JP3462948B2 - Polyester block copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyester block copolymer, a method for producing the same, a molded article and a fiber made of the polyester block copolymer, and the polyester block copolymer of the present invention is ,
Even if it stays in a molten state for a long time at a high temperature of 270 ° C or higher,
Since the randomization of the polymer structure does not occur and the block copolymer structure is not impaired, the excellent properties originally possessed by the polyester block copolymer are not lost. Therefore, the polyester block copolymer of the present invention can be melt-molded at a high temperature, can be used alone in a wide range of applications such as various molded articles and fibers, and polyethylene terephthalate that needs to be heated and melted at a high temperature. A composite product can be produced by carrying out melt molding or melt spinning in combination with a high melting point polymer such as

[0002]

Polyester block copolymers having a crystalline aromatic polyester as a hard segment and an aliphatic polyester having a low glass transition point such as polytetramethylene glycol or an aliphatic polyester such as polycaprolactone as a soft segment are , Known as polyester elastomers. Polyester elastomers have excellent properties such as heat resistance and oil resistance, and also have elastic properties. Therefore, by utilizing these properties, various applications such as automobile parts, electric / electronic parts, general equipment parts, fibers, etc. Widely used in.

Among the above-mentioned polyester elastomers, the polyester block copolymer having an aliphatic polyester as a soft segment is more resistant to heat aging and light than the polyester block copolymer having an aliphatic polyether as a soft segment. It has the advantage of being excellent in However, when a polyester block copolymer having an aliphatic polyester as a soft segment is retained in a molten state at a high temperature for a long time, a transesterification reaction occurs between the hard segment and the soft segment, and the block copolymer structure is lost. Therefore, it is not suitable for melt molding such as extrusion molding, which is often retained in a molten state at a high temperature for a long time because of the disadvantage of randomized structure. And, in the case of a polyester copolymer or a molded product thereof in which the block copolymer structure is lost and the structure is random,
Its original properties, such as elastic properties, are lost.

Therefore, in order to suppress the transesterification reaction between the hard segment and the soft segment, phosphoric acid, phosphorous acid, their esters, ammonium salts, metal salts, etc. are added (Japanese Patent Publication No. 46-35500). JP-A-51-41095), a method of adding a phosphorus compound in the presence of a titanium-based catalyst has been proposed. However, the effect is not sufficient in any of the methods, and particularly when the residence temperature in the molten state exceeds 250 ° C., it becomes difficult to suppress the transesterification reaction.

Further, in order to suppress the transesterification reaction between the hard segment and the soft segment, the N-acyl lactam is added after the blocking reaction by the melt mixing of the aromatic polyester and the aliphatic polyester is substantially completed. A method of adding (JP-A-51-111895) and a method of adding at least one of dicarboxylic acid diaryl ester, carbonic acid ester and orthocarbonate (JP-A-52-29892) have been proposed. However, according to the research conducted by the present inventors, the effect of suppressing randomization is greatly influenced by the compatibility between the polymers to be melt-mixed, and therefore, the melt-mixing of the aromatic polyester and the aliphatic polyester having a large compatibility with each other is not effective. It has been found that it is difficult to suppress the randomization due to the transesterification reaction in the molten retention state at a high temperature of 270 ° C. or higher even if the above-mentioned compounds used in the prior art are added.

On the other hand, a polyester block copolymer having an aliphatic polyether as a soft segment does not cause a transesterification reaction between the soft segment and the hard segment, but when it is retained in a molten state at a high temperature for a long time, Since the aliphatic polyether forming the soft segment portion has a drawback of being thermally deteriorated, it is also impossible to perform stable melt-composite molding at high temperature in combination with a high-melting point polymer such as polyethylene terephthalate.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to prevent polyester block copolymer from losing its block copolymer structure even if it is retained in a molten state at high temperature for a long time, that is, random structuring does not occur. The original excellent characteristics can be maintained, and therefore various molded products and fibers with excellent physical properties can be smoothly produced even if the polyester block copolymer is used alone, and heating and melting at high temperature are required. Polyester block copolymer and its production, which enables smooth production of composite products with excellent physical properties by melt-molding or melt-spinning at high temperature together with various polyethylene terephthalates and other high melting point polymers. Is to provide a method.

[0008]

[Means for Solving the Problems] The present inventors have conducted extensive studies in order to achieve the above object. As a result of such research, a specific aromatic polyester segment and a specific aliphatic polyester segment are contained in a predetermined ratio, and the hydroxyl group concentration is 10 μeq / g or less and the carboxyl group concentration is 20 μeq / g or less. It is excellent in various properties such as mechanical properties, hydrolysis resistance, cold resistance,
Moreover, we succeeded in producing a new polyester block copolymer having a high melting point. Then, the inventors further conducted various investigations and studies on the physical properties of the novel polyester block copolymer.

As a result, the above novel polyester block copolymer newly produced by the present inventors is 270 ° C.
Even if the polymer is allowed to stay in the molten state at a high temperature for a long time (for example, 60 minutes or more), the block copolymerization structure disappears due to the transesterification reaction between the aromatic polyester segment and the aliphatic polyester segment, and the random structure accompanying it disappears. The various excellent properties that the polyester block copolymer itself had before being retained in the molten state did not occur and were retained without being lost even after the melt retention at high temperature. It was found that there was no disappearance of the powder and no decrease in the melting point. Therefore, this novel polyester block copolymer is not only capable of being smoothly molded and spun alone, but also has a high melting point such as polyethylene terephthalate that needs to be melted at a high temperature. It has been found that it can be used in combination with a high melting point polymer and can be subjected to melt molding or melt spinning at a high temperature together with a high melting point polymer to produce various products complexed with the high melting point polymer. The present invention has been completed based on the above findings.

That is, the present invention is a polyester block copolymer, which comprises (i) an aromatic polyester segment (A) and an aliphatic polyester segment (B), and (a) the aromatic polyester segment ( A) is mainly composed of a dicarboxylic acid unit and a diol unit, 70 mol% or more of the dicarboxylic acid unit is an aromatic dicarboxylic acid unit, and 70 mol% or more of the diol unit is an aliphatic α having 2 to 4 carbon atoms. , Ω-diol unit and 1,
At least one diol unit selected from 4-cyclohexanedimethanol units; (b) the aliphatic polyester segment (B) is mainly composed of a dicarboxylic acid unit and a diol unit, and an aliphatic polyester segment (B ₁ ) and hydroxy. A saturated aliphatic dicarboxylic acid having at least one of the aliphatic polyester segment (B ₂ ) mainly composed of a carboxylic acid unit, wherein 60 mol% or more of the dicarboxylic acid unit in the aliphatic polyester segment (B ₁ ) has 6 to 14 carbon atoms. Units and 70 mol% of diol units
The above is an aliphatic diol unit having 5 to 12 carbon atoms, and 60 mol% or more of the hydroxycarboxylic acid unit in the aliphatic polyester segment (B ₂ ) has 6 carbon atoms.
10 to 10 saturated aliphatic hydroxycarboxylic acid units; (ii) the aromatic polyester segment (A) /
The weight ratio of the aliphatic polyester segment (B) is 95 /
5 to 30/70; (iii) the hydroxyl group concentration is 10 μeq / g or less; and (iv) the carboxyl group concentration is 20 μeq / g or less; is there.

