JPH06286044A - Glossy laminate and decorative yarn - Google Patents

Abstract

PURPOSE:To provide a laminate or decorative yarn having a tactual soft feeling and showing soft brightness rich in coloration. CONSTITUTION:In a laminate or decorative yarn wherein a membrane layer of a metal or metal compd. and a transparent resin layer is provided on the single surface or both surfaces of a base material, fine spherical. org. polymer particles with an average particle size of 2-200mum are dispersed in and mixed with the transparent resin layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to interior / exterior materials for automobiles, ships, aircrafts, cosmetic containers, caps, general-purpose packages, in-mold molded products, light electric appliances, interior / exterior building materials, high-grade sliding doors, railing, kimonos, obi. Laminates with novel glitter used for decoration of clothing, woodwork, furniture, plastic products, crafts, folk crafts, books, albums, and novel glitter used for textiles, knits, braids, etc. To a decorative thread having

[0002]

2. Description of the Related Art Conventionally, matte decorative sheets and matte decorative yarns are known, but they are generally constructed as follows. That is, a paint in which a delusterant is mixed is applied on a plastic film, or a metal thin film layer is provided on the plastic film, and a delusterant is mixed on the metal thin film layer for the purpose of protection and delustering. There is known a laminated body coated with, and a decorative thread obtained by cutting the laminated body into a narrow width. Examples of the matting agent include powders of inorganic materials such as silica, talc, calcium carbonate, precipitated barium sulfate, alumina, acid clay, clay, magnesium carbonate, carbon black, tin oxide, and titanium white, either alone or in combination. It is used.

Such a conventional matte laminate was reasonably satisfactory in terms of providing a matting effect from a visual point of view.

However, the conventional matte laminate lacks the tactile softness and the brilliant sensation with a soft and rich coloring. That is, the inorganic powders as described above which have been used as a matting agent are themselves hard, and therefore, in the case of a transparent resin layer obtained by dispersing and mixing these inorganic matting agents, the inorganic powder itself The hardness directly affects the surface hardness, flexibility, and elasticity of the resin layer, and there is no matting effect from the visual side, but tactile softness, so-called soft touch feeling is lacking. there were.
Also, these inorganic powders are opaque powders,
It had no luster itself, merely limiting the transmission of light rays, and its gloss was monotonous, and thus the resulting matte gloss was monotonous.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems that a conventional matting laminate having an inorganic matting agent dispersed therein has.

That is, an object of the present invention is to provide a layered product and a decorative yarn which have a tactilely soft feeling and which are rich in coloring and have a fantastic and soft luster.

[0007]

The present invention provides (1) a laminate in which a thin film layer of a metal or a metal compound and a transparent resin layer are provided in this order on one surface of a substrate, and the transparent resin layer has an average thickness. A laminate having a glittering property, in which spherical organic polymer fine particles having a particle size of 2 to 200 μm are dispersed and mixed, (2) a thin film layer of a metal or a metal compound on one surface of a base material, and a transparent resin layer In this order, and a transparent resin layer is provided on the other surface of the laminate, wherein spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm are dispersed and mixed in the transparent resin layer. Which has a glittering property on both sides, (3) a layered body in which a thin film layer of a metal or a metal compound and a transparent resin layer are provided in this order on both sides of the substrate, and the average particle size in the transparent resin layer is 2 to 200 μm spherical organic polymer particles dispersed A laminate having glittering properties on both sides, wherein (4) the laminate described in (1) above is laminated via an adhesive layer so that the substrate is on the inside. And a decorative yarn having a glittering property, characterized by cutting the laminate according to (1) to (4) into a width of 0.15 to 2 mm. Is provided.

[0008]

FUNCTION AND EXAMPLES The glittering laminate of the present invention comprises a glittering thin film layer made of a metal or a metal compound,
It is characterized by using a combination with a transparent resin layer provided thereon in which spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm are dispersed and mixed.

The spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm have flexibility and elasticity as compared with conventional inorganic matting agents, and are excellent in dispersibility in a matrix. It does not deteriorate the physical properties such as flexibility and elasticity and gives a tactile soft feeling.
Further, since the spherical organic polymer fine particles are excellent in transparency and retroreflective property, they soften the glittering property of the glittering thin film layer, but give a colorful and fantastic glittering property.

The substrate used in the glittering laminate and the decorative yarn of the present invention is not particularly limited, and it is a film which can be vapor-deposited and has been conventionally used for applications such as packaging and decorative yarn. Any of them can be used. For example, polyester, polyamide, polyamide-imide,
A resin film such as polyethylene, polypropylene, cellulose acetate, polycarbonate, polyvinyl chloride, or fluororesin is appropriately used. The thickness of the substrate is usually in the range of 4 to 500 μm, more preferably 6 to 500 μm.
Is appropriately selected from the range. Since the mechanical properties of the base material influence the mechanical properties of the laminate that can be obtained almost as they are, the base material is appropriately selected and used according to the application in consideration of this.

