cut due to an increase in tension applied to the decorative sheet or mechanical vibration. There was something that happened. In particular, when the decorative sheet is attached to the curved surface portion of the adherend substrate by lapping or the like, or when it is attached to the corner portion of the adherend substrate of a polygonal column, local concentration of stress occurs on the decorative sheet, There was a problem that the decorative sheet was easily broken.

Therefore, an object of the present invention is to improve the processability of a decorative sheet made of a paper base material having a surface resin layer formed by a cross-linked product of an ionizing radiation curable resin for surface properties such as abrasion resistance. And to provide a decorative material to which such a decorative sheet is attached.

[0006]

In order to solve the above-mentioned problems, the decorative sheet of the present invention comprises a paper substrate and JIS K6.
A high-elasticity resin layer having a tensile strength of 40 MPa or more according to 301 was formed, and a surface resin layer of a crosslinked material of an ionizing radiation curable resin was formed as a surface layer. By providing such a high-elasticity resin layer, even if the strength of the paper base material deteriorates because the cellulose molecules of the pulp of the paper base material are cut by the irradiation of ionizing radiation during the formation of the surface resin layer, it is possible to supplement the makeup. The strength of the entire sheet can be maintained. as a result,
A decorative sheet having surface properties such as abrasion resistance due to the surface resin layer and having good processability can be obtained. Therefore, at the time of laminating processing in which the decorative sheet is stuck to the adherend substrate with a roll laminator or the like, the conveyance is stopped every time mechanical vibration or a continuous strip-shaped decorative sheet is adhered to the (single sheet) adherent substrate. Shock when cutting (instantaneous increase in tension)
By doing so, you can prevent the decorative sheet from being cut.

In the decorative sheet of the present invention, in addition to the above constitution, the paper base material is made of softwood pulp. By using softwood pulp as the paper base material in this way, the strength of the paper base material can be raised compared to the case of using hardwood pulp, so even if the strength is deteriorated by irradiation with ionizing radiation, it can be used as a decorative sheet. Strength can be improved.

Further, in the decorative sheet of the present invention, in any one of the above constitutions, the paper base material further has at least one of a carboxyl group and a carbonyl group at the cut end where the cellulose molecule is cut. It is composed of pulp. In the present invention, the effect of the high elastic resin layer can be maximized in the case of the paper base material made of such pulp.

Further, the decorative material of the present invention has a constitution in which any one of the above decorative sheets is attached to an adherend substrate with an adhesive. With such a structure of the decorative material, the decorative material has surface physical properties such as abrasion resistance, and can prevent breakage of the sheet when the decorative sheet is attached to the adherend substrate, and thus can be manufactured with high yield. Becomes

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the decorative sheet and decorative material of the present invention will be described below.

First, FIG. 1 is a sectional view showing an example of one embodiment of the decorative sheet of the present invention. The decorative sheet S of FIG. 1 has a structure in which a high-elasticity resin layer 2, a pattern layer 3, and a surface resin layer 4 having specific mechanical properties are sequentially laminated on a paper base material 1. Further, FIG. 2 is a cross-sectional view showing an example of one embodiment of the decorative material of the present invention. The decorative material D shown in FIG. 2 is a decorative sheet S as shown in FIG.
However, the paper base material 1 side is laminated on the adherend base material 6 with the adhesive layer 5 interposed therebetween so that the paper base material 1 side faces the adherend base material 6 side.

As shown in FIG. 1, the decorative sheet S of the present invention has a structure in which a highly elastic resin layer 2 is formed on a paper base material 1 and a surface resin layer 4 is formed as a surface layer on the surface side of the decorative sheet.
Usually, in addition to this, a pattern layer 3 is often provided as shown. The high-elasticity resin layer 2 compensates for the strength deterioration of the paper base material due to ionizing radiation when the surface resin layer 4 is used as a crosslinked material. In addition, the positional relationship between the high-elasticity resin layer 2 and the surface resin layer 4 with respect to the paper base material is usually such that the high-elasticity resin layer 2 is on the same side as the surface resin layer 4, as shown in FIG. This is because the strength of the paper base material is deteriorated from the surface resin layer side by ionizing radiation applied to the paper base material from the surface resin layer side when the surface resin layer is cross-linked. However, the high-elasticity resin layer and the surface resin layer may be on opposite sides with respect to the paper base material (that is, the high-elasticity resin layer is below the paper base material 1 in FIG. 1). . Of course, among these layers, the pattern layer 3 is a layer provided as necessary, and the pattern layer can be omitted as appropriate if there is no problem in design. In addition, in view of physical properties, suitability for manufacturing, and the like, the pattern layer 3 and the surface resin layer 4 are appropriately used as necessary.
Other layers such as a primer layer may be provided between them.

