JP2005015794A - Decorative film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative film which is hard to cause any delamination and excellent in functions for trapping formaldehyde and in stain preventing properties, a fluororesin composition which constitutes this decorative film, a method of producing the decorative film, and a decorative material (a decorative wallpaper, a decorative steel sheet). <P>SOLUTION: The fluororesin composition is characterized in that a formaldehyde adsorptive material is added into a fluororesin having a melting point not higher than 200°C, and the decorative film is made up by laminating this fluororesin composition onto a resin base material layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a decorative film having a fluorine-containing resin layer.

  For interiors of walls and ceilings of houses, or building materials such as joinery and furniture, decorative materials or decorative boards with a decorative sheet attached to a base material made of a wooden base material via an adhesive are used. Yes. The woody base material is bonded by an adhesive, and as this adhesive, an adhesive of urea, melamine or phenolic resin is often used from the viewpoint of adhesive function and cost. However, these adhesives contain free formaldehyde, and formaldehyde is released by decomposition of the resin. When a decorative sheet is directly bonded to such a woody base material, there is a problem that formaldehyde, which is a toxic substance having a strong irritating odor, so-called formalin odor, is released and the sanitary environment is impaired.

  In addition, the adhesive used when pasting the wallpaper, such as a decorative sheet on the backing paper, to the base material of the wall surface, contains formaldehyde as an adhesive stabilizer and preservative. Even when these adhesives are used, there is a problem that formaldehyde is released into the air and the sanitary environment is also impaired.

In order to capture volatile organic substances such as formaldehyde, Patent Document 1 discloses a decorative film in which a hydrazine derivative is added to the surface layer.
Japanese Patent Laid-Open No. 10-258495

  Various resins have been disclosed as resins constituting the surface layer. However, when a non-fluorine resin is used, although there is a formaldehyde scavenging function, the antifouling property is not sufficient. Further, since non-fluorine resins generally do not easily transmit gas, there is a problem that the effect of the formaldehyde-adsorbing substance dispersed inside the resin is hardly exhibited.

  Then, this invention makes it a subject to provide the decorative film and cosmetics excellent in the formaldehyde capture | acquisition function and antifouling property.

The present invention will be described below.
A first aspect of the present invention is a fluororesin composition characterized in that a formaldehyde-adsorbing substance is added to a fluororesin having a melting point of 200 ° C. or lower.

  According to this invention, it is possible to provide a fluororesin composition excellent in formaldehyde capturing function and antifouling property.

  The fluororesin having a melting point of 200 ° C. or lower is preferably an adhesive fluororesin.

  According to this, it can be set as the decorative film in which delamination with a resin base material layer does not occur easily, and can provide the fluororesin composition excellent in the formaldehyde capture function and antifouling property.

  Here, the “adhesive fluororesin” refers to a fluororesin having a melting point of 150 ° C. to 250 ° C. and a 180 ° peel strength of a film prepared and evaluated by the following method of 4 N / cm or more. .

(Preparation of test film)
Rexpearl RA3150 (manufactured by Nippon Polyethylene Co., Ltd.), which is a kind of modified polyolefin resin, and fluororesin are pressed at 240 ° C. for 10 minutes at a sample pressure of 4 × 10 ^{5 to} 5 × 10 ⁵ Pa to obtain a laminated sheet. A test film is prepared by cutting into a width of 2.5 cm and a length of 25 cm.
(Evaluation of test film)
180 degree peel strength is measured at a peel rate of 5 mm / min and a temperature of 23 ° C. by a method according to JIS Z0237.

  The formaldehyde adsorbing substance is preferably an inorganic phosphate.

  According to this, the fluororesin composition excellent in the formaldehyde adsorption function can be provided at low cost.

  The second aspect of the present invention is a decorative film characterized in that the fluororesin composition is laminated on a resin base material layer.

  According to this invention, it is possible to provide a decorative film having the effects of the fluororesin composition.

  The resin base layer is preferably made of a modified polyolefin.

  According to this, it is possible to provide a decorative film in which the resin base material layer and the layer made of the fluororesin composition are excellent in adhesiveness and are difficult to peel off.

