Stock material or miscellaneous articles – Composite – Of addition polymer from unsaturated monomers
Reexamination Certificate
2000-02-25
2003-11-25
Jackson, Monique R. (Department: 1773)
Stock material or miscellaneous articles
Composite
Of addition polymer from unsaturated monomers
C428S515000, C428S522000
Reexamination Certificate
active
06652985
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel acrylic resin laminated film particularly having excellent melt-adhesion to a polyolefin-based resin, and a novel laminated article using the acrylic resin laminated film.
This acrylic resin laminated film is useful for providing characteristics such as ornamental property, transparency, surface hardness, weather-resistance and the like.
2. Description of related Art
Acrylic resins are used widely in various fields such as sign boards and illumination covers and the like because of excellent transparency, ornamental property, surface hardness, weather-resistance, oil-resistance and the like, however, have a problem that impact-resistance and bending strength thereof are not sufficient leading to cracking tendency.
Therefore, plates, sheets, films and the like occupying main portion of acrylic resin products can not basically be punched or bent, and there has been only an inefficient cutting work against recent increasing needs for sign boards having three-dimensional form and unique forms and the like.
On the other hand, polyolefin-based resins are often used, for example, for interior and exterior parts of automobiles, parts of domestic electric appliances and the like because of excellent molding processability, recycling property, punching and bending processability, heat-resistance, cold-resistance and the like, however, have problems that it is difficult to maintain gloss of a surface because hardness thereof is low causing scarce maintenance of gloss, and further, ornamental property and weather-resistance are poor.
It is expected that, if the surface of a substrate made of a polyolefin-based resin is coated with an acrylic resin, a laminated article having simultaneously excellent properties of both resins can be produced. However, a method in which a curable paint composed of an acrylic resin is coated on a substrate and baked for curing needs a lot of processes causing inefficiency, and additionally, tends to cause a environmental problem that an organic solvent contained in the paint is discharged in a drying process.
Further, there is also a problem that an acrylic resin film formed as described above are not sufficient particularly in surface hardness, weather-resistance, oil-resistance and ornamental property as compared with the usual plates, sheets, films and the like of an acrylic resin.
There is an investigation for producing a laminated article by using a so-called integrated adhering molding method and the like in which an acrylic resin sheet or film is set at given position in a cavity corresponding to the form of the laminated article, in a mold, and a polyolefin-based resin forming a substrate is heat-melted and poured into the cavity and cooled and solidified before being removed from the mold, for integration of them by melt-adhesion.
However, since they have basically no compatibility, they can not be directly melt-adhered.
Therefore, there are various acrylic resin laminated films suggested in which melt-adhesion to a polyolefin-based resin substrate is imparted by laminating a single or a plurality of intermediate layers having melt-adhesion to a polyolefin-based resin.
For example, Japanese Patent Application Laid-Open (JP-A) No. 9-234836 has disclosed a laminated film of multi-layer structure having three or more layers in which a polyolefin-based resin layer is laminated to the lower side of an acrylic resin layer as the surface layer via a layer of a curing type adhesive such as, for example, a two-pack curing type urethane-based resin and the like.
JP-A No. 9-193189 has also disclosed a laminated film of multi-layer structure having three or more layers in which a layer of a modified olefin polymer having a carboxyl group, acid anhydride group, hydroxyl group, glycidyl group and the like is inserted between an acrylic resin layer as the surface layer and a polyolefin-based resin layer.
In these laminated films, melt-adhesion to a polyolefin-based resin substrate is imparted by a polyolefin-based resin layer laminated to the lowest layer thereof.
However, since the above-described laminated film of multi-layer structure tends to necessarily have increased thickness, therefore, when a polyolefin-based resin substrate is melt-adhered by, for example, the integrated adhering molding method and the like, to the polyolefin-based resin side of the laminated substrate, a large difference in heat history is caused between the opposite acrylic resin layer which has been scarcely heated because of close contact with the mold. Therefore, there is a problem that large warping deformation which can not be prevented only by control of molding conditions and the like for example tends to occur in the resulted product.
There is a fear that the produced laminated article, because of large thickness as described above, easily causes fragile fracture even at temperature range in which a article composed only of a polyolefin-based resin causes ductile fracture, and this being a factor for reduction of mechanical abilities of a article at low temperature.
Further, there is also a problem that when a laminated film of multi-layer structure as described above is used, a lot of layers are required as described above, leading to increase in the cost of the product.
Japanese Patent Application Publication (JP-B) No. 6-26718 has disclosed the use of a chlorinated polyolefin-based adhesive (“Chlorinated polyolefin 343-1” manufactured by Eastman Kodak US) having excellent melt-adhesion to both of an acrylic resin and a polyolefin-based resin.
By the use of such a chlorinated polyolefin-based adhesive, solution of the above-described problems may be expected since a layer of a polyolefin-based resin can be omitted to reduce the number of layers in the laminated film.
However, this generates a fear regarding influences caused by chlorine and a compound thereof in discarding the laminated article and the like.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a novel acrylic resin laminated film which can reduce the number of layers than ever, has excellent melt-adhesion to a polyolefin-based resin substrate, and causes no fear regarding influences caused by chlorine and the like in discarding the laminated article and the like.
Another object of the present invention is to provide a laminated article which, due to the use of the above-described acrylic resin laminated film, has no fear to cause various problems such as the above-described warping deformation, reduction of mechanical abilities, increase in cost, influences caused by chlorine and a compound thereof, and the like, and further, has excellent abilities of both of an acrylic resin and a polyolefin-based resin simultaneously.
For solving the above-described problems, the present inventors have intensively studied particularly a resin composition constituting an adhesive layer of an acrylic resin laminated film.
Resultantly, the present inventors have found that a resin composition comprising (a) an acrylic resin and an olefin-based copolymer obtained by copolymerization of an olefin and at least one monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylates, unsaturated carboxylic anhydrides and vinyl acetate, or (b) an olefin-based copolymer obtained by copolymerization of an olefin and a monomer having glycidyl group in a side chain, has excellent melt-adhesion to both of an acrylic resin and a-polyolefin-based resin, and additionally, by using these resin composition or copolymer as an adhesive layer, the number of layers of an acrylic resin laminated film can be decreased, and a laminated article which, due to the use of the above-described acrylic resin laminated film, has no fear to cause various problems such as the warping deformation, reduction of mechanical abilities, increase in cost, influences caused by chlorine and a compound thereof and the like, and further has excellent abilities of both of an acrylic resin and a polyolefin-based resin simu
Tadokoro Yoshio
Tsukuda Yousuke
Fitch Even Tabin & Flannery
Jackson Monique R.
Sumitomo Chemical Company Limited
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