Each of these layers will be described in more detail below.

[Paper Base Material] As the paper base material 1, a known base paper for decorative paper or the like is used. In particular, the object of the present invention is that ionizing radiation (particularly electron beam) that has penetrated into the paper base material at the time of crosslinking and curing the surface resin layer as the surface layer causes the cellulose molecules of the pulp to be cut, resulting in the cutting. It is a pulp made of pulp whose strength is deteriorated by the formation of carboxyl groups and carbonyl groups at the ends. Examples of the paper base material include thin paper, kraft paper, fine paper, linter paper, baryta paper, sulfuric acid paper,
It is paper such as Japanese paper. The basis weight is usually about ²⁰ to 150 g / m ² , and the thickness is preferably about ²⁰ to 200 μm. In addition, as the pulp type, it is preferable to use a hardwood (L material) pulp from the viewpoints of printability such as a pattern layer and uniformity of formation. Further, the softwood (N material) pulp is inferior to the hardwood pulp in terms of printability and uniformity of formation, but it is stronger in terms of pulp strength, and therefore pulp produced by ionizing radiation (especially electron beam) is used. It is preferable in the sense of compensating for the decrease in strength and raising the pulp strength. In order to compensate for the deterioration of printability and formation uniformity due to N-material pulp, known sealer coating, calendering, addition of color pigment, etc. may be performed.

[High Elasticity Resin Layer] The high elasticity resin layer 2 is a resin layer exhibiting high elasticity such that the tensile strength of the layer according to JIS K6301 is 40 MPa (corresponding to about 400 kgf / cm ² ) or more. The resin for forming such a resin layer is basically not particularly limited as long as it is a resin that satisfies at least the above mechanical properties. For example, thermoplastic resin,
A thermosetting resin or the like can be used. Specifically, for the high-elasticity resin layer, a resin satisfying the above mechanical properties may be appropriately selected and used from resins such as polyester polyol resin, acrylic urethane resin made of acrylic polyol and isocyanate, or urethane resin. . The high-elasticity resin layer may be formed by applying a coating liquid made of such a resin onto a paper base material. The coating amount is the original strength of the paper base material, the amount of ionizing radiation when the surface resin layer is cross-linked, the application (required folding strength)
It is about 0.5 to 10 g / m ² (based on solid content) depending on the conditions.

By forming such a high-elasticity resin layer on the paper base material, the cellulose molecules of the paper base material are cut by irradiation of ionizing radiation (particularly electron beam) during crosslinking and curing of the surface resin layer formed as the surface layer. It is possible to compensate for the strength deterioration due to. Then, in order to improve the workability deterioration as a decorative sheet due to the strength deterioration, the tensile strength of the highly elastic resin layer is set to 4
It is preferably 0 MPa or more. By the way, although there is no particular upper limit to the tensile strength, the tensile strength of ordinary resin is 80 to 9
Since it is 0 MPa, the upper limit is naturally this level (up to about 90 MPa). The tensile strength is not a strength as a high elastic resin layer integrated with other decorative sheet constituent layers such as a paper base, that is, a decorative sheet, but a characteristic value of only the high elastic resin layer. This tensile strength is a value obtained by forming a single layer of only the high-elasticity resin layer and performing a tensile test on it. To form the high-elasticity resin layer as a single layer, for example, a release sheet such as a polyethylene terephthalate film whose surface is release-treated with a release agent such as wax, or a silicone resin coating is applied, not on a paper substrate. After forming a high-elasticity resin layer by applying a coating liquid on a release sheet such as release paper (the thickness may be thicker than that of the actual decorative sheet), only the high-elasticity resin layer is applied. It can be obtained by peeling it off. In the present invention, the tensile strength according to JIS K6301 (physical test method for vulcanized rubber) is a value measured according to the standard.

