Polyester compositions and laminates and processes for producing biaxially stretched polyester bottles

A polyester composition comprising:

• (A) a polyester in an amount of 1 to 99% by weight, said polyester being at least one selected from the group consisting of
• (iv) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from naphthalene-dicarboxylic acid or its derivative,
• diol constituent units derived from diols comprising ethylene glycol and a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• (v) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative,
• diol constituent units derived from diols comprising ethylene glycol and a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
• wherein the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units, and
• the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• and
• (vi) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• and
• (B) a second polyester in an amount of 1 to 99% by weight, said second polyester comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• and wherein a molding made from polyester (A) and polyester (B) has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less.

A polyester laminate having a multi-layer structure comprising:

• (I) a first resin layer formed from polyester compositions or a polyester selected from the group consisting of at least one of the following polyesters (i) to (vi):
• (i) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50,
• (ii) a polyester wherein, in the polyester (i), the dicarboxylic acid constituent units are derived from terephthalic acid or its ester derivative,
• (iii) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from terephthalic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the isophthalic acid or its ester derivative is in the range of 1 to 15% by weight based on the dicarboxylic acid constituent units;
• (iv) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its derivative,
• (v) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units,
• (vi) a polyester wherein, in any of preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• and wherein said polyester compositions comprise
• (A) a first polyester selected from the group consisting of at least one of the polyesters (i) to (vi) in an amount of 1 to 99% by weight and
• (B) a second polyester in an amount of 1 to 99% by weight, said second polyester (B) comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• wherein the first resin layer (I) has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less;
• and
• (II) a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester (B), (b) a polyamide and (c) a polyolefin.

A process for producing a biaxially stretched polyester bottle, comprising:

• (1a) a step of producing a preform from a polyester selected from the group consisting of at least one of the following polyesters (i) to (vi) and polyester compositions:
• (i) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50,
• (ii) a polyester wherein, in the polyester (i), the dicarboxylic acid constituent units are derived from terephthalic acid or its ester derivative,
• (iii) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from terephthalic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the isophthalic acid or its ester derivative is in the range of 1 to 15% by weight based on the dicarboxylic acid constituent units;
• (iv) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its derivative,
• (v) a polyester wherein, in the polyester (i), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units, and
• (vi) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• or
• (1b) a step of producing polyester compositions comprising
• (A) a first polyester selected from the group consisting of at least one of the polyesters (i) to (vi) in an amount of 1 to 99% by weight and
• (B) a second polyester in an amount of 1 to 99% by weight, said second polyester (B) comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• or
• (1c) a step of producing a laminate having a multi-layer structure comprising:
• (I) a first resin layer formed from a polyester selected from the group consisting of at least one of the polyesters (i) to (vi) and the polyester compositions;
• and
• (II) a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester (B), (b) a polyamide and (c) a polyolefin,
• (2) a step of heating the product of step (1a), (1b) or (1c);
• (3) a step of subjecting the product of step (1a), (1b), or (1c) to biaxial stretch blow molding to give a stretched bottle;
• and
• (4) a step of holding the stretched bottle in a mold at a temperature of not lower than 100° C.;
• wherein the biaxially stretched polyester bottle has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less.

A preform having a neck, which preform is formed from a polyester selected from the group consisting of at least one of the following polyesters (viii) to (xii):

• (viii) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from terephthalic acid or its ester derivative;
• and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (ix) a polyester consisting essentially of:
• dicarboxylic constituent units are derived from terephthalic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the isophthalic acid or its ester derivative is in the range of 1 to 15% by weight based on the dicarboxylic acid constituent units, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units;
• (x) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from naphthalene-dicarboxylic acid or its derivative, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (xi) a polyester consisting essentially of:
• dicarboxylic constituent units derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (xii) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50, and
• wherein a molding made from any of polyesters (viii)-(xii) has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less.

