JP2006037259A - Polyolefin film for surface skin of building material and wallpaper produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wallpaper having excellent scratch resistance, stain resistance and stain removability. <P>SOLUTION: The wallpaper is produced by laminating a polyolefin film to a foamed resin layer of a laminate obtained by laminating a foamed layer composed of a polyolefin composition on a substrate. The polyolefin film is composed of at least two layers, the surface layer (X) is composed of a polypropylene resin composition, the inner layer (Y) is composed of an ethylenic copolymer having a melting point of 80-140°C and the gloss of the surface layer measured at an incident angle of 60° is ≤50%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyolefin film for building material skin excellent in flexibility, scratch resistance, stain resistance, and decontamination property, and a wallpaper using the same.

The wallpaper has a structure in which a synthetic resin sheet is bonded to the front side of a paper base material, but a sheet made of vinyl chloride resin is widely used as a synthetic resin foam sheet. Vinyl chloride resin sheets are widely used because of their good moldability, flame retardancy, and low cost. However, since the wallpaper obtained from a vinyl chloride resin is inferior in scratch resistance, stain resistance, and decontamination, methods for improving these have been studied.
Japanese Patent Application Laid-Open No. 2000-281844 discloses a wallpaper in which a foamed resin layer formed from a polyolefin resin composition containing an ethylene (co) polymer as a main component is laminated on a base material.
Japanese Patent Application Laid-Open No. 9-193315 discloses a wallpaper in which an ethylene-vinyl acetate copolymer saponified product (EVOH) is laminated on a laminate made of a thermoplastic resin / polyolefin resin such as vinyl chloride resin.

Japanese Patent Application Laid-Open No. 2001-260287 discloses a wallpaper in which an ethylene-vinyl alcohol copolymer resin film is laminated on a foamed resin layer.
Although the wallpaper obtained from these polyolefin resin compositions is excellent in stain resistance etc. compared with a vinyl chloride wallpaper, it is still inadequate practically and the further improvement is desired.
In addition, it is possible to improve the scratch resistance and stain resistance by laminating an ethylene-vinyl alcohol copolymer resin film. Particularly when the foamed resin layer is a polyolefin resin composition, the foamed resin layer Adhesive strength with was insufficient.

Japanese Patent Application Laid-Open No. 2002-1883 discloses a polyolefin film for wall covering material in which an adhesive resin is provided on the inner layer. Even in the method according to the publication, particularly when the foamed resin layer is a polyolefin resin composition, the adhesive strength with the foamed resin layer is insufficient.
JP 2000-281844 A JP-A-9-193315 JP 2001-260287 A Japanese Patent Laid-Open No. 2002-1883

As a result of intensive studies on a polyolefin film excellent in flexibility, scratch resistance, stain resistance, decontamination property, and surface design for building material skins, especially wallpaper skins. The above problems have been solved by the multilayer polyolefin film obtained from the specific resin composition, and the present invention has been completed.

That is, the present invention
A film composed of at least two layers, wherein the surface layer (X) is composed of a polypropylene resin composition, and the inner layer (Y) is formed of an ethylene copolymer having a melting point in the range of 80 to 140 ° C. It is a polyolefin film for building material skin, characterized in that the gloss measured at an incident angle of 60 degrees is 50% or less,
In the foamed resin layer of the laminate, the foamed resin layer (B) formed from a polyolefin resin composition comprising an ethylene-based (co) polymer and a flame retardant and / or an inorganic filler is laminated on the substrate (A). The wallpaper is characterized in that the polyolefin film is laminated so that the inner layers (Y) face each other.

  The polyolefin film for building material skin of the present invention is excellent in flexibility, scratch resistance, stain resistance, and decontamination property, and also has excellent surface design. The wallpaper using the polyolefin film for building material skin of the present invention has less curling and excellent scratch resistance, and can reduce the gloss of the surface film, which has been a conventional problem. Furthermore, since a film excellent in adhesive strength with the base material is used, workability is also improved.

The present invention relates to a building material skin polyolefin film formed of a specific resin composition. Furthermore, the present invention relates to a wallpaper characterized in that the polyolefin film is laminated on a resin layer of a laminate in which a foamed resin layer (B) formed from a polyolefin resin composition is laminated on a substrate (A). .

