Heat-shrinkable laminate film, molded product and heat shrinkable label employing the film, and container
View Patent ↗The present invention relates to a heat-shrinkable laminate film comprising a surface layer composed mainly of polyester resin, an intermediate layer composed mainly of styrene resin, and an adhesive layer composed mainly of adhesive resin, wherein heat shrinkage in the main shrink direction is at least 10% and less than 30% when the film is dipped in water of 70° C. for 10 seconds, and at least 30% and at most 70% when dipped in water of 80° C. for 10 seconds, or its tensile modulus of elasticity in a direction perpendicular to the main shrink direction is at least 1,200 MPa. The heat-shrinkable film has excellent film elasticity, shrink finishing quality, transparency when incorporated as recycled, natural shrinkage, and suppressed delamination, making it suitable for application in shrink wrapping, shrink bundling wrapping, shrink label, and a plastic container provided with a heat shrinkable film made of such a film.
1. A heat-shrinkable laminate film comprising:
a surface layer comprising a polyester resin;
an adhesive layer comprising an adhesive resin; and
an intermediate layer comprising a styrene resin wherein the styrene resin contains as a main component, a mixture of at least two different copolymers of a styrene hydrocarbon with butadiene differing in styrene content; and one of the at least two different copolymers has a styrene content of 80 to 95 mass % and at least one of the other different copolymers has a styrene content of 60 to 80 mass %;
wherein the adhesive layer is adjacently positioned between the surface layer and the intermediate layer; and
wherein a heat shrinkage of the film in the main shrink direction is at least 10% and less than 30% when the film is dipped in water of 70° C. for 10 seconds, and at least 30% and at most 70% when the film is dipped in water of 80° C. for 10 seconds
wherein the intermediate layer includes the heat-shrinkable laminate film as recycled, in an amount of at most 40 mass % based on the total amount of the film, and the haze value of the film is at most 10% as measured in accordance with JIS K7105, and
wherein the heat-shrinkable laminate film has a five-layer structure, in order, of: a surface layer, an adhesive layer, an intermediate layer, an adhesive layer, a surface layer.
2. The heat-shrinkable laminate film according to claim 1 , wherein the adhesive resin included in the adhesive layer is a mixture of resins included in the surface layer and the intermediate layer.
3. The heat-shrinkable laminate film according to claim 1 , wherein the adhesive resin included in the adhesive layer is either one resin or a mixture of at least two resins selected from the group consisting of a soft styrene resin, a modified styrene resin, a resin having polar groups reactive with a polyester resin and being compatible with a styrene resin, and a resin having a high affinity with a polyester resin and being compatible with a styrene resin.
4. The heat-shrinkable laminate film according to claim 1 , wherein the styrene resin included in the intermediate layer is either a styrene-butadiene block copolymer, a styrene-isoprene-butadiene block copolymer, or a mixture of the styrene-butadiene block copolymer and the styrene-isoprene-butadiene block copolymer.
5. The heat-shrinkable laminate film according to claim 1 , wherein:
the polyester resin included in the surface layer comprises dicarboxylic acid residues and diol residues;
at least either the dicarboxylic acid residues or the diol residues include at least two residues; and
among said at least two residues, the total content of residues other than the most abundant residue is at least 10 mol % and at most 40 mol %, based on the sum, which is 200 mol %, of the total amount of 100 mol % of the dicarboxylic acid residues and the total amount of 100 mol % of the diol residues.
6. The heat-shrinkable laminate film according to claim 1 , wherein:
the adhesive layer comprising a resin including either a copolymer of a styrene hydrocarbon with a conjugated diene, or a hydrogenated derivative of the copolymer, a styrene content in either the copolymer or the hydrogenated derivative being at least 5 mass % and at most 40 mass %;
wherein a tensile modulus of elasticity of the film in a direction perpendicular to a main shrink direction is at least 1,200 MPa.
7. The heat-shrinkable laminate film according to claim 1 , wherein the polyester resin included in the surface layer is a resin including at least one polyester resin comprising polybasic carboxylic acid residues and polyhydric alcohol residues.
8. The heat-shrinkable laminate film according to claim 1 , wherein the polyester resin included in the surface layer is a resin including a non-crystalline polyethylene terephthalate resin comprising aromatic dicarboxylic acid residues and diol residues, wherein 1,4-cyclohexane dimethanol residues in all diol residues are at least 15 mol % and at most 50 mol %.
9. The heat-shrinkable laminate film according to claim 1 , wherein the film has a seal strength of at least 3N/15 mm width and at most 20N/15 mm width when the film is delaminated at a tensile rate of 200 mm/min in an environment of 23° C. under 50% RH.
10. A molded product employing the heat-shrinkable laminate film as defined in claim 1 as the base material.
11. A heat-shrinkable label employing the heat-shrinkable laminate film as defined in claim 1 as the base material.
12. A container provided with the molded product as defined in claim 10 .
13. A container provided with the heat-shrinkable label as defined in claim 11 .
14. The heat-shrinkable laminate film according to claim 1 , wherein the heat-shrinkable laminate film is produced by laminating the layers and then stretching the laminate.
