JPH11165352A - Manufacture of decorative sheet lapping base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a whitening phenomenon or cracks from occurring by applying an ozone injection treatment to a molten resin extruded from a mold and laminating a decorative sheet with an applied adhesive with the help of cylindrical rolls in accordance with the contour of the outer surface of the sheet. SOLUTION: A molten three-dimensional base material 10 is extruded from a mold 2 on an extrusion molder 1 and an ozone injection treatment is applied to the surface of the base material 10 using an ozone treatment device 3. On the other hand, a decorative sheet 8 is drawn from a decorative sheet take-up roll 13 and an adhesive 5 is applied to the surface of the decorative sheet 8 to be dried with the use of a drier 7. Next, a pressing roll R1 presses the top surface of the three-dimensional base material 10 along its contour to laminate the decorative sheet 8 to the base material 10. Further, the corner parts of the top face of the laminate are pressed by pressing rolls R2 , R2 and the perpendicular lateral faces following the top lateral face by pressing rolls R3 , R3 and the horizontal face following the perpendicular lateral faces by pressing rolls R4 , R4 respectively. Through this ozone injection treatment, the surface of the three-dimensional base material 10 is easily laminatable on account of the oxidation which takes place on the surface, so that the pressure-sensitive adhesive properties of the decorative sheet 8 with the adhesive layer are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a product for attaching a decorative sheet to a resin extruded product, and more particularly to a method for producing a three-dimensional base material for attaching a decorative sheet to a three-dimensional molten resin.

[0002]

2. Description of the Related Art Conventionally, a columnar body (rod-like body) having a concave-convex, polygonal or curved cross-section formed of a metal-based substrate such as aluminum or iron or a wood-based substrate such as natural wood or plywood. The thing which gave the pattern on the outer surface of the long object appropriately,
It is widely used as a building material such as window frames, sills, handrails, or as a component member of furniture and the like. The outer surface on which the pattern is applied is mainly the side surface.

As a method of attaching a decorative sheet to such a resin-extruded three-dimensional base material, a vinyl chloride resin is extrusion-molded, and the vinyl chloride resin decorative sheet is applied via an adhesive layer (primer) to the Japanese Patent Publication No. 61-5895. No., JP-A-5
There are known a method of laminating a three-dimensional base material by a so-called lapping method disclosed in Japanese Patent No. 330013, a method of extruding an olefin-based resin, and laminating a decorative sheet by lapping.
Furthermore, in order to improve the adhesiveness, it has been attempted to attach a decorative sheet after performing a corona discharge treatment on the extruded three-dimensionally shaped base material.

However, extrusion molding of vinyl chloride resin
The method of laminating the decorative sheet on the three-dimensional substrate via an adhesive layer (primer) uses a vinyl chloride resin as a material, so that toxic chlorinated substances are generated at the time of disposal and combustion. There's a problem.

Further, in the method of extruding an olefin resin and laminating a decorative sheet, the olefin resin has poor adhesion and poor adhesion to the decorative sheet. For this reason, heat fusion is conceivable, but due to the high temperature, the decorative layer on the sheet surface is liable to change and easily deformed when held down by a wrapping roll. Further, even if a method of corona-treating and laminating a columnar extruded resin molded product is applied, the corona treatment becomes uneven and insufficient because the extruded product has a three-dimensional shape. In addition, due to uneven elongation (so-called necking) when wrapping and bending a three-dimensionally shaped body, stress is locally concentrated on the bent portion, and whitening and cracks are likely to occur.

On the other hand, a method of coating a decorative sheet with a polyolefin-based resin film such as a polypropylene layer (ie,
Immediately after extrusion molding of a two-layer film composed of a polypropylene layer and a polyethylene layer containing an ethylene-α-olefin copolymer, at least Ozone treatment is performed by spraying a substrate containing ozone at a fixed rate on the surface of the polyethylene layer containing the ethylene-α-olefin copolymer whose surface portion is in a molten state. There is known a method for producing a laminate in which material sheets are bonded (Japanese Patent Laid-Open No. 62-609).
No. 70, etc.).