The present invention also provides the above-mentioned method for producing a polyester block copolymer, wherein (a ′) 70 mol% or more of the dicarboxylic acid unit is an aromatic dicarboxylic acid unit and the diol 70 mol% or more of the units are at least one diol unit selected from an aliphatic α, ω-diol unit having 1 to 4 carbon atoms and a 1,4-cyclohexanedimethanol unit, and mainly composed of a dicarboxylic acid unit and a diol unit. The intrinsic viscosity is 0.4 dl / g or more and the hydroxyl group concentration is 150 μeq /
g or less aromatic polyester (A '); and (b') 60 mol% or more of the dicarboxylic acid unit has 6 carbon atoms
To 14 saturated aliphatic dicarboxylic acid units and 70 mol% or more of the diol units are aliphatic diol units having 5 to 12 carbon atoms, and an intrinsic viscosity mainly composed of diol units is 0.4 dl / g or more. And an aliphatic polyester (B having a hydroxyl group concentration of 150 μeq / g or less)
₁ ') and 60 mol% or more of the hydroxycarboxylic acid unit is a saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms, the intrinsic viscosity of which is 0.4 dl / g or more and the hydroxyl group concentration is mainly composed of the hydroxycarboxylic acid unit. Is 15
0μ eq / g or less of the aliphatic polyester (B ₂ ') at least one aliphatic polyester selected from (B'); and aromatic polyester (A ') / aliphatic polyester (B') = 95/5 A method for producing a polyester block copolymer, which comprises using a weight ratio of ˜30 / 70 to carry out a transesterification reaction such that the hydroxyl group concentration of the product is 10 μeq / g or less.

Further, the present invention is a molded article and a fiber made of the above polyester block copolymer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyester block copolymer of the present invention comprises the aromatic polyester segment (A) and the aliphatic polyester segment (B) as described above. And the aromatic polyester segment (A)
Is mainly composed of dicarboxylic acid units and diol units, and 70 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units and 70 mol% of the diol units.
It is necessary that mol% or more is at least one diol unit selected from an aliphatic α, ω-diol unit having 1 to 4 carbon atoms and a 1,4-cyclohexanedimethanol unit [of the above (i) Requirements of (a)].

In the aromatic polyester segment (A), when the proportion of the aromatic dicarboxylic acid unit is less than 70 mol% based on all the dicarboxylic acid units constituting the aromatic polyester segment (A), the polyester block copolymer The heat resistance of the polymer is lowered, and a polyester block copolymer having good physical properties cannot be obtained. From the viewpoint of further improving the heat resistance of the polyester block copolymer, it is preferable that 80 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units, and 90 mol% or more are aromatic dicarboxylic acid units. It is more preferable.

The aromatic dicarboxylic acid unit in the aromatic polyester segment (A) has a molecular weight of 400.
It may be any aromatic dicarboxylic acid unit derived from the following aromatic dicarboxylic acid, and is not particularly limited, and examples thereof include phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfone. Examples thereof include units derived from aromatic dicarboxylic acids such as dicarboxylic acid, diphenylketone dicarboxylic acid, and sodium sulfoisophthalate. The aromatic polyester segment (A) is one or more of these aromatic dicarboxylic acid units. Can have. The aromatic polyester segment (A) is, if necessary, 30 mol% or less, preferably 20 mol% or less, more preferably 1 mol% or less.
0 mol% or less of other dicarboxylic acid units, eg 1,4
A cycloaliphatic dicarboxylic acid unit such as cyclohexanedicarboxylic acid unit, or one or more aliphatic dicarboxylic acid units composed of aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid You may have.

In the aromatic polyester segment (A), the proportion of at least one diol unit selected from aliphatic α, ω-diol units having 1 to 4 carbon atoms and 1,4-cyclohexanedimethanol unit is
When the amount is less than 70 mol% based on all the diol units constituting the aromatic polyester segment (A), the heat resistance of the polyester block copolymer is lowered and the polyester block copolymer having good physical properties can be obtained. Absent.
From the viewpoint of heat resistance of the polyester block copolymer, the proportion of at least one diol unit selected from an aliphatic α, ω-diol unit having 1 to 4 carbon atoms and a 1,4-cyclohexanedimethanol unit is aromatic. Of all diol units constituting the group A polyester segment (A)
It is preferably at least mol%, more preferably at least 90 mol%.

Examples of the aliphatic α, ω-diol unit having 2 to 4 carbon atoms include units consisting of 1,4-butanediol, 1,3-propanediol and 1,2-ethylene glycol. The polyester segment (A) may have only one type of these diol units and 1,4-cyclohexanedimethanol units, or may have two or more types.

The aromatic polyester segment (A) is, if necessary, 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less of another diol unit, for example, 1,5- Pentanediol,
1,6-hexanediol, neopentyl glycol,
3-methyl-1,5-pentanediol, 2-methyl-
1,8-octanediol, 1,9-nonanediol,
Aliphatic diol such as 1,10-decanediol; alicyclic diol such as cyclohexanediol; diol unit 1 composed of aromatic diol such as 1,4-bis (β-hydroxyethoxy) benzene and p-xylene glycol You may have 1 type or 2 or more types. Also,
If the aromatic polyester segment (A) is in a small amount (preferably 1 mol% or less of the total polyol), trimethylolethane, trimethylolpropane, glycerin, 1,2,6- hexanetriol, penta It may contain a unit composed of a polyhydric alcohol such as erythritol.

In the polyester block copolymer of the present invention, the aromatic polyester segment (A) has a poly (tetramethylene terephthalate) segment, a poly (tetramethylene-2,6-naphthalene dicarboxylate) segment and a poly (1). , 4-cyclohexanedimethylene terephthalate) segment is preferably used, because the polyester block copolymer has more excellent heat resistance and moldability.

In the polyester block copolymer of the present invention, the aliphatic polyester segment (B) is used.
But predominantly aliphatic polyester segment from dicarboxylic acid units and diol units (B ₁₎ and comprising at least one aliphatic polyester segment mainly composed of a hydroxycarboxylic acid unit (B _2), the aliphatic polyester segment (B ₁₎ 60 mol% or more of the dicarboxylic acid units in the above are saturated aliphatic dicarboxylic acid units having 6 to 14 carbon atoms and 70% of the diol units.
Mol% or more is an aliphatic diol unit having 5 to 12 carbon atoms, and 60 mol% or more of the hydroxycarboxylic acid unit in the aliphatic polyester segment (B ₂ ) is a saturated aliphatic hydroxycarboxylic acid having 6 to 10 carbon atoms. It is necessary to be a unit [requirement of (b) of (i) above].

In the aliphatic polyester segment (B ₁ ), the ratio of the saturated aliphatic dicarboxylic acid unit having 6 to 14 carbon atoms is 60 mol based on all the dicarboxylic acid units constituting the aliphatic polyester segment (B ₁ ). If it is less than%, the elasticity, elastic recovery and cold resistance of the polyester block copolymer are deteriorated, and a polyester block copolymer having good physical properties cannot be obtained. Improving the effect of suppressing random structuring of the block copolymer structure at the time of melt retention at a high temperature of 270 ° C or higher, and improving the properties such as elasticity, elastic recovery and cold resistance of the polyester block copolymer From this point of view, the proportion of the saturated aliphatic dicarboxylic acid unit having 6 to 14 carbon atoms is preferably 70 mol% or more, more preferably 80 mol% or more.

The aliphatic polyester segment (B
Examples of the saturated aliphatic dicarboxylic acid unit having 6 to 14 carbon atoms in ₁ ) include adipic acid, pimelic acid, suberic acid,
Examples thereof include saturated aliphatic dicarboxylic acid units composed of saturated aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, monodecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Aliphatic polyester segment (B ₁ ) May have one or more of these saturated aliphatic dicarboxylic acid units.

