JPH1076617A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which its weather resistance is satisfactory and its interlayer bonding force is not weakened in the laminate obtained by laminating olefin material. SOLUTION: In the laminate obtained by laminating at least a base material, olefin resin having a polar functional group, and a transparent or translucent olefin resin layer, ultraviolet absorbent is dispersed in the olefin resin layer, and ultraviolet permeability of the olefin resin layer with a wave length of 350nm after exposure of 100 hours by an eye super-UV tester is 30% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate obtained by laminating olefin-based materials.

[0002]

Heretofore, as this type of laminate, a laminate of a substrate, an adhesive layer made of an olefin resin having a polar functional group, and a transparent or translucent olefin resin layer has been laminated. (See, for example, JP-A-55-11122, JP-B-7-55102, JP-B-3-4030, etc.). In this laminate, the olefin-based resin layer is embrittled by a weathering accelerated exposure test, for example, exposure for 24 hours using an eye super UV tester, and the adhesive strength of the adhesive layer / olefin-based resin layer is reduced to about 200 g / inch width. turn into. In the case of a building material product, an adhesive strength of about 1 kg / inch width is generally required to prevent peeling during V-cutting or cutting, so that such processing cannot be performed.

Therefore, in consideration of weather resistance to ultraviolet rays,
For example, it is conceivable to add a benzophenone-based ultraviolet absorber or a hindered amine-based radical scavenger to the olefin-based resin layer, for example, in an amount of about 0.5% by weight. Adhesive strength with olefin resin layer is also 200g / inc
h width.

[0004] The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate formed by laminating olefin materials, which has good weather resistance and interlayer adhesion. Another object of the present invention is to provide a laminate which does not become weak.

[0005]

To achieve the above object, the present invention provides at least a substrate, an adhesive layer comprising an olefin resin having a polar functional group, and a transparent or translucent olefin resin layer. A UV absorber is dispersed in the olefin resin layer, and the UV transmittance of the olefin resin layer at a wavelength of 350 nm after exposure for 100 hours with an iSuper UV tester is 30. % Or less.

[0006] Eye Super UV Tester (manufactured by Iwasaki Electric Co., Ltd.) is a 295 that is not included in sunlight reaching the ground surface.
This is a weather resistance tester that cuts the wavelength of ultraviolet light of nm or less and the visible light of 450 nm or more with a special filter, eliminates the effects of extra wavelengths, and promotes realistic degradation close to outdoor exposure. The test conditions in the present invention are as follows.
mW / cm ² , distance from light source 240 mm, black panel temperature 46 ° C. And, since exposure for 100 hours is equivalent to about one year of outdoor exposure, the specifications required for interior to semi-exterior building materials are sufficient (standard). Further, it has been found that the UV spectrum of 295 to 450 nm has a high correlation with the deterioration of the interlayer adhesion of the olefin resin, and the wavelength of 350 nm is a substantially intermediate wavelength in the wavelength band of ultraviolet rays which affects the interlayer adhesion. The UV absorption (or transmission) rate in such a wavelength band that correlates with the interlayer adhesion of the polyolefin resin, and the UV absorption spectrum of a common UV absorber such as benzotriazole described later are also continuous spectra including 350 nm. From
This 350 nm is selected as a representative wavelength for evaluating the correlation with the interlayer adhesion of the olefin resin.

[0007] In addition, it has been found from the results of various experiments that the sheet is exposed to a temperature higher than room temperature during exposure, regardless of the low transmittance of ultraviolet rays before the exposure test (this is due to the accelerated test or the outdoor exposure). Depending on the situation, up to 40-80
° C), and if the UV absorber is lost from the sheet by bleeding or sublimation, subsequent UV exposure cannot be shielded. Therefore,
Even when the desired maximum durable exposure time has elapsed, it is necessary to have sufficient ultraviolet absorption (shielding) performance, and the value is such that the transmittance at a representative wavelength of 350 nm of the olefin-based resin at a representative wavelength of 350 nm is 30% or less. Has been found, which has led to the present invention.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a substrate, resin sheets (or films) such as polyester resin, polyolefin resin and polyvinyl chloride resin, paper, nonwoven fabric, woven fabric, metal foil,
Any of a wood board, an inorganic board, a resin board, and a metal board can be used. The substrate is subjected to a desired decoration treatment. The decoration process includes coloring by adding a pigment (when the base material is resin), printing by printing, metal thin film, embossing (heating press), and unevenness by hairline processing. Colored inks can also be filled.