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a method of attaching a decorative sheet to a three-dimensional substrate made of an olefin resin,
It is an object of the present invention to provide a three-dimensional substrate on which a decorative sheet that does not cause whitening or cracking even during bending is laminated.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a three-dimensional molten resin made of an olefin-based resin is melt-extruded as a rod from a deformed mold, and then the molten resin is subjected to an ozone spraying treatment. The present inventors have found that a three-dimensional base material obtained by wrapping a decorative sheet coated with an adhesive can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention provides a step of melt-extruding a three-dimensional molten resin composed of an olefin resin from a mold, and a step of spraying ozone to the molten resin.
A decorative sheet coated with an adhesive, using a plurality of rolls having a shape matching each surface shape constituting the outer surface of the molten resin as an outer surface side of the molten resin, or a plurality of cylindrical rolls, And a step of sequentially and stepwise attaching to each side surface.

In the method for producing a three-dimensionally shaped substrate according to the present invention, the decorative sheet is preferably obtained by decorating a thermoplastic resin, and more preferably, the decorative sheet is formed of an olefin resin or an acrylic resin. And a decorative treatment comprising a single layer or a laminate of two or more layers selected from the group consisting of polyester resin, fluororesin, ABS resin, polystyrene resin and polycarbonate resin.

[0011] The thermoplastic resin is preferably
Isotactic polypropylene (hard segment)
And Attack Polypropylene (Soft Segment)
Olefinic thermoplastic elastomers, blends of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment) with a compound having a polar functional group, or ethylene-propylene-
Any of thermoplastic elastomers of butene copolymer.

Hereinafter, the present invention will be described in detail. As the olefin resin used in the present invention, polyethylene,
Ethylene / propylene copolymer, ethylene / butene-1
Copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-2, butene-1 / propylene / ethylene / 3 terpolymer, butene-1 / hexene / octene-1 / 3 terpolymer, poly Methylpentene, Tokuho 6
JP-A-23278 / 89 discloses a polypropylene-based olefin-based thermoplastic elastomer having a hard segment of isotactic polypropylene and a soft segment of atactic polypropylene, and ethylene described in JP-A-5-77371 and JP-A-9-111055. −
An olefin-based thermoplastic elastomer such as a propylene-butene terpolymer-based olefin-based thermoplastic elastomer can be used. These resins may be used alone or in combination of two or more.

Of these, in particular, those excellent in moldability, transparency and light resistance are described in the above-mentioned JP-B-6-232.
No. 78 is described. Further, among the experiments and evaluations conducted by the inventor of the present application, it has been found that the following is particularly optimal. That is, in this kind of polypropylene-based olefin-based thermoplastic elastomer, by setting the weight ratio of the atactic polypropylene as a soft segment to 5% by weight or more, the three-dimensional shape,
In addition, it is possible to eliminate uneven deformation of the sheet due to necking when forming into an article having an uneven shape, and cracks, whitening, distortion of a picture, and the like of the sheet due to stress concentration accompanying the necking. In particular, the weight ratio of atactic polypropylene is 20.
The case where the content is not less than% by weight is good.

On the other hand, if the weight ratio of the atactic polypropylene is too large, the sheet itself tends to be deformed, and when the sheet is passed through a printing machine, the sheet is deformed, the pattern is distorted, and the multicolor printing is expected. Are likely to occur, such as mismatching. Further, it is not preferable because it is easily broken during molding. The upper limit of the weight ratio of the atactic polypropylene is 50% by weight or less, more preferably 40% by weight or less, when the decorative layer is printed using a normal rotary printing machine such as rotary gravure printing.

The thickness of the layer of the olefin-based thermoplastic elastomer is about 50 to 500 μm, and any of a stretched sheet and an unstretched sheet can be used. Is better. There is no particular limitation on the cross-sectional shape of the three-dimensional base material forming the columnar body used in the present invention, and a cross-section where a decorative sheet can be stuck on the outer surface by a conventionally known lapping laminating machine (curved laminating machine). Any shape is acceptable. For example, a three-dimensional base material having an arbitrary cross section such as a convex polygonal shape, a concave polygonal shape, a circular shape, an elliptical shape, and a square shape can be used. The three-dimensionally shaped base material can be obtained by extrusion molding a molten resin using a mold having a predetermined shape (die).