The aliphatic polyester segment (B
₁ ) is 40 mol or less, preferably 30 mol, if necessary.
Mol% or less, more preferably 20 mol% or less of another dicarboxylic acid unit, for example, saturated alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid; maleic acid, Unsaturated aliphatic dicarboxylic acid such as fumaric acid and itaconic acid; One or two dicarboxylic acid units consisting of halogen-containing dicarboxylic acid such as tetrabromophthalic acid
Can have more than one species. In addition, the aliphatic polyester segment (B ₁ ) is a small amount (preferably 1 mol% or less of all acid units) together with the above-mentioned dicarboxylic acid unit.
If so, it may contain a unit composed of a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid, and tricarballylic acid.

Further, in the aliphatic polyester segment (B ₁ ), the proportion of the aliphatic diol unit having 5 to 12 carbon atoms is 70 mol% based on all the diol units constituting the aliphatic polyester segment (B ₁ ). When it is less than 270 ° C., the effect of suppressing random structuring of the block copolymer structure at the time of melting and holding at a high temperature of 270 ° C. or more decreases, and the polyester block copolymer has high elongation, elastic recovery, cold resistance, etc. And the polyester block copolymer having good physical properties cannot be obtained. In the aliphatic polyester segment (B ₁ ), the proportion of the aliphatic diol unit having 5 to 12 carbon atoms is 80 in order to obtain a polyester block copolymer having better physical properties as described above.
It is preferably at least mol%, more preferably at least 90 mol%.

The aliphatic diol unit having 5 to 12 carbon atoms in the aliphatic polyester segment (B ₁ ) is as follows:
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-monodecanediol, Linear aliphatic diol unit consisting of 1,12-dodecanediol; neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3 -Methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and other branched aliphatic diol units may be mentioned, and the aliphatic polyester segment (B ₁ ) is the aliphatic You may have only 1 type of diol unit, or may have 2 or more types. In order to improve the properties such as cold resistance, elongation and elastic recovery of the polyester block copolymer, the aliphatic diol unit having 5 to 12 carbon atoms in the aliphatic polyester segment (B ₁ ) is branched. It is preferable that the proportion of the aliphatic diol unit having 5 to 12 carbon atoms having 30 mol% or more is 40 mol% or more.
It is more preferably at least mol%, further preferably at least 50 mol%.

The aliphatic polyester segment (B ₁ ) is, if necessary, 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less of one or two other diol units. The other diol units may have the above, and examples of other diol units include alicyclic diols such as cyclohexanediol and cyclohexanedimethanol; and aromatic compounds such as 1,4-bis (β-hydroxyethoxy) benzene and p-xylene glycol. Examples thereof include diol units composed of diols and the like. If necessary, the aliphatic polyester segment ( B ₁ ) may be trimethylolethane, trimethylolpropane, glycerin, 1,2,6 -hexane as long as it is in a small amount (preferably 1 mol% or less of the total polyol). It may contain a unit composed of a polyhydric alcohol such as triol or pentaerythritol.

In the aliphatic polyester segment (B ₂ ), the ratio of the saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms is all the hydroxycarboxylic acid units constituting the aliphatic polyester segment (B ₂ ). On the other hand, if it is less than 60 mol%, the elasticity, elastic recovery and cold resistance of the polyester block copolymer will be deteriorated and a polyester block copolymer having good physical properties cannot be obtained. Improving the effect of suppressing random structuring of the block copolymer structure at the time of melt retention at a high temperature of 270 ° C or higher, and improving the properties such as elasticity, elastic recovery and cold resistance of the polyester block copolymer From the point of doing
The proportion of the saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms is preferably 80 mol% or more, more preferably 90 mol% or more.

The saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms in the aliphatic polyester segment (B ₂ ) is a saturated aliphatic unit such as ε-hydroxycaproic acid, 6-hydroxyenanthic acid, 7-hydroxycaprylic acid. A unit derived from a hydroxycarboxylic acid may be mentioned, and the aliphatic polyester segment (B ₂ ) may have one kind or two or more kinds of these saturated aliphatic hydroxycarboxylic acid units.

The polyester block copolymer of the present invention has the aliphatic polyester segment (B ₁ ) as the aliphatic polyester segment (B ₁ ) even if it has only the above-mentioned aliphatic polyester segment (B ₁ ).
₂ ) alone, or both of the aliphatic polyester segment (B ₁ ) and the aliphatic polyester segment (B ₂ ), and the aliphatic polyester segment (B ₁ ) It is preferable that it is resistant to thermal decomposition at high temperatures.

In the polyester block copolymer of the present invention, it is necessary that the above-mentioned aromatic polyester segment (A) / aliphatic polyester segment (B) is 95/5 to 30/70 in weight ratio. Yes [Requirement (ii) above]. Aromatic polyester segment (A)
If the proportion of the aromatic polyester segment (A) exceeds 95% by weight based on the total weight of the aromatic polyester segment (B) and the aliphatic polyester segment (B), the elastic recovery property of the polyester block copolymer becomes poor, while the aromatic If the proportion of the polyester segment (A) is less than 30% by weight, the heat resistance of the polyester block copolymer will be poor. From the viewpoint of elastic recovery characteristics and heat resistance of the polyester block copolymer, the aromatic polyester segment (A) / aliphatic polyester segment (B) is preferably in a weight ratio of 90/10 to 40/60,
The weight ratio of 80/20 to 40/60 is more preferable.

Further, in the polyester block copolymer of the present invention, in order to improve mechanical properties such as strength and elongation, the aromatic polyester segment (A) constituting the polyester block copolymer is The number average molecular weight is about 500 to 10,000, and the number average molecular weight of the aliphatic polyester segment (B) is about 500 to 1,000.
0 is preferable, and the intrinsic viscosity of the polyester block copolymer is 0.7 dl / g or more when measured at 30 ° C. in a phenol / tetrachloroethane mixed solvent (1/1 weight ratio). Preferably 0.8 dl /
It is more preferably at least g, and even more preferably at least 1.0 dl / g.

In the polyester block copolymer of the present invention, it is extremely important that the hydroxyl group concentration is 10 μeq / g or less [Requirement (iii) above]. If the hydroxyl group concentration of the polyester block copolymer exceeds 10 μeq / g, it will remain between the aromatic polyester segment (A) and the aliphatic polyester segment (B) when retained in a molten state at a high temperature of 270 ° C. or higher. The transesterification reaction of (1) occurs, and the block copolymer structure is lost to form a random structure, and the original properties of the polyester block copolymer, such as elastic properties, are lost. In order to more effectively prevent the disappearance of the block copolymer structure when the polyester block copolymer is retained in a molten state at a high temperature, the hydroxyl concentration of the polyester block copolymer is preferably 5 μeq / g or less,
It is more preferably 3 μeq / g or less. The value of the "hydroxyl group concentration" in the present invention means the hydroxyl group concentration measured by the method described in the following examples.

Furthermore, the polyester block copolymer of the present invention must have a carboxyl group concentration of 20 μeq / g or less [Requirement (iv) above]. The carboxyl group concentration of the polyester block copolymer is 20
When it exceeds μ equivalent / g, the transesterification reaction between the aromatic polyester segment (A) and the aliphatic polyester segment (B) tends to be promoted when the polyester is retained in a molten state at a high temperature. If the original properties of the block copolymer, such as elasticity, are easily lost, and the carboxyl group concentration exceeds 20 μeq / g,
The durability such as hydrolysis resistance and heat aging resistance of the polyester block copolymer is also reduced. The carboxyl group concentration of the polyester block copolymer is preferably 10 μeq / g or less, more preferably 5 μeq / g or less. The value of "carboxyl group concentration" in the present invention means the carboxyl group concentration measured by the method described in the following examples.

