JP2006142624A - Surface film for building material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface film for building materials which uses a material replacing a vinyl chloride resin, has abrasion resistance and scratch resistance, and does not generate a fault when processed into a building material such as a floor or a wall. <P>SOLUTION: The film has at least three layers. A surface layer (A) is made of a resin compound (A)containing 50-98 wt% of a polypropylene resin of a specified composition and 50-2 wt% of an ionic copolymer. An intermediate layer (B) contains a polypropylene resin of a specified composition different from that of the surface layer (A). A back layer (C) (a layer in contact with a substrate) is made of a resin composition (C) containing at least one selected from the group consisting of a polypropylene resin or linear low density polyethylene, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-ethyl methacrylic acid copolymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a surface film for building materials that is used for a floor, a wall, and the like by laminating a substrate such as a design film, a foam, a resin layer highly containing an inorganic filler, glass fiber, and nonwoven fabric on the back surface.

Conventionally, vinyl chloride, rubber and the like have been used as plastic floors, and most of them used vinyl chloride. However, vinyl chloride is said to generate hydrogen chloride gas during combustion and cause dioxins, and there is an increasing demand for conversion to non-vinyl chloride materials. Therefore, for example, a flooring using a non-vinyl chloride resin as disclosed in Patent Document 1 has been proposed, but a hard resin is used in order to impart abrasion resistance and scratch resistance to the surface layer. Or a surface protective layer is provided. When such a hard film is used as a flooring or wall surface material and it is going to be processed into a building material, it is difficult to process by printing, laminating to other members, etc. There is a risk that problems may occur, such as being difficult to construct after processing into flooring or wall materials.
JP-A-9-143888

  The present invention provides a surface film for a building material that has wear resistance and scratch resistance using a material that replaces a vinyl chloride resin, and that does not cause problems when processed into a building material such as a floor or a wall. It is in.

Hereinafter, the present invention will be described in detail.
The invention of claim 1 is a polypropylene resin having a film having at least three layers, the surface layer (A) having a melting point of 140 ° C. or higher and a weight average molecular weight (Mw) in the range of 100,000 to 300,000. The amount of resin elution from 0 ° C. to 70 ° C. by the cross fractionation method is 0 to 30% by weight of the total polypropylene resin amount, and the resin elution amount from 70 ° C. to 125 ° C. is 70% of the total polypropylene resin amount. A resin composition (A) comprising 50 to 98% by weight of a polypropylene resin having a composition in the range of ˜100% by weight and 50 to 2% by weight of an ionic copolymer,
The intermediate layer (B) is a polypropylene resin having a melting point of 160 ° C. or higher and a weight average molecular weight (Mw) in the range of 160,000 to 250,000, and resin elution at 0 ° C. or higher and 10 ° C. or lower by the cross fractionation method. The amount is 45 to 55% by weight of the total amount of polypropylene resin, and the resin elution amount at 10 to 70 ° C. is 15 to 25% by weight of the total polypropylene resin amount, and 70 to 95 ° C. Polypropylene having a composition in which the resin elution amount is 1 to 5% by weight of the total polypropylene resin amount, and the resin elution amount in the range of 95 ° C. to 125 ° C. is 25 to 35% by weight of the total polypropylene resin amount. Containing resin,
The back layer (C) opposite to the surface layer (A) (layer in contact with the base material) is a polypropylene resin or linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, It is a surface film for building materials formed from a resin composition (C) containing at least one selected from the group consisting of an ethylene-methyl methacrylate copolymer and an ethylene-ethyl methacrylic acid copolymer. .

  The invention according to claim 2 is the surface film for building material according to claim 1, wherein a pigment is added only to the intermediate layer (B).

  The polypropylene resin of the surface layer (A) needs to have a melting point of 140 ° C. or higher and a weight average molecular weight (Mw) in the range of 100,000 to 300,000 from the viewpoint of scratch resistance of the film. When the molecular weight is low, the slipperiness is poor and there is a risk of problems in secondary processing, and when the molecular weight is high, film formation tends to be difficult.