In the high elastic resin layer, if necessary, for adjusting physical properties such as coating suitability or for design expression, etc.,
Known extender pigments, colorants and the like may be contained. If a colorant is contained, it can be used also for all solid layers of the pattern layer described below. The high-elasticity resin layer does not impregnate (penetrate) into the paper base material at all, and may be a separate layer adjacent to the paper base material, or partially impregnated into the paper base material. Therefore, the high-elasticity resin layer and the paper substrate may be overlapped and integrated in the vicinity of the interface.

[Picture Layer] The picture layer 3 is a layer for expressing a picture or the like, and is usually provided, but may be omitted if not necessary. When the pattern layer is provided, the content of the pattern layer such as the method of forming the pattern layer, the material, the pattern, etc. is not particularly limited.
The pattern layer is usually formed using ink by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing. The pattern is, for example, a wood pattern, a stone pattern, a cloth pattern, a tile pattern, a brick pattern, a leather pattern,
It can be letters, geometric patterns, full-scale solid, etc. Further, when the entire surface is solid, it can be formed by coating with a coating liquid. The ink (or coating liquid) used for forming the pattern layer is a vehicle made of a binder or the like, a colorant such as a pigment or a dye, and various additives such as an extender pigment, a stabilizer, a plasticizer, a catalyst and a curing agent, which are appropriately added thereto. However, the binder resin may be appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin and the like according to the required physical properties, printability and the like. For example, cellulosic resins such as nitrocellulose, cellulose acetate, and cellulose acetate propionate, poly (meth) acrylate, poly (meth) acrylate butyl, methyl (meth) acrylate-
Acrylic resin such as butyl (meth) acrylate-dihydroxy (meth) acrylate copolymer, urethane resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, etc., or a mixture containing them is used. . As the colorant, titanium white, carbon black, red pigment, yellow lead, inorganic pigments such as ultramarine, aniline black, quinacridone, isoindolinone, organic pigments such as phthalocyanine blue, titanium dioxide coated mica, foil such as aluminum. A bright pigment such as powder or other dye is used.

If a coloring agent is added to the high-elasticity resin layer itself or the paper base material itself and the design expression by the layer is sufficient, this pattern layer may be omitted.

[Surface Resin Layer] The surface resin layer 4 is a surface layer on the outermost surface of the decorative sheet, and is composed of a crosslinked product of an ionizing radiation curable resin. The surface resin layer is formed by applying a liquid ionizing radiation curable resin (composition) by gravure coating, roll coating, or the like, and crosslinking the coating film by irradiation with ionizing radiation to form a crosslinked product. Note that all solid printing such as gravure printing may be performed. The coating amount is 1
It is about 30 g / m ² (based on solid content).

As the ionizing radiation curable resin, specifically, a prepolymer (including a so-called oligomer) and / or a monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule is appropriately mixed. A composition that is crosslinkable and curable by ionizing radiation is preferably used. Here, the ionizing radiation means an electromagnetic wave or charged particles having energy capable of polymerizing or crosslinking a molecule, and usually an electron beam (EB) or an ultraviolet ray (UV) is generally used. However, compared with ultraviolet rays, electron beams are more likely to cause strength deterioration due to cellulose molecule division of the paper substrate,
Since the purpose of the present invention is to make up for this strength deterioration, an ionizing radiation curable resin of the type utilizing electron beam irradiation for crosslinking is particularly suitable.

The above-mentioned prepolymer or monomer specifically has a radically polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group in the molecule. Consisting of a compound having. These prepolymers and monomers may be used alone or in combination of two or more. Here, for example, a (meth) acryloyl group means an acryloyl group or a methacryloyl group. Further, as the ionizing radiation curable resin, a polyene / thiol prepolymer obtained by combining a polyene and a polythiol is also preferably used.

Examples of the prepolymer having a radically polymerizable unsaturated group in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate. Etc. can be used.
A molecular weight of about 250 to 100,000 is usually used. Note that (meth) acrylate means acrylate or methacrylate.

Examples of the monomer having a radically polymerizable unsaturated group in the molecule include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. In addition, polyfunctional monomers include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.

Examples of the prepolymer having a cationically polymerizable functional group in the molecule include epoxy resins such as bisphenol type epoxy resin and novolac type epoxy compound,
There are prepolymers of vinyl ether resins such as fatty acid vinyl ether and aromatic vinyl ether. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. In addition, as the polyene, there is a polyene in which allyl alcohol is added to both ends of polyurethane made of diol and diisocyanate.

