JP2002067068A - Cosmetic material manufacturing method - Google Patents

Abstract

[Problem] To provide a method for producing a cosmetic material capable of suppressing the occurrence of cracks in a surface protective layer and the like, and improving the surface characteristics such as stain resistance and abrasion resistance and the design. I do. A foamable resin layer is formed by dispersing a thermally expandable microcapsule-type foaming agent in a thermoplastic resin binder on a base sheet.
a to expand and expand the foaming agent to form a foamed resin layer 11
And at least the surface protective layer 1
Form 3 The pattern layer 1 is formed on the foam resin layer 11.
4 is printed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cosmetic material suitably used for building interiors such as wallpaper.

[0002]

2. Description of the Related Art A decorative material obtained by laminating a foamed resin layer on a base sheet such as a backing sheet is widely used for interior decoration of buildings, or for surface decoration such as furniture, home appliances, or the cover of a photo book. Has been.

[0003] For example, JP-A-64-45628 discloses the above-mentioned decorative material. As shown in the cross-sectional view of FIG. 9, a base material sheet (hereinafter also simply referred to as a base material)
A foamed resin layer 11 is formed on the foamed resin layer 10. The foamed resin layer 11 has a convex foamed resin pattern (not shown) protruding from the surface of the foamed resin layer and a foaming suppression pattern (not shown) which is concave and concave. Is formed. On the surface of the foamed resin layer 11 of the decorative material, for example, a picture layer 14 having an ink pattern or the surface protective layer 1
3 are formed.

As the base sheet 10, for example, paper, glass fiber mixed paper, woven fabric, asbestos sheet and the like are used. The foamed resin layer 11 is formed by adding a foaming agent to a thermoplastic synthetic resin and foaming a heat-foamable material formed into a film or a sheet. Examples of the thermoplastic synthetic resin include polyethylene and polypropylene. Polyolefins such as polyolefins, polyolefin copolymers such as ethylene-vinyl alcohol copolymer, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, synthetic resin such as acrylic resin, as a foaming agent For example, inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, sodium boron hydride, silicon oxyhydride, azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, paratoluenesulfonyl hydrazide, 4,4 -Oxybisbenze Select from organic foaming agents such as sulfonyl hydrazide in consideration of the softening point of the synthetic resin used, the foaming temperature, or the combination with the foaming inhibitor, and furthermore, a plasticizer, a stabilizer, a colorant, a foaming accelerator, a lubricant , A solvent, a diluent or the like are appropriately kneaded to form a composition.

[0005] A method for producing the above-described decorative material will be described. First, as shown in FIG. 10A, a foamable resin layer 11a, which is a heat-foamable material before foaming the foamed resin layer 11, is formed on the base material 10. Next, as shown in FIG. 10B, a heat-foamable pattern or a foam-suppressing pattern (not shown) is formed on the surface of the foamable resin layer 11a, or a pattern layer 14 having a normal ink pattern is printed. If necessary, after a product is formed, the surface of the decorative material is protected and a surface protective layer 13 for imparting abrasion resistance is applied and formed. Next, the foaming resin layer 11a is foamed by heating the whole after that, and it is set as the foaming resin layer 11, and it is set as the decorative material of a desired structure shown in FIG.

[0006]

However, in the above-mentioned conventional decorative material, in the step of foaming the foamable resin layer 11a, irregularities are generated on the surface 11b of the foamed resin layer 11 obtained by the bubbles 12 generated. In addition, the surface area also increases, and as a result, cracks C appear in the picture layer 14 and the surface protection layer 13 formed on the foamable resin layer 11a.
Is formed. When the above cracks are formed, stains penetrate into the cracks, so that stain resistance is deteriorated. In addition, cracks also enter the pattern layer, the surface of the surface protective layer becomes rough, and the sharpness of the pattern decreases,
There is a drawback that the design is poor.

In order to avoid the occurrence of cracks in the picture layer and the surface protective layer, a method of forming the picture layer and the surface protective layer after foaming the foamable resin layer has been considered. FIG. 11 is a cross-sectional view of the decorative material formed by the above method. A foamed resin layer 11 is formed on a base material 10,
A pattern layer 14 having an ink pattern is printed on the surface, and a surface protective layer 13 is formed by coating.

A method for producing the above-mentioned decorative material will be described. First, as shown in FIG. 12A, a foamable resin layer 11a which is a heat-foamable material before foaming of the foamed resin layer 11 is formed on the base material 10, and then, as shown in FIG. As described above, the foamable resin layer 11 a is foamed by the heat treatment to form the foamed resin layer 11. Next, a pattern layer 14 of an ink pattern is printed on the surface of the foamed resin layer 11, and the surface protection layer 1 is further printed.
3 is applied to form a decorative material having a desired structure shown in FIG.