  The resin base material layer is preferably a laminate of two or more kinds of modified polyolefins.

  According to this, it is possible to provide a decorative film in which the resin base material layer and the layer made of the fluororesin composition are excellent in adhesiveness and are difficult to peel off.

  The ratio of the thickness of the layer made of the fluororesin composition to the thickness of the resin base material layer is preferably 1: 5 to 1:30.

  According to this, it is possible to provide a decorative film in which the resin base material layer and the layer made of the fluororesin composition are excellent in adhesiveness and are difficult to peel off.

  The thickness of the layer made of the fluororesin composition is preferably 1 to 5 μm.

  According to this, since the fluororesin layer is thin, the amount of expensive fluororesin used can be reduced, so that a decorative film excellent in economy can be provided.

  According to a third aspect of the present invention, there is provided a method for manufacturing a decorative film, wherein the layer made of the fluororesin composition and the resin base material layer in the decorative film are manufactured by coextrusion molding. It is.

  According to the present invention, it is possible to provide a method for producing a decorative film that is less likely to cause delamination and has an excellent formaldehyde capturing function and antifouling property at low cost.

  A fourth aspect of the present invention is a decorative wallpaper characterized in that a wallpaper base material is bonded to a surface of the resin base material layer of the decorative film opposite to the surface on which the fluororesin composition is laminated. is there.

  According to this invention, delamination hardly occurs, and a wallpaper excellent in formaldehyde capturing function and antifouling property can be provided.

  The fifth aspect of the present invention is a decorative steel sheet, characterized in that a steel sheet is bonded to a surface of the resin base layer of the decorative film opposite to the surface on which the fluororesin composition is laminated.

  According to the present invention, it is possible to provide a decorative steel sheet that hardly causes delamination and has an excellent formaldehyde capturing function and antifouling property.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative film excellent in a formaldehyde capture | acquisition function and antifouling property, the fluororesin composition which comprises this cosmetic film, the manufacturing method of a decorative film, and a decorative material (decorative wallpaper, decorative steel plate) are provided. be able to.

  The fluororesin composition of the present invention is obtained by adding a formaldehyde-adsorbing substance to a fluororesin having a melting point of 200 ° C. or lower. Since fluororesin is excellent in antifouling property and gas permeability, it is considered that there are few factors that inhibit the effect of the added formaldehyde-adsorbing substance compared to other resins, and the adsorption effect can be exerted more. . Further, since a fluororesin having a relatively low melting point is employed, a formaldehyde-adsorbing substance that is weak against heat can be added without being altered or decomposed.

  Examples of the fluororesin having a melting point of 200 ° C. or lower include tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and an adhesive fluororesin defined below.

  In the present invention, the formaldehyde-adsorbing substance refers to a substance having an action of adsorbing formaldehyde, or a substance that decomposes formaldehyde by chemically reacting with formaldehyde. Examples of substances having such properties include urea, ethylene urea, hydrazide compounds, nitrogen-containing compounds such as azole compounds or azine compounds in organic compounds, and natural zeolites, acid clay, diatomaceous earth, synthetic substances in inorganic substances. Zeolite, artificial zeolite, activated carbon, titanium oxide, phosphate and the like can be mentioned. Among these, condensed aluminum phosphate compounds such as aluminum dihydrogen triphosphate are preferable from the viewpoints of cost and formaldehyde adsorptivity. The amount added varies depending on the formaldehyde-adsorbing substance to be added. For example, in the case of aluminum dihydrogen tripolyphosphate, 0.1 to 30% by mass is added to the fluororesin based on the mass of the fluororesin (100% by mass). It is preferable to add 1 to 10% by mass, and it is more preferable to add. In general, the formaldehyde adsorbing substance is preferably added in an amount of 1 to 10% by mass with respect to the fluororesin based on the mass of the fluororesin (100% by mass).

  The fluororesin composition of the present invention is mainly used in the form of a decorative film. The decorative film has a configuration in which a fluororesin composition is laminated on at least one resin substrate.

