JP2014040013A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that can be used in outdoor environment, having excellent weather resistance for the long term and excellent interlayer adhesion.SOLUTION: A laminate includes at least a pattern layer 2, an adhesive layer 3, an anchor coat layer 4, and an ionomer film 5 on an olefinic thermoplastic resin base material 1 in this order. The adhesive layer is composed of polycarbonate urethane, and the anchor coat layer is composed of polycarbonate urethane, and acrylic polyol and isocyanate.

Description

  The present invention relates to a laminate used for a flooring, a surface of a building member, or a label used by bonding to various other surfaces, in particular, a conventional polyvinyl chloride resin in terms of physical properties such as flexibility, surface hardness and warpage. The present invention relates to a laminate that has the same performance as the laminate of the above, but does not contain a polyvinyl chloride resin, has no problem of generation of harmful substances during combustion, and has excellent surface weather resistance and interlayer adhesion.

  Conventionally, a laminate made of a polyvinyl chloride resin, which is flexible, easy to process, and inexpensive, has been most frequently used as the laminate for the above-mentioned use. However, since polyvinyl chloride resin generates toxic substances such as hydrogen chloride and dioxin during combustion, problems such as fire and environmental pollution caused by incineration after use are pointed out, and its use is regarded as a problem. Thus, there has been a demand for the appearance of a laminate having a performance equivalent to that of a material made of polyvinyl chloride resin instead of polyvinyl chloride resin.

  Therefore, for example, a decorative sheet using a thermoplastic resin not containing chlorine other than polyvinyl chloride, such as polyolefin resin, acrylic resin, and polyester resin, has already been developed and put to practical use, and a decorative sheet made of polyvinyl chloride resin. Substitution of is gradually progressing.

  However, all of these alternative resins are inferior in thermal adhesiveness compared to polyvinyl chloride resin, and as in the case of a decorative sheet using conventional polyvinyl chloride resin, cosmetics are applied by thermal lamination. When trying to manufacture a sheet, there is a problem that it is difficult to obtain a necessary adhesive strength. In particular, when a polyolefin-based resin is used, the range of temperature conditions in which heat bonding can be performed is very narrow, and the temperature is too high, so that defective lamination such as sheet breakage, elongation, deformation, and deterioration occurs. Further, even if heat lamination is performed in a low temperature range where these disadvantages do not occur, the laminate strength is extremely low, and it is impossible to obtain a sheet that can be used practically as a decorative sheet.

  In order to cope with such problems, a thermoadhesive resin layer made of vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as vinyl acetate) -acrylic resin is provided between the thermoplastic resin substrate and the surface resin layer. A method of providing it has also been proposed (Patent Document 1). According to this method, laminating is performed by interposing a heat-adhesive resin layer that is sufficiently thermally activated and exhibits adhesiveness in a low-temperature region where no breakage, elongation, deformation, deterioration, or the like of the sheet occurs. There is an advantage that sufficient laminate strength can be achieved without causing defects. In particular, the vinyl chloride-based resin improves the adhesion between the thermoplastic resin substrate and the surface resin layer.

  However, the heat-adhesive resin layer may be made of a resin having inferior heat resistance, and the resulting decorative sheet may have inferior heat resistance. For example, in the case of semi-exterior applications, when water is immersed on the surface of a decorative surface and heated by direct sunlight, the heat-adhesive resin layer is softened by the hot water, and fine voids are generated in the heat-adhesive resin layer, resulting in a surface condition. There is a problem that it appears whitened due to diffused reflection of light. This problem will theoretically be improved if a heat-adhesive resin with a high heat softening temperature is used, but if this is done, it will inevitably require an increase in the laminating temperature. This leads to poor lamination such as breakage, elongation, deformation, and deterioration, and the intended purpose cannot be achieved.

  Therefore, a cross-linking agent such as an isocyanate compound is blended in the thermoadhesive resin, and the adhesiveness is expressed by the heat at the time of laminating to bond the thermoplastic resin substrate and the surface resin layer, and at the same time, thermal adhesiveness. It is also conceivable to improve the heat resistance after laminating by causing a cross-linking reaction inside the resin. However, according to such a method, after applying the heat-adhesive resin to the thermoplastic resin base material, if a time is taken until the heat laminating process, the cross-linking reaction proceeds during that time. Since it will no longer develop, it is necessary to immediately heat laminate. Therefore, the progress management of the decorative sheet manufacturing process is cumbersome, and it is not possible to make a large amount of printed thermoplastic resin base coated with a heat-adhesive resin, so it is possible to produce a variety of products in small quantities. There are problems such as being very difficult to deal with.