Next, the extruded three-dimensional substrate is subjected to an ozone spraying treatment. In the present invention, ozone is contained on the surface of the substrate whose polyolefin is not decomposed, that is, immediately after extrusion molding at an extrusion temperature of 300 ° C. or less, preferably at least the surface of which is in a molten state. The surface of the base material is oxidized by blowing a blowing gas to improve the adhesiveness with a decorative sheet having an adhesive layer formed by an adhesive on another surface. The gas containing ozone whose surface portion is blown against the surface of the polyolefin in a molten state can be obtained by supplying air or oxygen to a normal ozone generator.
It is preferable to blow in a ratio of ^{mg / m 2 ~80mg / m 2} . When the ozone concentration of the gas blown onto the surface of the polyolefin base material is less than 40 mg / m ² , the degree of oxidation of the surface of the polyolefin base material is not sufficient in the gas blowing step, and the surface is bonded with an adhesive. It is impossible to obtain a strong adhesive strength with another decorative sheet having an agent layer, and the object of the present invention cannot be achieved.

On the other hand, if the ozone concentration exceeds 80 mg / m ² , the effect of spraying ozone is saturated and the temperature of the heated substrate surface is undesirably cooled. The decorative sheet used in the present invention,
It has a configuration in which decoration processing is performed on a thermoplastic resin sheet. As the thermoplastic resin, a polyolefin resin,
Examples thereof include an acrylic resin, a polyester resin, a fluororesin, a polystyrene-based resin, and a polycarbonate resin. A single layer of these resins or a laminate of two or more layers can be used.

The polyolefin resin includes polyethylene, ethylene / propylene copolymer, ethylene / propylene
Butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-2, butene-1 / propylene / ethylene / 3 terpolymer, butene-1 / hexene / octene-1 / 3 terpolymer Copolymer, polymethylpentene, polypropylene-based olefin-based thermoplastic elastomer having isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment described in JP-B-6-23278, ethylene-propylene-butene terpolymer system Olefinic thermoplastic elastomers, etc., and those obtained by graft-polymerizing a compound having a polar functional group such as a carboxyl group such as fumaric acid and maleic anhydride, and a hydroxyl group onto the olefinic thermoplastic elastomer, or an olefinic thermoplastic elastomer. Non-elastomer Fin-based thermoplastic resins. These resins may be used alone or in combination of two or more.

For example, (1) polyethylene, polypropylene or copolymers thereof, and (2) polyolefins selected from unsaturated carboxylic acids such as acrylic acid, maleic acid and fumaric acid, and derivatives thereof such as acid anhydrides and esters. And at least one of them is 10 ^-4 to 10% by weight, preferably 10 ^-3.
A modified polyolefin obtained by graft copolymerization in the range of 5 to 5% by weight, and (3) one layer of polyethylene, ethylene and α, β such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, and fumaric acid. -Extrusion lamination of a copolymer of unsaturated carboxylic acid copolymer or a coextruded molten web having another layer of a metal neutralized product on a substrate, (4) JP-A-5-77371, Ethylene-propylene-butene terpolymer copolymer olefin-based thermoplastic elastomers described in, for example, Japanese Unexamined Patent Publication No. Hei 9-111055, such as a random copolymer of propylene having a propylene content of 90% by weight or more with ethylene or / and butene. To 100 parts by weight of the polyolefin resin of the formula (I):

[0020]

Embedded image

0.1 to 0.50 parts by weight of a transparent nucleating agent containing a phosphate aryl ester compound represented by the following formula as a main component:
And an aliphatic amide having 12 to 22 carbon atoms 0.003 to 0.
A polyolefin composition obtained by melt-kneading 3 parts by weight. As butene, any of 1-butene, 2-butene and isobutylene can be used.
-Butene is preferred. (5) Propylene component content is 5
0 to 100% by weight of amorphous polyolefin
% By weight, and a resin composition containing 80 to 0% by weight of crystalline polypropylene, and a laminate thereof.

Examples of the acrylic resin include poly (meth) acrylate, poly (ethyl) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate.・
(Meth) butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene
An acrylic resin comprising a homo- or copolymer containing a (meth) acrylate such as a methyl (meth) acrylate copolymer can be given.

