JP2002200717A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material capable of forming a ruggedness position tuned with a design without using a vinyl chloride resin in a foamed resin layer. SOLUTION: The decorative material D comprises the ruggedness 3 turned with a foaming suppressing ink layer 2 in thin foamed resin layer directly under the layer 2, on a foamed resin layer 1 for forming a polyolefin resin composition added with a thermal decomposition type foaming agent and a foaming accelerator suitably formed on a backing base 4. In this case, a melt viscosity of a polyolefin resin composition in which only a foaming agent is unadded is 1.0×102 to 8.0×102 Pa.s at a temperature T of TLOWER<T<TUPPER, wherein TLOWER is a foaming starting temperature of the foamed resin layer of the foaming suppressing ink layer non-formed part and TUPPER is a foaming starting temperature of the foaming resin layer of the forming suppressing ink layer forming part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material having irregularities formed by a foamed resin layer, which is used for various applications such as wallpaper and flooring.

[0002]

2. Description of the Related Art Conventionally, decorative materials having surface irregularities by a chemical embossing method in which a foamed resin layer is foamed into a desired pattern with a foaming suppressing ink as a wallpaper or a flooring material have been widely known. For example, on a paper base material, a plastisol of a vinyl chloride resin containing a foaming agent is applied to form a foamable resin layer, and then a foaming suppressor ink containing a foaming inhibitor is printed thereon to suppress foaming. A decorative material or the like in which a pattern is formed by an ink layer, and then heated to expand the foamable resin layer into a pattern corresponding to the pattern to form a foamed resin layer, and to form unevenness in position with the pattern. (See Japanese Patent Publication No. 43-28636).

[0003]

However, those which have been put into practical use as a decorative material provided with an uneven pattern of a foamed resin layer by a chemical embossing method, the foamed resin layer has properties, workability, cost, etc. In general, vinyl chloride resins have been used because of their excellent properties. However, recently, vinyl chloride resin has been avoided as a building material in consideration of environmental issues. For this reason, a cosmetic material using a chlorine-free resin as the resin of the foamable resin layer has been desired. Was. From such a viewpoint, for example, a cosmetic material using an acrylic resin as the resin of the foamed resin layer (JP-A-6-33380, JP-A-6-33399)
However, these have been foamed to a uniform thickness and have not been cosmetic embossing decorative materials formed with irregularities using a foam-suppressing ink. Therefore, as described above, a product having a high design feeling due to the surface unevenness synchronized with the pattern has not been obtained.

Accordingly, an object of the present invention is to provide a decorative material capable of forming surface irregularities in synchronism with a pattern without using a vinyl chloride resin for a foamed resin layer.

[0005]

In order to solve the above-mentioned problems, a cosmetic material of the present invention comprises a polyolefin-based foam containing a pyrolytic foaming agent and a foaming accelerator for lowering the foaming start temperature of the foaming agent. A foam-suppressing ink layer for reducing the effect of the foaming accelerator is partially formed on a foaming resin layer formed by foaming a resin composition, and the foaming resin layer has a foam-suppressing ink layer forming portion. A decorative material in which the thickness immediately below is smaller than the thickness immediately below the foam-suppressing ink layer non-formation portion, and the foamed resin layer is formed with unevenness aligned with the shape of the foam-suppression ink layer formation portion, T _LOWER is the foaming start temperature of the foamed resin layer before foaming immediately below the portion where the foaming suppression ink layer is not formed, and T _UPPER is the foaming start temperature of the foamed resin layer before foaming just below the foaming suppression ink layer forming portion. When _{TLO WER} <T _UPPER ), T _LOWER <
At a temperature T such that T <T _UPPER , only the foaming agent has a melt viscosity of 1.0 × 10 ^{2 to} 8.0 × 10 ² Pa · s of the polyolefin resin composition before addition. did.

With such a configuration, even when a polyolefin resin is used in place of the vinyl chloride resin as the resin of the foamed resin layer, a cosmetic with good surface irregularities formed by the foaming suppressing effect of the foaming suppressing ink layer. Material. Therefore, it becomes a decorative material of high design.

Further, the decorative material of the present invention has a configuration in which a foamed resin layer is further laminated on the surface of the backing substrate in the above-mentioned configuration.