Polyolefin film for building material skin The polyolefin film for building material skin of the present invention is a film comprising at least two layers, the surface layer (X) is made of a polypropylene resin composition, and the inner layer (Y) has a melting point of 80 to 140 ° C. A polyolefin film for a skin of a building material, characterized in that the gloss is 50% or less as measured at an incident angle of 60 degrees on the surface layer side.

Examples of the polypropylene resin composition forming the surface layer (X) include propylene homopolymers, random copolymers having 2 to 10 carbon atoms excluding propylene and propylene, propylene-ethylene block copolymers, and propylene (copolymers). ) A composition of a polymer and an ethylene polymer can be mentioned. Ethylene polymer used in the compositions, a low-density polyethylene or high density polyethylene having a density of 0.920~0.970g / cm ^3, preferably low density polyethylene having a density of 0.930~0.970g / cm ³ Or it is a high density polyethylene, More preferably, it is a high density polyethylene of a density 0.940-0.970 g / cm < ³ >. The melt flow rate (190 ° C., 2.16 kg load, hereinafter abbreviated as MFR) of the ethylene polymer is in the range of 0.01 to 10 g / 10 minutes, preferably 0.05 to 5 g / 10 minutes.

  Preferable examples of the propylene (co) polymer used for the polypropylene resin composition include a propylene-ethylene block copolymer. The ethylene content in the block copolymer is 3 to 15% by weight, preferably 4 to 12% by weight. The amount of the rubber component in the block copolymer is 5 to 20% by weight, preferably 7 to 18% by weight. Here, the amount of the rubber component is determined by the dissolved amount when the block copolymer is dissolved in p-xylene by heating and then precipitated at room temperature. The MFR (230 ° C., 2.16 kg load) is in the range of 1 to 30 g / 10 minutes, preferably 3 to 20 g / 10 minutes.

Further, in forming the composition of the propylene (co) polymer and the ethylene polymer, the ratio MFR (p) of the propylene (co) polymer MFR (p) to the ethylene polymer MFR (e) ( p) / MFR (e) is in the range of 5-50, preferably 10-40, more preferably 15-30. By doing so, a film having good gloss as a surface layer of the polyolefin film for building materials can be obtained.
The amount of the ethylene polymer component in the polypropylene resin composition is 0 to 50% by weight, preferably 5 to 40% by weight.

As an ethylene-type copolymer which forms an inner layer (Y), the ethylene-alpha-olefin copolymer which exists in the range of 80-140 degreeC of melting | fusing point can be mentioned. A preferable melting point is 85 to 130 ° C, more preferably 90 to 120 ° C. The melt flow rate (190 ° C., 2.16 kg load) is in the range of 0.05 to 30 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes. The density is in the range of 0.880 to 0.940 g / cm ³ , preferably 0.890 to 0.935 g / cm ³ , more preferably 0.900 to 0.930 g / cm ³ . A particularly preferred ethylene copolymer is a copolymer of ethylene and α-olefin obtained using a metallocene catalyst. Preferable examples of the α-olefin include 1-butene, 1-pentene, 1-hexene and 1-octene.

In such a polypropylene resin composition and / or ethylene-based copolymer, other synthetic resins and rubbers, or antioxidants, if necessary, as long as the performance as a polyolefin film for building materials of the present invention is not impaired. Additives such as a heat resistance stabilizer, a weather resistance stabilizer, a slip agent, an antiblocking agent, an antistatic agent, a crystal nucleating agent, a pigment, and a hydrochloric acid absorbent may be included.
About the manufacturing method of the polyolefin film for building materials of this invention, the well-known method which can obtain polyolefin films, such as T-die shaping | molding, inflation shaping | molding, and calendar shaping | molding, is employable. In the present invention, a film obtained by stretching the obtained film in at least one direction can be used as the polyolefin film. Furthermore, it can also be used as a laminated film with other polyolefin films, nylon films, polyester films, EVOH films and the like.

  The thickness of the surface layer (X) in the polyolefin film is 3 to 30 μm, preferably 5 to 20 μm, and the thickness of the inner layer (Y) is 1 to 20 μm, preferably 1 to 10 μm.