  In addition, there are proposals for melt extrusion laminating as an alternative to thermal laminating, but these require large-scale and expensive manufacturing equipment, and are difficult to respond to high-mix low-volume production and short delivery times. Due to the problem that the types of resin that can be used are limited, the heat laminating method cannot be substituted.

  There is also a proposal to use an acrylic resin with excellent weather resistance for the surface transparent resin layer by the dry laminating method, but when the thermoplastic resin substrate is an olefin substrate, there is no good adhesive layer and it is suitable for exterior use Usable adhesiveness was not obtained.

JP2003-53920A JP2004-17510

The present invention has been made to solve such problems. That is, the decorative sheet of the present invention is a laminate excellent in long-term weather resistance and adhesion between layers that can be used even in an outdoor environment. Is to provide.

  The present invention solves this problem, that is, the invention according to claim 1 is provided with an image layer, an adhesive layer, an anchor coat layer, and an ionomer film in this order on an olefin-based thermoplastic resin substrate. In the laminate, the adhesive layer is made of polycarbonate urethane, and the anchor coat layer is made of polycarbonate urethane, acrylic polyol and isocyanate.

The invention is the second aspect, wherein the coating amount of the adhesive layer is ^4g / m ² ~9g / m 2 after drying, the coating amount of the anchor coat layer after drying 0.5 g / a laminate according to claim 1, characterized in that the ^{m 2} ~7g / m ^2.

  The invention according to claim 3 is characterized in that the ratio of polycarbonate urethane to acrylic polyol in the anchor coat layer is in the range of 35:65 to 45:55. It is a laminate.

  According to the present invention, a layer using an adhesive of polycarbonate urethane and an anchor agent made of polycarbonate urethane, acrylic polyol and isocyanate is provided between the olefinic thermoplastic resin substrate and the ionomer film. Thus, it becomes possible to obtain a laminate having excellent appearance and excellent weather resistance and interlayer adhesion.

  According to the second aspect of the present invention, it is possible to obtain more production stability by limiting the coating amounts of the adhesive layer and the anchor coat layer.

  According to the third aspect of the present invention, it is possible to obtain longer-term weather-resistant interlayer adhesion by limiting the ratio of the polycarbonate urethane and the acrylic polyol as the anchor agent.

It is explanatory drawing which shows the structure of the cross section of one Example of the laminated body of this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the laminate of the present invention. A pattern layer 2, an adhesive layer 3, an anchor coat layer 4, and an ionomer film 5 are provided on the olefin-based thermoplastic resin substrate 1 in this order at least.

  The olefinic thermoplastic resin substrate 1 in the present invention is not particularly limited, and for example, any known olefinic resin sheet that is conventionally used as a sheet material for providing a pattern layer 2 described later is used. be able to. Specific examples include polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, vinyl acetate copolymers or saponified products thereof, and ethylene- (meth) acrylic acid (ester) copolymers. Among them, the most suitable is a polypropylene-based resin, that is, a homopolymer or a copolymer mainly composed of polypropylene, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, And a propylene-α- containing 15 mol% or more of a comonomer of 2 to 20 carbon atoms other than propylene, preferably ethylene, butene-1,4-methylpentene-1, hexene-1 or octene-1. An olefin copolymer etc. can be illustrated. Further, modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, which are usually used for softening polypropylene resins can be added. .

  In general, the laminate in the present invention often requires concealment of the surface color and defects of the adherend substrate. In order to give sufficient concealability, the olefinic thermoplastic resin substrate 1 can be used as a concealing layer by adding a concealing pigment to the thermoplastic resin constituting the olefinic thermoplastic resin substrate 1. . Further, instead of using the olefinic thermoplastic resin substrate 1 as a concealing layer, a concealing solid printing layer (not shown) made of a printing ink composition containing a concealing pigment on the front or back surface of the olefinic thermoplastic resin substrate 1. ) May be provided, or both may be used in combination.