The metal or metal compound thin film layer used in the present invention imparts glitter to the glittering laminate and the decorative yarn of the present invention, and is provided on one side or both sides of the substrate. For the thin film layer, metals such as gold, silver, aluminum, chromium, nickel, copper, titanium, palladium, indium, lead, platinum, zinc and tin are usually used. Among these, gold, silver, platinum, palladium and the like are used for high-grade products, and aluminum is used when cost is important. Further, for the thin film layer, for example, nickel chrome alloy, silver-copper alloy, brass, alloys such as zinc sulfide, and metal compounds are appropriately used. Further, the thin film layer may be formed of one kind of material, but may be formed of two or more kinds, and further may be formed of two or more layers.

The thickness of the thin film layer is usually 20 to 100 nm.
The range is appropriately selected from the range of about 35 to 60 nm. When the thickness of the thin film layer is less than 20 nm, the glittering property is poor, which is not preferable. On the other hand, even if it exceeds 100 nm, the gloss does not increase any more, and the cost becomes high, which is not preferable.

The method for forming the thin film layer of the metal or metal compound is not particularly limited, but, for example, a resistance heating method using the metal, alloy or compound as the evaporation raw material,
It can be formed by a conventional vacuum vapor deposition method such as a high frequency induction heating method or an electron beam heating method, or a thin film forming method such as an ion plating method, a sputtering method or an ion beam method.

The transparent resin layer used in the present invention protects a thin film layer of a metal or a metal compound, and has spherical organic polymer fine particles dispersed and mixed therein to provide a tactilely soft feeling and a fantastic and soft glittering property. It is to be applied to the obtained laminated body and decorative yarn. The vehicle that forms the transparent resin layer is not particularly limited, and any vehicle that is used in ordinary paints can be used. For example, polyurethane resin, acrylic resin, polyester resin, urethane-acrylic resin, epoxy-acrylate resin, polyester-acrylate resin, polyethylene resin, melamine resin, urea resin, urea melamine resin, benzoguanamine resin. Resins, phenolic resins, alkyd resins, ester rubbers, fibrous resins, linseed oil, tung oil, degreased castor oil, synthetic resins such as shellac and rosin, artificial resins, natural resins, etc. either alone or as the main component A mixture is used. The resin layer may be transparently colored with an appropriate pigment or dye.

The spherical organic polymer fine particles used by being dispersed and mixed in the vehicle in the present invention include (meth)
Examples thereof include spherical fine particles such as acrylic polymers, styrene polymers, urethane polymers, acrylonitrile polymers, polyester polymers, and epoxy polymers. Among them, alkyl (meth) acrylate polymers, etc. A urethane polymer such as a (meth) acrylic polymer, a polyether urethane polymer, a polyester urethane polymer, or a polyester ether urethane polymer is preferable because fine particles having a wide range of elasticity can be obtained. Here, the spherical shape includes not only a true spherical shape but also a spherical shape slightly deviated from the true spherical shape.

As the spherical organic polymer fine particles, those having an average particle diameter of 2 to 200 μm are used. When the average particle diameter is less than 2 μm, the resin layer surface has very small irregularities and a tactile soft feeling cannot be obtained, while the average particle diameter is 2
If the particles are larger than 00 μm, the graininess becomes too strong, which is not preferable. As long as the average particle size is in the range of 2 to 200 μm, it may be monodisperse or polydisperse.

The spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm have transparency, flexibility and retroreflective property. Therefore, by using them, a tactile and soft feeling can be obtained. Moreover, a laminated body and a decorative yarn having a fantastic and soft luster can be obtained.

Further, as the spherical organic polymer fine particles,
If desired, uncolored fine particles, fine particles transparently colored with a pigment or dye, or a mixture of both can be used. Further, if necessary, a material containing an ultraviolet absorber, a drier, etc. may be used.

The spherical organic polymer fine particles have a true specific gravity of 1 to
From the viewpoint of dispersibility, about 3.4 is preferable.

The transparent resin layer in which the spherical organic polymer fine particles are dispersed and mixed is formed by, for example, a gravure method, a reverse method, a spray method or the like. The thickness of the transparent resin layer is not particularly limited, and is usually appropriately selected from the range of about 2 to 500 μm.