[0008] With such a configuration, the thickness, strength, and the like required for the decorative material can be carried by the backing substrate, and the foamed resin layer is formed only by the thickness necessary for the height difference of the uneven pattern. It is also possible to make it thin. Therefore, it is possible to achieve both the height difference required for the design expression and the thickness required for the decorative material, and to reduce the cost because the foamed resin layer can be made thinner by the backing substrate. Further, by forming the foamed resin layer on the surface of the backing substrate, the shape can be easily maintained, and a configuration in which the foamed resin layer is difficult to form a film as a single body can be realized.

Further, the cosmetic material of the present invention has any one of the constitutions described above, and further comprises forming a normal ink layer containing a colorant without a foaming inhibitor on the surface of the foamed resin layer. Configuration.

[0010] By adopting such a configuration, the design expression by the ink layer is usually taken into account, and the design can be further enhanced.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the decorative material of the present invention will be described below with reference to the drawings.

[Outline] FIG. 1 is a cross-sectional view illustrating one embodiment of a decorative material according to the present invention. Cosmetic material D shown in FIG.
Reduces the effect of the foaming accelerator on a foamed resin layer 1 formed by foaming a polyolefin-based resin composition to which a pyrolytic foaming agent and a foaming accelerator for lowering the foaming start temperature of the foaming agent are added. The foaming suppression ink layer 2 is partially formed, and the thickness of the foaming resin layer is
The thickness immediately below the formation part of the foaming suppression ink layer 2 is smaller than the thickness immediately below the non-formation part of the foam suppression ink layer 2, and the foamed resin layer is formed with irregularities 3 synchronized with the shape of the foam suppression ink layer formation part. And the melt viscosity of the polyolefin resin composition is 1.0 × 10 ^{2 to} 8.0 × 10 ² Pa · s, and the foamed resin layer 1 is laminated on the surface of the backing substrate 4. This is the configuration that is performed. Here, T _LOWER is the foaming start temperature of the foamed resin layer 1 before foaming immediately below the non-formation portion of the foam suppressing ink layer 2, and T _UPPER is
This is the foaming start temperature of the foamed resin layer just before foaming immediately below the portion where the foaming suppression ink layer 2 is formed (provided that T _LOWER <T
_UPPER ). The configuration having the backing substrate 4 is one mode of the decorative material of the present invention, but may be omitted as appropriate if the backing substrate 4 is unnecessary depending on the application.

FIG. 2 is a cross-sectional view illustrating another embodiment of the present invention. The decorative material D illustrated in the figure is obtained by further forming a normal ink layer 5 containing a colorant on the surface of the foamed resin layer 1 on the surface of the foamed resin layer 1 in addition to the structure of the decorative material shown in FIG. In the embodiment shown in the figure, the normal ink layer 5 is formed (partly) on the surface of the foaming resin layer 1 and the foaming suppressing ink layer 2 where the foaming suppressing ink layer is not formed. It is. Incidentally, the cosmetic material of the present invention,
In addition to the above-described configuration, if it has a configuration with the specific foamed resin layer and the foaming suppression ink layer of the present invention, other conventionally known configurations, for example, a primer layer, a surface protective layer,
A configuration having a backside adhesive layer or the like as appropriate may be used.

Hereinafter, the present invention will be described in more detail.

[Foam Resin Layer] The foam resin layer 1 is formed as a foam of a polyolefin resin composition to which a pyrolytic foaming agent and a foaming accelerator for lowering the foaming start temperature of the foaming agent are added. However, in the present invention, since the foam is formed by the chemical embossing method, the foam is formed as a foam under the influence of the foam suppressing ink layer formed in a pattern.

In the present invention, a polyvinyl chloride resin is not used as the resin of the foamed resin layer, but a polyolefin-based resin is particularly used as a chlorine-free resin. As a result, environmental problems such as the generation of hydrogen chloride gas during waste combustion, which are problems of the conventional cosmetic material using a vinyl chloride resin, are avoided, and the cosmetic material is environmentally friendly. Further, the use of a polyolefin-based resin has an advantage that the cost can be reduced as compared with an acrylic resin or the like. As the polyolefin resin, polyethylene, polypropylene,
In addition to homopolymers of olefinic monomers such as polymethylpentene and polybutene, copolymers of olefinic monomers composed of ethylene and α-olefin, specifically, for example, ethylene-propylene copolymer, ethylene-butene A copolymer, a propylene-butene copolymer, an ethylene-propylene-butene copolymer, or an olefin monomer and a chlorine-free monomer other than the olefin monomer, for example, (meth) acrylic acid, (meth) ) Various acrylic monomers such as acrylic acid esters [however, (meth) acryl means acryl or methacryl). And a copolymer with a monomer such as a vinyl acetate monomer, specifically, for example, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-ethyl methacrylate copolymer, or the like.

