Thermoplastic resin composition for cooling medium transportation pipes, and cooling medium transportation pipe
Provided is a thermoplastic resin composition for cooling medium transportation pipes, which has high barrier performance, is flexible and has good extrusion moldability. A thermoplastic resin composition which comprises a matrix that comprises a thermoplastic resin and a domain that comprises a rubber and is dispersed in the matrix, the thermoplastic resin composition being characterized by having an oxygen permeability coefficient (cm 3 ·mm/(m 2 ·day·mmHg)) of 0.02 or less at 21° C. and at a humidity of 0%, and being also characterized in that the melt viscosity of the thermoplastic resin constituting the matrix is 300 Pa·s or less at 250° C. and at a shear rate of 243.2 s −1 , the thermoplastic resin comprises a thermoplastic resin having a melting point or a glass transition temperature of 150° C. or higher and a thermoplastic resin having an oxygen permeability coefficient of 0.004 or less or comprises a thermoplastic resin having a melting point or a glass transition temperature of 150° C. or higher and an oxygen permeability coefficient of 0.004 or less, and the rubber comprises an isobutylene-based block copolymer and an olefin- or styrene-based polymer having an epoxy group, an amino group, a hydroxyl group, an acid anhydride group or a carboxyl group.
1. A thermoplastic resin composition for a cooling medium transportation pipe, comprising a matrix comprising a thermoplastic resin and a domain comprising a rubber dispersed in the matrix, wherein the thermoplastic resin composition has an oxygen permeability coefficient of not more than 0.02 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, the thermoplastic resin constituting the matrix has a melt viscosity of not more than 300 Pa·s at a temperature of 250° C. and at a shear rate of 243.2 s −1 , wherein the thermoplastic resin comprises (i) a combination of a thermoplastic resin having a melting point or glass transition point of not less than 150° C. and also a thermoplastic resin having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, or wherein the thermoplastic resin comprises (ii) a thermoplastic resin having a melting point or glass transition point of not less than 150° C. and having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, and the rubber comprises an isobutylene-based block copolymer comprising a styrene-isobutylene-styrene triblock copolymer, and also an olefin-based or styrene-based polymer having at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group and a carboxyl group.
2. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin composition has a stress at 10% strain (10% modulus) of not more than 10 MPa at a temperature of 25° C. and at a relative humidity of 50% in a tensile test according to JIS K7161.
3. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 2 , wherein the thermoplastic resin is at least one selected from the group consisting of a polyamide, a polyester, an ethylene-vinyl alcohol copolymer, a polycarbonate and a polyketone.
4. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 2 , wherein the olefin-based or styrene-based polymer having at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group and a carboxyl group is at least one selected from the group consisting of an acid anhydride-modified α-olefin-based thermoplastic elastomer, an acid anhydride-modified styrene-ethylene-butylene-styrene block copolymer, an acid anhydride-modified styrene-ethylene-propylene-styrene block copolymer and an acid anhydride-modified ethylene-ethyl acrylate copolymer.
5. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 2 , wherein the thermoplastic resin composition comprises the matrix at a volume ratio of 25 to 50% by volume and the domain at a volume ratio of 50 to 75% by volume.
6. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 2 , wherein the proportion of the total amount of the (i) combination of the thermoplastic resin having a melting point or glass transition point of not less than 150° C., and also the thermoplastic resin having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, or (ii) the thermoplastic resin having a melting point or glass transition point of 150° C. or more and having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0% in the matrix, is not less than 50% by weight.
7. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin is at least one selected from the group consisting of a polyamide, a polyester, an ethylene-vinyl alcohol copolymer, a polycarbonate and a polyketone.
8. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 7 , wherein the olefin-based or styrene-based polymer having at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group and a carboxyl group is at least one selected from the group consisting of an acid anhydride-modified α-olefin-based thermoplastic elastomer, an acid anhydride-modified styrene-ethylene-butylene-styrene block copolymer, an acid anhydride-modified styrene-ethylene-propylene-styrene block copolymer and an acid anhydride-modified ethylene-ethyl acrylate copolymer.
9. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 7 , wherein the thermoplastic resin composition comprises the matrix at a volume ratio of 25 to 50% by volume and the domain at a volume ratio of 50 to 75% by volume.
10. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 7 , wherein the proportion of the total amount of the (i) combination of the thermoplastic resin having a melting point or glass transition point of not less than 150° C., and also the thermoplastic resin having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, or (ii) the thermoplastic resin having a melting point or glass transition point of 150° C. or more and having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0% in the matrix, is not less than 50% by weight.
11. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the olefin-based or styrene-based polymer having at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group and a carboxyl group is at least one selected from the group consisting of an acid anhydride-modified α-olefin-based thermoplastic elastomer, an acid anhydride-modified styrene-ethylene-butylene-styrene block copolymer, an acid anhydride-modified styrene-ethylene-propylene-styrene block copolymer and an acid anhydride-modified ethylene-ethyl acrylate copolymer.
12. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 11 , wherein the thermoplastic resin composition comprises the matrix at a volume ratio of 25 to 50% by volume and the domain at a volume ratio of 50 to 75% by volume.
13. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 11 , wherein the proportion of the total amount of the (i) combination of the thermoplastic resin having a melting point or glass transition point of not less than 150° C., and also the thermoplastic resin having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, or (ii) the thermoplastic resin having a melting point or glass transition point of 150° C. or more and having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0% in the matrix, is not less than 50% by weight.
14. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin composition comprises the matrix at a volume ratio of 25 to 50% by volume and the domain at a volume ratio of 50 to 75% by volume.
15. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the proportion of the total amount of the (i) combination of the thermoplastic resin having a melting point or glass transition point of not less than 150° C., and also the thermoplastic resin having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, or (ii) the thermoplastic resin having a melting point or glass transition point of 150° C. or more and having an oxygen permeability coefficient of not more than 0.004 cm 3 ·mm/(m 2 ·day·mmHg) at a temperature of 21° C. and at a relative humidity of 0%, in the matrix is not less than 50% by weight.
16. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the proportion of the isobutylene-based block copolymer in the domain is 50 to 95% by weight.
17. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin composition comprises 0.5 to 5 parts by weight of at least one selected from the group consisting of a fatty acid, a fatty acid metal salt, a fatty acid ester and a fatty acid amide based on 100 parts by weight of the rubber in the thermoplastic resin composition.
18. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin composition comprises 0.5 to 10 parts by weight of a divalent metal oxide based on 100 parts by weight of the rubber in the thermoplastic resin composition.
19. The thermoplastic resin composition for a cooling medium transportation pipe according to claim 1 , wherein the thermoplastic resin composition comprises 0.1 to 8 parts by weight of a trihydric alcohol having a triazine backbone based on 100 parts by weight of the rubber in the thermoplastic resin composition.
20. A cooling medium transportation pipe comprising a layer of the thermoplastic resin composition according to claim 1 , as an inner layer.