  The polypropylene resin of the surface layer (A) used in the present invention has a resin elution amount in the range of 0 ° C. or more and 70 ° C. or less by the cross fractionation method of 0 to 30% by weight of the total polypropylene resin amount, and exceeds 70 ° C. and 125 ° C. or less. It is important to have a composition in the range where the elution amount of is 70 to 100% by weight of the total amount of polypropylene resin.

  When the resin elution amount at 0 ° C. or more and 70 ° C. or less exceeds 30% by weight, there is a possibility that problems such as insufficient scratch resistance or blocking may occur. If the resin elution amount at 70 ° C. and 125 ° C. is less than 70%, sufficient scratch resistance may not be obtained. The polypropylene resin may be a homopolymer of propylene, a copolymer obtained by copolymerizing propylene with an α-olefin other than propylene, and may be a block (co) polymer or a random (co) polymer. Examples of the α-olefin include 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, neohexene, 1-heptene, 1-octene, 1 -Decene and the like can be mentioned, among which 1-butene is preferably used.

  Among the polypropylene resins, homopolypropylene is preferable from the viewpoint of scratch resistance, but is not particularly limited. When more wear resistance and scratch resistance are required, a crystallized nucleus material may be added to the surface layer (A). The core material is not particularly limited as long as it has a nucleating action on a polypropylene polymer, and examples thereof include metal salts of organic carboxylic acids, benzaldehydes and their condensates of polycyclic alcohols and polymers, polymers Examples include nucleating agents.

  The surface layer (A) is formed from a resin composition (A) containing 50 to 98% by weight of the polypropylene resin and 2 to 50% by weight of an ionic copolymer.

  If the polypropylene resin is less than 50% by weight, the interlayer strength with the intermediate layer (B) may be insufficient. If it exceeds 98% by weight, there is a possibility that sufficient wear resistance as an object of the present invention cannot be obtained.

  When the content of the ionic copolymer is 2% by weight or less, sufficient abrasion resistance and scratch resistance intended by the present invention cannot be obtained, and when it exceeds 50% by weight, the intermediate layer (B) and There is a risk that the interlaminar strength will be insufficient.

  The ionic copolymer used in the present invention is a molecular chain in which a carboxyl group of a copolymer of an α-olefin and an α, β-ethylenically unsaturated carboxylic acid is partially or completely neutralized with a metal ion. It has a cross-linked structure, and exhibits a characteristic as a crosslinked polymer in a solid state and a characteristic as an uncrosslinked thermoplastic polymer in a molten state.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, and monoethyl maleate. Is acrylic acid or methacrylic acid.

  The types of metals that partially or completely neutralize the carboxyl group of the copolymer include alkaline metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, zinc, copper, cobalt, nickel, Typical examples include transition metals and the like such as chromium and lead, and alkali metals, alkaline earth metals, and zinc are particularly preferably used.

  Examples of the ionic copolymer include a product name “HIMILAN” manufactured by Mitsui DuPont Polychemical Co., Ltd.

  The polypropylene resin of the intermediate layer (B) has a melting point of 160 ° C. or higher and a weight average molecular weight (Mw) in the range of 160,000 to 250,000 from the viewpoint of scratch resistance and flexibility of the film. is required. Film formation tends to be difficult even when the molecular weight increases or decreases.

  The polypropylene resin of the intermediate layer (B) has a resin elution amount of 0 ° C. or more and 10 ° C. or less by the cross fractionation method of 45 to 55% by weight of the total polypropylene resin amount, and is a resin at a temperature exceeding 10 ° C. and 70 ° C. or less. The elution amount is 15 to 25% by weight of the total polypropylene resin amount, and the resin elution amount at 70 ° C. to 95 ° C. or less is 1 to 5% by weight of the total polypropylene resin amount, to 95 ° C. or more and 125 ° C. or less. It is necessary to have a composition within the range where the resin elution amount is 25 to 35% by weight of the total polypropylene resin amount.

  The weight average molecular weight of the propylene-based resin is measured by, for example, high temperature GPC (150 CV) manufactured by WATERS.