The surface layer and / or inner layer of the polyolefin film of the present invention is subjected to a known treatment for oxidizing the polyolefin film surface, such as corona treatment, flame treatment, and plasma treatment, for the purpose of improving printability and adhesion. May be.
The polyolefin film of the present invention thus obtained has a gloss of 50% or less, preferably 2 to 30%, as measured at an incident angle of 60 degrees.

  In the present invention, by laminating a polyolefin film having the above-described characteristics to a foamed resin layer, which will be described later, the adhesive strength with the foamed resin layer is high, and scratch resistance and stain resistance are excellent. By laminating a polyolefin film on the applied foamed resin layer and embossing it, a wallpaper with low gloss and excellent design can be obtained.

Wallpaper The base material (A) in the wallpaper of the present invention is generally a paper base material. The paper substrate is selected according to the intended use for wallpaper, such as paper made from natural pulp or synthetic pulp, and paper made by mixing them with inorganic substances. When the foamed resin layer (B) (hereinafter sometimes referred to as a foamed resin sheet (layer)) has its own water resistance and flame retardancy, the paper substrate is particularly required to have such properties. Although it can be used for general purposes, the use of flame retardant paper containing an inorganic substance as the base material (A), for example, paper containing aluminum hydroxide or the like, further improves flame retardancy. preferable.

  The foamed resin layer (B) which is laminated on the base material (A) and constitutes the wallpaper of the present invention is a polyolefin resin composition mainly composed of an ethylene-based (co) polymer. Specific examples of the ethylene (co) polymer include high-density polyethylene, high-pressure low-density polyethylene, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, an ethylene-vinyl acetate copolymer, ethylene -Methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, etc., or a mixture thereof.

  Specific examples of the ethylene (co) polymer used in the polyolefin resin composition include a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms or a mixture of other ethylene (co) polymer. preferable. Preferred α-olefins of a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms (ethylene (co) polymer) are 1-butene, 1-hexene and 1-octene. The density of the ethylene-based (co) polymer is 0.850 to 0.920 g / cm 3, preferably 0.850 to 0.900 g / cm 3, more preferably 0.855 to 0.890 g / cm 3, and MFR ( 190 ° C.) is 0.1 to 100 g / 10 min, preferably 1 to 50 g / 10 min.

  The polyolefin resin composition is also preferably a resin composition of an ethylene (co) polymer and a high-pressure low-density polyethylene. In that case, the ethylene (co) polymer is 50 to 90% by weight, preferably 60 to 80% by weight, 10 to 50% by weight, preferably 20 to 40% by weight of high-pressure low-density polyethylene.

  Examples of the flame retardant include metal hydrated oxides such as aluminum hydroxide and magnesium hydroxide. Examples of the inorganic filler include calcium carbonate, talc, barium sulfate, magnesium sulfate and the like. When the polyolefin resin composition contains a flame retardant and / or an inorganic filler, 20 to 150 parts by weight, preferably 30 to 120 parts by weight, more preferably 30 to 90 parts by weight of the flame retardant and / or inorganic filler per 100 parts by weight of the polyolefin resin. Can be blended in part.

  By setting the resin composition in such a preferable range as the foamed resin layer (B), the adhesive strength with the polyolefin film of the present invention is improved, and an adhesive layer such as an adhesive is not required between these layers, and flame retardant From the viewpoint of safety and hygiene. In such a resin composition, as long as it does not impair the performance as wallpaper of the present invention, other synthetic resins and rubbers, or antioxidants, heat stabilizers, weathering stabilizers, slip agents, antiseptics as necessary. It may contain additives such as blocking agents, crystal nucleating agents, pigments, hydrochloric acid absorbents and the like.

  Further, after blending each component of the polyolefin resin composition and various additives as required, for example, with a mixer such as a Henschel mixer, a Banbury mixer, a tumbler mixer, a roll or an extruder, calender molding, T-die molding It can be used for a known sheet forming machine such as a sheet.

  A foaming resin layer is obtained by adding a foaming agent to such a resin layer and foaming it by placing it under a foaming temperature and pressure condition. As a method for producing the foamed resin layer, a method may be employed in which a non-foamed sheet is once formed from a resin composition to which a foaming agent has been added in advance, and then the temperature is raised to change to a foamed resin sheet. The method of obtaining a foamed resin sheet directly from the added resin composition may be used.