However, in the above-mentioned decorative material, the surface 11b of the foamed resin layer 11 obtained has irregularities, and the bubbles generated by the thermal decomposition of the pyrolytic foaming agent become uneven in size. Then, the gas generated by the thermal decomposition blows out through the surface of the foamed resin layer to form a crater. For this reason, the surface irregularities are also uneven and large (rough), and it is difficult to sufficiently cover the entire surface even if the pattern layer 14 and the surface protective layer 13 are formed on the upper layer, and the same as above. However, the drawback of poor stain resistance and design was left.

[0010] Further, a method of avoiding the generation of cracks in the picture layer and the surface protective layer by suppressing the foaming rate to a low level is conceivable. However, this method cannot make use of the inherent properties of the foamed resin layer such as cushioning and soft touch. .

Although a method in which a protective layer is not formed on the surface is conceivable, the surface characteristics of the surface of the foamed resin layer 11 such as stain resistance and abrasion resistance are insufficient, and the surface gloss is also desired. There is a disadvantage that it cannot be adjusted to the extent.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to suppress the occurrence of cracks in a surface protective layer and the like, and to improve surface characteristics such as stain resistance and abrasion resistance. Another object of the present invention is to provide a method for producing a decorative material capable of improving the design.

[0013]

Means for Solving the Problems To achieve the above object, a method for producing a decorative material according to the present invention comprises dispersing a thermally expandable microcapsule type foaming agent in a thermoplastic resin binder on a base sheet. Forming a foamable resin layer comprising: heating the foamable resin layer to expand and foam the foaming agent to form a foamed resin layer; and forming at least a surface protection layer on the foamed resin layer. And

Preferably, in the method for producing a decorative material of the present invention, a pattern layer is formed on the foamed resin layer after the step of forming the foamed resin layer and before the step of forming the surface protective layer. The method further includes a printing step.

According to the method for producing a decorative material of the present invention, a foamable resin layer formed by dispersing a thermally expandable microcapsule-type foaming agent in a thermoplastic resin binder is formed on a base sheet. The layer is heated to expand and foam the foaming agent to form a foamed resin layer. Next, after printing a pattern layer in some cases, at least a surface protection layer is formed on the foamed resin layer.

In the method for producing a decorative material of the present invention, a thermally expandable microcapsule type foaming agent is used in place of the previously used pyrolytic type foaming agent such as diazocarbonamide. The heat-expandable microcapsule-type foaming agent can generate uniform bubbles having a small particle size, and the irregularities due to the protrusion of the bubbles on the surface of the foamed resin layer are reduced. In addition, the foaming gas does not erupt on the surface of the foamed resin layer to form crater-like irregularities, so that the smoothness is improved, and a picture layer is printed on this surface. When the protective layer is applied, it is possible to cover 80% or more of the surface area normally required for obtaining sufficient smoothness on the surface of the foamed resin layer. Therefore, surface roughening (skin roughness) is small, and a decrease in sharpness due to cracks in the picture layer is suppressed, and the design is improved. In addition, cracks in the surface protective layer are reduced, and surface characteristics such as stain resistance are improved.

Further, in the case of a conventional pyrolytic foaming agent such as diazocarbonamide, the foaming rate of the foamed resin layer is at most a maximum in order to maintain the smoothness of the surface and to secure a certain degree of print coating permeability. In contrast to the case where the thermal expansion microcapsule type foaming agent is used, a foaming rate of about 3 times or more can be obtained while maintaining sufficient surface smoothness. Due to this high foaming ratio, a sufficient film thickness can be secured, and when embossing after printing of the pattern layer and coating of the surface protective layer, deeper embossing than before can be performed, which is higher than before. A design property can be imparted.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for producing a decorative material according to the present invention will be described with reference to the drawings.

First Embodiment FIG. 1 is a sectional view of a decorative material manufactured by the method for manufacturing a decorative material according to the present embodiment. A foamed resin layer 11 is formed on a base material sheet (hereinafter also simply referred to as a base material) 10, and a surface protective layer 13 is formed on the surface of the foamed resin layer 11. The bubbles 12 in the foamed resin layer 11 are uniform and have a smaller particle size than the bubbles in the foamed resin layer of the conventional decorative material. Further, the surface of the foamed resin layer 11 has less unevenness due to the protrusion of bubbles on the surface of the foamed foamed resin layer than the foamed resin layer of the conventional decorative material, and has a higher smoothness. 13 covers 80% or more of the surface of the foamed resin layer 11.

A method for producing the above-described decorative material will be described. First, as shown in FIG. 2A, a foamable resin layer 11a which is a heat-foamable material before foaming of a foamed resin layer 11 is formed on a base material 10.