The polyester block copolymer of the present invention is excellent in various properties such as mechanical properties, hydrolysis resistance and cold resistance because it has the above-mentioned requirements (i) to (iv). In addition, it has a high melting point, and even if it is kept in a molten state at a high temperature of 270 ° C. or higher for a long time, a transesterification reaction between the aromatic polyester segment (A) and the aliphatic polyester segment (B) occurs. Since the block copolymer structure is well maintained without random structuring, it is possible to maintain the excellent properties originally possessed by the polyester block copolymer itself even after being exposed to the molten state at high temperature. it can.

In the polyester block copolymer of the present invention, (a ') 70 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units and 70 mol% or more of the diol units are aliphatic groups having 2 to 4 carbon atoms. At least one diol unit selected from α, ω-diol units and 1,4-cyclohexanedimethanol units, which is mainly composed of dicarboxylic acid units and diol units, has an intrinsic viscosity of 0.4 dl / g or more and a hydroxyl group concentration. Is 150μ equivalent /
g or less aromatic polyester (A '); and (b') 60 mol% or more of the dicarboxylic acid unit has 6 carbon atoms
To 14 saturated aliphatic dicarboxylic acid units and 70 mol% or more of the diol units are aliphatic diol units having 5 to 12 carbon atoms, and an intrinsic viscosity mainly composed of diol units is 0.4 dl / g or more. And an aliphatic polyester (B having a hydroxyl group concentration of 150 μeq / g or less)
₁ ') and 60 mol% or more of the hydroxycarboxylic acid unit is a saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms, the intrinsic viscosity of which is 0.4 dl / g or more and the hydroxyl group concentration is mainly composed of the hydroxycarboxylic acid unit. Is 15
At least one aliphatic polyester (B ′) selected from aliphatic polyesters (B ₂ ′) of 0 μeq / g or less;
Are used in a weight ratio of aromatic polyester (A ′) / aliphatic polyester (B ′) = 95/5 to 30/70, so that the hydroxyl group concentration of the product is 10 μeq / g or less. The reaction can be performed by the above-described method of the present invention.

Here, in the above-mentioned manufacturing method of the present invention,
The content of the dicarboxylic acid unit and the diol unit in the aromatic polyester (A ′) and the aliphatic polyester (B ₁ ′) and the content of the hydroxycarboxylic acid unit in the aliphatic polyester (B ₂ ′) are the same as those of the polyester block of the present invention. It is the same as described in detail above for the polymer.

The polyester block copolymer of the present invention can be obtained by subjecting an aromatic polyester (A ′) and an aliphatic polyester (B ′) to a transesterification reaction. The aromatic polyester (A ′) and the aliphatic polyester When polyester produced using potassium titanium oxalate as a catalyst is used for at least one of (B '), a polyester block copolymer having excellent durability and color tone such as hydrolysis resistance and heat aging resistance is obtained. It is preferable because it is possible. In particular, aromatic polyester (A ')
In the case of using polybutylene terephthalate, it is preferable to use one produced by using potassium titanium oxalate as a catalyst because a polyester block copolymer having a further excellent effect can be obtained. As used herein, potassium titanium oxalate means that the carboxyl group of oxalic acid is in the form of a salt with titanium and potassium. Generally, about 0.5 mol of titanium atoms and about 0.5 mol of potassium atoms are contained per mol of oxalic acid. Approximately 1 mole bond, typically chemical formula; K ₂ TiO
It is represented by (C ₂ O ₄ ) ₂ · nH ₂ O. Such potassium titanium oxalate can be produced, for example, by reacting it with potassium titanate obtained by sufficiently hydrolyzing oxalic acid, but the production method is not limited, and is represented by the above-mentioned chemical formula. Any potassium titanium oxalate can be used.

The transesterification reaction of the aromatic polyester (A ') and the aliphatic polyester (B') is usually carried out by melt-kneading both polyesters, and the transesterification reaction at that time is carried out by a catalyst. Or without a catalyst, such as tetraisopropyl titanate, tetrabutyl titanate, titanium oxyacetyl titanate.

In carrying out the transesterification reaction of the aromatic polyester (A ') and the aliphatic polyester (B'), the polyester block copolymer of the present invention is produced.
The most important issue is how to appropriately form the block copolymer structure. The present inventors have selected aromatic polyesters (A ′) and aliphatic polyesters (B ′) having a hydroxyl group concentration of 150 μeq / g or less and an intrinsic viscosity of 0.4 dl / g or more. The requirements (i) to (iv) described above are obtained by subjecting both polyesters to an ester exchange reaction under melt-kneading while controlling the hydroxyl group concentration in the reaction system using each of them.
In particular, the requirement of (iii) above (the hydroxyl group concentration is 10 μeq / g
The following) and the requirement (iv) (carboxyl group concentration is 20 μeq / g or less) can be extremely smoothly and stably produced with an excellent polyester block copolymer of the present invention.

From this point of view, the aromatic polyester (A ')
When a polyester block copolymer is produced by transesterification of a polyester with an aliphatic polyester (B '), it is important that the hydroxyl concentration of both polyesters is 150 μeq / g or less. ')
When the hydroxyl group concentration of one or both of the aliphatic polyester (B ′) and the polyester group is higher than 150 μeq / g, it becomes difficult to sufficiently control the hydroxyl group concentration during melt kneading (during the transesterification reaction), and the hydroxyl group concentration becomes high. Of 10 μeq / g or less makes it difficult to produce a polyester block copolymer.

Further, when the polyester block copolymer is produced by subjecting the aromatic polyester (A ') and the aliphatic polyester (B') to a transesterification reaction, in order to adjust the hydroxyl group concentration appropriately, Group polyester (A ')
And the intrinsic viscosity of the aliphatic polyester (B ') must be 0.4 dl / g or more, respectively, and the intrinsic viscosity of both polyesters is preferably 0.5 dl / g or more, and 0.6 dl / g It is more preferably g or more. One or both of the aromatic polyester (A ′) and the aliphatic polyester (B ′) has an intrinsic viscosity of 0.4 dl / g
When it is less than 1, the compatibility between the aromatic polyester (A ') and the aliphatic polyester (B') increases, making it difficult to control the hydroxyl group concentration, and the polyester block having a hydroxyl group concentration of 10 μeq / g or less. A copolymer cannot be obtained.

Then, during the melt-kneading of the aromatic polyester (A ') and the aliphatic polyester (B'), a dediol reaction by transesterification, an esterification reaction between a carboxyl group and a hydroxyl group, a terminal diol is a cyclic ether. As a result of the elimination reaction, the concentration of hydroxyl groups in the reaction system decreases. The rate of the transesterification reaction varies depending on the compatibility between the aromatic polyester (A ') and the aliphatic polyester (B'), the reaction conditions during the transesterification reaction, and so on. The hydroxyl group concentration of the aromatic polyester (A ') or the aliphatic polyester (B') used is adjusted to control the hydroxyl group concentration of the reaction system, and the hydroxyl group concentration of the finally obtained polyester block copolymer is 10 μm as described above. It can be adjusted to the equivalent / g or less.

In some cases, the hydroxyl group concentration of the reaction system is controlled by adding a compound having a group capable of reacting with the hydroxyl group present in the reaction system to the reaction system at an appropriate time and in an appropriate amount. It is possible to adjust the hydroxyl group concentration of the finally obtained polyester block copolymer to 10 μeq / g or less. In that case, the compound having a group capable of reacting with a hydroxyl group (hereinafter referred to as “hydroxyl group-reactive compound”) is a compound that reacts with a hydroxyl group existing in the reaction system and does not release a hydroxyl group again after the reaction. And a compound having a boiling point of 200 ° C. or higher. The boiling point of the hydroxyl-reactive compound is 200
If the temperature is lower than 0 ° C, the hydroxyl group-reactive compound is out of the system during the transesterification reaction (melt kneading) of the aromatic polyester (A ') and the aliphatic polyester (B') which is usually carried out at a temperature of 200 ° C or higher. it can not perform its function sufficiently in the distillate.