The foaming agent that can be used is appropriately selected from chemical foaming agents and gas foaming agents (physical foaming agents) based on the molding method and molding temperature of the foamed resin sheet.
Chemical foaming agents include azo compounds such as azodicarbonamide and azobisisobutyronitrile, hydrazide compounds such as benzosulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), dinitrosopentamethylenetetramine Nitroso compounds such as these, or a mixture thereof, etc., and these decompose by themselves under molding conditions to generate gas for foam molding. Moreover, you may use a foaming adjuvant with these foaming agents as needed. Examples of the foaming aid include zinc compounds such as zinc oxide and zinc stearate, and organic acids such as salicylic acid, phthalic acid, and oxalic acid.

  Examples of the gas foaming agent (physical foaming agent) include hydrocarbons such as carbon dioxide, halogenated hydrocarbons such as difluorodichloromethane, butane, pentane, hexane, cyclobutane, and cyclohexane. It itself becomes a gas and contributes to foam molding. As the gas foaming agent (physical foaming agent), carbon dioxide gas, butane gas, chlorofluorocarbon gas and the like are suitable. One type of foaming agent may be used, or a plurality of types may be used in combination.

  When forming a foamed sheet, an unfoamed resin sheet is once formed from a resin composition to which a foaming agent has been added using a roll or a T-die, and then the resin sheet is transferred to foaming conditions to produce a foamed resin sheet. In the case of this method, it is preferable to use a chemical foaming agent rather than a gas foaming agent. The foam molding can be performed by using an air oven or a heating roll.

  On the other hand, when a resin composition is supplied to an extruder and a foaming agent is press-fitted from another supply port of the extruder to form a foamed resin sheet directly from a die, a gas foaming agent (physical foaming agent) is generally used. used. Moreover, the resin composition which added the chemical foaming agent previously can be supplied to an extruder, and a foamed resin sheet can also be taken out from a die | dye similarly. The foamed resin layer (B) of the wallpaper of the present invention is obtained by adding a known foaming agent and foaming. As thickness of a foamed resin layer (B), it is 0.1-2 mm normally, Preferably it is 0.2-1 mm. The surface of the foamed sheet layer (foamed resin layer (B)) is designed as wallpaper by printing, embossing or embossing.

The foamed resin sheet thus obtained becomes a laminate which is a part of the structure of the present invention by being laminated with the base material (A) such as the paper described above.
The production of the laminate of the base material (A) and the foamed resin layer (B) can be performed, for example, by laminating a resin sheet previously foam-molded on a paper base material and laminating using an adhesive between both layers. Alternatively, it may be laminated by extruding a molten polyethylene resin or the like between layers. As another method, an unfoamed resin sheet molded in advance on a paper substrate is laminated and bonded, or an unfoamed resin sheet is laminated on the paper substrate, and then the laminate is heated. It is possible to obtain a laminate in which a foamed resin sheet is laminated on a paper substrate by placing the foamed material under a foaming condition such as passing through a furnace or a heating roll. In addition, a resin composition to which a foaming agent is added can be directly laminated on a paper base material from an extruder or a calender roll.

In the wallpaper of the present invention, the polyolefin film for building materials of the present invention described above is further opposed to the foamed resin layer (B) of the laminate, with the inner layer (Y) of the polyolefin film facing the foamed resin layer (B). Obtained by laminating as described above.
As a method of laminating the polyolefin film and the foamed resin layer (B), a dry lamination method using an adhesive between both layers, a polyolefin film and / or a foamed resin layer are heated by a heating roll or the like, and laminated by heat. Or an extrusion lamination method in which a raw material resin of a polyolefin film is extruded from a die and laminated with a foamed resin layer in a molten resin state. In addition, the raw material resin of the polyolefin film and the resin composition used for the foamed resin layer can be laminated by a co-extrusion method. Among these, since the curl is less in the wallpaper after lamination and the adhesive strength is high, the lamination method using an extrusion lamination method or a heating roll can be preferably used. Alternatively, a polyolefin film may be laminated on the unfoamed resin layer in advance, and then foamed to obtain the wallpaper of the present invention.

EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited to this.
[Production Example 1]
An ethylene / 1-butene random copolymer (19-butene content 19 mol%) having an MFR (190 ° C.) of 3.6 g / 10 min and a density of 0.860 g / cm 3 is 70% by weight, and the MFR (190 ° C.) is 9 0.5 g / 10 min, high-pressure low-density polyethylene 30% by weight with a density of 0.917 g / cm 3, 70 parts by weight of calcium carbonate having an average particle size of 3.4 μm with respect to 100 parts by weight, and further as a blowing agent 5 parts by weight of azodicarbonamide was added, and an unfoamed resin sheet having a thickness of 130 μm was obtained at a die temperature of 140 ° C. using a T-die molding machine equipped with a 40 mmφ extruder. The obtained unfoamed resin sheet was bonded to a paper base material (plain paper) having a basis weight of 65 g / m 2 by heating to 140 ° C. Further, this was passed through a continuous foaming furnace set at 210 ° C. for 2 minutes to obtain a laminate having a foamed resin layer with a foaming ratio of 4.5 times.

[Production Example 2]
Propylene-ethylene block co-polymer with a 300 mm wide multi-layer T-die molding machine, MFR (230 ° C.) 7.0 g / 10 min, ethylene content 8% by weight, rubber component 11% by weight for the surface layer A resin composition comprising 80% by weight of coalescence (PP-1) and 20% by weight of MFR (190 ° C.) having a density of 0.963 g / cm ³ and 0.3 g / 10 min high density polyethylene (HDPE-1) is used. As an inner layer, an ethylene / 1-hexene copolymer (LLDPE-1) (produced with a metallocene catalyst) having a density of 0.914 g / cm ³ and an MFR (190 ° C.) of 3.6 g / 10 min, a resin temperature of 220 ° C. A polyolefin film having a surface layer thickness of 15 μm and an inner layer thickness of 5 μm was obtained. Table 1 shows the gloss value (60 degrees) of the obtained film. Furthermore, the inner layer side of the obtained film was subjected to corona treatment so that the wetting tension was 40 mN / m, and used for the production of wallpaper described later.

[Example 1]
The foamed resin layer obtained in Production Example 1 is coated with the polyolefin film obtained in Production Example 2 using a heated embossing roll (manufactured by Yuri Roll Co., Ltd.) at a temperature of 105 ° C., a pressure (linear pressure) of 1 t, and a rotation speed. A wallpaper sample was prepared by laminating under the condition of 5 m / min. Table 1 shows the evaluation results (scratch resistance, adhesive strength, curl) of the obtained wallpaper.

  Scratch resistance: The back of the wallpaper and the front were rubbed together, the polyolefin film surface was observed, and scratch resistance was evaluated.

    Adhesive strength: A commercially available gummed tape was adhered to the wallpaper sample surface at a constant load (0.2 MPa). When this was peeled off, the surface condition of the wallpaper was evaluated.

    Curling: The degree of warpage of the wallpaper sample in the TD direction was observed to evaluate curl.

[Examples 2 to 4, Comparative Example 1]
A wallpaper was obtained in the same manner as in Example 1 except that a polyolefin film having the composition described in Table 1 (the production method was the same as in Production Example 2) was used. The evaluation results of the obtained wallpaper are shown in Table-1.

Since the polyolefin film of the present invention is excellent in strength (scratch resistance) and adhesion to a substrate, it is suitable as a surface protective film for wallpaper. Further, since the polyolefin film of the present invention has a lower gloss than the conventional film, a surface protective wallpaper having an excellent texture can be obtained by using this.

Claims (2)

A film composed of at least two layers, wherein the surface layer (X) is composed of a polypropylene resin composition, and the inner layer (Y) is formed of an ethylene copolymer having a melting point in the range of 80 to 140 ° C. A polyolefin film for a skin of building materials, characterized in that the gloss measured at an incident angle of 60 degrees is 50% or less. In the foamed resin layer of the laminate, the foamed resin layer (B) formed from a polyolefin resin composition comprising an ethylene-based (co) polymer and a flame retardant and / or an inorganic filler is laminated on the substrate (A). A wallpaper, wherein the polyolefin film according to claim 1 is laminated so that the inner layers (Y) face each other.