As the thermal decomposition type foaming agent, an appropriate foaming agent may be used from conventionally known ones according to the resin system to be foamed. Examples of the foaming agent include azo foaming agents such as azodicarbonamide (ADCA), hydrazine foaming agents such as paratoluenesulfonyl hydrazide and 4,4'-oxybisbenzenesulfonyl hydrazide (OBSH), and other thermal decomposition agents. A mold blowing agent is used alone or in combination. Among them, a typical one is azodicarbonamide (ADCA), and good results can be obtained in terms of expansion ratio, difference in expansion ratio, cost, and the like. In addition,
The amount of the foaming agent is usually about 1 to 10 parts by mass based on 100 parts by mass of the resin component.

The foaming accelerator is a compound which lowers the foaming start temperature of the thermal decomposition type foaming agent, and conventionally known ones corresponding to the thermal decomposition type foaming agent can be used. For example, when the blowing agent is an azo-based azodicarbonamide, examples of the foaming accelerator include compounds such as zinc, lead, and calcium, such as zinc oxide, dibasic lead sulfate, tribasic lead sulfate, and tribasic lead sulfate. In addition to basic lead maleate, dibasic lead phthalate, lead stearate, etc., urea, oxalic acid, ethanolamine, etc. may be used alone or as a mixture of two or more. The addition amount of the foaming accelerator is usually about 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.

In the chemical embossing method utilizing the foaming suppressing action of the foaming suppressing ink layer, the foaming start temperature of the foaming agent is once lowered by the action of the foaming accelerator, and the foaming is accelerated. This is a method utilizing the effect of suppressing the promotion effect of the accelerator in the direction of returning the foaming start temperature to the original temperature by reducing the foaming inhibitor.
Therefore, this foaming accelerator is an essential component together with the pyrolytic foaming agent and the foaming accelerator.

The polyolefin resin composition to be used as the foamed resin layer is a resin composition containing at least a polyolefin resin, a pyrolytic foaming agent and a foaming accelerator, as described above. If necessary, other additives can be added. For example, various known additives such as a filler, a flame retardant, a colorant, a plasticizer, an ultraviolet absorber, and a light stabilizer. For example, fillers such as calcium carbonate and clay, aluminum hydroxide and magnesium hydroxide as flame retardants, titanium white and carbon black as coloring agents, propylene glycol fatty acid esters, glycerin fatty acid esters as plasticizers, Fatty acid esters such as sorbitan fatty acid ester and sucrose fatty acid ester, or dibutyl phthalate (DBP), dioctyl phthalate (DOP) and the like, benzotriazole-based and benzophenone-based as ultraviolet absorbers, and hindered amine-based radical as light stabilizers Agents and the like are used.

The foamable resin layer is made of a (non-foamed) polyolefin resin composition containing at least a polyolefin resin, a pyrolytic foaming agent, and a foaming inhibitor as described above. Temperature (T
_(Lower temperature than _LOWER ), and is formed as a non-foamed foamable resin layer by a known appropriate film forming method such as an extrusion method, a calendar method, a melt coating method, or an aqueous paste coating method. . Then, after forming a foaming suppression ink layer on this foamable resin layer, it is heated and foamed,
It is a foamed resin layer.