As pigments to be added to the base material (resin), inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa yellow A, organic pigments (including dyes) such as quinacridone, permanent red 4R, phthalocyanine blue, Indasulenburi RS, and aniline black; metal pigments such as aluminum and brass; titanium dioxide-coated mica; basic lead carbonate and other foil powders Pearl luster (pearl) pigments. These are added and dispersed as powder or scaly foil pieces. The coloring by adding the pigment may be transparent coloring or opaque (concealing) coloring.

The printing pattern can be formed by ink (or paint) by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, and the like. Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a geometric figure, a character, a symbol, and a solid surface. The pattern is provided on the front surface, the back surface, the front and back surfaces, or between the layers of the sheet. As ink (or paint), chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, acrylic, vinyl acetate, vinyl chloride-vinyl acetate copolymer, cellulose resin as binder Or a mixture of two or more kinds of polyamide resins and the like, to which the known pigments listed above are added.

In order to form a pattern with a metal layer, a metal such as aluminum or chromium is formed by vacuum evaporation. Such a metal layer may be formed on the entire surface, or may be formed in a pattern so as to obtain the above-described pattern. A known technique such as vapor deposition of metal over the entire surface provided in a desired pattern, followed by washing with water to remove the metal layer immediately above the removal layer together with the above-described removal layer is used. Of course, the metal layer previously formed on the transfer sheet may be transferred to the surface on which the pattern is formed by the transfer printing method.

The embossing is performed by heating and softening a thermoplastic resin sheet, pressurizing and shaping the sheet with an embossing plate, and cooling and fixing the sheet. A known sheet-fed or rotary embossing machine is used for the embossing. Used. As the shape of the uneven pattern,
Wood-grained pipe conduits, stone-plate surface irregularities (granite cleavage planes, etc.), cloth surface texture, satin finish, grain, hairlines, and linear grooves.

The concave portions of the concavo-convex pattern are filled with a coloring ink as required by a known wiping method.
As the coloring ink, a urethane resin, an acrylic resin, a polyester resin, or a conventional vehicle to which a pigment or a dye is added is selectively used. The vehicle is a two-liquid curing type having good adhesion and solvent resistance. preferable. Wiping may be performed by any of conventional wiping methods such as a doctor blade method and a roll coating method. That is, the coloring ink is applied to the entire surface of the concave and convex pattern, and then the ink of the convex portion is scraped off to leave the coloring ink in the concave portion.

The resin forming the adhesive layer is obtained by copolymerizing a monomer having a functional group with an olefin resin, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid having a polar functional group. Itaconic acid, methyl acrylate, methyl methacrylate, etc. are preferably copolymerized, especially graft-polymerized. Examples of the olefin resin include polypropylene-polyethylene random polymer, ethylene-methyl acrylate copolymer, and polypropylene homopolymer. Copolymers, such as polyethylene copolymers, block copolymers, EPR, and EPDM may be used. Preferably soluble in a solvent, such as chlorinated polypropylene or chlorinated polyethylene, a polypropylene copolymer having a high comonomer content, disclosed in Japanese Patent Publication No. Hei 6-23278,
Mixtures of isotactic polypropylene and atactic polypropylene are preferred. The copolymerization ratio between the olefin monomer and the monomer having a functional group is (monomer having a functional group) / (olefin monomer) = 1/3.
(Weight ratio)% or less is preferable. Further, olefin-based fine particles may be added. As a method for forming the adhesive layer, there are means such as painting, coating (including an EC coat), and printing.

As the transparent or translucent olefin resin, polyethylene, ethylene / propylene copolymer,
Ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-1, butene-1 / propylene / ethylene / 3 terpolymer, butene-
1, hexene-1, octene-1, terpolymer, polymethylpentene, olefin elastomer described in Japanese Patent Publication No. 23278/1994, or JP-A-6-16832.
And the like. These resins may be used alone or in combination of two or more. The thickness is about 50 to 500 μm, and any of a stretched sheet and an unstretched sheet can be used. However, the unstretched sheet is better in terms of formability such as V-cut processing.

[0016] If necessary, a coloring agent comprising a pigment or a dye is added to these resins to make them transparent. As pigments, titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, inorganic pigments such as carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue,
Organic pigments (or dyes) such as Indaslenbury RS and aniline black, metal pigments such as aluminum and brass, pearlescent (pearl) pigments made of foil powder such as titanium dioxide coated mica and basic lead carbonate are used. Can be In addition, extenders (fillers) such as calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), and barium sulfate are added as necessary. When it is necessary to impart flame retardancy, a flame retardant is added. As the flame retardant, magnesium hydroxide, aluminum hydroxide, antimony trioxide and the like are used. The addition amount is about 10 to 100 parts by weight based on 100 parts by weight of the resin according to the desired flame retardant grade.