A polyester composition comprising:

• (A) at least one polyester selected from the group consisting of:
• (x) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from naphthalene-dicarboxylic acid or its derivative, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (xi) a polyester consisting essentially of:
• dicarboxylic constituent units derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the dial constituent units,
• (xii) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• and
• (B) an additional polyester in an amount of 1 to 99% by weight, said additional polyester comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol, wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and
• the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• and wherein a molding made from polyester (A) and polyester (B) has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less.

A polyester laminate having a multi-layer structure comprising resin layers (I) and (II), wherein

• (I) a first resin layer formed from a polymer composition or a polyester selected from the group consisting of at least one of the following polyesters (vii) to (xii):
• (vii) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (viii) a polyester wherein, in the polyester (vii), the dicarboxylic acid constituent units are derived from terephthalic acid or its ester derivative,
• (ix) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from terephthalic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the isophthalic acid or its ester derivative is in the range of 1 to 15% by weight based on the dicarboxylic acid constituent units;
• (x) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its derivative,
• (xi) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units,
• (xii) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• wherein said polymer compositions comprise (A) a first polyester selected from the group consisting of at least one of the polyesters (vii) to (xii) in an amount of 1 to 99% by weight and (B) a second polyester in an amount of 1 to 99% by weight,
• said second polyester (B) comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• and wherein the resin layer (I) made from polyester (A) and polyester (B) has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less;
• and
• (II) a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester (B), (b) a polyamide and (c) a polyolefin.

A process for producing a biaxially stretched polyester bottle, comprising:

• (1a) a step of producing a preform formed. from a polyester selected from the group consisting of at least one of the following polyesters (vii) to (xii):
• (vii) a polyester consisting essentially of:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols consisting essentially of ethylene glycol, a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, and at least one other diol which is an aliphatic glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50, and
• the constituent units derived from the other diol are contained in an amount of not more than 15% per mol based on the diol constituent units,
• (viii) a polyester wherein, in the polyester (vii), the dicarboxylic acid constituent units are derived from terephthalic acid or its ester derivative,
• (ix) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from terephthalic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the isophthalic acid or its ester derivative is in the range of 1 to 15% by weight based on the dicarboxylic acid constituent units;
• (x) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its derivative,
• (xi) a polyester wherein, in the polyester (vii), the dicarboxylic constituent units are derived from naphthalenedicarboxylic acid or its ester derivative and isophthalic acid or its ester derivative, and the proportion of the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative is in the range of 99 to 55% by weight based on the dicarboxylic acid constituent units,
• (xii) a polyester wherein, in any of the preceding polyesters, the polyalkylene glycol is polytetramethylene glycol having an alkylene chain of 4 carbon atoms and a polymerization degree (n) of 5 to 50;
• or
• (1b) a step of producing polyester compositions comprising
• (A) a first polyester selected from the group consisting of at least one of the polyesters (vii) to (xii) in an amount of 1 to 99% by weight and (B) a second polyester in an amount of 1 to 99% by weight,
• said second polyester comprising:
• dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
• diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol,
• wherein the proportion of constituent units derived from the polyalkylene glycol is less than 0.001% by weight based on the diol constituent units, and the polyalkylene glycol has a polymerization degree (n) of 5 to 50;
• or
• (1c) a step of producing a laminate having a multi-layer structure comprising:
• (I) a first resin layer formed from a polyester selected from the group consisting of at least one of the polyesters (vii) to (xii) and the polyester compositions;
• and
• (II) a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester (B), (b) a polyamide and (c) a polyolefin;
• (2) a step of heating the product of step (1a), (1b) or (1c),
• (3) a step of subjecting the product of step (1a), (1b) or (1c) to biaxial stretch
• (4) a step of blow molding to give a stretched bottle, and
• (5) a step of holding the stretched bottle in a mold at a temperature of not lower than 100° C.;
• and wherein the biaxially stretched polyester bottle has a carbon dioxide transmission rate of 17.5 cc·mm/m2·day·atm or less.