In the present invention, the foaming is not foamed as much as possible at the time of the film formation, the foaming is performed by heating after the film formation, and the action of the foaming suppression by the foaming suppression ink layer is sufficiently effective. As for the polyolefin resin composition to which only the heat-decomposable foaming agent has not been added so that irregularities can be obtained, the viscosity at the time of heat-foaming is determined as the viscosity of the foamed resin layer just before foaming immediately below the portion where the foam-suppressing ink layer is not formed. foaming start temperature T _LOWER, foaming start temperature of at before foaming of the foamed resin layer directly under foam suppressing ink layer forming portion is taken as a T _{UPPE R (where, T LOWER <T UPPER),} T
_At a temperature T such that _LOWER <T <T _UPPER , the melt viscosity of the polyolefin-based resin composition to which only the foaming agent has not been added,
The range is from 1.0 × 10 ^{2 to} 8.0 × 10 ² [Pa · s]. If the melt viscosity in the temperature range is less than 1.0 × 10 ² , the gas generated during heating and foaming due to the low viscosity is not taken into the inside of the layer and escapes to the outside of the layer. A foamed resin layer cannot be formed, and a sufficient expansion ratio difference cannot be obtained. On the other hand, if the melt viscosity in the above temperature range is more than 8.0 × 10 ² , the gas generated at the time of heating and foaming due to the excessively high viscosity pushes out the surrounding resin composition to form sufficient voids in the foamed resin. It is not possible to mold inside the layer, and as a result, it is not possible to form a sufficient expansion ratio and unevenness due to a sufficient expansion ratio difference. In addition, in order to adjust the melt viscosity of the resin composition, in the case of an ethylene-vinyl acetate copolymer, to lower the viscosity, the copolymerization ratio of vinyl acetate is increased, and the degree of polymerization is reduced. The amount of the plasticizer added may be increased, and the degree of crystallinity may be reduced. On the other hand, in order to increase the viscosity, the opposite may be performed. The melt viscosity was measured using a capillary rheometer (“Tokyo Seiki Seisakusho Co., Ltd.,“ Capillograph ”).
Capillary length L = 10 mm, capillary diameter D = 1 m
m, barrel diameter B = 9.5 mm, apparent shear rate γa
= 1.125 × 10 ^-2 [s ^-1 ].

The reason why the polyolefin-based resin composition subject to the above-mentioned melt viscosity is a resin composition to which only a foaming agent is not added is that the final composition of the resin composition to which the foaming agent is added is measured. Naturally, when the measurement is not under the influence of the foaming suppressing ink layer, the measurement is performed at a temperature exceeding T _LOWER , the foaming occurs during the measurement, and the measured value cannot be determined. Moreover, a composition excluding only the foaming agent is considered to exhibit a viscosity that is not much different from that of the composition to which the foaming agent has been added.

The foamed resin layer before foaming, that is, the foamable resin layer is usually formed simultaneously with lamination on the backing substrate, and thereafter, the foaming suppressing ink layer is printed on the foamable resin layer. After forming, the foamable resin layer is heated and foamed under the influence of the foam suppressing ink layer to form a foamed resin layer. However, as the decorative material of the present invention, the production method is not limited, and in addition to the production method described above, for example, a foamable resin layer and a backing substrate once formed as a single sheet, After laminating by a suitable laminating method such as dry lamination or wet lamination via an adhesive as appropriate to form a laminate, a foam-suppressing ink layer is formed by printing on the foamable resin layer surface of the laminate, and then heated and foamed. It may be a method of making it.

The thickness of the foamable resin layer before foaming may be determined according to the intended use.
It is about 00 μm. The thickness of the foamed resin layer after foaming depends on the foaming ratio (normally 1 to 10 times).
It is about 000 μm.

[Bubble Inhibition Ink Layer] Bubble Inhibition Ink Layer 2
Is partially formed on a foamed resin layer using a foaming suppressing ink containing a foaming inhibitor for reducing the effect of the foaming accelerator. As the foaming inhibitor, a known foaming inhibitor having a foaming-suppressing effect with respect to the combination of the thermal decomposition type foaming agent and the foaming accelerator can be used. For example, trimellitic anhydride,
Organic acids such as maleic acid, fumaric acid, adipic acid and 1,2-phthalic acid are used. Above all, trimellitic anhydride and benzotriazole-based compounds are typical compounds.

The foam-suppressing ink layer can be formed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing, etc., using an ink obtained by adding a foaming inhibitor to a vehicle made of a binder resin or the like. As the binder resin, for example, one or a mixture of two or more known resins such as an acrylic resin, an ethylene-vinyl acetate copolymer, an alkyd resin, a urethane resin, and a cellulose resin are used.

Examples of the acrylic resin include, for example, poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and (meth) acrylic acid. Methyl acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate Copolymer, methyl (meth) acrylate-butyl (meth) acrylate- (2-hydroxyethyl methacrylate) -styrene copolymer,
Acrylic resin such as ethyl (meth) acrylate-butyl (meth) acrylate--2-hydroxyethyl (meth) acrylate [((meth) acryl means acrylic or methacryl). ] Is used alone or as a mixture of two or more.