Examples of the hydroxyl-reactive compound are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, toluic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid. Compounds having a carboxyl group such as; acid anhydrides such as succinic anhydride and phthalic anhydride; N such as acetylcaprolactam, acetyllaurolactam, benzoylcaprolactam, benzoyllaurolactam, terephthaloylbiscaprolactam, terephthaloylbislaurolactam -Acyl lactam can be mentioned, and one or more of these hydroxyl group-reactive compounds can be added to the reaction system as necessary.

Further, the above-mentioned aromatic polyester (A ')
The reaction temperature, pressure, and the like in the transesterification reaction between the aromatic polyester (B ') and the aliphatic polyester (B') can be adjusted according to the content of the aromatic polyester (A ') or the aliphatic polyester (B') used. However, in general, both polyesters are melt-kneaded at a temperature about 10 to 30 ° C. higher than the melting point of the polyester having a high melting point [usually aromatic polyester (A ′)], and reacted under a reduced pressure of 1 mmHg or less. .

In the transesterification reaction of the aromatic polyester (A ') and the aliphatic polyester (B'), if the transesterification reaction of both polyesters is insufficient, a large amount of the portion remains in the mixed state. As a result, a polyester block copolymer having the desired properties cannot be obtained. On the other hand, when the transesterification reaction of both polyesters proceeds too much, the aromatic polyester segment (A) and aliphatic polyester segment (A) constituting the polyester block copolymer ( B) length (number average molecular weight)
Is too small to exhibit properties close to those of a random copolymer, so it is necessary to pay sufficient attention. Whether or not the transesterification reaction between the aromatic polyester (A ′) and the aliphatic polyester (B ′) is favorably carried out and whether or not a desired polyester block copolymer is produced is determined by the reaction product produced by the transesterification reaction. It can be confirmed by sequentially examining the elastic recovery, but usually, it is judged by whether the system in which the aromatic polyester (A ') and the aliphatic polyester (B') are melt-kneaded is transparent in the molten state. You can That is, when the melt-kneaded system becomes transparent,
When the hydroxyl group concentration of the polyester block copolymer is 10 μeq / g or less, the transesterification reaction is naturally stopped. When the carboxyl group concentration of the polyester block copolymer obtained by the transesterification reaction exceeds 20 μeq / g, a carboxyl group-capping agent such as a compound having an oxazoline group or a compound having a carbodiimide group is reacted. And the carboxyl group concentration is 2
It should be 0 μeq / g or less.

In the polyester block copolymer of the present invention, the aromatic polyester segment (A) and / or the aliphatic polyester segment (B) has a sulfonate group so that cationic dyeing is possible, if necessary. It may be modified with a compound, or may be modified with a phosphorus-containing compound to make it flame-retardant, and further, an additive known to be conventionally added to a polyester block copolymer as necessary, Colorants, flame retardants,
UV absorbers, antioxidants, hydrolysis stabilizers, antifungal agents, sulfonic acid chlorides, various additives such as internal release agents,
Various fibers such as glass fiber, organic fiber, talc, silica, other inorganic fillers, various coupling agents, etc.
It may be added as appropriate before, during, and after the melt-kneading for the transesterification reaction.

The polyester block copolymer of the present invention is thermoplastic and excellent in melt moldability, and has a high temperature, for example, 27.
Even if it is retained in a molten state at a high temperature of 0 ° C or higher for a long time, its block copolymer structure is not lost, physical properties are not deteriorated due to random structuring, and heat resistance is very excellent (thermogravity loss initiation High temperature). Therefore, various moldings, fibers, etc. can be smoothly manufactured by performing melt molding, melt spinning, etc. using the polyester block copolymer of the present invention alone. Further, the polyester block copolymer of the present invention is used in combination with polyethylene terephthalate or other high melting point polymer which is required to be melted at a high temperature, and melt-mixed at a high temperature to obtain a high content with the polyester block copolymer of the present invention. It is possible to produce a composition in which a melting point polymer is blended, or to perform melt molding or melt spinning at high temperature to produce a composite molded product of a polyester block copolymer and a high melting point polymer, a composite fiber, or the like. In particular, when the polyester block copolymer of the present invention is used, the polyester block copolymer of the present invention and polyethylene terephthalate can be obtained by performing extrusion molding or the like which requires residence in a molten state at high temperature for a long time. It is possible to smoothly produce the above-mentioned blend composition with a high melting point polymer such as polyamide, a composite molded article, a composite fiber and the like.

Without limitation, the polyester block copolymers of the present invention, alone or in combination with other polymers, can be used in sheets, films, belts, rolls, curl cords, hoses, tubes, packings. Materials, anti-vibration materials, damping materials, cushion materials, shoe soles, sports shoes,
It can be effectively used for a wide range of applications such as machine parts, automobile parts, electric / electronic parts, various molded products such as sports goods, elastic fibers, and raw materials for adhesives. Then, in producing the above-mentioned molded article and the like from the polyester block copolymer of the present invention, various melt molding methods conventionally used for thermoplastic resins and thermoplastic elastomers, for example, extrusion molding, injection Various molding methods such as molding, extrusion blow molding, injection blow molding, calender molding, and press molding can be adopted, and when fibers are produced, melt spinning can be performed.

[0050]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the intrinsic viscosity of the aromatic polyester (A ′), the aliphatic polyester (B ′) and the polyester block copolymer, the aromatic polyester (A ′), the aliphatic polyester (B ′) and the polyester block copolymer Hydroxyl group concentration and carboxyl group concentration of the coalescence, melting point before melt-kneading of the polyester block copolymer, melting point after melt-kneading of the polyester block copolymer, tensile strength of the film made of the polyester block copolymer, tensile elongation, resistance Measurement, calculation or evaluation of hydrolyzability, cold resistance, melting point and elastic recovery rate, and melting point, tensile strength, tensile elongation and elastic recovery rate of elastic yarn made of polyester block copolymer were performed as follows. .

[Intrinsic viscosity] Aromatic polyester (A '),
The aliphatic polyester (B ') or the polyester block copolymer was dissolved in a mixed solvent of phenol / tetrachloroethane (1/1 weight ratio) and measured at 30 ° C.

[Hydroxyl Concentration] The hydroxyl concentration of the aromatic polyester (A ′), the aliphatic polyester (B ′) and the polyester block copolymer is determined by proton NMR (apparatus: JEOLGX-500NM manufactured by JEOL Ltd.).
R ").

[Concentration of Carboxyl Group] The aromatic polyester (A ′), aliphatic polyester (B ′) or polyester block copolymer is dried and diluted with benzyl alcohol to give 2
The mixture was dissolved at a temperature of 15 ° C. for 3 minutes, chloroform was added after the dissolution, and then titration was performed using phenol red as an indicator using a methanol solution of potassium hydroxide to obtain a neutralization point, and a carboxyl group concentration was calculated. .

[Melting Point Before Melt-Kneading] The melting point of the polyester block copolymer before melt-kneading is measured by using a differential scanning calorimeter (DSC) manufactured by Mettler Co., Ltd. under a nitrogen stream and shown in Table 1 below. ~ Step 3 was sequentially performed and the melting peak temperature at that time was determined.

[0055]

[Table 1] Starting point temperature Ending point temperature Ending point holding time Temperature rising / falling temperature (℃) (℃) (min) (℃ / min) Stroke 1 20 250 5 20 stroke 2 250 50 1 20 stroke 3 50 250 0 20

[Melting point after melt-kneading] Using a Labo Plastomill “20R200” manufactured by Toyo Seiki Seisakusho, Ltd., 270 ° C.
Melt-kneading for 60 minutes while flowing nitrogen at a temperature of, and the melting point of the polyester block copolymer after the melt-kneading treatment is measured in the same manner as the melting point of the polyester block copolymer before the melt-kneading described above. It was measured.