As the base material 10, for example, a rice basis weight of 7
A backing sheet such as a nonwoven fabric or a woven fabric made of paper, cotton, glass fiber, or the like of about 0 to 120 g / m ² is used.
Preferably, a flame retardant such as aluminum hydroxide is added for use.

As the foamable resin layer 11a, a foamable resin obtained by dispersing a heat-expandable microcapsule-type foaming agent in a thermoplastic resin binder is coated at a coating amount of 50 to 200 g /.
It is formed by coating with a roll coater, a gravure roll coater, or the like, with a thickness of about m ² (about 50 to 200 μm).

The above-mentioned thermoplastic resin binder is capable of dispersing and holding a heat-expandable microcapsule type foaming agent,
There is no particular limitation as long as the resin can be formed into a layer. For example, polyethylene, polyolefin-based homopolymer such as polypropylene, ethylene-vinyl acetate copolymer resin, polyolefin-based copolymer resin such as ethylene-vinyl alcohol copolymer resin, acrylic resin, polyester resin, polyvinyl chloride, Polyvinyl acetate, vinyl chloride
A vinyl resin such as a vinyl acetate copolymer, or another thermoplastic resin such as polystyrene or nylon can be used. Of the above, the use of an ethylene-vinyl acetate copolymer resin, an acrylic resin, or a mixture thereof is particularly preferred.

The ethylene-vinyl acetate copolymer resin is prepared by mixing ethylene and vinyl acetate at 150 to 250 ° C. for 100 hours.
A resin obtained by reacting at 0 to 2000 atm in the presence of an organic peroxide or oxygen. The content of vinyl acetate in the ethylene-vinyl acetate copolymer resin is preferably about 1 to 40% by weight, and the average degree of polymerization is preferably about 400 to 900.
If necessary, a copolymer of a monomer having a carboxyl group or a hydroxyl group such as maleic acid or vinyl alcohol can also be used.

The acrylic resin is mainly obtained by polymerizing acrylic acid (including methacrylic acid) and its derivatives such as acrylamide and acrylonitrile, and other acrylic resins such as other acrylates, ethylene and styrene. It is a copolymer resin with a monomer.

As such an acrylic resin, for example,
Poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer,
Ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate-hydrhydroxyethyl (meth) acrylate copolymer And those composed of a homo- or copolymer containing a (meth) acrylate. Here, (meth) acrylic acid is used in the meaning of acrylic acid and methacrylic acid.

The heat-expandable microcapsule type foaming agent dispersed in the thermoplastic resin binder is, for example, a spherical shell made of a thermoplastic resin such as polyacrylonitrile or polyvinylidene chloride having a particle size of 5 to 15 μm. A low-molecular-weight hydrocarbon gas such as isopentene, butane, and hexane is sealed as an encapsulating gas, and has a microcapsule structure having a solid content of, for example, 70% by weight.
For example, 1 to 10 parts by weight of the above microcapsule type foaming agent is dispersed in 100 parts by weight of a thermoplastic resin binder to form a foamable resin, and the obtained foamable resin is applied to form a foamable resin layer. By heating at 150 ° C. for 1 minute, the microcapsule-type foaming agent can be foamed by heating to form a foamed resin layer (foamed resin layer). The above-mentioned heat-expandable microcapsule-type foaming agent is a foaming agent in which isopentene is encapsulated in a spherical shell made of polyacrylonitrile and having a particle size of 5 to 15 μm. F-55 (manufactured by Matsumoto Yushi Co., Ltd., trade name) from which is obtained is preferably used.

Fine particles of an inorganic moisture-absorbing / desorbing material may be further added to the above-mentioned foamable resin, so that the resulting cosmetic agent can have a moisture-absorbing / releasing function. As the above-mentioned moisture-absorbing and releasing material, activated clay (montmorillonite), acid clay, sepiolite, diatomaceous earth, tobermorite, ettringite, and other clay minerals, and inorganic substance particles such as scallop shells can be used. Of these, moisture absorbing and releasing materials, and from the viewpoint of their reproducibility, activated clay or sepiolite is preferable, and also in consideration of resin moldability in the state of compounding with the resin, workability such as film formation, Activated clay is more preferred.

The above-mentioned activated clay (montmorillonite) is clay which has been subjected to an acid treatment to enhance its activity. Normally, natural acid clay or clay similar thereto is dried at room temperature to form a powder, which is heated at a temperature of 90 ° C. or more under normal pressure or pressure with an appropriate amount of dilute acid, and then filtered and filtered. Washed, 120
What was dried at -200 ° C is used. The average particle size of the activated clay used in the present embodiment is preferably about 0.1 to 100 μm. In addition, the average pore diameter is set at a humidity of 40 to 60.
%, It is preferable to use one having a temperature of about 20 to 30 °.