In the case of crosslinking with ultraviolet rays, a photopolymerization initiator is added to the ionizing radiation curable resin. In the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or as a mixture 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 metallocene 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 with respect to 100 parts by weight of the ionizing radiation curable resin.

If desired, various additives may be added to the ionizing radiation curable resin. Examples of these additives include thermoplastic resins such as vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, and cellulosic resin, calcium carbonate, barium sulfate, and lubricants such as those described below. Examples include extender pigments (fillers) made of powder, silicone resins, lubricants such as waxes, dyes, and coloring agents such as pigments.

The anti-friction agent is added as required when the wear resistance is further improved. Hard inorganic particles are used as the lubricant. As the material of the inorganic particles,
Alumina (alpha-alumina etc.), silica, glass, silicon carbide, diamond etc. are mentioned. The shape of the inorganic particles is spherical, polygonal, scaly, or amorphous. The average particle size of the inorganic particles is preferably about 3 to 30 μm. If the average particle size is too small, the effect of improving the wear resistance decreases, and if it is too large, the surface smoothness decreases. The addition amount of the inorganic particles is about 5 to 30 mass% with respect to the total amount of the resin content.

As the electron beam source of ionizing radiation, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. And use 100
~ 1000 keV, preferably 200-300 keV
The one that irradiates the electron with the energy of is used.
In addition, as the ultraviolet source, ultra high pressure mercury lamp, high pressure mercury lamp,
Light sources such as a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp are used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is usually mainly used.

[Decorative Material] The decorative sheet of the present invention can be obtained by adhering the above-mentioned decorative sheet of the present invention to the surface of the adherend substrate with an adhesive. The decorative material D shown in the cross-sectional view of FIG. 2 is one form thereof. In the decorative material D of the same figure, the decorative sheet S of the present invention having the constitution as exemplified in FIG.
It has a structure in which it is adhered to the adherend substrate 6.

[Adhering Substrate] The adhering substrate is not particularly limited. For example, the material of the adhered substrate is an inorganic non-metallic material, a metal material, a wood material, a plastic material, or the like. In particular,
Inorganic non-metal type, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, gypsum slag, etc. Non-ceramic ceramic materials, earthenware,
Inorganic materials such as ceramics such as pottery, porcelain, pottery, glass and enamel are available. Further, in the metal system, for example, iron,
There are metal materials such as aluminum and copper. In the case of wood materials, there are, for example, veneer made of cedar, cypress, oak, lauan, teak, etc., plywood, particle board, fiber board, and laminated wood. In the plastic system, there are resin materials such as polypropylene, ABS resin, and phenol resin.
The shape of the adhered substrate is arbitrary such as flat plate, curved plate, and polygonal prism.

[Adhesive] There is no particular limitation on the adhesive as the adhesive layer 5 for bonding the decorative sheet and the adherend. An appropriate adhesive may be selected and used from known adhesives according to the material, application, required physical properties, etc. of the adherend substrate.
For example, as the adhesive, an adhesive made of a thermoplastic resin such as a polyamide resin, an acrylic resin, a vinyl acetate resin, or a curable resin such as a thermosetting urethane resin is used. The adhesive may be applied by a known coating method such as roll coating.
The adhesive is applied to the adherend substrate, the decorative sheet, or both, and then the decorative sheet is attached to the adherent substrate.

[Use] The use of the decorative sheet and the decorative material of the present invention is not particularly limited, but it is an interior material for buildings such as walls, floors and ceilings, fittings such as doors, door frames and window frames, rims, It is used for building parts such as skirting boards, chest of drawers, furniture such as cabinets.

[0034]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples.

Example 1 A decorative sheet S (decorative paper) having a structure as shown in FIG. 1 was produced as follows. A thin paper for building materials made of L material pulp (hardwood pulp) having a basis weight of 30 g / m ² is used for the paper base material 1 as a base paper, and a polyester polyol having an average molecular weight of 20,000 is used by gravure printing on one side of the paper. High elastic resin layer 2 (tensile strength 40
(MPa) to a coating amount of 1 g / m ² based on the solid content, and then a colored solid layer as the pattern layer 3 and a pattern pattern layer of a wood pattern are sequentially formed by gravure printing to obtain a printing paper. did. In addition, for the colored solid layer, a mixed resin of acrylic resin and nitrocellulose was used as a binder, and as the colorant, an ink containing titanium white, yellow lead, and a red pattern as main components was used.
In addition, for the pattern layer, a mixed resin of nitrocellulose and an alkyd resin was used as a binder, and coloring was performed using an ink containing a valve pattern and carbon black as a main component.