As the ultraviolet absorber, those having a shielding region by absorption or reflection in the ultraviolet region which is correlated with the ultraviolet deterioration of the interlayer adhesion of the olefin resin, that is, in the range of 295 to 450 nm including 350 nm (representative value). Is used. For example, examples of the organic compound include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2′-hydroxy-3′-tert-). Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-
(Hydroxy-3′-tert-amyl-5′-isobutylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3′-isobutyl-5′-methylphenyl) -5-chlorobenzotriazole, 2-
2 ′ such as (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole
-Hydroxyphenyl-5-chlorobenzotriazole ultraviolet absorbers, 2- (2′-hydroxy-3 ′,
2′-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as 5′-di-tert-butylphenyl) benzotriazole and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2′-dihydroxy -4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxybenzophenone-based UV absorbers such as 2,2 ', 4,4'-tetrahydroxybenzophenone, and 2-hydroxybenzophenone-based agents such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone UV absorbers, salicylic acid ester based UV absorbers such as phenyl salicylate and 4-t-butyl-phenyl-salicylate, 2-ethyl-hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano- Cyanoacrylate-based ultraviolet absorbers such as 3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate are used. In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton is also used. Further, as the inorganic compound, zinc oxide, iron oxide, titanium oxide having a particle diameter of 1 μm or less, and more preferably 0.2 μm or less in terms of visible light transparency,
Inorganic oxide ultraviolet absorbers such as cerium oxide are used. In particular, metal oxides such as benzotriazole or fine particles of cerium oxide, which can reduce the weight loss due to bleeding or sublimation when exposed to ultraviolet light or heat, and have a relatively small addition amount, are preferred.

[0018] The deterioration of each layer due to ultraviolet rays is further prevented,
In order to improve weather resistance, it is preferable to add a radical scavenger as another light stabilizer. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)
Hindered amine radical scavengers and piperidyl radical scavengers such as sebacate and other compounds disclosed in, for example, Japanese Patent Publication No. 4-82625 are used. When a light stabilizer comprising a hindered amine radical scavenger is added to the polyolefin, not only the polyolefin resin, but also an ink layer adjacent to the polyolefin resin sheet, a layer such as an adhesive layer, a polyurethane resin, a polyolefin resin, Use of a resin containing no chlorine atom in the molecule, such as a polyamide resin, is favorable in terms of improving weather resistance. If vinyl chloride vinyl acetate copolymer,
When a resin containing a chlorine atom in the molecule, such as chlorinated polyolefin, is used, hydrogen chloride is generated from these resins by the action of ultraviolet light or heat in a dechlorination reaction, which reacts with a hindered amine radical scavenger and loses its action. Because it activates and inhibits, the weather resistance is not sufficiently improved.

[0019]

【Example】

Example 1 A decorative layer was formed by using a polyethylene-based elastomer ("Tuffer" manufactured by Tatsuno Chemical) as a base material and performing gravure printing with a polyester urethane ink on the base material. Then, an adhesive (“UNISTOR P-802” manufactured by Mitsui Petrochemical) is applied on the entire surface of the decorative layer to form an adhesive layer, and an olefin-based resin layer is laminated via the adhesive layer. Decorative sheet (laminate)
Was prepared. In this example, polypropylene ("E-2600" manufactured by Idemitsu Petrochemical) was used as the olefin-based resin, and 0.3% by weight of a benzotriazole-based ultraviolet absorber ("LA-36" manufactured by Asahi Denka Kogyo) was used. , Hindered amine radical scavenger ("LA-6" manufactured by Asahi Denka Kogyo)
An olefin-based resin layer was formed by extruding and laminating 0.3% by weight of 2 ").

Example 2 In Example 1, the ultraviolet absorber added to the polypropylene was changed. That is, a benzophenol-based ultraviolet absorber (“SU” manufactured by Sumitomo Chemical Co., Ltd.)
MISORB 103 ”) was added in an amount of 1.5% by weight, and the other conditions were the same to prepare a decorative sheet (laminate).

Comparative Example In Example 2, the amount of the benzophenol-based ultraviolet absorber added to polypropylene was reduced. That is, the addition amount is changed to 0.3% by weight,
Otherwise, a decorative sheet (laminate) was prepared in the same manner.