  As the concealing pigment, it is desirable to use an inorganic pigment having a high refractive index and excellent concealing property. Specifically, for example, yellow lead, yellow iron oxide, cadmium yellow, titanium yellow, barium yellow, quinacridone, aureolin, molybdate orange, cadmium red, petal, red lead, cinnabar, mars violet, manganese violet, cobalt violet, Colored pigments such as cobalt blue, cerulean blue, ultramarine blue, bitumen, emerald green, chrome vermilion, chromium oxide, viridian, iron black, carbon black, etc., for example, titanium oxide (titanium white, titanium white), zinc oxide (zinc white) White pigments such as basic lead carbonate (lead white), basic lead sulfate, zinc sulfide, lithopone, and titanox can be used.

  Above all, as a pigment that is excellent in concealment and light resistance and is suitable for design, use petals as colored pigments, iron oxide pigments such as yellow iron oxide and iron black, and titanium oxide pigments as white pigments. Is most desirable. Of course, other concealing or non-concealing inorganic pigments or organic pigments can be used together for the purpose of adjusting the color tone, in which case organic pigments such as cobalt blue and carbon black can be used. In the case of a pigment, it is preferable to use a pigment having excellent weather resistance such as a phthalocyanine pigment such as phthalocyanine blue. In addition, extender pigments such as silica, calcium carbonate, and barium sulfate can be used in combination as necessary.

  In addition, the thermoplastic resin constituting the olefin-based thermoplastic resin substrate 1 may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plastic, depending on the intended use of the laminate. One or more conventionally known various additives such as an agent, a lubricant, an antistatic agent, a flame retardant, and a filler may be added.

  Examples of the antioxidant added to the olefin-based thermoplastic resin base material 1 include phenol-based, sulfur-based, and phosphorus-based materials, and examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, and formamidine. Type, oxanilide type, etc., as a light stabilizer, for example, hindered amine type, nickel complex type, etc., as a heat stabilizer, for example, hindered phenol type, sulfur type, hydrazine type, etc. Phthalic acid ester, phosphoric acid ester, fatty acid ester, aliphatic dibasic acid ester, oxybenzoic acid ester, epoxy, polyester, etc., such as fatty acid ester, fatty acid, metal soap, Fatty acid amide, higher alcohol, paraffin, etc. For example, cationic, anionic, nonionic, amphoteric, etc., flame retardants such as bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, zirconium, etc. As the filler, for example, one or two or more mixed systems selected from calcium carbonate, barium sulfate, talc, wax, kaolin and the like are used.

  Specifically, the thickness of the olefinic thermoplastic resin substrate 1 is about 20 to 300 μm, more preferably about 50 to 200 μm, although it depends on the use of the decorative sheet and the type of resin.

  As a molding method of the olefinic thermoplastic resin substrate 1, for example, an extrusion molding method, an inflation molding method, a calendar molding method, a cast molding method, or the like can be used.

  The pattern layer 2 is provided for the purpose of imparting a desired design of the desired pattern to the target laminate. In the present invention, a pattern layer 2 having an appropriate pattern is provided on the surface of the olefinic thermoplastic resin substrate 1 by means such as a printing method.

  There are no restrictions on the constituent material and the forming method of the picture layer 2, and any image forming material or image forming method that has been conventionally applied as the picture layer of the laminate can be applied as appropriate. Specifically, for example, a printing ink or a coating agent in which a colorant such as a dye or a pigment is dissolved or dispersed in an appropriate solvent together with an appropriate binder resin can be used.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazines. Organic pigments such as pigments, metal powder pigments such as gold powder, silver powder, copper powder, aluminum powder, and bronze powder, pearl luster pigments such as fish scale powder, basic lead carbonate, bismuth oxide chloride, and titanium oxide-coated mica, fluorescent pigments, night light A pigment or the like, or a mixture of two or more selected from these can be used.

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, polyvinyl resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, and melamine resins. , Using various synthetic resins such as fluororesins, silicone resins, vinyl chloride resins, vinyl acetate resins, fiber derivatives, rubber resins, or a mixture or copolymer of two or more thereof. Can do.

  Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate. Ester organic solvent, alcoholic organic solvent such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, ketone organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran, and chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene It can be used various kinds and organic solvents such as solvents, inorganic solvents such as water, or two or more mixed solvents thereof.

  In addition, for example, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, drying agents, heat stabilizers, weathering stabilizers, curing agents, curing accelerators, curing retarders, etc. These various additives can also be added as appropriate.