Then, 60 parts by mass of polyester acrylate prepolymer, 10 parts by mass of trimethylolpropane triacrylate, 1,
An ionizing radiation (electron beam) curable resin coating material containing 29 parts by mass of 6-hexanediol diacrylate and 1 part by mass of silicone acrylate was applied by a roll coating method so that the coating amount was 10 g / m ² (based on solid content). After coating, electron beam irradiation (175 keV, 30 kGy (3 Mrad))
Then, the surface resin layer 4 was formed as a crosslinked product to obtain a decorative sheet S.

Next, the decorative sheet S is attached to the adhered substrate 6
As shown in FIG. 2, after applying a vinyl acetate adhesive to an MDF (medium fiber board) having a thickness of 3 mm, the paper base side of the decorative sheet faces the adherend, and a roll laminator is used. A decorative material (decorative board) of the present invention as described above was obtained. That is, the decorative material D of FIG. 2 has a paper base material 1, a high-elasticity resin layer 2, a pattern layer 3 and a surface resin layer 4 from the adhered base material side via the adhesive layer 5 on the adhered base material 6. Decorative sheet S consisting of
Is attached and laminated.

[Example 2] A decorative sheet was obtained in the same manner as in Example 1 except that the high-elasticity resin layer had a tensile strength of 60 MPa. Then, using this decorative sheet, a decorative material was obtained in the same manner as in Example 1.

Example 3 The same as Example 2 except that a thin paper for building materials made of N-material pulp (softwood pulp) having a basis weight of 30 g / m ² was used as the paper base material. I got a makeup sheet. Then, using this decorative sheet, a decorative material was obtained in the same manner as in Example 2.

[Comparative Example 1] FIG. 4 is the same as Example 1 except that the formation of the high-elasticity resin layer is omitted.
A decorative sheet Sa like that was obtained. Then, using this decorative sheet, a decorative material was obtained in the same manner as in Example 1.

[Comparative Example 2] A decorative sheet was obtained in the same manner as in Example 1 except that the high elastic resin layer had a tensile strength of 30 MPa. Then, using this decorative sheet, a decorative material was obtained in the same manner as in Example 1.

Comparative Example 3 A decorative sheet was obtained in the same manner as in Example 1 except that the high elastic resin layer had a tensile strength of 20 MPa. Then, using this decorative sheet, a decorative material was obtained in the same manner as in Example 1.

[Evaluation of Performance] In each of the examples and comparative examples, the folding endurance (see Table 1 and FIG. 3) and the workability (see Table 2) were evaluated.

(1) Folding endurance: TAPPI T511
By [Folding strength of paper (MIT tester)], the number of reciprocal bending until the test piece of the decorative sheet was broken was evaluated as the folding strength. It is considered that the strength deterioration of the paper base material due to irradiation with ionizing radiation is due to intramolecular cleavage of cellulose, and the folding endurance test, which is a method of measuring the strength of cellulose fiber, is the most sensitive. This is because it is considered to reflect that effect on. The folding endurance was measured in two directions, the MD direction (longitudinal direction) and the CD direction (horizontal direction) of the paper substrate. By the way, the strength of the paper substrate is
The MD direction becomes stronger due to the orientation of the fibers of the pulp, but when the cellulose is cut by the irradiation of ionizing radiation and the strength is deteriorated, the originally weak CD direction becomes further lower, which is considered to be a problem. That is, when laminating a decorative sheet in a continuous strip shape, the tension direction for transporting the decorative sheet without slack is the MD direction, but shaking during transport of the adherend substrate, cutting step of the decorative sheet, etc. Therefore, the strength required for the decorative sheet is not limited to the strength in the tension direction (MD direction). Therefore,
This is because the decorative sheet tends to tear in the weak direction, and strength in the CD direction is considered to be a problem. Therefore, the folding endurance as workability is C rather than MD.
It is considered that the folding endurance in the D direction is important. Further, in relation to the workability described later, the folding strength of the decorative sheet was measured and evaluated this time as an index of strength deterioration of the paper base material. It is also possible to evaluate the tear strength, tensile strength, etc. of a paper base material on which an elastic resin layer has been formed.