The above-mentioned sepiolite is a clay mineral having a double-chain structure type. The main component is a fibrous crystal composed of a hydrous magnesium silicate, having a specific surface area of about 878 m ² / g and an average pore diameter of 100 to 100 μm. It is preferably about 1000 °.
The average particle size of sepiolite used in the present embodiment is 0.1
It is preferably about 100 μm. The average pore diameter is
In order to keep the humidity at 40 to 60%, it is preferable to use a material having a temperature of about 100 °, and from the viewpoint of its moisture absorption / release properties, a short fiber material is preferred. In order to increase the strength of the sheet, it is preferable to perform a treatment in water for the purpose of loosening the fibers. Further, by supporting an appropriate amount of calcium chloride, the moisture absorption rate can be improved.

The average diameter of the diatomaceous earth used in the present embodiment is preferably about 0.1 to 100 μm. The average pore diameter is 2 to 6 μm in the sense of keeping the humidity at 40 to 60%,
It is preferable to use one having a specific surface area of 100 m ² / g or more. Specifically, it is more preferable to use the diatomaceous earth of the Wakkanai layer having a preferable average pore diameter from the deposited state.

The moisture-absorbing and desorbing material comprises a resin 10
It is preferably used in an amount of 5 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 0 parts by weight. 5
When the amount is less than the weight part, the moisture absorption / release performance is not sufficiently exhibited. On the other hand, if it is added in an amount of 200 parts by weight or more, the processing and molding suitability of the resin layer such as coating and film formation is not practically sufficient, which is not preferable.

The foamable resin layer may be colored with a coloring agent such as a dye or a pigment. The coloring may be either transparent coloring or opaque coloring. As a coloring agent,
Examples include inorganic pigments such as titanium white, carbon black, nickel titanium yellow, red iron oxide, ultramarine blue, etc., organic pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, and pearl pigments composed of titanium dioxide-coated mica foil powder. Can be

The foamable resin may further contain a flame retardant such as magnesium hydroxide, aluminum hydroxide and antimony oxide, a fungicide such as 10,10'-oxybisphenoxyarsine, and a silver ion, if necessary. Antibacterial agents such as supported zeolites, heat stabilizers, plasticizers, calcium carbonate,
Extenders such as calcium silicate and barium sulfate, bis-
(2,2,6,6-tetramethyl-4-piperidinyl)
Hindered amine radical scavengers such as sebacate,
Light stabilizers such as radical scavengers such as piperidine radical scavengers, antioxidants such as alkylphenols, amines and quinones, various ultraviolet absorbers such as benzophenones, salicylates, benzotriazoles, and acrylonitriles, and silicon A dispersant such as an antifoaming agent, a foaming agent or a polycarboxylic acid may be added.

After the foamable resin layer 11a is coated as described above, the microcapsules in the foamable resin layer 11a are subjected to a heat treatment at, for example, 130 ° C. for 1 minute and dried, and further to a heat treatment at 150 ° C. for 1 minute. The mold foaming agent is foamed to generate air bubbles 12 to form a foamed resin layer 11 as shown in FIG. Foam resin layer 11 formed as described above
The bubbles 12 in the inside are smaller and more uniform in size than the bubbles in the conventional foamed resin layer due to the adoption of the heat-expandable microcapsule-type foaming agent, and the crater-shaped bubbles do not penetrate. Therefore, even when foaming is performed at a high foaming ratio (three times or more), the unevenness of the surface 11b of the foamed foamed resin layer 11 due to the protrusion of the bubbles is smaller than before, and the smoothness is improved.

Next, the surface 11b of the foamed resin layer 11
A surface protective layer 13 is formed thereon to obtain a decorative material having a desired structure shown in FIG. The surface protective layer uses, for example, a resin such as an acrylic resin, a urethane resin, or polyvinyl chloride as a resin component. If necessary, a flame retardant such as magnesium hydroxide, aluminum hydroxide, or antimony oxide may be used in the resin. Fungicides such as, 10'-oxybisphenoxyarsine; antibacterial agents such as zeolite carrying silver ions; heat stabilizers; plasticizers; extender pigments such as calcium carbonate, calcium silicate and barium sulfate;
Light stabilizers such as hindered amine radical scavengers such as 6,6-tetramethyl-4-piperidinyl) sebacate, radical scavengers such as piperidine radical scavengers, and antioxidants such as alkylphenols, amines and quinones; Various ultraviolet absorbers such as benzophenone-based, salicylate-based, benzotriazole-based, and acrylonitrile-based, silicone-based or non-silicon-based antifoaming agents, foaming agents, and dispersants such as polycarboxylic acids are added. It is formed by coating with a roll coater, a gravure roll coater or the like at a coating amount of about 10 to 10 g / m ² .