  As the adhesive layer 3 in the present invention, a polycarbonate urethane-based adhesive is used. Specifically, those made of a urethane adhesive having a polycarbonate resin as the main chain are used. As a result, the hardener made of an isocyanate compound contained in the anchor coat layer 4 causes a crosslinking reaction inside the adhesive layer 3 and the anchor coat layer 4 after being laminated by dry lamination with the anchor coat layer 4 described later. Thus, a strong interlayer adhesion strength can be obtained.

As a method of providing the adhesive layer 3 in the present invention, the adhesive layer 3 is coated on the olefin-based thermoplastic substrate 1 provided with the pattern layer 2. The coating amount, the device such that ^4g / ^{m 2 ~9g} / m 2 after drying is preferred. If it is less than 4 g / m ^2, the interlaminar adhesion over time is inferior. If it is more than 9 g / m ² , the residual solvent is large, and air production and wrinkles increase, resulting in unstable production.

  As the anchor coat layer 4 in the present invention, a layer made of polycarbonate urethane, acrylic polyol and isocyanate is used. Specifically, a two-component curable resin to which isocyanate is added with polycarbonate urethane and acrylic polyol as the main chain is used. This is dry-laminated with the adhesive layer 3, and after lamination, the isocyanate of the anchor coat layer 4 causes a crosslinking reaction with the polycarbonate urethane adhesive of the adhesive layer 3 to obtain a strong interlayer adhesive strength. Become.

  The anchor coat layer 4 in the present invention preferably has a ratio of polycarbonate urethane to acrylic polyol in the range of 35:65 to 45:55. When the ratio of the polycarbonate is lower than 35, the adhesion in a normal state is inferior, and when it is higher than 45, the appearance and the adhesion with time are inferior.

As a method of providing the anchor coat layer 4 in the present invention, it is applied to the back surface of an ionomer film 5 to be described later, and the pattern layer 2 of the olefinic thermoplastic substrate 1 coated with the adhesive layer 3. Bonded to the side. The coating amount, the degree to which a 0.5g ^{/ m 2} ~7g ^/ m 2 after drying is preferred. When the amount is less than 0.5 g / m ^2, the adhesiveness with time is inferior, and when it is more than 7 g / m ² , wrinkles easily occur and production is not stable.

  As the ionomer film 5 in the present invention, a film made of an ionomer resin is used, and additives are added as necessary. The ionomer resin is generally a resin in which organic and inorganic components are bonded by a covalent bond and an ionic bond. Examples of the ionomer resin that is particularly preferably used in the present invention include resins in which the intermolecular molecules of the copolymer are crosslinked with metal ions.

  Examples of the copolymer in this case include an acrylate copolymer, such as an ethylene-methacrylic acid copolymer. Examples of the metal ion include sodium, potassium, magnesium, zinc and the like.

  In order to obtain an ionomer resin, for example, an ethylene polymer obtained by copolymerizing a monomer having a carboxyl group in the side chain (for example, acrylic acid), a metal hydroxide such as sodium, potassium, magnesium, or zinc, A method of neutralizing an acid group by adding an appropriate amount of alkoxide or a lower fatty acid salt can be mentioned.

  As a result, the carboxyl anions distributed along the molecular chain are electrostatically combined with the metal cations existing between the molecular chains to form a kind of cross-linking, and the inter-copolymer molecules are completely bonded with the metal ions. Alternatively, an ionomer resin having a partially crosslinked structure is obtained.

  For the ionomer film 5 in the present invention, a film to which an appropriate additive such as an ultraviolet absorber, a light stabilizer, or a heat stabilizer is added as necessary, for example, an extrusion method, a calendering method, an inflation method, or the like can be used. It is obtained by forming into a sheet shape by the method.

  The thickness of the ionomer film 5 in the present invention is not particularly limited in the present invention, but usually a thickness of about 100 to 1000 μm is appropriate.

  A colored polypropylene resin film having a thickness of 60 μm (manufactured by Riken Technos Co., Ltd .: “Rivest TPO”) was used as the olefin-based thermoplastic resin substrate 1, and 3% by weight of an isocyanate curing agent was blended with a polyester polyol-based vehicle on this surface. The pattern layer 2 was provided by a gravure printing method using a two-component curable urethane-based ink (manufactured by Toyo Ink Manufacturing Co., Ltd.).