The thermoplastic polyester resin includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as acid components, and aliphatic diols such as ethylene glycol, diethylene glycol, butanediol and hexanediol as alcohol components. And a copolymer obtainable as an ester of both, for example, polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate.
An isophthalate copolymer is exemplified.

Examples of the fluororesin include polyvinyl fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer and the like. Examples of the polystyrene-based resin include polystyrene, acrylic styrene, and ABS.

The polycarbonate has --OR-- in the main chain.
It is a linear polymer having O-CO- and can be produced by, for example, reacting glycol with a dihydric phenol and phosgene, or reacting with a carbonate ester.
Bisphenol A and the like can be mentioned.

Of the above materials, the following materials can be preferably used as decorative sheet materials. That is, (1) an olefin-based thermoplastic elastomer composed of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), and a mixture of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment) Blended (Tokuhei 6
(See JP-A-23278), (2) a thermoplastic elastomer of an ethylene-propylene-butene terpolymer system (see JP-A-5-77371, JP-A-9-11055, etc.), and (3) Tokuhei 6 No. 23278-isotactic polypropylene described in the hard segment,
Polypropylene-based thermoplastic elastomer having an atactic polypropylene as a soft segment, and this polyolefin-based thermoplastic elastomer, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and these Polymers obtained by graft polymerization of a compound having a polar functional group such as a carboxyl group or a hydroxyl group such as an acid anhydride may be used.

The decorative sheet used in the present invention is provided with an adhesive layer. The adhesive layer is a layer for adhering the decorative sheet to the three-dimensional substrate, and can be selected from heat-sensitive adhesives, solvent-activated adhesives, and ionizing radiation-curable adhesives depending on the application. , Urethane resin, preferably 2
Liquid-curable urethane resins are mainly used.

The two-component urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent). As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyester polyol,
Polycarbonate polyol or the like can be used.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used later. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4-diphenylmethane diisocyanate, or aliphatic (such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate) Or alicyclic) isocyanate.

In the present invention, the decorative sheet is subjected to a decoration treatment as desired. For the decoration treatment, for example, a method of coloring the thermoplastic sheet by adding a pigment, a method of laminating a transparent thermoplastic sheet on a thermoplastic sheet colored by the addition of a pigment by a known method, There are a method of printing a pattern such as a pattern on the transparent thermoplastic sheet with ink, paint, or the like, and a method of forming a concavo-convex pattern on the thermoplastic sheet by embossing (hot pressing), hairline processing, or the like.

Examples of the pigments to be added include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindolinone, Hansa Yellow A, quinacridone, and permanent red 4.
R, phthalocyanine blue, Induslen Buri RS,
Organic pigments (including dyes) such as annin phosphorus black; metal pigments such as aluminum and brass; mica coated with titanium dioxide; and pearlescent (pearl) pigments made of foil powder such as basic lead carbonate. The coloring by the addition of the pigment may be a transparent job or an opaque (concealing) coloring. They are,
It is added and dispersed as powder or scaly foil.

As the pattern printing, a pattern can be formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid surface. The pattern can be provided on the front, back, front and back, or between layers of the decorative sheet.

As inks or paints, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and cellulosic resins are used as binders. And the like, and these may be used alone or in combination of two or more. For this, those to which the above-listed pigments are added are used.

When printing directly on an olefin resin, chlorinated polyolefin, urethane resin or the like is preferable as a binder in terms of adhesiveness. However, if an easy-adhesion primer is appropriately selected to form a layer, other binders may be used. However, sufficient adhesiveness can be imparted even by using.

In the embossing, the olefin resin is heated and softened, pressurized and shaped with an embossed plate, and fixed by cooling. A known sheet-fed or rotary embossing machine is used. As the uneven shape, there are a wood channel groove, a stone plate surface unevenness (granite cleavage surface or the like), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like.

Further, upon request, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

As a method for attaching the decorative sheet to the three-dimensional substrate, for example, using a known lapping machine, while the adhesive layer of the decorative sheet is not completely cured, As described in JP-A-5895, the decorative sheet is used as the outer surface side of the three-dimensional base material, and a plurality of rolls having a shape matching each surface shape constituting the outer surface of the three-dimensional shape base material are used. There is a method of sequentially and stepwise attaching (see FIG. 1C).