According to the method for manufacturing a decorative material according to the present embodiment, the unevenness due to the protrusion of bubbles on the surface of the foamed foamed resin layer is reduced and the smoothness is increased. When the surface protective layer is applied, it becomes possible to cover 80% or more of the surface of the foamed resin layer. Therefore, cracks in the surface protective layer are reduced, surface characteristics such as stain resistance are improved, and surface roughening (skin roughness) is reduced.
A decorative material having good design properties can be obtained.

Second Embodiment FIG. 3 is a sectional view of a decorative material manufactured by the method of manufacturing a decorative material according to the present embodiment. It has substantially the same configuration as the decorative material according to the first embodiment shown in FIG.
On one surface, a pattern layer 14 of an ink pattern is printed, and a surface protective layer 13 is formed thereon by coating. Similar to the first embodiment, the bubbles 12 of the foamed resin layer 11 are uniform bubbles having a smaller particle size than the bubbles in the foamed resin layer of the conventional decorative material. Further, the surface of the foamed resin layer 11 has less unevenness due to the protrusion of bubbles on the surface of the foamed foamed resin layer than the foamed resin layer of the conventional decorative material, and has a higher smoothness. 13 covers 80% or more of the surface of the foamed resin layer 11.

A method for producing the above-described decorative material will be described. First, as shown in FIG. 4A, a foamable resin layer 11a which is a heat-foamable material before foaming of a foamed resin layer 11 is formed on a base material 10 using the same material as in the first embodiment. After that, the microcapsule-type foaming agent in the foamable resin layer 11a is foamed by a heat treatment at 130 ° C. for 1 minute and dried by a heat treatment at 150 ° C. for 1 minute to generate bubbles 12, Layer 11. The bubbles 12 in the foamed resin layer 11 formed as described above have a smaller particle size and are more uniform than the bubbles of the conventional foamed resin layer due to the use of the thermally expandable microcapsule-type foaming agent.
Surface 11b of foamed resin layer 11 that has been foamed due to protrusion of air bubbles
Are smaller than before and the smoothness is higher.

Next, as shown in FIG. 4B, an ink pattern 14 is formed on the surface of the foamed resin layer 11 by printing. The printing of the picture layer is performed using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, etc., using ink (or paint).
Can form a picture pattern. Examples of the picture pattern include a cleavage face pattern of a granite, a grain pattern, a stone pattern, a grain pattern, a leather pattern, a geometric pattern, a character symbol, and a solid surface.

As the ink or paint, it is possible to use a colorant such as a binder, a pigment or a dye, and, if necessary, a mixture obtained by appropriately mixing an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like. it can. As the binder, for example, vinyl chloride-vinyl acetate copolymer, acrylic resin, urethane resin, chlorinated polypropylene, or a mixture thereof can be used. As an example of mixing these binders, in the case of a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer, an acrylic resin / vinyl chloride-vinyl acetate copolymer = 1/9
To 9/1 is preferred.

Next, a surface protective layer 13 similar to that of the first embodiment is applied on the foamed resin layer 11 and the picture layer 14 to form a decorative material having a desired structure as shown in FIG.

According to the method of manufacturing a decorative material according to the present embodiment, the unevenness due to the protrusion of bubbles on the surface of the foamed foamed resin layer is reduced and the smoothness is improved. When the surface protective layer is applied, it becomes possible to cover 80% or more of the surface of the foamed resin layer. Therefore, surface roughening (skin roughening) is small, and a decrease in sharpness due to cracks in the picture layer or poor transfer inlay is suppressed, and the design is improved. In addition, cracks in the surface protective layer are reduced, and surface characteristics such as stain resistance are improved.

Third Embodiment FIG. 5 is a sectional view of a decorative material manufactured by the method for manufacturing a decorative material according to the present embodiment. It has substantially the same configuration as the decorative material according to the first embodiment shown in FIG.
1 and the surface protection layer 13 are different from each other in that a concavo-convex pattern forming E is formed by embossing, hairline processing, or the like.

To manufacture the decorative material according to this embodiment,
After the same decorative material as in the first embodiment is manufactured, a concave and convex pattern shaping forming process is performed by embossing from the surface side of the surface protective layer 13. The concavo-convex pattern may cover the entire surface of the sheet or may be partial. The embossing is performed to impart a desired texture such as a wood surface or a stone surface to the interior decorative material surface, and to further enhance the design effect. The embossing is performed, for example, by heating and softening the resin of the moisture-permeable sheet by heat conduction due to contact with a heating drum, and further using an infrared radiation heater at 160 to 180 ° C.
It is heated to a certain degree, pressurized and shaped with a metal or ceramic embossed plate provided with a desired pattern of irregularities on the surface, formed by cooling and fixing, and is a known sheet-fed or rotary embossing machine. Is used. Examples of the uneven pattern include a wood grain conduit groove, a cleavage surface unevenness of granite, a grain of sand, a satin finish, a skin squeezing, a hairline, and the like.