[Tensile Strength and Tensile Elongation] The polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and a test piece of 8 cm × 0.5 cm was taken from the film. , Using the test piece, tensile speed 200 mm / min, temperature 23 ° C, humidity 65
A tensile test was performed under the conditions of% RH to measure the tensile strength and the tensile elongation.

[Hydrolysis resistance] The polyester block copolymer was hot pressed at a temperature of 270 ° C. to a thickness of 100 μm.
2cm x 1 from this film after manufacturing
A 0 cm test piece was taken, the test piece was immersed in hot water of 100 ° C. for 5 days, and the retention rate (%) of the intrinsic viscosity after the immersion treatment with respect to the intrinsic viscosity of the test piece before immersion was calculated, The hydrolysis resistance was evaluated.

[Cold resistance] The polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and 3 cm × 0.5 c was formed from this film.
m test piece was collected and the dynamic viscoelasticity of the test piece was measured by
Using "DVE-VEDVE Rheospectler" manufactured by Rheology, measurement was performed at a frequency of 11 Hz, and the temperature (Tα) at which the dynamic loss elastic modulus E "reached a peak was determined, thereby evaluating cold resistance.

[Melting Point of Film] The melting point of the film having a thickness of 100 μm obtained by hot-pressing the polyester block copolymer at a temperature of 270 ° C. is the melting point of the polyester block copolymer before melt kneading described above. It measured by the method similar to measurement.

[Elastic Recovery of Film] The polyester block copolymer was hot-pressed at a temperature of 270 ° C. to a thickness of 1
After producing a film of 00 μm, 2
cm × 10 cm test piece is sampled, pulling speed 200 mm
/ Min, 100% elongation, hold for 3 seconds after elongation, stress is then removed, and the length L ₁ (cm) of the film at the moment when the stress is removed is measured. I asked.

[0062]

## EQU1 ## Elastic recovery rate of film (%) = [{10- (L ₁
-10)} / 10] × 100

[Melting point of elastic yarn] The polyester block copolymer was spun at a spinning temperature of 27 using a spinning machine equipped with a single-screw extruder.
Melt spinning was performed at 0 ° C. and a spinning speed of 1000 m / min to produce an unstretched elastic yarn of 75 denier / 8 filament. The melting point of this elastic yarn was measured by the same method as the method for measuring the melting point of the polyester block copolymer before melt kneading described above.

[Tensile Strength and Tensile Elongation of Elastic Yarn] The polyester block copolymer was melt-spun with a spinning machine equipped with a single-screw extruder at a spinning temperature of 270 ° C. and a spinning speed of 1000 m / min to give 75. An undrawn elastic yarn of denier / 8 filament was produced. A test piece with a length of 5 cm was sampled from this elastic thread, and the test piece was used to pull at a speed of 200 m.
/ Min, temperature 23 ° C., humidity 65% RH, a tensile test was performed to measure the tensile strength and tensile elongation at break.

[Elastic recovery rate of elastic yarn] The polyester block copolymer was melt-spun at a spinning temperature of 270 ° C and a spinning speed of 1000 m / min using a spinning machine equipped with a single-screw extruder to obtain 75 denier / 8. An undrawn elastic yarn of filaments was produced. A 10 cm long test piece was sampled from this elastic yarn, stretched 100% at a pulling speed of 200 mm / min, held for 3 seconds after stretching, the stress was removed, and the length of the elastic yarn at the moment the stress was removed L ₂ (cm) was measured, and the elastic recovery rate of the elastic yarn was calculated by the following formula.

[0066]

## EQU1 ## Elastic recovery rate (%) of elastic yarn = [{10− (L ₂ −
10)} / 10] × 100

The relationship between the compounds used in the following Examples and Comparative Examples and their abbreviations is as shown in Table 2 below.

[0068]

[Table 2] Abbreviation: Compound name SbA: Sebacic acid AdA: Adipic acid AzA: Azelaic acid IPA: Isophthalic acid TPA: Terephthalic acid MPD: 3-Methyl-1,5-pentanediol ND: 1,9-Nonanediol MOD: 2-Methyl- 1,8-octanediol BD: 1,4-butanediol EG: ethylene glycol HD: 1,6-hexanediol OCA: hydroxycaproic acid TCL: terephthaloylbiscaprolactam DPT: diphenylterephthalate DCP: diphenylcarbonate TPOC: tetraphenyl Orthocarbonate CI: Carbodiimide compound CHDM: 1,4-Cyclohexanedimethanol (cis / trans = 30/70)

Reference Example 1 Production of Polyester (a) Under a nitrogen stream, sebacic acid (Sb having 10 carbon atoms)
20.2 kg of A) and 14.2 kg of 3-methyl-1,5-pentanediol (MPD) having 6 carbon atoms
Was charged into a reactor, and an esterification reaction was carried out at a temperature of 200 ° C. under normal pressure while the produced water was distilled out of the system. When the acid value of the reaction product became 10 or less, 11 g of potassium titanium oxalate [ K ₂ TiO (C ₂ O ₄ ) ₂ · nH ₂ O] catalyst was added, and the temperature was adjusted to 200 mmHg to 100 mm at 250 ° C.
The reaction was continued while gradually reducing the pressure to mmHg. When the acid value of the reaction product reached 1.0, the degree of vacuum was gradually increased with a vacuum pump to complete the reaction. As a result, a polyester having an intrinsic viscosity of 0.95 dl / g, a hydroxyl group concentration of 80 μeq / g and a carboxyl group concentration of 5 μeq / g was obtained [polyester (a)].

Reference Examples 2 to 20 [Production of Polyester (b) to Polyester (t)] Tables were prepared in the same manner as in Reference Example 1 except that the acid component, diol component and catalyst shown in Table 3 below were used. Polyesters having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in 3 were respectively prepared [Polyester (b)-
Polyester (t)].

Example 1 [Production of Polyester Block Copolymer] As shown in Table 4 below, 6000 g of the polyester (i) obtained in Reference Example 9 and the polyester (a) obtained in Reference Example 1 were used. ) 4000 g and sebacic acid (SbA) 30
g was reacted for 150 minutes at a temperature of 250 ° C. under a reduced pressure of 0.3 mmHg. As a result, as shown in Table 5 below, the intrinsic viscosity was 1.45 dl / g and the hydroxyl group concentration was 3
A polyester block copolymer having a μ equivalent / g and a carboxyl group concentration of 5 μ equivalent / g was obtained. Melting point of this polyester block copolymer before melt-kneading, 270 ° C.
The melting point after melt-kneading was measured by the method described above, and it was as shown in Table 5 below. Further, this polyester block copolymer is hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm,
The tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery rate of this film were measured or evaluated by the methods described above, and the results are shown in Table 5 below.