The laminate according to the first embodiment of the present invention is one in which a thin film layer of a metal or a metal compound and a transparent resin layer in which spherical organic polymer fine particles are dispersed and mixed are provided in this order on one surface of a substrate. Is. In the first embodiment, when a transparent base material is used, a laminate having a fantastic and soft glitter on one surface and a strong glitter on the other surface can be obtained.

The laminate according to the second embodiment of the present invention has a thin film layer of a metal or a metal compound and a transparent resin layer in which spherical organic polymer fine particles are dispersed and mixed in this order on one surface of a substrate, A transparent resin layer in which spherical organic polymer fine particles are dispersed and mixed is provided on the surface. In the second embodiment, when a transparent base material is used, a laminate having a fantastic and soft glitter on both sides can be obtained.

The laminate according to the third embodiment of the present invention comprises a substrate and a vapor-deposited layer of a metal or a metal compound, and a transparent resin layer in which spherical organic polymer particles are dispersed and mixed, which are provided in this order on both sides of the substrate. Is. In the third embodiment, regardless of whether the substrate is transparent or opaque, a laminate having a fantastic and soft glitter on both sides can be obtained.

The laminate of the fourth embodiment of the present invention is obtained by laminating two laminates of the first embodiment with an adhesive layer so that the base material is on the inside. Also in the fourth embodiment, a laminate having a fantastic and soft glittering property on both sides can be obtained regardless of whether the substrate is transparent or opaque.

The adhesive used for the adhesive layer is not particularly limited and may be appropriately selected and used from the adhesives conventionally used for packaging, decorative threads and the like. For example, an acrylic resin-based, vinyl acetate resin-based, vinyl chloride resin-based, polyethylene-based, styrene-butadiene resin-based emulsion adhesive alone or a mixture containing these as a main component, an ethylene-vinyl acetate resin-based adhesive, Organic solvent type adhesive such as chlorinated polypropylene type, vinyl chloride-vinyl acetate type, phenol resin type, xylene resin type, urea resin type, alkyd resin type, epoxy resin type, urethane resin type, silicone resin type or the like It is appropriately selected and used from adhesives containing these mixtures as main components.

The thickness of the adhesive layer is not particularly limited, but it is usually appropriately selected from the range of about 1 to 5 μm.

The decorative yarn of the present invention can be obtained by cutting the laminate of each of the above embodiments into a width of 0.15 to 2 mm.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A uniform aluminum thin film layer having a thickness of 50 nm was formed on one side of a transparent polyethylene terephthalate film having a thickness of 25 μm by a resistance heating method using aluminum as an evaporation source. 50 parts by weight of acrylic resin (parts by weight,
The same applies hereinafter), 25 parts of isocyanate, 5 parts of methyl isobutyl ketone, 5 parts of ethyl cellosolve, 5 parts of cyclohexanone, and 10 parts of methyl ethyl ketone have an average particle size of 2
A coating solution obtained by mixing and dispersing 10 parts of true spherical particles of crosslinked polymethylmethacrylate (Techpolymer MBX-20, manufactured by Sekisui Chemical Co., Ltd.) having a true specific gravity of 1.19 and a specific gravity of 0. A transparent resin layer having a thickness of 30 μm was formed to obtain a glittering laminate.

Example 2 A transparent resin layer was further formed on the polyethylene terephthalate film surface of the laminate obtained in Example 1 in the same manner as in Example 1 to obtain a glittering laminate.

Example 3 A uniform aluminum thin film layer having a thickness of 50 nm and a transparent resin layer having a thickness of 30 μm were formed on both surfaces of a transparent polyethylene terephthalate film having a thickness of 50 μm in the same manner as in Example 1. A glittering laminate was obtained.

Example 4 Two pieces of the glittering laminate obtained in Example 1 were used to prepare a urethane resin adhesive layer having a thickness of 0.5 μm (thickness after drying) (50 parts of urethane resin, isocyanate). 5 parts, toluene 15 parts, methyl ethyl ketone 15 parts, butyl acetate 15
The transparent resin layer side was laminated so that the transparent resin layer side was the outer side, and a laminate having a glittering property was obtained.

Example 5 The laminates having glittering properties obtained in Examples 1 to 4 were manufactured with a width of 0.
It was cut into 5 mm to obtain a decorative yarn having glitter.

Comparative Example 1 A coating solution prepared by mixing and dispersing 10 parts of spherical particles of crosslinked polymethylmethacrylate in the coating solution used in Example 1 and 10 parts of silica (SiO ₂ ) powder (average particle size 9 μm). A matte laminate was obtained in the same manner as in Example 1 except that was used.

Comparative Example 2 A transparent resin layer was formed on the polyethylene terephthalate film surface of the matte laminate obtained in Comparative Example 1 in the same manner as in Comparative Example 1 to obtain a matte laminate.