The “adhesive fluororesin” in the present invention has a melting point of 150 ° C. to 250 ° C., and Rexpearl RA3150 (manufactured by Nippon Polyethylene Co., Ltd.), which is a kind of modified polyolefin resin, and fluororesin are 4 × 10 ⁵ to A laminated sheet was prepared by pressing at 240 ° C. for 10 minutes at a sample pressure of 5 × 10 ⁵ Pa, and a sample collected by cutting to a width of 2.5 cm and a length of 25 cm was applied to a method according to JIS Z0237. It means a fluororesin having a 180 degree peel strength of 4 N / cm or more when a 180 degree peel strength is measured at a peel rate of 5 mm / min and a temperature of 23 ° C.

Further, IR spectrum of the "adhesive fluororesin" in the present invention ^has an absorption peak between 1780cm ^-1 ~1880cm -1. Preferably, IR spectrum of the "adhesive fluorocarbon ^resin", between 1790 cm -1 between ～1800Cm ^-1 and ^{1845cm -1 ~1855cm} -1, have a absorption peak due to anhydride such as maleic anhydride groups and, ^{alternatively,} have an absorption peak due to end carbonate groups between 1800cm ^-1 ~1815cm -1, ^or between 1790cm ^-1 ~1800cm ^-1, between 1845cm ^-1 ~1855cm -1 and 1800 cm ^{- Between 1 and} 1815 cm ⁻¹ , it has an absorption peak due to a mixture of anhydrides such as maleic anhydride groups and terminal carbonate groups.

More preferably, IR spectrum of the "adhesive fluorocarbon ^resin", between 1790 cm -1 ～1800Cm between ^-1 and ^{1845cm -1 ~1855cm} -1, an absorption peak due to anhydride such as maleic anhydride groups Or an absorption peak due to the terminal carbonate group between 1800 cm ^{−1 and} 1815 cm ⁻¹ .

Further, the main chain due to the CH ₂ groups of the absorption peak near 2881cm ^-1 to the height of the absorption peaks between ^{1790cm -1 ~1800cm} -1 attributed to anhydride such as maleic anhydride groups of height The ratio is 0.5 to 1.5, preferably 0.7 to 1.2, and more preferably 0.8 to 1.0.

Moreover, the ratio of the height of the absorption peak between 1800 cm ⁻¹ to 1815 cm ⁻¹ due to the terminal carbonate group to the height of the absorption peak near 2881 cm ⁻¹ due to the CH ₂ group of the main chain is 1. It is 0-2.0, Preferably it is 1.2-1.8, More preferably, it is 1.5-1.7.

  As such a fluororesin having adhesive strength, for example, a homopolymer or copolymer having a tetrafluoroethylene unit, such as a carbonate group, a carboxylic acid halide group, a hydroxyl group, a carboxyl group, or an epoxy group at the terminal or side chain A resin having a functional group of A plurality of resins may be mixed as long as the melting point and the adhesive strength are expressed. Examples of commercially available fluororesins having adhesive strength as described above include Neoflon EFEP (manufactured by Daikin Industries) and Fullon LM-ETFE AH2000 (manufactured by Asahi Glass Co., Ltd.).

  Among the above-mentioned adhesive fluororesins, those having a melting point of 200 ° C. or lower can be used in the present invention.

  Various additives can be added to the adhesive fluororesin layer in addition to the adsorptive substance having a formaldehyde adsorption function in order to have a function as a cosmetic material. Examples include ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and cyanoacrylate compounds, inorganic fillers of inorganic pigments such as talc, titanium oxide, and silica, color pigments, flame retardants, and the like. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as a resin base material, The thing with favorable adhesiveness with adhesive fluororesin is preferable. For example, nylon, ethylene-vinyl alcohol copolymer, modified polyolefin and the like can be mentioned, among which modified polyolefin is preferable.

  The “modified polyolefin resin” in the present invention refers to a resin obtained by graft-reacting a base polyolefin resin with an acid such as an inorganic acid, an unsaturated carboxylic acid or a derivative thereof by an arbitrary method. As the base polyolefin, for example, polyethylene or polypropylene is used. As unsaturated carboxylic acids, for example, boronic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, acid anhydrides, esters, amides, imides, metal salts, and the like are used. As the modified polyolefin resin, a copolymer of ethylene and glycidyl methacrylate is preferable. Examples of such a copolymer of ethylene and glycidyl methacrylate include Lexpearl RA3150 (manufactured by Nippon Polyethylene Co., Ltd.) and Bond First E (manufactured by Sumitomo Chemical Co., Ltd.).