If necessary, the concave portions of the concave and convex pattern may be filled with a coloring ink by wiping or the like to further enhance the design of the interior decorative material. The wiping process is a method known from Japanese Patent Publication No. 58-14312 or the like, and is a process of filling ink while scratching the surface of a concave portion provided by embossing with a doctor blade.

The decorative material produced as described above has reduced surface cracking of the surface protective layer, improved surface properties such as stain resistance, less surface roughening (skin roughness), and improved design. Is improved. The foaming rate of the foamed resin layer in the case of the conventional pyrolytic foaming agent such as diazocarbonamide was about twice or more, whereas the foaming rate of the foaming resin layer was 3 times in the case of using the heat-expandable microcapsule foaming agent. A foaming ratio of about twice as high can be obtained. Due to this high foaming ratio, a sufficient film thickness can be secured, and when embossing after printing of the pattern layer and coating of the surface protective layer, deeper embossing than before can be performed, which is higher than before. A design property can be imparted.

Fourth Embodiment FIG. 6 is a sectional view of a decorative material manufactured by the method for manufacturing a decorative material according to the present embodiment. It has a configuration substantially the same as that of the decorative material according to the second embodiment shown in FIG. 3, and as in the third embodiment, the foamed resin layer 11, the picture layer 14, and the surface protection layer 1
The surface of No. 3 is formed with an embossed pattern E or a hairline processing or the like to form an uneven pattern E.

To manufacture the decorative material according to the present embodiment,
After manufacturing the same decorative material as in the second embodiment, as in the third embodiment, an embossing process is performed from the surface side of the surface protective layer 13 by embossing. In the decorative material manufactured as described above, cracks in the surface protective layer are reduced, surface characteristics such as stain resistance are improved, surface roughening (skin roughness) is reduced, and design is improved. . In particular, due to the high foaming ratio of the foamed resin layer, a sufficient film thickness can be ensured, deeper embossing can be performed than in the past, and higher designability can be imparted than before.

Example 1 A foamable resin having the following composition A was prepared.

<Composition A> Resin: Ethylene-vinyl acetate copolymer resin (“BE-920” manufactured by Chuo Rika Chemical Industry Co., Ltd.): 23 parts by weight Blowing agent: Thermal expansion type microcapsule type blowing agent (Matsumoto Yushi Co., Ltd. ) “F-55”): 3.5 parts by weight Hygroscopic material: activated clay (average pore diameter 25 mm, average particle diameter 20 μm) (“Galleon Earth V2R” manufactured by Mizusawa Chemical Co., Ltd.): 23 parts by weight Agent: polycarboxylic acid: 1 part by weight Antifoaming agent: polyethylene glycol: 1 part by weight

Next, the foamable resin of the above composition A was applied on a backing paper having a basis weight of 120 g / m ² with a comma coater to a thickness of 170 μm (when dry), and then heat-treated at 130 ° C. for 1 minute. Then, the foamed resin layer was subjected to a heat treatment at 150 ° C. for 1 minute to foam the foamable resin layer so that the foaming ratio (thickness after foaming / thickness before foaming) was tripled. Next, using a gravure roll coater, a water-dispersed emulsion of a urethane-based resin was applied on the foamed resin layer at 5 g / m ² (when dried), and dried at 130 ° C. for 30 seconds. As mentioned above,
A decorative material having the same configuration as the decorative material of the first embodiment shown in FIG. 1 was produced.

(Example 2) As in Example 1, rice basis weight 1
^On a backing paper of 20 g / m ² , the foamable resin of the above composition A is applied with a comma coater to a film thickness of 170 μm (when dry), heat-treated at 130 ° C. for 1 minute, dried, and further dried at 150 ° C. For 1 minute to foam the foamable resin layer so that the foaming ratio becomes 3 times. Next, the cleavage surface pattern of the granite is formed on the foamed resin layer using an ink obtained by adding a pigment to a binder resin composed of a 1: 1 mass ratio mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. Was printed by a gravure printing method, and a water-dispersed emulsion of a urethane resin was applied at 5 g / m ² (at the time of drying) by a gravure roll coater, and dried at 130 ° C. for 30 seconds. As described above, a decorative material having the same configuration as the decorative material of the second embodiment shown in FIG. 3 was produced.