By adding a coloring agent to the foam-suppressing ink layer, the pattern of the partially formed and foamed foam-suppressing ink layer and the uneven surface pattern of the foamed resin layer are positioned. The design is in harmony with the design, and it is possible to provide a cosmetic material with a higher design. As the colorant, known colorants, for example, titanium white, carbon black, red iron oxide, graphite, inorganic pigments such as ultramarine blue, aniline black, quinacridone red, isoindolinone yellow,
Organic pigments such as phthalocyanine blue, glittering pigments such as titanium dioxide-coated mica foil powder, and other dyes are used.

The pattern formed by the foam suppressing ink layer may be a pattern according to the intended use.
A cloth pattern, a tile pattern, a brick pattern, a leather pattern, a character, a geometric pattern, and the like are used alone or in combination.

Incidentally, the foam suppressing ink layer is usually
The pattern is partially printed on the backing substrate or on the foamable resin layer formed as a single layer.

Then, when the foaming suppressing ink layer is formed on the foaming resin layer (unfoamed foaming resin layer), and then heated to a temperature higher than the foaming temperature of the foaming agent contained in the foaming resin layer,
The foamable resin layer immediately below the portion where the foaming suppressing ink layer is not formed is foamed under the influence of the foaming inhibitor and increases in thickness to become a foamed resin layer. On the other hand, the foamable resin layer immediately below the foam-suppressing ink layer forming section is a foamed resin layer whose foaming is inhibited by the influence of the foam-suppressing layer and whose thickness does not increase as much as above. Therefore,
Relatively, only the portion where the foaming suppressing ink layer is present has a concave portion on the surface of the decorative material. When the foaming suppression ink layer is colored, the concave portions exactly match the colored pattern of the foaming suppression ink layer formed in a pattern, so that surface irregularities with high designability can be obtained. become.

[Backing Substrate] The backing substrate 4 is a material which imparts a desired strength and shape to the decorative material as needed, and a conventionally known substrate depending on the application can be used. When the shape of the decorative material is a sheet, the decorative material is used, for example, as a wallpaper, a floor material, and the like, and a sheet-like base material suitable for these uses is used. For example, for wallpaper, paper, non-woven fabric, woven fabric, etc., which have been subjected to flame-retardant processing as necessary, are used. As the paper, flame retardant paper for wallpaper having a basis weight of 50 to 100 g / cm 2 is used. In addition, as the fibers of the nonwoven fabric, inorganic fibers such as glass and silica, and organic fibers such as polyester, vinylon, and acryl are used. In particular, when flame retardancy or nonflammability is required, non-woven fabrics made of aluminum hydroxide paper, inorganic fibers such as glass fiber, alumina fiber, and silica fiber are used.

The backing substrate may be a plate material such as a flat plate or a curved plate. For example, wood veneer, wood plywood, particle board, wood board such as MDF (medium fiber board), metal board made of iron, aluminum, etc., glass, gypsum board, ALC (lightweight foam) Concrete non-metallic plates such as plates, resin plates made of acrylic resin, polypropylene and the like. The backing substrate is
A three-dimensional article made of the above various materials may be used.

[Normal Ink Layer] The ordinary ink layer 3 is formed by using a so-called ordinary ink containing a coloring agent without containing a foaming inhibitor, and the surface of the foamed resin layer where the foaming inhibiting ink layer is not formed. , The surface of the foam suppressing ink layer, or a layer formed by printing on these surfaces. The printing may be performed by a known printing method as described for the foam suppressing ink layer. Normally, the ink layer 3 is formed so as to be on the foam-suppressing ink layer or on the foaming resin layer in the portion where the foam-suppressing ink layer is not formed, as in the case of the decorative material D illustrated in FIG. The normal ink layer may be formed so as to be between the foamed resin layer and the foam-suppressing ink layer, but if the normal ink layer is present between the foamed resin layer and the foam-suppressing ink layer, the normal ink layer This is because the foaming suppression effect of the suppression ink layer is reduced. However, the present invention does not exclude a configuration in which a normal ink layer is provided between the foamed resin layer and the foam-suppressing ink layer. As the ink of the ordinary ink layer, a known binder resin, a coloring agent, and the like, which are the same as those described as the foaming suppressing ink, can be used, except that the coloring agent is contained without containing the foaming suppressing agent. Therefore, further description is omitted. The normal ink layer may be partially formed in a pattern as described in the foaming suppressing ink layer to express a pattern, or may be entirely formed as a solid surface. As a result, the entire surface can be colored. At this time, it goes without saying that the color of the ink layer is usually colored and transparent so that the pattern colored by the lower foaming suppression ink layer can be seen through.