Comparative Example 3 A uniform aluminum thin film layer having a thickness of 50 nm and a transparent resin layer having a thickness of 30 μm were formed on both surfaces of a transparent polyethylene terephthalate film having a thickness of 50 μm in the same manner as in Comparative Example 1. A matte laminate was obtained.

COMPARATIVE EXAMPLE 4 Two matte laminates obtained in Comparative Example 1 were prepared to have a thickness of 0.5.
μm (thickness after drying) urethane resin adhesive layer (50 parts urethane resin, 5 parts isocyanate, 15 toluene)
Part, 15 parts by weight of methyl ethyl ketone, and 15 parts by weight of butyl acetate were applied and dried) so that the transparent resin layer side faced the outside to obtain a matte laminate.

Comparative Example 5 The matte laminates obtained in Comparative Examples 1 to 4 were cut into a width of 0.5 mm to obtain matte decorative threads.

Comparative Test When the laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were attached to a wall material and compared with each other (the laminates of Examples 1 and 2 and Comparative Examples 1 and 2 are metallic. The thin film layer side was attached to the outside), and those of Examples 1 to 4 diffused and reflected the light of the room light and had no glare, and had a bright, fantastic and soft pearl-like brilliance. It was In addition, it had a soft touch feeling. On the other hand, in Comparative Examples 1 to 4, white turbidity and almost no glitter were observed, and neither the appearance nor the tactile feeling was soft.

The decorative yarn having each glittering property obtained in Example 5 and each matte decorative yarn obtained in Comparative Example 5 were used as warp yarns, and 100 denier Tetoron yarn was used as the weft yarns for plain weaving. For cloth. All of the samples of Example 5 diffused and reflected the light source of the room light and had no glare, and had a bright, fantastic and soft pearl-like brilliance. In addition, it had a soft touch feeling. On the other hand, in Comparative Example 5, white turbidity and almost no glitter were observed, and neither the appearance nor the tactile feeling was soft.

20 denier nylon yarns were entwined in the SZ direction from the left and right with the decorative yarn having each glittering property obtained in Example 5 and each matte decorative yarn obtained in Comparative Example 5 to obtain a twisted twisted yarn. The scarf was knitted up using the knitting yarn.
The scarves obtained from those of Example 5 all diffused and reflected the sun's rays and had no glare, and had a bright, fantastic and soft pearl-like brilliance. In addition, it had a soft touch feeling. On the other hand, the product obtained from Comparative Example 5 was clouded and almost no glitter was observed, and neither the appearance nor the tactile feeling was soft.

[0042]

According to the present invention, the transparent resin layer, which is the outermost layer of the laminate or the decorative yarn, has elasticity as compared with the conventional inorganic powder and is excellent in dispersibility in the matrix.
By dispersing and mixing the spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm, the physical properties are not deteriorated.
In addition to providing a tactile and soft sensation that is not possible with conventional inorganic powders, it also provides a fantastically soft pearl-like brilliant laminate and decorative threads that can be used in automobiles. Interior and exterior materials for ships, aircraft, cosmetics containers, caps, general-purpose packages, in-mold molded products,
Excellent decoration effect is exhibited by using it for light electrical appliances, interior / exterior building materials, high-grade sliding doors, railing, kimono, obi, clothes, woodwork, furniture, plastic products, crafts, folk crafts, books, albums, etc. Practical value is high.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masanari Seguchi 125, Takeda Mukoyo-cho, Fushimi-ku, Kyoto, Kyoto Prefecture Oike Development Laboratory Co., Ltd.

Claims (5)

[Claims] 1. A laminate in which a thin film layer of a metal or a metal compound and a transparent resin layer are provided in this order on one surface of a substrate,
A laminate having a glittering property, wherein spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm are dispersed and mixed in the transparent resin layer. 2. A laminate in which a thin film layer of a metal or a metal compound and a transparent resin layer are provided in this order on one surface of a base material, and a transparent resin layer is provided on the other surface, in the transparent resin layer an average. A layered product having glitter on both sides, wherein spherical organic polymer fine particles having a particle size of 2 to 200 μm are dispersed and mixed. 3. A laminate in which a thin film layer of a metal or a metal compound and a transparent resin layer are provided in this order on both surfaces of a base material,
A laminated body having glitter on both sides, wherein spherical organic polymer fine particles having an average particle diameter of 2 to 200 μm are dispersed and mixed in the transparent resin layer. 4. A laminate having glitter on both sides, wherein the laminate according to claim 1 is laminated with an adhesive layer so that the base material is on the inside. 5. A decorative yarn having glitter, which is obtained by cutting the laminate according to claim 1, 2, 3 or 4 into a width of 0.15 to 2 mm.