(Example 3) The decorative material of Example 1 was prepared,
In a state where the foamed resin layer is heated to 130 ° C., using a heating press machine, the surface of the iron plate is etched by photoetching to form a cleavage-like irregular pattern of granite, and the surface is made of metal obtained by chrome plating. The embossing die is pressed on the heated foamed resin layer at 45 gf / cm ² for 30 seconds, and after cooling, the embossing die is released and embossed.
A decorative material having the same configuration as the decorative material of the third embodiment shown in FIG. 5 was produced.

(Example 4) The decorative material of Example 2 was prepared.
Embossing treatment was performed with a heating press machine under the same conditions as in Example 3 to produce a decorative material having the same configuration as the decorative material of the fourth embodiment shown in FIG.

(Comparative Example 1) FIG. 7 is a sectional view of a decorative material according to this comparative example. A foamed resin layer 11 is formed on a base sheet 10, and a picture layer 14 and a surface protection layer 13 are formed on the surface of the foamed resin layer 11.

The above decorative material was formed as follows. First, as shown in FIG. 8 (a), on a backing paper having a rice basis weight of 120 g / m ² , which is a base sheet 10, a comma coater is used.
The foamable resin of the composition A is coated with a film thickness of 170 μm (when dried), dried by heat treatment at 130 ° C. for 1 minute,
The foamable resin layer 11a was formed. Next, as shown in FIG. 8B, a pigment is added to a binder resin composed of a 1: 1 mass ratio mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin on an unfoamed foamable resin layer. The pattern layer 14 of the cleavage face pattern of the granite is printed by gravure printing using the resulting ink, and a water-dispersed emulsion of a urethane resin is applied at 5 g / m ² (when dry) using a gravure roll coater. This was dried at 130 ° C. for 30 seconds to form the surface protective layer 13. After that, the entire sheet is
By heating at 0 ° C. for 1 minute, the foamable resin layer 11a was foamed at a foaming ratio of 3 times to form the foamed resin layer 11, and the decorative material shown in FIG. 7 was obtained.

Comparative Example 2 A foamable resin having the following composition B was prepared.

<Composition B> Resin: polyvinyl chloride resin (average degree of polymerization: 1200): 100 parts by weight Plasticizer: dioctyl phthalate: 70 parts by weight Blowing agent: azodicarbonamide: 3 parts by weight Heat stabilizer: calcium-zinc Heat stabilizer: 1 part by weight Heat stabilizer: Epoxidized soybean oil: 3 parts by weight Hygroscopic material: Activated clay (average pore diameter 25 mm, average particle diameter 20 μm) (“Galeon Earth V2R” manufactured by Mizusawa Chemical Co., Ltd.) ): 100 parts by weight Diluent solvent: Petroleum-based solvent: Appropriately added and diluted until the viscosity of the coating liquid becomes 3000 cps

Next, a foaming resin of the above composition B is applied to a backing paper having a basis weight of 120 g / m ² with a comma coater to a thickness of 170 μm (when dry), and then heat-treated at 190 ° C. for 1 minute. And dried and gelled (solidified) to form a foamable resin layer (unfoamed state). Next, heat treatment was further performed at 210 ° C. for 1 minute to foam the foamable resin layer. Next, the pattern of the cleavage surface pattern of the granite is printed by gravure printing using an ink obtained by adding a pigment to a binder resin composed of a 1: 1 mass ratio mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. The layer was printed, and a water-dispersed emulsion of a urethane resin was applied at 5 g / m ² (at the time of drying) using a gravure roll coater, and dried at 130 ° C. for 30 seconds. As described above, a decorative material having the same configuration as the conventional decorative material shown in FIG. 11 was produced.

(Comparison of Appearance of Picture Print Layer and Surface Protective Layer) The samples of Example 2 and Comparative Examples 1 and 2 were compared by observing the sharpness of the picture print layer and the smoothness of the surface protective layer. . In each of Comparative Examples 1 and 2, the pattern printing layer was whitened and the sharpness was low, and the surface of the surface protective layer was rough. However, the pattern printing layer of Example 2 was dark and clear, and the surface protection The layer was smooth.

(Stain Resistance Test) For each of the samples of Examples 1 to 4 and Comparative Examples 1 and 2,
Each sample surface was contaminated with soy sauce, crayon, lipstick, water-based ink, and coffee, and left for 24 hours. After this, the soy sauce and coffee are wiped off with gauze soaked in water,
In the case of other contaminants, they were wiped off with a gauze soaked with a neutral detergent stock solution, and the degree of remaining contaminant coloring was visually observed. The results are shown in Table 1 below.