  As a resin base material, you may make it the structure which laminated | stacked 1 or more types of resin further on the surface on the opposite side to an adhesive fluororesin surface even with a single layer. The resin used in that case is not particularly limited, but for example, modified polyolefin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyamide resin, polyurethane resin, acrylic resin, epoxy resin, etc. Coalescence can be used. Among them, it is preferable from the viewpoint of durability such as interlayer adhesion that the modified polyolefin is laminated and the two modified polyolefins are laminated.

  Various additives can also be added to the resin base material, specifically, additives that can be added to the above-mentioned adhesive fluororesin are mentioned, but formaldehyde adsorptivity similar to that added to the adhesive fluororesin Substances may be added.

  The method for producing the decorative film of the present invention is not particularly limited, but a method of separately forming a film to be each layer and adhering with an adhesive, a method of simultaneously forming two layers by coextrusion, and the like are conceivable. Of these, it is preferable from the viewpoints of productivity, cost, and fluororesin thinning to obtain the desired decorative film at the same time by co-extrusion with a multi-manifold die or a feed block. Furthermore, the embossing etc. can also be given to the decorative film of this invention as needed.

  The decorative film of the present invention is used as a decorative material (decorative wallpaper, decorative steel plate, etc.) by being laminated on a substrate. As the mating base material, any base material such as metal, glass, resin, and wood can be used. However, the decorative film of the present invention is preferably laminated on a wallpaper base material or a steel plate to make a decorative material ( Can be used as decorative wallpaper, decorative steel plate).

  As the wallpaper base material, a conventionally used backing paper or the like can be typically used. Specifically, inorganic paper such as flame retardant paper, kraft paper, and aluminum hydroxide paper, woven fabric, non-woven fabric, and the like can be used.

  Moreover, as a steel plate, a decorative steel plate, such as a mild steel plate, a stainless steel plate, an electroformed iron foil, and those plated with one or more metals of zinc, tin, aluminum, copper, chromium, nickel, etc. are conventionally used. As long as it is generally used for the purpose, it can be used without any limitation.

  The method of laminating the decorative film on the substrate is, for example, a method of applying an adhesive to the resin substrate surface of the decorative film and sticking it to the substrate, joining the resin substrate surface of the decorative film to the heated substrate, A method of laminating by thermocompression bonding, a method of coextruding a resin to be a decorative film on a substrate, and directly laminating on the substrate, and the like can be mentioned.

<1> Preparation of sample for evaluation In the structure shown in Table 1, the target films of Examples 1-2 and Comparative Examples 1-4 were obtained by the following method. The numbers in Table 1 are the proportions (parts by mass) of each component when the weight of each layer is 100 parts by mass.

<Production of decorative film>
(Example 1)
Using the two-layer multi-manifold die so as to have the structure shown in Table 1, it was coextruded at a die temperature of 230 ° C. to obtain a target film. The thicknesses of the adhesive fluororesin layer and the resin base material layer were 5 μm and 30 μm, respectively. The obtained decorative film was heat-laminated with a wallpaper substrate (backing paper (made by Tokushu Paper Industries Co., Ltd.) with polyethylene applied) to obtain a wallpaper.

(Example 2)
Using the three-layer multi-manifold die so as to have the structure shown in Table 1, it was coextruded at a die temperature of 230 ° C. to obtain the intended film. The thicknesses of the adhesive fluororesin layer and the resin base material layer were 5 μm and 30 μm (upper layer (15 μm) + lower layer (15 μm)), respectively. The obtained decorative film was heat laminated to a steel sheet to obtain a decorative steel sheet.

(Comparative Examples 1 and 2)
A decorative film and wallpaper were obtained in the same manner as in Example 1 so as to have the structure shown in Table 1. The thicknesses of the surface layer and the resin base material layer were 5 μm and 30 μm, respectively.