Using a film obtained by adding a benzotriazole ultraviolet absorber and a hindered amine light stabilizer to a transparent ionomer resin having a thickness of 90 μm as the ionomer film 5 (“1706TPMB” manufactured by Enshu Kasei Kogyo Co., Ltd.), A two-component curable anchor agent in which 10% by weight of an isocyanate curing agent is added to the main chain of the anchor coat layer 4 having a ratio of polycarbonate urethane to acrylic polyol of 40/60 (“EX20412-1” manufactured by DIC Corporation). Was applied by gravure coating so that the coating amount after drying was 1.4 g / m ² , thereby providing an anchor coat layer 4.

A coating amount after drying polycarbonate urethane (“A1102 / A3070” manufactured by Mitsui Chemicals, Inc.) made of urethane-based adhesive having polycarbonate as the main chain on the pattern layer 2 is 5.3 g / m ^2. Then, the adhesive layer 3 was provided and dried on the anchor coat layer 4 side of the ionomer film 5 to obtain a laminate of the present invention.

<Comparative Example 1>
A laminate was obtained in the same manner as in Example 1 except that the adhesive used for the adhesive layer 3 was a urethane-based adhesive (“TM593 / CAT-RT85” manufactured by Toyo Morton Co., Ltd.).

<Comparative example 2>
A laminate was obtained in the same manner as in Example 1 except that the anchor coat layer 4 was not provided.

<Comparative Example 3>
A laminate was obtained in the same manner as in Example 1 except that the resin used for the anchor coat layer 4 was only acrylic polyol (DIC 20315-3 manufactured by DIC Corporation).

<Comparative Example 4>
A laminate was obtained in the same manner as in Example 1 except that the ratio of polycarbonate urethane and acrylic polyol in the anchor coat layer 4 was 50/50.

<Comparative Example 5>
A laminate was obtained in the same manner as in Example 1 except that the coating amount after drying of the adhesive layer 3 was 2.0 g / m ² .

<Comparative Example 6>
A laminate was obtained in the same manner as in Example 1 except that the coating amount after drying of the adhesive layer 3 was 11.0 g / m ² .

<Comparative Example 7>
A laminate was obtained in the same manner as in Example 1 except that the coating amount after drying of the anchor coat layer 4 was 0.3 g / m ² .

<Comparative Example 8>
A laminate was obtained in the same manner as in Example 1 except that the coating amount after drying of the anchor coat layer 4 was 8.0 g / m ² .

<Performance evaluation>
The laminated body of the above Example 1 and Comparative Examples 1-8 was evaluated with the following test methods.

<Normal adhesion>
The laminated film cut to 1 inch width is immersed in ethyl acetate, and the ionomer film and the olefin film are peeled off. After sufficiently drying, each end is pulled at a speed of 50 mm / min with a tensile tester in an environment of 25 ° C. ± 2 ° C., and the laminate adhesion strength is measured.

<Metal weather>
As a weather resistance test, a metal halide lamp type super-accelerated weather resistance tester (manufactured by Daipura Wintes Co., Ltd.) was used for evaluation at an illuminance of 650 W / m ² and a black panel temperature of 53 ° C. The case where there was no significant change was marked as ◎, the case where slight deterioration was observed was marked as ◯, and the case where marked deterioration was recognized as x.

<Production stability>
The case where stable production was possible at a line speed of 40 m / min was marked with ◎.
The results are shown in Table 1.

  The laminate of the present invention can be used as a label or the like used by being bonded to a flooring, the surface of a building member, or other various surfaces.

DESCRIPTION OF SYMBOLS 1 ... Olefin-type thermoplastic resin base material 2 ... Picture layer 3 ... Adhesive layer 4 ... Anchor coat layer 5 ... Ionomer film

Claims (3)

  In a laminate in which a pattern layer, an adhesive layer, an anchor coat layer, and an ionomer film are provided in this order on an olefin-based thermoplastic resin base material, the adhesive layer is made of polycarbonate urethane, and the anchor coat layer is A laminate comprising polycarbonate urethane, acrylic polyol and isocyanate. The possible coating amount of the adhesive layer is ^4g / ^{m 2 ~9g} / m 2 after drying, the coating amount of the anchor coat layer is 0.5g ^{/ m 2} ~7g ^/ m 2 after drying The laminate according to claim 1.   The laminate according to claim 1 or 2, wherein the anchor coat layer has a ratio of polycarbonate urethane to acrylic polyol in a range of 35:65 to 45:55.