[Other Layers] As the outermost layer of the decorative material, a surface layer may be provided as necessary. The surface layer is provided for improving surface physical properties such as scratch resistance, abrasion resistance, and chemical resistance, and for adjusting the gloss of the surface (with gloss, matting, etc.). The surface layer may be formed by coating with a coating liquid such as a resin,
Alternatively, it may be formed by melt coating a resin. As the resin used for the surface layer, a thermoplastic resin such as an acrylic resin or a polyolefin resin, a curable urethane resin such as a two-component curable type or a one-component curable type, an epoxy resin, or an ionizing radiation cured by an ultraviolet ray or an electron beam. A known resin such as a conductive resin can be used. In the surface layer, a matting agent such as silica, a lubricant such as alumina, a lubricant such as wax, a coloring agent, an extender, an ultraviolet absorber, and a light stabilizer are appropriately added as necessary. I do.

The surface layer is usually transparent so that a colored foam-suppressing ink layer or a pattern (picture) formed by the normal ink layer can be seen through. In the case where only the concave and convex pattern of the foamed resin layer by the layer is a design, it may be opaque. Further, in order to form the surface layer by coating, as a coating method capable of coping with the difference in surface unevenness, a known coating method such as spray coating, curtain flow coating, roll coating using a soft rubber roll or a sponge roll, or the like is used. Good.

[0038] In addition to the above-described constitution, the decorative material of the present invention may have other conventionally known constituent elements provided that it has the foamed resin layer and the foam-suppressing ink layer specified in the present invention. For example, a configuration in which a primer layer, a back surface adhesive layer, and the like are appropriately provided may be employed.

[0039]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 As a polyolefin-based resin composition for forming a foamed resin layer, a resin composition having the composition (basic composition) shown in Table 1 below was prepared. That is, as a polyolefin resin, 70 parts by mass of an ethylene-vinyl acetate copolymer [manufactured by Sumitomo Chemical Co., Ltd., part number D5020 (vinyl acetate content: 10% by mass, MFR75); 20% by mass, MFR15
0) used as a mixture with 30 parts by mass] 100 parts by mass,
The foaming agent was 6 parts by mass of azodicarbonamide (ADCA) (manufactured by Eiwa Kasei Kogyo Co., Ltd., product name “Vinihole AC # 3”, foaming temperature 208 ° C. = T _UPPER ), and zinc oxide powder (Asahi Denka) as a foaming accelerator Made by Kogyo Co., Ltd., part number OF
101) 5 parts by mass, flame retardant (aluminum hydroxide) 50
Parts by mass, silicone-based flame retardant (Dow Corning Toray)
A resin composition (T _LOWER = 180 ° C.) comprising 5 parts by mass of Silicone Co., Ltd., product number DC4-7081) and 15 parts by mass of a coloring agent (titanium dioxide powder). In addition,
This polyolefin-based resin composition was extruded with a twin-screw extruder under conditions of a cylinder temperature of 70 to 80 ° C and a die temperature of 60 to 70 ° C, and was once prepared as pellets. For this polyolefin-based resin composition, a measurement composition excluding only the foaming agent was separately prepared in the same manner as described above.
The melt viscosity at 0 ° C. was measured to be 2.5 × 10 ² Pa
-It was s. The above melt viscosity is measured by a capillary rheometer (“Capillograph” manufactured by Toyo Seiki Seisaku-sho, Ltd.)
Using a capillary length L = 10 mm, a capillary diameter D = 1 mm, a barrel diameter B = 9.5 mm, an apparent shear rate γa = 1.125 × 10 ⁻² [s ⁻¹ ], and a sample temperature of 19
The measurement was performed at 0 ° C. The melt viscosity measured at 182 ° C. was 2.8 × 10 ² Pa · s.

[0041]

[Table 1]

Next, the pellets of the polyolefin resin composition were subjected to a backing substrate 4 made of a backing paper for wallpaper (basis weight 70 g / m ² ) by a single screw extruder using a T die.
100 μm thick foamable resin layer 1A
Was formed. Next, after the surface of the foamable resin layer is subjected to corona discharge treatment, trimellitic acid 15% by weight as a foaming inhibitor is used.
And a gravure printing of a foam-suppressing ink containing carbon black as a coloring agent in a pattern of a brick joint part to form a foam-suppressing ink layer 2, as shown in FIG.
An intermediate sheet S was produced.