(Comparative Example 3)
The resin that becomes the resin base layer shown in Table 1 is melt-film molded at 230 ° C. with a T-type manifold die, and then the gravure coat is made by adding aluminum phosphate to the acrylic resin-based paint that becomes the surface layer. I got a decorative film. The thicknesses of the surface layer and the resin base material layer were 5 μm and 30 μm, respectively. The obtained decorative film was heat-laminated with a wallpaper substrate (backing paper (made by Tokushu Paper Industries Co., Ltd.) with polyethylene applied) to obtain a wallpaper.

(Comparative Example 4)
Using the two-layer multi-manifold die so as to have the structure shown in Table 1, it was coextruded at 340 ° C. to obtain the intended film. The thicknesses of the adhesive fluororesin layer and the resin base material layer were 5 μm and 30 μm, respectively. The obtained decorative film was heat-laminated with a wallpaper substrate (backing paper (made by Tokushu Paper Industries Co., Ltd.) with polyethylene applied) to obtain a wallpaper.

<2> Evaluation of decorative material The above-prepared decorative film was evaluated according to the following evaluation items. The evaluation results are summarized in Table 2.
(1) Formaldehyde adsorption evaluation The sheet | seat produced by each Example and the comparative example was bonded together on the wall of a 3x3x3m room | chamber interior with the adhesive agent which contains formaldehyde. When the room is closed for 24 hours, and 10 subjects are put in the room at a time and stay in the atmosphere for 10 minutes, if there is a subject who feels pain in the eyes, sore throat, or bad smell, ○.

(2) Antifouling property Characters were written on the surface with an oil-based felt pen and judged from the following criteria based on the remaining amount of ink when the surface was wiped off with water after 60 seconds.
○: Can be wiped clean.
Δ: Some ink remains.
X: Almost no wiping off and ink remains.

(3) Cost The cost for film production was evaluated.
○: Cost is not required.
X: Cost is required.

  As shown in Table 2, the decorative films of the present invention (Example 1 and Example 2) had good results in all of formaldehyde adsorption ability, antifouling property, and cost. On the other hand, those not added with formaldehyde adsorbent (Comparative Example 1) and those added with formaldehyde adsorbent but added to a high melting point fluororesin (Comparative Example 4) had poor formaldehyde adsorption evaluation. Moreover, those whose surface layer is not a fluororesin (Comparative Examples 2 and 3) were poor in antifouling property.

While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. Rather, the fluororesin composition, the decorative film, the method of manufacturing the decorative film, and the decorative wallpaper can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification. A decorative steel sheet is also to be understood as being included within the scope of the present invention.

Claims (11)

A fluororesin composition comprising a formaldehyde-adsorbing substance added to a fluororesin having a melting point of 200 ° C or lower. The fluororesin composition according to claim 1, wherein the fluororesin having a melting point of 200 ° C or lower is an adhesive fluororesin. The fluororesin composition according to claim 1 or 2, wherein the formaldehyde adsorbing substance is an inorganic phosphate. A decorative film, wherein the fluororesin composition according to any one of claims 1 to 3 is laminated on a resin base material layer. The decorative film according to claim 4, wherein the resin base material layer is made of a modified polyolefin. The decorative film according to claim 4, wherein the resin base material layer is a laminate of two or more kinds of modified polyolefins. The decorative film according to any one of claims 4 to 6, wherein the ratio of the thickness of the layer made of the fluororesin composition and the thickness of the resin base material layer is 1: 5 to 1:30. The decorative film according to any one of claims 4 to 7, wherein the layer made of the fluororesin composition has a thickness of 1 to 5 µm. The decorative film according to any one of claims 4 to 8, wherein the decorative film is produced by coextrusion molding of the layer made of the fluororesin composition and the resin base material layer. Production method. The makeup | decoration characterized by bonding the wallpaper base material to the surface opposite to the surface on which the said fluororesin composition was laminated | stacked in the resin base material layer of the decorative film in any one of Claims 4-8. wallpaper. A decorative steel sheet, wherein a steel sheet is bonded to a surface of the resin base layer of the decorative film according to any one of claims 4 to 8 opposite to the surface on which the fluororesin composition is laminated.