Decorative film
The object of the present invention is to provide a decorative film excellent in moldability and tensile strength; and a method for producing a three-dimensionally molded article with a decorative film. The decorative film of the present invention is used for decorating a three-dimensionally molded article. It is a decorative film comprising at least a substrate film layer and a clear layer, wherein the clear layer is made of a fluorinated polymer comprising units based on a fluoroolefin, units based on a monomer having no crosslinkable group, which is at least one member selected from the group consisting of a vinyl ether, a vinyl ester, an allyl ether, an allyl ester and a (meth)acrylic acid ester, and units having a crosslinkable group; and the content of the units based on a fluoroolefin is from 20 to 70 mol % to all units which the fluorinated polymer comprises.
1. A decorative film for decorating a three-dimensionally molded article, comprising at least a substrate film layer and a clear layer, wherein
the clear layer is made of a fluorinated polymer comprising units based on a fluoroolefin, units based on a monomer having no cross-linkable group, which is at least one member selected from the group consisting of a vinyl ether, a vinyl ester, an allyl ether, an allyl ester and a (meth)acrylic acid ester, and units having a crosslinkable group,
a content of said units based on a fluoroolefin is from 20 to 70 mol % based on all units contained in said fluorinated polymer, and
the fluorinated polymer has a number average molecular weight of from 7,000 to 30,000 and a glass transition temperature of from 30 to 120° C.
2. The decorative film according to claim 1 , wherein a content of said units having a crosslinkable group is from 3 to 40 mol % based on all units contained in said fluorinated polymer.
3. The decorative film according to claim 1 , wherein
said units based on a monomer having no crosslinkable group have a C 4-8 alkyl group represented by formula —C(Y 10 ) 3 or a C 6-10 cycloalkyl group, and
Y 10 in the formula —C(Y 10 ) 3 are each independently a C 1-5 alkyl group.
4. The decorative film according to claim 1 , wherein the fluorinated polymer has a hydroxy value of from 30 to 150 mgKOH/g.
5. The decorative film according to claim 1 , wherein the clear layer contains a plasticizer.
6. The decorative film according to claim 5 , wherein the plasticizer is a plasticizer made of a (meth)acrylic resin having a weight average molecular weight of from 1,000 to 20,000.
7. The decorative film according to claim 5 , wherein the plasticizer is a plasticizer made of a polyether glycol having a weight average molecular weight of from 100 to 10,000.
8. The decorative film according to claim 1 , wherein the clear layer contains a compound having two or more isocyanate groups in one molecule.
9. The decorative film according to claim 1 , wherein the clear layer contains at least one member selected from the group consisting of an organic ultraviolet absorber and an organic light stabilizer.
10. The decorative film according to claim 1 , wherein the three-dimensionally molded article is an automobile exterior member or an automobile interior member.
11. The decorative film according to claim 1 , further comprising a bonding layer, wherein the bonding layer, the clear layer and the substrate film layer are sequentially laminated in this order so that the clear layer and the substrate film layer are laminated in contact with each other.
12. The decorative film according to claim 1 , further comprising a bonding layer, wherein the bonding layer, the substrate film layer and the clear layer are sequentially laminated in this order.
13. The decorative film according to claim 1 , wherein said units based on a monomer having no crosslinkable group have a C 4-8 alkyl group represented by formula —C(Y 10 ) 3 and each Y 10 is independently a C 1-5 alkyl group.
14. The decorative film according to claim 1 , wherein a content of said units based on a monomer having no crosslinkable group is from 5 to 60 mol % based on all units contained in said fluorinated polymer.
15. The decorative film according to claim 1 , wherein the crosslinkable group in said units having a crosslinkable group is at least one selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and an alkoxysilyl group.
16. A method for producing a three-dimensionally molded article with a decorative film, the method comprising
press-bonding the bonding layer of the decorative film according to claim 12 and a surface to be decorated of the three-dimensionally molded article in a reduced pressure atmosphere by a vacuum molding method, and then
peeling off the substrate film layer, thereby obtaining the three-dimensionally molded article with the decorative film, which has the clear layer on the outermost surface.
17. A method for producing a three-dimensionally molded article with a decorative film, the method comprising
press-bonding the bonding layer of the decorative film according to claim 12 and a surface to be decorated of the three-dimensionally molded article in a reduced pressure atmosphere by a vacuum molding method, thereby obtaining the three-dimensionally molded article with the decorative film, which has the clear layer on the outermost surface.