Next, the foamed resin layer 1A is foamed by heating at 200 ° C. in the foamed portion for 60 seconds to form the foamed resin layer 1.
A decorative material D having a configuration as shown in FIG. 2 was produced. Good results were obtained by the following evaluation. The evaluation result is
The results are shown in Table 2 together with the melt viscosity.

In the evaluation, the foam suppressing effect of the foam suppressing ink layer was evaluated based on the expansion ratio. That is, the foaming ratio (thickness of the foamed resin layer / thickness of the foamable resin layer) was compared between the portion immediately below the portion where the foaming suppression ink layer was not formed and the portion immediately below the portion where the foaming suppression ink layer was formed. Anything above was considered good.

Example 2 As a polyolefin resin composition for forming a foamed resin layer, the composition used in Example 1 was used as a basic composition. In addition to this basic composition, a plasticizer glycerin fatty acid ester (manufactured by Riken Vitamin Co., Ltd.) , TG-1
2) A cosmetic material was prepared in the same manner as in Example 1, except that a resin composition containing 10 parts by mass was used. Melt viscosity is 19
1.5 × 10 ² Pa · s at 0 ° C., 1.7 × 1 at 182 ° C.
0 ² Pa · s, and the evaluation result was good.

Example 3 As a polyolefin resin composition for forming a foamed resin layer, the composition used in Example 1 was used as a basic composition. In addition to this basic composition, 20 parts by mass of the same plasticizer as in Example 2 was used. Other than using the added resin composition,
A decorative material was produced in the same manner as in Example 1. Melt viscosity is 1
1.0 × 10 ² Pa · s at 90 ° C., 1.3 × at 182 ° C.
A 10 ² Pa · s, the evaluation results were good.

Example 4 As a polyolefin-based resin composition for forming a foamed resin layer, the composition used in Example 1 was used as a basic composition, and only the polyolefin-based resin used in this basic composition was ethylene-vinyl acetate. Other than changing from a copolymer to an ethylene-methyl acrylate copolymer,
A decorative material was produced in the same manner as in Example 1. Melt viscosity is 1
5.5 × 10 ² Pa · s at 90 ° C., 6.2 × at 182 ° C.
A 10 ² Pa · s, the evaluation results were good.

Example 5 As a polyolefin-based resin composition for forming a foamed resin layer, a resin composition obtained by further adding 10 parts by mass of the same plasticizer as in Example 2 to the formulation used in Example 4 was used. A decorative material was produced in the same manner as in Example 1. The melt viscosity is 3.5 × 10 ² Pa · s at 190 ° C.,
It was 4.0 × 10 ² Pa · s at 82 ° C., and the evaluation result was good.

Comparative Example 1 As a polyolefin resin composition for forming a foamed resin layer, the composition used in Example 1 was used as a basic composition, and only the polyolefin resin used in this basic composition was ethylene-vinyl acetate. Other than changing from a copolymer to an ethylene-ethyl acrylate copolymer,
A decorative material was produced in the same manner as in Example 1. Melt viscosity is 1
9.0 × 10 ² Pa · s at 90 ° C., 1.0 × at 182 ° C.
The evaluation result was 10 ³ Pa · s, and the evaluation result was that both the foam suppressing portion and the non-suppressing portion had little foaming and were defective.

Example 6 A polyolefin resin composition for forming a foamed resin layer was the same as that used in Example 2 except that 10 parts by mass of a plasticizer was further added to the composition used in Comparative Example 1. A decorative material was produced in the same manner as in Example 1. The melt viscosity is 6.5 × 10 ² Pa · s at 190 ° C., 1
It was 7.5 × 10 ² Pa · s at 82 ° C., and the evaluation result was good.

[Example 7] As a polyolefin-based resin composition for forming a foamed resin layer, the composition used in Example 1 was used as a basic composition, and only the polyolefin-based resin used in this basic composition was ethylene-vinyl acetate. A cosmetic material was produced in the same manner as in Example 1 except that the copolymer was changed to linear low-density polyethylene. Melt viscosity is 3.5 at 190 ° C
× 10 ² Pa · s and 3.8 × 10 ² Pa · s at 182 ° C, and the evaluation result was good.

[Comparative Example 2] A polyolefin resin composition for forming a foamed resin layer was the same as that used in Example 7 except that 10 parts by mass of a plasticizer was further added to the composition used in Example 7. A decorative material was produced in the same manner as in Example 1. The melt viscosity is 7.0 × 10 ¹ Pa · s at 190 ° C.,
It is 9.0 × 10 ¹ Pa · s at 82 ° C.
Foaming occurred, but the gas escaped to the outside of the layer, which was defective.