As another method of attaching the decorative sheet to the three-dimensional base material, an adhesive was applied to one surface using a known lapping machine as described in JP-A-5-330013. The decorative sheet is supplied, and on the other hand, the three-dimensional base material is horizontally conveyed at a speed synchronized with the supply speed of the decorative sheet, and the end of the decorative sheet is adhered by a large number of cylindrical roll-shaped holding jigs. A curved laminating method or the like in which the adhesive-applied surface side of the decorative sheet is sequentially and gradually pressed to the substrate for each small area while maintaining a state in which the decorative sheet is not applied, and the decorative sheet is heated and adhered to the substrate surface is also preferable (FIG. 1 (B)).

The three-dimensional decorative sheet wrapping base material of the present invention has been subjected to ozone treatment before the surface of the three-dimensional decorative base material made of polyolefin is adhered to the decorative sheet, so that the surface of the three-dimensional decorative base material is not oxidized. It is easy to adhere to. Therefore, the adhesiveness with the adhesive layer on the decorative sheet is excellent.

Further, since a three-dimensional base material made of polyolefin is used in place of the conventional vinyl chloride resin, the generation of toxic chlorinated products is extremely small when discarded or burned. Furthermore, the material of the decorative sheet is made of an olefin-based thermoplastic elastomer made of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), isotactic polypropylene (hard segment) and atactic polypropylene (soft segment). ), A compound obtained by graft-polymerizing a compound having a polar functional group, or a thermoplastic elastomer of an ethylene-propylene-butene copolymer is uniformly stretched during bending. It is excellent.

[0041]

DETAILED DESCRIPTION OF THE INVENTION The decorative sheet wrapping three-dimensional base material of the present invention can be manufactured as follows. First Embodiment FIG. 1 shows a production example of a decorative sheet wrapping three-dimensional base material of the present invention.

First, the molten three-dimensional substrate 10 is extruded from the mold 2 of the extruder 1, and the surface of the three-dimensional substrate is subjected to ozone treatment by the ozone treatment device 3. The ozone treatment is
It is preferable to perform it while the three-dimensional base material is still hot immediately after being extruded. The temperature of the ozone treatment is usually 200 to
It is about 300 ° C. The gas containing ozone sprayed on the surface of the olefin-based resin in a molten state can be obtained by supplying air or oxygen to a normal ozone generator such as a silent discharge system, but in the present invention, the ozone concentration is at least 40 mg. / M ^{2 to} 80 mg / m ² is preferably sprayed. The ozone treatment device 3 is preferably covered with a sealed tank (chamber) except for the entrance and exit of the three-dimensional substrate, so that ozone is not leaked to the outside.

On the other hand, the decorative sheet 8 with the decoration is pulled out from the decorative sheet take-up roll 13 located at the upper side at a speed synchronized with the transfer speed of the three-dimensional substrate 10, and a plurality of cylindrical pressing rolls are provided. By R _{1 to} R ₅ , the three-dimensionally shaped substrate 10 is adhered to the outer surface of the three-dimensionally shaped substrate 10. That is,
When the decorative sheet 8 is pulled out from the take-up roll 13, the adhesive 5 is applied to the surface of the decorative sheet 8, and is passed through the dryer 7 to the pressing rolls R _{1 to} R _{5 on the} three-dimensional substrate 10.
Thereby, the three-dimensionally shaped base material 10 is brought into close contact with the shape. Contact is pressing the surface of the uppermost in the pressing roll R ₁ of each side constituting the outer surface, and bonding, the following sequence, the corners of the top side in the pressing roll R _2, R _2, followed by the top side The vertical side surface is pressed by the pressing rolls R ₃ and R ₃ , and the subsequent horizontal surface is pressed by the pressing rolls R ₄ and R ₄ .

The three-dimensional decorative sheet wrapping substrate produced in this manner is subjected to ozone treatment on the surface of the three-dimensional substrate made of polyolefin before the decorative sheet is attached thereto. The surface is oxidized to be easily adhered. Therefore, the adhesiveness with the adhesive layer on the decorative sheet is excellent. Second Embodiment FIG. 2 shows another example of manufacturing the decorative sheet wrapping three-dimensional base material of the present invention.