Examples 2 to 6 [Production of Polyester Block Copolymer] The aromatic polyester (A '), aliphatic polyester (B') and additives shown in Table 4 below are shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration, and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 1 except that the reaction was conducted at the reaction times shown in Table 4 below. did. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Example 7 [Production of Polyester Block Copolymer] As shown in Table 4 below, 8000 g of the polyester (i) obtained in Reference Example 9 and the polyester (a) obtained in Reference Example 1 Using 2000 g, the reaction was carried out at a temperature of 250 ° C. under a reduced pressure of 0.3 mmHg for 190 minutes, and then terephthaloylbiscaprolactam (TCL) 20
0g was added and it was made to react under reduced pressure for 30 minutes. As a result, as shown in Table 5 below, the intrinsic viscosity was 1.37 dl.
/ G, the hydroxyl group concentration was 3 μeq / g, and the carboxyl group concentration was 7 μeq / g. A polyester block copolymer was obtained. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, the polyester block copolymer was hot-pressed at a temperature of 270 ° C. to give a thickness of 100.
A film having a thickness of μm was produced, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery rate of this film were measured or evaluated by the methods described above, and the results are shown in Table 5 below. It was

Example 8 [Production of Polyester Block Copolymer] As shown in Table 4 below, 6000 g of the polyester (i) obtained in Reference Example 9 and the polyester (l) obtained in Reference Example 12 Using 4000 g and 30 g sebacic acid, 160 at a temperature of 250 ° C. under a reduced pressure of 0.3 mmHg.
After reacting for minutes, 200 g of a carbodiimide compound (CI) (“Stabaxol I” manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added as a carboxyl group-capping agent, and the mixture was stirred under normal pressure for 10 minutes. As a result, as shown in Table 5 below, a polyester block copolymer having an intrinsic viscosity of 1.39 dl / g, a hydroxyl group concentration of 3 μeq / g and a carboxyl group concentration of 14 μeq / g was obtained. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Example 9 [Production of Polyester Block Copolymer] Aromatic polyester (A ') and aliphatic polyester (B') shown in Table 4 below were used in the proportions shown in Table 4 below. In the same manner as in Example 8, a polyester block copolymer having the intrinsic viscosity, hydroxyl group concentration and carboxyl group concentration shown in Table 5 below was produced. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, a film having a thickness of 100 μm was produced by hot pressing the polyester block copolymer at a temperature of 270 ° C., and the tensile strength, tensile elongation, hydrolysis resistance, and cold resistance of the film were measured.
The melting point and elastic recovery rate were measured or evaluated by the methods described above, and the results are shown in Table 5 below.

Example 10 Production of Polyester Block Copolymer 6000 g of polyester (p) obtained in Reference Example 16 and polyester (r) obtained in Reference Example 18 are shown in Table 4 below. Using 4000 g, a reaction was performed at a temperature of 250 ° C. under a reduced pressure of 0.3 mmHg for 210 minutes, and then 200 g of a carbodiimide compound (CI) was added to the mixture to give 1
The mixture was stirred for 0 minutes under normal pressure. As a result, as shown in Table 5 below, the intrinsic viscosity was 1.44 dl / g and the hydroxyl group concentration was 3
A polyester block copolymer having a μ equivalent / g and a carboxyl group concentration of 7 μ equivalent / g was obtained. The melting point of the polyester block copolymer before melt kneading and 27
The melting point after melt-kneading at 0 ° C. was measured by the above-mentioned method and was as shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Example 11 Production of Polyester Block Copolymer Aromatic polyester (A ') and aliphatic polyester (B') shown in Table 4 below were used in the proportions shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 1 except that the reaction was performed for the reaction time shown in Table 4 above. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Example 12 Production of Polyester Block Copolymer Aromatic polyester (A ') and aliphatic polyester (B') shown in Table 4 below were used in the proportions shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 7 except that the reaction was performed for the reaction time shown in Table 4 above. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Comparative Example 1 [Production of Polyester Block Copolymer] The aromatic polyester (A ′) and the aliphatic polyester (B ′) shown in Table 4 below were used in the proportions shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 10 except that the reaction was performed for the reaction time shown in Table 4 above. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the above method,
The results are shown in Table 5 below.

Comparative Examples 2 to 4 [Production of Polyester Block Copolymer] The aromatic polyester (A '), aliphatic polyester (B') and additives shown in Table 4 below are shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration, and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 8 except that the reaction was carried out in the proportions shown in Table 4 below. . The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Comparative Example 5 [Production of Polyester Block Copolymer] As shown in Table 4 below, 6000 g of the polyester (k) obtained in Reference Example 11 and the polyester (f) obtained in Reference Example 6 Using 4000 g, the mixture was reacted at a temperature of 250 ° C. under a reduced pressure of 0.3 mmHg for 15 minutes, and as shown in Table 5 below, an intrinsic viscosity of 1.19 dl / g, a hydroxyl group concentration of 25 μeq / g and a carboxyl group. Group concentration is 5
A 5 μeq / g polyester block copolymer was obtained.
The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below.
Further, this polyester block copolymer was treated at 270 ° C.
A film having a thickness of 100 μm was produced by hot pressing at a temperature of, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery rate of this film were measured or evaluated by the methods described above. , As shown in Table 5 below.

Comparative Example 6 [Production of Polyester Block Copolymer] The aromatic polyester (A ′) and the aliphatic polyester (B ′) shown in Table 4 below were used in the proportions shown in Table 4 below, and A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 7 except that the reaction was performed for the reaction time shown in Table 4 above. The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Comparative Example 7 Production of Polyester Block Copolymer Comparative Example except that the time of the transesterification reaction was 55 minutes and the reaction time after adding terephthaloylbiscaprolactam was changed to 5 minutes. Same as 6 below, Table 5 below
A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration, and a carboxyl group concentration shown in was produced. The melting point of the polyester block copolymer before melt kneading and 270
The melting point after melt-kneading at 0 ° C. was measured by the above-mentioned method, and it was as shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Comparative Examples 8 to 13 [Production of Polyester Block Copolymer] The aromatic polyester (A '), aliphatic polyester (B') and additives shown in Table 4 below are shown in Table 4 below. A polyester block copolymer having an intrinsic viscosity, a hydroxyl group concentration and a carboxyl group concentration shown in Table 5 below was produced in the same manner as in Example 7 except that the reaction was carried out in the proportions shown in Table 4 below and the reaction was performed for the reaction time shown in Table 4 below. . The melting point of this polyester block copolymer before melt-kneading and the melting point after melt-kneading at 270 ° C. were measured by the methods described above, and the results are shown in Table 5 below. Further, this polyester block copolymer was hot-pressed at a temperature of 270 ° C. to produce a film having a thickness of 100 μm, and the tensile strength, tensile elongation, hydrolysis resistance, cold resistance, melting point and elastic recovery of this film were obtained. When the rate was measured or evaluated by the method described above, it was as shown in Table 5 below.

Examples 13 to 24 [Production of Elastic Yarn] As shown in Table 6 below, a spinning machine equipped with a single-screw extruder was prepared using the polyester block copolymers obtained in Examples 1 to 12. Using, spinning temperature 270 ℃, spinning speed 1000
Melt-spun under conditions of m / min to produce an unstretched elastic yarn of 75 denier / 8 filaments. The melting point, the tensile strength, the tensile elongation, and the elastic recovery rate of this elastic yarn were measured or evaluated by the methods described above, and the results are shown in Table 6 below.

Comparative Examples 14 to 26 [Production of Elastic Yarn] As shown in Table 6 below, the polyester block copolymers obtained in Comparative Examples 1 to 13 were used, and a spinning machine with a single-screw extruder was used. Spinning temperature of 270 ° C., spinning speed of 100
Melt-spun under the condition of 0 m / min to produce an unstretched elastic yarn of 75 denier / 8 filament. The melting point, the tensile strength, the tensile elongation, and the elastic recovery rate of this elastic yarn were measured or evaluated by the methods described above, and the results are shown in Table 6 below.