15. The heat-shrinkable laminate film according to claim 1 , wherein the haze value after the return is incorporated is at most 7.0% as measured in accordance with JIS K7105.
16. A heat-shrinkable laminate film comprising:
a surface layer comprising a polyester resin;
an adhesive layer comprising an adhesive resin; and
an intermediate layer comprising a styrene resin selected from the group consisting of a copolymer of a styrene hydrocarbon with a conjugated diene, a mixture of at least two different copolymers of a styrene hydrocarbon with a conjugated diene differing in styrene content, a copolymer of said styrene hydrocarbon-conjugated diene copolymer with a monomer copolymerizable with a styrene hydrocarbon or conjugated diene, and combinations thereof;
wherein the adhesive layer is adjacently positioned between the surface layer and the intermediate layer; and
wherein a heat shrinkage of the film in the main shrink direction is at least 10% and less than 30% when the film is dipped in water of 70° C. for 10 seconds, and at least 30% and at most 70% when the film is dipped in water of 80° C. for 10 seconds
wherein the intermediate layer includes the heat-shrinkable laminate film as recycled, in an amount of at most 40 mass % based on the total amount of the film, and the haze value of the film is at most 7% as measured in accordance with JIS K7105, and
wherein the heat-shrinkable laminate film has a five-layer structure, in order, of: a surface layer, an adhesive layer, an intermediate layer, an adhesive layer, a surface layer.
17. The heat-shrinkable laminate film according to claim 16 , wherein the adhesive resin included in the adhesive layer is a mixture of resins included in the surface layer and the intermediate layer.
18. The heat-shrinkable laminate film according to claim 16 , wherein the adhesive resin included in the adhesive layer is either one resin or a mixture of at least two resins selected from the group consisting of a soft styrene resin, a modified styrene resin, a resin having polar groups reactive with a polyester resin and being compatible with a styrene resin, and a resin having a high affinity with a polyester resin and being compatible with a styrene resin.
19. The heat-shrinkable laminate film according to claim 16 , wherein the styrene resin included in the intermediate layer is either a styrene-butadiene block copolymer, a styrene-isoprene-butadiene block copolymer, or a mixture of the styrene-butadiene block copolymer and the styrene-isoprene-butadiene block copolymer.
20. The heat-shrinkable laminate film according to claim 16 , wherein:
the polyester resin included in the surface layer comprises dicarboxylic acid residues and diol residues;
at least either the dicarboxylic acid residues or the diol residues include at least two residues; and
among said at least two residues, the total content of residues other than the most abundant residue is at least 10 mol % and at most 40 mol %, based on the sum, which is 200 mol %, of the total amount of 100 mol % of the dicarboxylic acid residues and the total amount of 100 mol % of the diol residues.
21. The heat-shrinkable laminate film according to claim 16 , wherein:
the adhesive layer comprising a resin including either a copolymer of a styrene hydrocarbon with a conjugated diene, or a hydrogenated derivative of the copolymer, a styrene content in either the copolymer or the hydrogenated derivative being at least 5 mass % and at most 40 mass %; and
wherein a tensile modulus of elasticity of the film in a direction perpendicular to a main shrink direction is at least 1,200 MPa.
22. The heat-shrinkable laminate film according to claim 16 , wherein the polyester resin included in the surface layer is a resin including at least one polyester resin comprising polybasic carboxylic acid residues and polyhydric alcohol residues.
23. The heat-shrinkable laminate film according to claim 16 , wherein the polyester resin included in the surface layer is a resin including a non-crystalline polyethylene terephthalate resin comprising aromatic dicarboxylic acid residues and diol residues, wherein 1,4-cyclohexane dimethanol residues in all diol residues are at least 15 mol % and at most 50 mol %.
24. The heat-shrinkable laminate film according to claim 16 , wherein the film has a seal strength of at least 3N/15 mm width and at most 20N/15 mm width when the film is delaminated at a tensile rate of 200 mm/min in an environment of 23° C. under 50% RH.
25. A molded product employing the heat-shrinkable laminate film as defined in claimed 16 as the base material.
26. A heat-shrinkable label employing the heat-shrinkable laminate film as defined in claim 16 as the base material.
27. A container provided with the molded product as defined in claim 25 .
28. A container provided with the heat-shrinkable label as defined in claim 26 .
29. The heat-shrinkable laminate film according to claim 16 , wherein the heat-shrinkable laminate film is produced by laminating the layers and then stretching the laminate.
30. The heat-shrinkable laminate film according to claim 16 , wherein the intermediate layer comprises a styrene resin, wherein the styrene resin contains as a main component, a mixture of at least two different copolymers of a styrene hydrocarbon with butadiene differing in styrene content; and one of the at least two different copolymers has a styrene content of 80 to 95 mass % and at least one of the other different copolymers has a styrene content of 60 to 80 mass %.