First, the molten three-dimensional substrate 10 is extruded from the mold 2 of the extruder 1, and the surface of the three-dimensional substrate 10 is subjected to ozone treatment by the ozone treatment device 3. As in the first embodiment, the ozone treatment is preferably performed while the solid substrate is still hot immediately after extrusion. The temperature of the ozone treatment is usually about 200 to 300 ° C. The gas containing ozone sprayed on the surface of the polyolefin in a molten state can be obtained by supplying air or oxygen to a usual ozone generator. In the present invention, the ozone concentration is at least 40 mg / m ^{2 to} 80 mg / m ² .
It is preferable to spray at a rate of m ² .

Ozone-treated three-dimensional substrate 10
Then, the three-dimensional substrate is transported to a coating chamber 28, and a curable resin adhesive is applied to the outer surface of the three-dimensional substrate by a spray nozzle 27. On the other hand, the decorative sheet 29 with the decoration is drawn out from the decorative sheet take-up roll 13 positioned above at a speed synchronized with the transfer speed of the three-dimensional substrate 10, and a plurality of pressing rolls R _{6 to} R ₆ are drawn.
Into close contact with adaptation to the outer surface of the three-dimensional shape base material 10 by _10. In other words, the decorative sheet 29 is
From the pressing rolls R ₆ to
The R _10, are in close contact along the shape of the stereo shape base material 10.

In the same manner as in the first embodiment, the three-dimensional decorative sheet wrapping substrate thus produced is also treated with ozone before the decorative sheet is attached to the surface of the three-dimensional substrate made of an olefin resin. , The surface of the three-dimensionally shaped base material is oxidized and easily adhered. Therefore,
The adhesiveness with the adhesive layer on the decorative sheet is excellent.

The three-dimensional decorative sheet wrapping substrate of the present invention produced as described above can be suitably used for various surface materials, sashes (window frames), door frames, handrails and the like.

[0049]

EXAMPLE 1 A thermoplastic film colored by kneading an extender and a color pigment (a polypropylene film obtained by mixing a hard segment of isotactic polypropylene and a soft segment of atactic polypropylene in a weight ratio of 80:20). After applying corona discharge treatment to both front and back surfaces of a thermoplastic elastomer, a wood grain pattern is printed on its surface using a gravure plate with a two-component curable urethane resin colored primer (composed of polyester polyol and hexamethylene diisocyanate). did. Next, a thermoplastic resin film containing 0.2% by weight of a transparent benzotriazole-based ultraviolet absorber (ethylene-
Propylene-1-butene terpolymer thermoplastic elastomer) was dry-laminated using a two-component curable urethane resin adhesive (composed of polyester polyol and hexamethylene diisocyanate). The laminated film thus obtained is embossed with the unevenness of the wood channel, and then coated with a gloss adjusting coat using a two-component curable urethane resin (composed of acrylic polyol and hexamethylene diisocyanate). I got a sheet.

Next, the colored polypropylene resin was melted and extruded from a mold to obtain a rod-like shape as shown in FIG. 1 (A). Next, when extruded from the mold, the amount is 40 mg / m ^{2 with} respect to the area of the bar.
The substrate was passed through an ozone atmosphere to oxidize the surface of the substrate.

Next, a two-component curable urethane resin-based adhesive (composed of acrylic polyol and tolylene diisocyanate) was applied to the surface of the decorative sheet obtained first, and the above-described decorative sheet was applied as shown in FIGS. 1 (A) and 1 (B). Was wrapped on the substrate by the lapping bonding machine shown in (1). No cracks or whitening were observed in the bent part (corner part) of the decorative sheet. Comparative Example A rod-shaped decorative sheet wrapping substrate was obtained in the same manner as in Example 1 except that the surface of the substrate was not subjected to the ozone treatment. Peeling strength test The peeling strength test was performed using the stick-shaped decorative sheet wrapping base material obtained in the above Examples and Comparative Examples. That is, using the peeling strength test apparatus shown in FIG. 5, two cuts reaching the interface between the decorative sheet and the base material of the previously obtained rod-shaped decorative sheet wrapping base material are cut in parallel with a cutter knife with a width of 1 inch. The end of the decorative sheet is peeled off, one end of the three-dimensional base material part from which the decorative sheet has been peeled off is fixed with a fixing device 19, and one end of the stick-shaped decorative sheet wrapping substrate on which the decorative sheet is wrapped is fixed with a fixing device 20. At 25 ° C., the fixing device 20 was fixed at 100 mm /
This was performed by pulling up at a speed of min and measuring the tension value when the decorative sheet 8 was peeled from the rod-shaped substrate 10. The measurement was performed on three test pieces in both the examples and comparative examples.