(2) Workability: As workability, the presence or absence of sheet breakage (paper breakage) was evaluated when a continuous strip-shaped decorative sheet was attached to an adherend substrate with an adhesive using a roll laminator. If there was no breakage, it was judged as good, and if it occurred, it was judged as bad.

[0046]

[Table 1]

[0047]

[Table 2]

[Discussion of Results] First, as shown in Table 1 and FIG. 3, the folding endurance is stronger (greater) in each of the MD direction and the CD direction in each example than in each comparative example. Showed the value. In addition, in Example 3 in which the pulp of the paper base material was changed from L material to N material in comparison with Example 2, the folding endurance showed a stronger value. As for the workability, as shown in Table 2, in each of the examples, a high-elasticity resin layer having a tensile strength of 40 MPa or more was provided, and thus the workability was good. On the other hand, in each comparative example,
In Comparative Example 1 in which the high-elasticity resin layer was omitted, and in all Comparative Examples 2 and 3 in which the tensile strength was less than 40 MPa even with the (high) -elasticity resin layer, sheet breakage occurred and it was defective. It was Incidentally, the folding endurance (CD direction) is 1 in each example.
Although it was 50 (times) or more, the comparative examples were all less than 150, and the comparative example 3 which was the largest among the comparative examples also had 118. Therefore, it can be said that a preferable value of the folding endurance strength as an index for workability is about 130 or more in terms of CD.

[0049]

According to the decorative sheet of the present invention, since the highly elastic resin layer having specific mechanical properties is provided, the cellulose molecules in the pulp of the paper base material are cut by the irradiation of ionizing radiation when the surface resin layer is formed. Even if the strength of the paper base material deteriorates, the strength of the decorative sheet as a whole can be maintained by compensating for it. As a result, the surface resin layer has physical properties such as abrasion resistance, and also has good workability. Therefore, when laminating the decorative sheet to the adherend using a roll laminator, mechanical vibration of the processing machine,
Each time a continuous strip-shaped decorative sheet is attached to an (adhered) substrate, it is possible to prevent the decorative sheet from being cut off (paper-out) due to mechanical shock when the transportation is stopped and cut. it can. Furthermore, if softwood pulp is used for the paper base material, the strength of the paper base material can be increased compared to when using hardwood pulp.
Even if the strength is deteriorated by irradiation with ionizing radiation, the strength as a decorative sheet can be improved. Further, in any of the above, when the paper base material is made of pulp having at least one of a carboxyl group and a carbonyl group at the cut end where the cellulose molecule is cut, the effect of the highly elastic resin layer Can be maximized.

According to the decorative material of the present invention, by virtue of the effect of the decorative sheet, the decorative sheet is adhered to the adherend substrate while having surface properties such as abrasion resistance and good workability. As it is attached, you can prevent the sheet from running out when sticking,
It becomes a cosmetic material that can be manufactured with high yield.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating one form of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view illustrating one form of the decorative material of the present invention.

FIG. 3 is a view showing the folding endurance of each example and comparative example.

FIG. 4 is a sectional view showing an example of a conventional decorative sheet.

[Explanation of symbols]

1 Paper base material 2 High elasticity resin layer 3 picture layers 4 Surface resin layer 5 Adhesive layer 6 Adhering substrate D cosmetic material S makeup sheet Sa Conventional makeup sheet

Claims (4)

(57) [Claims] 1. A highly elastic resin layer having a tensile strength of 40 MPa or more according to JIS K6301 is formed on a paper substrate,
A decorative sheet having a surface resin layer formed of a crosslinked product of an ionizing radiation curable resin as a surface layer. 2. The decorative sheet according to claim 1, wherein the paper base material is made of softwood pulp. 3. A paper base material having one of a carboxyl group and a carbonyl group at a cut end where a cellulose molecule is cut.
The decorative sheet according to claim 1 or 2, which is composed of pulp having at least one kind. 4. A decorative material obtained by bonding the decorative sheet according to claim 1 to an adherend substrate with an adhesive.