  The measurement of the elution amount of the polypropylene resin by the cross fractionation method used in the present invention is performed as follows. First, the polypropylene resin is dissolved in o-dichlorobenzene at a temperature at which the polypropylene resin is completely dissolved, cooled at a constant rate, and a thin polymer layer is formed on the surface of an inert carrier prepared in advance in order of high crystallinity and large molecular weight. Generate in order. Next, the polymer layer thus formed is heated continuously or stepwise, the concentration of the components eluted in sequence is detected, and the composition distribution (crystallinity distribution) is measured <temperature rising elution fractionation>. At the same time, the molecular weight and molecular weight distribution of the component are measured by high temperature GPC. Such a measurement is performed, for example, by a cross-fractionation chromatograph apparatus <CFC-T150A type including the temperature rising elution fractionation (TREF = TemperatureRising Elution Fraction) portion and the high temperature GPC (SEC = Size Extraction Chromatography) portion as a system. : Made by Mitsubishi Oil Chemical Co., Ltd.

  When the amount of resin elution at 0 ° C. or more and 10 ° C. or less by the above-described polypropylene resin cross fractionation method is less than 45% by weight, the flexibility of the film is insufficient, and when it exceeds 55% by weight, the stretchability of the film is inferior. When the resin elution amount is 10 ° C. or more and 70 ° C. or less, the film lacks flexibility when it is less than 15% by weight. When the amount of resin elution at 70 ° C. and 95 ° C. is less than 1% by weight, the film has poor deformation recovery properties. If the resin elution amount is over 95 ° C. and below 125 ° C., if it is less than 25% by weight, sufficient strength as a film cannot be obtained, and if it exceeds 35% by weight, the flexibility of the film is inferior.

  In the polypropylene resin used for the surface layer (A) and the intermediate layer (B) constituting the surface film for building materials of the present invention, the melting point, molecular weight, and elution amount in each temperature range are within the above ranges. Very important. The film elastic modulus, strength, heat resistance, secondary workability, etc. are controlled in a suitable range by using a polypropylene resin whose melting point, molecular weight, and elution amount in each temperature range in the cross fractionation method are within the above ranges. As a result, it is possible to obtain the flexibility to ensure workability when constructing the building material sheet using the building material surface film of the present invention. On the other hand, in order to obtain a polypropylene resin having flexibility intended in the present invention using a general polypropylene resin, conventionally, it is necessary to add a large amount of a thermoplastic elastomer such as a vinyl aromatic elastomer, It was not easy technically and economically. However, according to the present invention, the object can be easily achieved.

  The back layer (C) opposite to the surface layer (A) is made of polypropylene resin or linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer. And at least one resin composition (C) selected from ethylene-methacrylic acid copolymers. When two or more kinds of resins are used as a mixture, it is necessary to mix them so as not to impair the intent of the present invention, such as compatibility with each other.

  In addition, the surface layer (A), the intermediate layer (B), and the back layer (C) layer of the surface film for building materials according to the present invention have a pigment, a dye, an antioxidant, an ultraviolet ray, or the like as long as the intention of the invention is not impaired. Additives such as an absorbent, a weathering agent, and an antistatic agent may be added. However, it is more preferable to add the pigment only to the intermediate layer (B) layer. If a pigment is added to the surface layer (A), if there is a scratch, the scratch may be noticeable. Moreover, when added to the back surface layer (C), the adhesive strength with the base material layer may be lowered depending on the addition amount.

  A method for producing the surface film for building material of the present invention is not particularly limited, and a known method for molding a resin sheet or film can be used. For example, an extrusion molding method using a T-die method or an inflation method. Examples thereof include a method of laminating a film for forming each layer by a calendering method, a laminating method, a multilayer extrusion molding method by a T-die method or an inflation method, etc., and a multilayer extrusion method is suitably used.

  The thickness of the surface film for building materials of the present invention is not particularly limited, and is appropriately determined depending on the use and the required texture. However, the ratio of the surface layer (A) to the entire layer is preferably 5% or more and 30% or less. If the ratio of the surface layer (A) is less than 5%, sufficient scratch resistance may not be obtained. If it exceeds 30%, the flexibility of the film is insufficient and the secondary workability or building material sheet There is a possibility that construction suitability after formation may not be obtained. Further, the thickness of the back layer (C) is not particularly limited, but the ratio to the thickness of all layers is preferably 50% or less. If it exceeds 50%, the scratch resistance may be insufficient depending on the application. Moreover, coating etc. may be given to the surface film surface for building materials of this invention as needed.

  Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

Example 1
Polypropylene resin (PP2) 80 wt%, ionic copolymer (trade name “HIMILAN 1705” (manufactured by Mitsui DuPont Polychemical Co., Ltd.) (density = 0.950 g / cm ³ , melt mass flow rate (Table 1) MFR) = 5 g / 10 min) surface layer (A) containing 20 wt%, intermediate layer (B) containing polypropylene resin (PP1), back layer containing linear low density polyethylene having a density of 0.925 g / cm ³ ( C), the thickness ratio is layer (A) / layer (B) / layer (C) = 1/10/1, and three layers are extruded using a T-die so that the total thickness is 200 μm. A surface film was produced.

(Example 2, Comparative Examples 1-3)
Except having changed into each structure shown in Table 2 using the resin shown in Table 1, it carried out similarly to Example 1, and carried out the three-layer extrusion using the T die, and manufactured the 200-micrometer-thick surface film for building materials. .

  About the surface film for building materials obtained above, it evaluated by the following method about abrasion resistance, secondary workability, and workability.

<Abrasion resistance>
The Taber abrasion test was conducted under the conditions of the wear wheel H-18 and the load of 7.35 (N), and the following determination was made based on the weight loss after rotating 1500 times.
○: Less than 0.1 g Δ: 0.1 g or more and less than 0.3 g ×: 0.3 g or more

<Secondary workability>
Three-color printing was performed on a film having a width of 1000 mm, and the ease of printing at that time was evaluated based on the following indices.
○: Appropriate flexibility and no problem in processing.
Δ: Slightly difficult to process, but can be processed.
X: It is very difficult to process because the stiffness is too hard.

<Workability>
The laminated sheet of the said implementation film of 1 m width and a base material sheet (sheet | seat of adhesive evaluation use use) was created, and construction was performed. The ease of construction at that time was evaluated based on the following indicators. Table 2 shows the evaluation results.
○: Appropriate flexibility and no problem in construction. △: Slightly uncomfortable, but not so uncomfortable in construction. ×: Very hard to construct because it is too stiff.

Claims (2)

A film having at least three layers, wherein the surface layer (A) is a polypropylene resin having a melting point of 140 ° C. or higher and a weight average molecular weight (Mw) in the range of 100,000 to 300,000, and a cross fractionation method The resin elution amount from 0 ° C. to 70 ° C. is 0 to 30% by weight of the total polypropylene resin amount, and the resin elution amount at 70 ° C. to 125 ° C. is 70 to 100% by weight of the total polypropylene resin amount. A resin composition (A) containing 50 to 98% by weight of a polypropylene resin having an internal composition and 50 to 2% by weight of an ionic copolymer,
The intermediate layer (B) is a polypropylene resin having a melting point of 160 ° C. or higher and a weight average molecular weight (Mw) in the range of 160,000 to 250,000, and resin elution at 0 ° C. or higher and 10 ° C. or lower by the cross fractionation method The amount is 45 to 55% by weight of the total amount of polypropylene resin, and the resin elution amount at 10 ° C. to 70 ° C. is 15 to 25% by weight of the total polypropylene resin amount, at 70 ° C. to 95 ° C. Polypropylene having a composition in which the resin elution amount is 1 to 5% by weight of the total polypropylene resin amount and the resin elution amount at 95 ° C. to 125 ° C. or less is 25 to 35% by weight of the total polypropylene resin amount. The back layer (C) (layer in contact with the base material), which contains a resin and is opposite to the surface layer (A), is a polypropylene resin or linear low density polyethylene, ethylene-vinyl acetate. It is formed from a resin composition (C) containing at least one selected from the group consisting of a polymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-methacrylic acid copolymer. A characteristic surface film for building materials. The surface film for building materials according to claim 1, wherein a pigment is added only to the intermediate layer (B).