As a result, the tension value of the product of the present invention subjected to the ozone treatment was 2.5 to 3.2 kg force / inch, and the tension value of the base material of the comparative example not subjected to the ozone treatment was 0%. 0.1 to 0.2 kg force / inch, and it was revealed that the product of the present invention has remarkably excellent adhesion between the base material and the decorative sheet.

[0053]

As described above, the three-dimensional decorative sheet wrapping substrate of the present invention is subjected to ozone treatment before the decorative sheet is attached to the surface of the three-dimensional substrate made of an olefin resin. Therefore, the surface of the three-dimensional base material is oxidized and easily adhered. Therefore, the adhesiveness with the adhesive layer on the decorative sheet is excellent.

Since a three-dimensional substrate made of polyolefin is used in place of the conventional vinyl chloride resin, the generation of toxic chlorinated products is extremely small when discarded or burned, which is environmentally friendly. It is. Furthermore, the material of the decorative sheet is made of an olefin-based thermoplastic elastomer made of a blend of isotactic polypropylene (hard segment) and atactic polypropylene (soft segment), isotactic polypropylene (hard segment) and atactic polypropylene (soft segment). ), And a thermoplastic elastomer of any of ethylene-propylene-butene copolymer obtained by graft-polymerizing a compound having a polar functional group, or a thermoplastic elastomer of ethylene-propylene-butene copolymer. , And has excellent moldability.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a manufacturing process of a decorative sheet wrapping three-dimensional base material of the present invention.

FIG. 2 is a schematic view showing a manufacturing process of the decorative sheet wrapping three-dimensional base material of the present invention.

FIG. 3 is a diagram showing a peeling test apparatus.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Extruder, 2 ... Die, 3 ... Ozone treatment apparatus, 4 ...
Ozone-containing substrate, 5,14 ... adhesive, 6,9 ... roll,
7 ... dryer, 8 and 16 ... decorative sheet, 10 ... three-dimensional base material, 10 '... three-dimensional base material coated with adhesive, 11,
12 ... belt conveyor, 13 ... take-up roll, 15 ...
Painting room, 17, 18 ... roll, 19, 20 ... fixture,
R, R _{1 to} R ₁₀ … Pressing roll

Claims (4)

[Claims] 1. A step of melt-extruding a three-dimensional molten resin comprising an olefin resin from a mold, a step of spraying ozone to the molten resin, and bonding a decorative sheet and the molten resin between the decorative sheet and the molten resin. In pasting through the agent layer, using a plurality of rolls having a shape matching each surface shape constituting the outer surface of the molten resin as the outer surface side of the molten resin, or using a plurality of cylindrical rolls ,
A step of sequentially and stepwise attaching to each side surface, a method for producing a three-dimensionally shaped base material. 2. The method for producing a three-dimensional base material according to claim 1, wherein the decorative sheet is a decorative sheet obtained by decorating a thermoplastic resin. 3. The decorative sheet according to claim 1, wherein the decorative sheet is a polyolefin resin, an acrylic resin, a polyester resin, a fluororesin,
The method for producing a three-dimensionally shaped base material according to claim 1, wherein the decorative sheet is a decorative sheet made of a kind of a single layer or a laminate of two or more layers selected from the group consisting of a BS resin, a polystyrene resin, and a polycarbonate resin. 4. An olefinic thermoplastic elastomer comprising a blend of an isotactic polypropylene (hard segment) and an atactic polypropylene (soft segment), wherein the thermoplastic resin is a blend of an isotactic polypropylene (hard segment) and an atactic polypropylene. 3. The three-dimensional substrate according to claim 2, wherein the blend is a thermoplastic elastomer of a compound obtained by further graft-polymerizing a compound having a polar functional group, or an ethylene-propylene-butene copolymer. Manufacturing method.