[0063]

[Table 1]

In Table 1, ◎ indicates that “contaminants fall off to such an extent that they cannot be visually discriminated”, and ○ indicates that the contaminants can be discriminated by visual observation, but the coloring falls to a very slight degree.
Indicates that "the contaminant is visually reduced, but drops to the extent that it remains at a high concentration", and x indicates that "the contaminant does not fall off at all" (however, these are relative evaluations). From Table 1, it was confirmed that all of Examples 1 to 4 had better stain resistance than Comparative Examples 1 and 2.

The present invention is not limited to the above embodiment. For example, the foamable resin layer is formed by coating. However, it is also possible to process the foamable resin in a sheet shape in advance, and then bond the foamed resin to a base sheet to laminate the foamed resin. In this case, if necessary, an easy adhesion treatment such as a primer treatment or a corona discharge treatment is performed, and the adhesion can be performed using a normal adhesive or a pressure-sensitive adhesive. In addition, various changes can be made without departing from the spirit of the present invention.

[0066]

According to the method for producing a cosmetic material of the present invention, a thermally expandable microcapsule type foaming agent is used in place of the conventionally used pyrolytic foaming agent such as diazocarbonamide. The microcapsule type foaming agent has a small particle size and can generate uniform air bubbles, so that the protrusion of air bubbles on the surface of the foamed foamed resin layer or the unevenness due to the eruption of the crater is reduced, resulting in smoothness. And when a pattern layer is printed on the surface of the foamed foamed resin layer or when a surface protective layer is applied, 80% or more of the surface of the foamed resin layer can be covered. Therefore, surface roughening (skin roughening) is small, cracking of the picture layer, or deterioration of sharpness due to inking or poor transfer is suppressed, and the design is improved. In addition, cracks, deposits, and poor transfer of the surface protective layer are reduced, and surface characteristics such as stain resistance are improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a decorative material according to a first embodiment.

FIGS. 2A and 2B are cross-sectional views illustrating a manufacturing process of a method for manufacturing a decorative material according to the first embodiment, in which FIG. 2A illustrates up to a step of forming a foamable resin layer, and FIG. The process up to the foaming step is shown.

FIG. 3 is a cross-sectional view of a decorative material according to a second embodiment.

FIGS. 4A and 4B are cross-sectional views illustrating a manufacturing process of a method for manufacturing a decorative material according to a second embodiment, in which FIG. 4A is up to a foam resin layer forming process, and FIG. Is shown.

FIG. 5 is a sectional view of a decorative material according to a third embodiment.

FIG. 6 is a sectional view of a decorative material according to a fourth embodiment.

FIG. 7 is a sectional view of a decorative material according to Comparative Example 1.

FIGS. 8A and 8B are cross-sectional views illustrating a manufacturing process of a method for manufacturing a decorative material according to Comparative Example 1, in which FIG. 8A is a process up to a foaming resin layer forming process, and FIG. Up to

FIG. 9 is a cross-sectional view of a decorative material according to a first conventional example.

FIGS. 10A and 10B are cross-sectional views showing manufacturing steps of a method for manufacturing a decorative material according to a first conventional example, in which FIG. 10A shows up to a step of forming a foamable resin layer, and FIG. The steps up to the process are shown.

FIG. 11 is a sectional view of a decorative material according to a second conventional example.

FIG. 12 is a cross-sectional view showing a manufacturing process of a method of manufacturing a decorative material according to a second conventional example, in which (a) shows a process up to a foaming resin layer forming process, and (b) shows a process of forming the foaming resin layer. The process up to the foaming step is shown.

[Description of Signs] 10: sheet base material, 11: foamed resin layer, 11a: foamable resin layer, 11b: surface, 12: bubbles, 13: surface protective layer, 14: picture layer, C: crack, E: unevenness Pattern shaping.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 101: 12 B29L 9:00 B29L 9:00 B29C 67/22 F-term (Reference) 4D075 AC45 AE03 BB30Y CA02 CA34 CB04 CB34 DA04 DA06 DB12 DB13 DB18 DB20 DC01 DC18 DC31 DC38 EA29 EB13 EB14 EB15 EB19 EB22 EB35 EB38 EB39 EC24 EC41 4F212 AD05 AD06 AD16 AG03 AG20 AH48 UA01 UB02 UB13 UB30 UE06 UG02 UH21 UN0621

Claims (2)

[Claims] A step of forming a foamable resin layer on a base sheet by dispersing a heat-expandable microcapsule-type foaming agent in a thermoplastic resin binder; and heating the foamable resin layer by heating the foamable resin layer. A method for producing a decorative material, comprising: a step of expanding and expanding a foaming agent to form a foamed resin layer; and a step of forming at least a surface protective layer on the foamed resin layer. 2. The cosmetic according to claim 1, further comprising a step of printing a pattern layer on the foamed resin layer after the step of forming the foamed resin layer and before the step of forming the surface protective layer. The method of manufacturing the material.