Example 3 An iron plate coated with a polyester paint was used as a base material, and an adhesive (“UNISTOR Q-220” manufactured by Mitsui Petrochemical) was applied over the entire surface to form an adhesive layer. A decorative board (laminate) was formed by forming the laminate and laminating an olefin-based resin layer via the adhesive layer. In this example, a polypropylene-polyethylene copolymer ("FW363" manufactured by Sumitomo Chemical Co., Ltd.) was used as the olefin-based resin, and a benzotriazole-based ultraviolet absorber ("LA-36" manufactured by Asahi Denka Kogyo Co., Ltd.) was added to the copolymer. An olefin-based resin layer was formed by heat laminating a resin to which 0.3% by weight of a hindered amine radical scavenger ("LA-62" manufactured by Asahi Denka Kogyo) was added.

(Example 4) A colored paper-reinforced paper ("CB FIX 30" manufactured by Sanko Paper) is used as a base material, and gravure printing is performed on the base material with an acrylic urethane-based ink to form a decorative layer. did. Then, an adhesive ("PP-HS" manufactured by Showa Ink Kogyo Co., Ltd.) is applied to the entire surface of the decorative layer to form an adhesive layer, and an olefin-based resin layer is laminated via the adhesive layer to make up the makeup. A sheet (laminate) was produced. In this example, a polypropylene-polyethylene copolymer (“FW36 manufactured by Sumitomo Chemical Co., Ltd.
3 "), to which 0.3% by weight of a benzotriazole-based ultraviolet absorber (" LA-36 "manufactured by Asahi Denka Kogyo) was added.
Hindered amine radical scavenger (“L” manufactured by Asahi Denka Kogyo
A-62 ") was extruded and laminated by adding 0.3% by weight to form an olefin-based resin layer.

Example 5 In Example 4, the amount of the benzotriazole-based ultraviolet absorber added to the polypropylene-polyethylene copolymer was reduced. That is, a decorative sheet (laminate) was prepared in the same manner except that the addition amount was changed to 0.2% by weight.

Example 6 A decorative sheet (laminate) was prepared in the same manner as in Example 5, except that the hindered amine radical scavenger was not added to the polypropylene-polyethylene copolymer.

A single-layer film identical to the olefin-based resin layer in the laminates produced in each of the above Examples and Comparative Examples was separately prepared by the same film-forming method as in each of the Examples and Comparative Examples, and was used to reduce the ultraviolet transmittance. The test film was measured. Then, the initial ultraviolet transmittance at a wavelength of 350 nm of each film is
It was measured with a U-2000 double beam spectrophotometer (manufactured by Hitachi, Ltd.). Further, the same olefin-based resin film as described above was measured with an eye super UV tester.
After performing the exposure test for 0 hour, the ultraviolet transmittance at a wavelength of 350 nm was measured. Further, the adhesion between the adhesive layer and the olefin-based resin layer after the exposure test of the laminates prepared in the above Examples and Comparative Examples was performed by a 180 degree peeling test. Specifically, a sample of the decorative sheet cut out to a width of 1 inch was pulled in a direction perpendicular to the width direction and the tensile direction of each layer was set to 50 degrees / 50 mm /
The tensile force at the time of peeling of the interlayer interface was measured by pulling at an ambient temperature of 20 ° C. for a minute. In addition, changes in the appearance of the surface layer, such as discoloration and cracks, were visually observed, and those showing no change before and after the exposure test were rated as good. Table 1 shows the results.

[0027]

[Table 1]

From the results shown in Table 1, the wavelength 3 after the exposure test was
When the UV transmittance at 50 nm is 30% or less, the interlayer adhesive strength is stronger than a normally required value (1 kg / inch width), and the weather resistance is good.

[0029]

As described above, the laminate of the present invention comprises at least a base material, an adhesive layer composed of an olefin resin having a polar functional group, and a transparent or translucent olefin resin layer. By adding an ultraviolet absorber to the transparent or translucent olefin-based resin layer to make the UV transmittance at 350 nm after exposure for 100 hours with an iSuper UV tester to 30% or less, And the interlayer adhesion strength between the adhesive layer and the olefin-based resin layer does not decrease.

Claims (3)

[Claims] 1. A laminate comprising at least a base material, an adhesive layer made of an olefin resin having a polar functional group, and a transparent or translucent olefin resin layer, wherein the olefin resin layer has an ultraviolet ray. A laminate having an absorbent dispersed therein, wherein the olefin-based resin layer has an ultraviolet transmittance of 30% or less at a wavelength of 350 nm after exposure to an I-Super UV tester for 100 hours. 2. The laminate according to claim 1, wherein a hindered amine radical scavenger is further added to the olefin resin layer. 3. The laminate according to claim 1, wherein a decorative layer is formed on the base material, and the adhesive layer and the olefin-based resin layer are laminated thereon.