[0053]

[Table 2]

[0054]

(1) According to the decorative material of the present invention, even if a polyolefin resin is used as the resin of the foamed resin layer instead of the vinyl chloride resin, the surface unevenness is improved by the foaming suppressing effect of the foaming suppressing ink layer. Is formed on the decorative material. Therefore, it becomes a decorative material of high design. (2) Furthermore, if the backing base material is laminated under the foamed resin layer, the thickness, strength, etc. required as a decorative material can be carried by the backing base material, and the foamed resin layer is formed only by an uneven pattern. It is also possible to reduce the thickness required for the height difference between the two. Therefore, it is possible to achieve both the height difference required for the design expression and the thickness required for the decorative material, and to reduce the cost because the foamed resin layer can be made thinner by the backing substrate. Further, by forming the foamed resin layer on the surface of the backing substrate, the shape can be easily maintained, and a configuration in which the foamed resin layer is difficult to form a film as a single body can be realized. (3) Further, if a normal ink layer containing a colorant without a foaming inhibitor is further formed on the surface of the foamed resin layer, the design expression by the normal ink layer is taken into consideration, and the design can be further enhanced.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating one embodiment of a cosmetic material of the present invention.

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

FIG. 3 is a cross-sectional view showing a state before foaming in one embodiment of the decorative material of the present invention.

[Explanation of symbols]

1 Foamed Resin Layer 1A Foamable Resin Layer (Unfoamed Foamed Resin Layer) 2 Foaming Inhibition Ink Layer 3 Roughness 4 Backing Material D Cosmetic Material S Intermediate Sheet T _LOWER Foaming Start Temperature (immediately below the foaming suppressing ink layer non-formed portion) T _UPPER foaming start temperature (immediately below the foam suppression ink layer forming section)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 23:00 B29L 9:00 B29L 9:00 B29C 67/22 (72) Inventor Yoshiaki Nezu Tokyo 1-1-1, Ichigaya-Kagacho, Shinjuku-ku Dainippon Printing Co., Ltd. (72) Inventor Yu Okamoto 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dainippon Printing Co., Ltd. (72) Inventor Noriyuki Ono 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Yoshiko Fujita 1-1-1 Ichigaya-Kagamachi, Shinjuku-ku, Tokyo F-term (reference) 4F055 AA12 AA17 BA17 BA21 CA03 DA03 DA12 FA05 FA07 FA38 HA15 HA18 4F100 AA25A AA37B AK03A AK68A AL05A AT00C BA02 BA03 BA07 BA10B BA10C CA01A CA08A CA13A CA13B CC00B DD01 DG10C DJ00A EJ55 GB08 4F212 AA03 AB02 AG03 AG20 AH48 UA09 UB22 UG05 UN21 UP02 UP10

Claims (3)

[Claims] An effect of the foaming accelerator on a foamed resin layer formed by foaming a polyolefin resin composition to which a pyrolytic foaming agent and a foaming accelerator for lowering the foaming start temperature of the foaming agent are added. The foaming resin layer is partially formed, and the thickness of the foaming resin layer is such that the thickness immediately below the foaming suppressing ink layer forming portion is smaller than the thickness immediately below the foaming suppressing ink layer non-forming portion, What is claimed is: 1. A decorative material comprising a foamed resin layer having irregularities aligned with the shape of the foaming suppression ink layer forming portion, wherein the foaming of the foaming resin layer before foaming immediately below the foaming suppression ink layer non-forming portion. _Assuming that the starting temperature is T _LOWER and the foaming start temperature of the foamed resin layer immediately before foaming immediately below the foam suppressing ink layer forming portion is T _UPPER (where T _LOWER <T
_UPPER ), T _LOWER <T <T At a temperature T such that _UPPER , only the foaming agent has a melt viscosity of 1.0 × 10 ^{2 to} 8.0 × 10 ² Pa · s, a cosmetic material. 2. The decorative material according to claim 1, wherein the foamed resin layer is laminated on the surface of the backing substrate. 3. The surface of the foamed resin layer where the foaming suppression ink layer is not formed, the surface of the foaming suppression ink layer, or the surface thereof contains a coloring agent without containing a foaming inhibitor. 2. The ink composition according to claim 1, wherein the ink layer is formed.
Or the cosmetic material according to claim 2.