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

[Table 6]

From the results of Tables 3 to 6 above, the aromatic polyester segment (A) and the aliphatic polyester segment (B) satisfying the above-mentioned requirements (i) and (ii) were used, and the hydroxyl group concentration was 10 μeq / g
The requirement of (iii) that it is below, and the above (iv) that the concentration of the carboxyl group is 20 μeq / g or less
When the polyester block copolymer of the present invention satisfying the requirement of No. 1 is melt-kneaded at a high temperature of 270 ° C. for 60 minutes, the melting point after the melt-kneading does not change from the melting point before the melt-kneading and the melting point is lowered. It can be seen that there is no melting point or there is a slight decrease in the melting point. From these results, the polyester block copolymer of the present invention having a hydroxyl group concentration of 10 μeq / g or less and a carboxyl group concentration of 20 μeq / g or less, particularly a hydroxyl group concentration of 10 μm
The polyester block copolymer of the present invention, which has an equivalent weight / g or less, of the aromatic polyester segment (A) and the aliphatic polyester segment (B) even when retained in a molten state at a high temperature of 270 ° C. or higher for a long time. No transesterification reaction occurs between them, therefore the disappearance of the block copolymer structure and the random structuring accompanying it do not occur, and the physical properties originally possessed by the polyester block copolymer are well maintained even after melt-kneading, This allows not only smooth melt-forming and melt-spinning by itself, but also melt-forming and melting in combination with polyethylene terephthalate and other high-melting point polymers that need to be melt-retained at high temperature. This proves that spinning can be performed smoothly.

Furthermore, from the results of Tables 3 to 6 above, the polyester block copolymers of the examples of the present invention satisfying the above-mentioned requirements (i) to (iv) were found to have a block copolymer structure after melt kneading. It has a high melting point, good mechanical properties typified by tensile strength, tensile elongation, and elastic recovery, as well as hydrolysis resistance and cold resistance. It can be seen that it is excellent and has extremely high practical value.

From the results of Tables 3 to 6 above, the polyester block copolymers of Comparative Examples which did not satisfy the requirements (i) to (iv) were melt-kneaded at a high temperature of 270 ° C. for 60 minutes. At that time, the melting point after the melt-kneading is significantly lower than the melting point before the melt-kneading, and when the melting point is retained in a molten state at a high temperature, the aromatic polyester segment (A) and the aliphatic polyester segment (B) are separated from each other. It can be seen that the block copolymerization structure collapses and the randomization occurs due to the transesterification reaction, and various properties originally possessed by the polyester block copolymer are significantly deteriorated.

[0094]

The polyester block copolymer of the present invention having the above-mentioned requirements (i) to (iv) can be retained even in a molten state at a high temperature (for example, 270 ° C. or higher) for a long time. Since the structure is not lost and random structuring does not occur, various excellent properties of the polyester block copolymer before melt-kneading can be maintained even after melting, and therefore, the polyester block copolymer can be obtained. Even when used alone, it can smoothly produce various molded products and fibers with excellent physical properties, and melt molding at high temperature together with polyethylene terephthalate and other high melting point polymers that need to be melted by heating at high temperature. It is possible to smoothly produce a composite product having excellent physical properties by performing spinning or melt spinning. Furthermore, the polyester block copolymer of the present invention,
It is also extremely excellent in various properties such as mechanical properties represented by tensile strength, tensile elongation, elastic recovery rate, hydrolysis resistance, and cold resistance. The polyester block copolymer of the present invention is an aromatic polyester (A ') satisfying the requirement (a') and an aliphatic polyester (B ') satisfying the requirement (b').
Can be smoothly produced by subjecting both polyesters to transesterification reaction.

Claims (10)

(57) [Claims] 1. A polyester block copolymer comprising: (i) an aromatic polyester segment (A) and an aliphatic polyester segment (B), wherein (a) the aromatic polyester segment (A) is a dicarboxylic acid. Mainly composed of acid units and diol units, 70 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units, and 70 mol% or more of the diol units are aliphatic α, ω-diols having 2 to 4 carbon atoms. Unit and 1,
At least one diol unit selected from 4-cyclohexanedimethanol units; (b) the aliphatic polyester segment (B) is mainly composed of a dicarboxylic acid unit and a diol unit, and an aliphatic polyester segment (B ₁ ) and hydroxy. A saturated aliphatic dicarboxylic acid having at least one of the aliphatic polyester segment (B ₂ ) mainly composed of a carboxylic acid unit, wherein 60 mol% or more of the dicarboxylic acid unit in the aliphatic polyester segment (B ₁ ) has 6 to 14 carbon atoms. Units and 70 mol% of diol units
The above is an aliphatic diol unit having 5 to 12 carbon atoms, and 60 mol% or more of the hydroxycarboxylic acid unit in the aliphatic polyester segment (B ₂ ) has 6 carbon atoms.
10 to 10 saturated aliphatic hydroxycarboxylic acid units; (ii) the aromatic polyester segment (A) /
The weight ratio of the aliphatic polyester segment (B) is 95 /
5 to 30/70; (iii) the hydroxyl group concentration is 10 μeq / g or less; and (iv) the carboxyl group concentration is 20 μeq / g or less; 2. An aliphatic polyester segment (B ₁ )
The polyester block copolymer according to claim 1, wherein 30 mol% or more of the aliphatic diol unit having 5 to 12 carbon atoms in (1) is a branched aliphatic diol unit having 5 to 12 carbon atoms. 3. The polyester block copolymerization according to claim 1, wherein at least one of the aromatic polyester segment (A) and the aliphatic polyester segment (B) is a polyester segment produced by using a potassium titanium oxalate catalyst. Coalescing. 4. The polyester block copolymer according to claim 1, which has an intrinsic viscosity of 0.7 dl / g or more. 5. A method of producing a polyester block copolymer, wherein 70 mol% or more of the (a ′) dicarboxylic acid unit is an aromatic dicarboxylic acid unit and 70 mol% or more of the diol unit has 2 to 2 carbon atoms. 4, which is at least one diol unit selected from the aliphatic α, ω-diol units and 1,4-cyclohexanedimethanol units, and which has an intrinsic viscosity of 0.4 dl / g or more, which is mainly composed of dicarboxylic acid units and diol units. And the hydroxyl group concentration is 150 μeq /
g or less aromatic polyester (A '); and (b') 60 mol% or more of the dicarboxylic acid unit has 6 carbon atoms
To 14 saturated aliphatic dicarboxylic acid units and 70 mol% or more of the diol units are aliphatic diol units having 5 to 12 carbon atoms and an intrinsic viscosity mainly composed of a diol unit and a hydroxyl group of 0.4 or more Concentration is 1
Intrinsic viscosity mainly composed of an aliphatic polyester (B ₁ ′) of 50 μeq / g or less, and a hydroxycarboxylic acid unit in which 60 mol% or more of the hydroxycarboxylic acid unit is a saturated aliphatic hydroxycarboxylic acid unit having 6 to 10 carbon atoms There 0.4 dl / g and a hydroxyl group concentration of more than 150μ eq / g or less of the aliphatic polyester (B ₂ ') at least one aliphatic polyester selected from (B'); and aromatic polyester (a ') / aliphatic polyester (B ') = 95 / 5~30 / 70 used in a weight ratio of claims hydroxyl group concentration of the product is equal to or to be an ester exchange reaction so as to be less than 10μ equivalents / g 1 description
A method for producing a polyester block copolymer according to claim 1. 6. The production method according to claim 5, which comprises adding a compound having a functional group capable of reacting with a hydroxyl group and having a boiling point of 200 ° C. or higher during the transesterification reaction. 7. The aliphatic diol unit having 5 to 12 carbon atoms in the aliphatic polyester (B ₁ '), wherein 30 mol% or more of the aliphatic diol unit having 5 to 12 carbon atoms is a branched aliphatic diol unit having 5 to 12 carbon atoms. Manufacturing method. 8. The polyester according to claim 5, wherein at least one of the aromatic polyester (A ′) and the aliphatic polyester (B ′) is a polyester produced using a potassium titanium oxalate catalyst. Production method. 9. A molded article made of the polyester block copolymer according to claim 1. 10. A fiber comprising the polyester block copolymer according to any one of claims 1 to 4.