Stock material or miscellaneous articles – Web or sheet containing structurally defined element or... – Adhesive outermost layer
Reexamination Certificate
1999-11-04
2002-07-02
Hampton-Hightower, P. (Department: 1711)
Stock material or miscellaneous articles
Web or sheet containing structurally defined element or...
Adhesive outermost layer
C428S411100, C428S421000, C428S432000, C264S298000, C264S299000, C264S300000, C264S319000, C264S328100, C264S331110, C264S331140, C427S248100, C427S490000, C427S497000, C427S498000, C219S386000, C219S495000, C219S518000, C219S519000, C099S339000
Reexamination Certificate
active
06413630
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a decorative film, in particular, a decorative film having a decorative metal layer on the surface of the adhered side of a transparent layer, more particularly, a decorative film which can be used for decoration as a label, sticker, stripe tape, etc., or which can alternatively be used for insert molding. The decorative film of the present invention, while naturally exhibiting an excellent decorative effect with a metal luster appearance, can also be attached to a substrate surface having a complex three-dimensional curvature or shape, and particularly insert molded products, without creating defects resulting in a poor appearance, etc. The present decorative film also has excellent long-term weather resistance and stain resistance.
BACKGROUND OF THE INVENTION
A variety of decorative films having a decorative metal layer on the surface of the adhered side of a transparent layer are well-known, and most of the conventional decorative films have a structure with a metal vapor coating film on a transparent layer made of a fluorine-containing resin. For example, Japanese Unexamined Patent Publication (Kokai) No. 60-71249 discloses a process for producing a composite material used as a surface material for automobile side moldings, bumper moldings, window moldings, etc. which comprises a step of laying aluminum, to a thickness of 100-300 Å, on one side of a 12-50 gm-thick transparent fluorine-containing film, by vapor coating. A tetrafluoroethylene-ethylene copolymer resin is used to make this transparent film. Also, Japanese Unexamined Patent Publication (Kokai) No. 1-174584 discloses a metal luster adhesive sheet which can be attached particularly to a substrate with three-dimensional curvature, and which has a metal thin-film layer on at least one side of a fluorine-containing film, with a pressure-sensitive adhesive layer also formed thereon. This fluorine-containing film is polyvinyl fluoride or polyvinylidene fluoride, or a copolymer thereof A similar metal luster adhesive sheet is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 2-64187. The metal luster adhesive sheet described in this publication has a metal thin-film layer on one side of a fluorine-containing film substrate and on the other side a plasma treated layer with a fluorine content of less than 65% with respect to the substrate and an oxygen content of one or more atoms to 20 atoms of carbon, with an adhesive layer formed on the surface of the metal thin-film layer.
The applicant has also filed a patent application for the laminate film with a metal-based luster disclosed in Japanese Unexamined Patent Publication (Kokai) No. 4-35938. This laminate film has, in order from the top, a first resin layer whose main component is a mixture of a vinylidene fluoride resin/polymethacrylic acid ester-based resin, a second resin layer whose main component is a mixture of a vinylidene fluoride resin/polymethacrylic acid ester-based resin with a different weight ratio, and a metal layer. The invention described here gives the effect of expressing a beautiful color tone by using a high fluorine content resin with excellent heat resistance as a highly heat-accumulating inner layer (second resin layer), to provide strength for withstanding even temperatures of 120° C., while also using a low fluorine content resin, with excellent adhesion with ink, etc., as the surface layer (first resin layer) to allow freer colorability, as well as layering of an additional transparent colored resin layer thereon.
In the decorative films disclosed in the above-mentioned and other unexamined patent publications, the fluorine-containing resins used are generally polyvinyl fluoride, polyvinylidene fluoride, polytrifluorochloroethylene, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylenehexafluoropropylene copolymer, polyvinylidene fluoride/polymethyl methacrylate mixtures, etc. These fluorine-containing resins are usually used to make monolayer extruded films or, as disclosed for example in Japanese Unexamined Patent Publication (Kokai) No. 4-35938, double-layer coextruded films. The decorative films of the past which employed fluorine-containing transparent films have exhibited satisfactory properties, particularly three-dimensional curvature emulating properties, compared to decorative films using a polyethylene terephthalate (PET) transparent film(s).
However, decorative films with a conventional fluorine containing transparent layer or film(s) still do not exhibit sufficient three-dimensional curvature emulating properties. Furthermore, all of the fluorine-containing transparent layers for decorative films currently on the market, including those disclosed in the examples of the unexamined patent publications cited above, are films formed by melt extrusion molding of the fluorine-containing resins. The production process for this molding technique tends to produce appearance defects such as the well-known “fish-eye” phenomenon, which has become a major cause of reduced product yields. In addition, films produced by melt extrusion molding generally have inferior thickness precision. Thus, these transparent films tend to have non-uniform sections and therefore when coated with a metal layer by vacuum deposition or the like, surface waviness is produced on the transparent film, producing appearance defects such as vapor deposition lines.
SUMMARY OF THE INVENTION
The aforementioned and other problems are overcome, in accordance with the present invention, by providing a decorative film having a desirable decorative effect, a desirable degree of transparency of its transparent layer, three-dimensional curvature emulating properties, three-dimensional curvature formability, and long-term weather resistance and stain resistance.
Compared to the present decorative film, prior decorative films with a conventional fluorine containing transparent layer or film do not exhibit three-dimensional curvature emulating properties sufficient, in particular, for producing insert-molded or in-molded decorative articles with complex three-dimensional surfaces, such as emblems for vehicles including automobiles and motorcycles. That is, an important element during insert-molding is the pre-adhesion of the decorative film to a complex and intricately-shaped inner wall of a mold. In practice, numerous gaps can be produced between the inner wall of the mold and the decorative film as a result of stretching of the film, etc. The formation of these gaps produces defects in the shape of the resulting molded product. Irregular stretching of the film can also cause breakage of the film. In addition, when the film fails to emulate the intricate shape of the mold, it becomes very difficult to obtain a molded product with a shape of the desired design.
As discussed above, the fluorine containing transparent films used in prior decorative films are formed by melt extrusion molding, which tends to result in the undesirable “fish-eye” phenomenon and generally inferior thickness precision. By casting its transparent layer, the present decorative film can avoid these. problems. In addition, there are problems associated with trying to cast the transparent layers used in prior decorative films. For example, when attempting to form a decorative film by casting a transparent support layer of polyvinylidene fluoride, it is highly difficult to prepare a casting solution of the polyvinylidene fluoride. Polyvinylidene fluoride is insoluble in common organic solvents, and is soluble only in certain polar solvents such as such as N-methylpyrrolidone, but even there its solubility is at a very low level (less than 10 wt %, and generally only a few weight-percent). Since only solutions of low solid content can be prepared, only thin films can be formed using the prior art fluorine containing resins, even with the casting process.
Furthermore, because of hazing of the film when polyvinylidene fluoride is used alone, an acrylic resin or the like must also be used for anti-hazing. Oth
3M Innovative Properties Company
Hampton-Hightower P.
Knecht III Harold C.
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