WO2015194661A1 - Resin composition, polyester film, and molded article - Google Patents

Abstract

The present invention addresses the problem of providing an aliphatic polyester resin composition which has hydrolytic resistance and which, during kneading, etc., generates no volatilization gas and is inhibited from increasing in viscosity. This resin composition comprises an aliphatic polyester and a compound represented by the following general formula (1). Also provided are a polyester film and a molded article which comprise the resin composition. In general formula (1), R² represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group; R³ represents a specific alkyl group or a specific aryl group; and R¹¹, R¹², and R¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. AA General formula (1)

Description

Resin composition, polyester film and molded article

The present invention relates to a resin composition, a polyester film and a molded product containing an aliphatic polyester and a terminal blocking agent.

Polyester films such as polyethylene terephthalate (PET) films are widely used industrially because they are excellent in heat resistance, mechanical properties and chemical resistance. However, since polyester films have poor hydrolysis resistance, the molecular weight decreases due to hydrolysis, and embrittlement progresses, resulting in a decrease in mechanical properties. For this reason, as a means for improving the hydrolysis resistance of polyester, a method of sealing a terminal carboxyl group of polyester using a terminal blocking agent has been studied.

Examples of the terminal blocking agent that seals the carboxylic acid remaining at the terminal of the polyester include a carbodiimide compound or a cyclic imino ether compound. For example, Patent Document 1 discloses a polyester film containing a cyclic carbodiimide compound. Patent Document 2 discloses a polyester film containing a carbodiimide compound or a cyclic imino ether compound. In these documents, it is proposed to improve the dimensional stability and hydrolysis resistance of polyester by reacting a carbodiimide compound or a cyclic imino ether compound with a carboxylic acid at the terminal of the polyester. In Patent Document 3, an oxazoline compound or an oxazine compound is used as the cyclic imino ether compound.

In recent years, attention has been focused on using aliphatic polyesters such as polylactic acid as industrial materials from the viewpoint of biomass. For example, aliphatic polyester is used in the housings, mechanism parts, automobile parts, and the like of home appliances and OA equipment. However, polylactic acid is a material that is easily hydrolyzed in a moist heat environment, is difficult to use as an industrial material, and has poor versatility.

As a means for improving the hydrolysis resistance of polylactic acid, it has been studied to use a terminal blocking agent. For example, Patent Document 3 discloses a resin composition containing a polylactic acid resin and a terminal blocking agent. Here, tetramethylene bisoxazoline is used as a terminal blocking agent.

International publication WO2011 / 093478 JP 2010-31174 A JP 2007-77193 A

By adding an end-capping agent as described above to the polyester, hydrolysis of the polyester can be suppressed to some extent. However, when the carbodiimide compound described in Patent Document 2 is used, there is a problem that free isocyanate is volatilized. Since such a volatilizing gas is an irritating gas, it has been desired that the volatilization be suppressed.

As end-capping agents that are thought to generate less volatilization gas, it is conceivable to use a cyclic carbodiimide compound as described in Patent Document 1 or a cyclic imino ether compound as described in Patent Document 2. However, when a cyclic carbodiimide compound is used, there is a problem that the polyester resin composition is thickened. In addition, it is known that the cyclic imino ether compound is self-polymerized. When the cyclic imino ether compound is used, the present inventors have found that the self-polymerized cyclic imino ether compound exists as a gel component in the polyester resin. It became clear by examination.

Patent Document 3 discloses a resin composition containing tetramethylene bisoxazoline and polylactic acid. However, when tetramethylene bisoxazoline is used as an end-capping agent, there is a problem that volatilization gas is generated. It was.

Therefore, in order to solve the problems of the prior art, the present inventors are an aliphatic polyester resin composition having hydrolysis resistance, which is an aliphatic polyester that does not generate volatilization gas during kneading. Investigations have been made for the purpose of providing a polyester resin composition. Furthermore, the present inventors proceeded with studies for the purpose of providing an aliphatic polyester resin composition that does not thicken during kneading.

As a result of intensive studies to solve the above problems, the present inventors have used an imino ether compound having a specific structure as an end-capping agent and mixed it with an aliphatic polyester, thereby improving hydrolysis resistance. It has been found that an aliphatic polyester resin composition having a low volatilization gas can be obtained. Furthermore, the present inventors have found that such a resin composition does not thicken during kneading or the like and is excellent in processing stability.
Specifically, the present invention has the following configuration.

[1] A resin composition comprising an aliphatic polyester and a compound represented by the following general formula (1);

In general formula (1), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ³ represents an alkyl group represented by the following general formula (2) or an aryl group represented by the following general formula (3), and R ¹¹ , R ¹² and R ¹³ are each independently Represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ² , R ³ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring. However, when R ³ is represented by the following general formula (2), the bond formed by at least one of R ¹¹ to R ¹³ and at least one of R ³¹ to R ³³ is a bond having two or more linking atoms.

In the general formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. R ³¹ , R ³² and R ³³ may be connected to each other to form a ring. In General Formula (3), R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. N represents an integer of 0 to 5. In general formulas (2) and (3), * represents a position bonded to a nitrogen atom.
[2] Aliphatic polyester is polylactic acid resin, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polyglycolic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid and hydroxybutyric acid / hydroxyvaleric acid The resin composition according to [1], which is at least one selected from copolymers.
[3] The resin composition according to [1] or [2], wherein the aliphatic polyester is at least one selected from a polylactic acid resin, polybutylene succinate, and polyglycolic acid.
[4] 0.1 to 5% by mass of the compound represented by the general formula (1) with respect to the total mass of the aliphatic polyester and the compound represented by the general formula (1) [1] to [3 ] The resin composition in any one of.
[5] The resin composition according to any one of [1] to [4], wherein the compound is represented by the following general formula (4);

In general formula (4), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5.
[6] The resin composition according to any one of [1] to [5], wherein the compound is represented by the following general formula (5);

In general formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ and R ⁴¹ each independently represent a substituent. When a plurality of R ²¹ and R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5, and m represents an integer of 0 to 5.
[7] The resin composition according to any one of [1] to [6], wherein the compound is represented by the following general formula (6):

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ¹ represents an alkylene part which may have a substituent, a cycloalkylene part which may have a substituent, or a substituent at the bond terminal to the carbon atom. The p-valent group which is the arylene part which may have or the alkoxylene part which may have a substituent is represented.
[8] The resin composition according to any one of [1] to [7], wherein the compound is represented by the following general formula (7);

In general formula (7), R ² has an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. P represents an integer of 2 to 4, and L ² represents an arylene moiety that may have a substituent, or a cycloalkylene moiety that may have a substituent, at the bond terminal to the nitrogen atom. Represents a p-valent group.
[9] The resin composition according to any one of [1] to [8], wherein the compound is represented by the following general formula (8);

In general formula (8), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ³ represents a p-valent group in which the bond terminal to the oxygen atom is an alkylene part. However, in the alkylene part of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
[10] A polyester film comprising the resin composition according to any one of [1] to [9].
[11] The polyester film according to [10], which is a biaxially oriented film.
[12] A molded article comprising the resin composition according to any one of [1] to [9].

According to the present invention, the hydrolysis resistance of the aliphatic polyester resin composition can be enhanced by sealing the terminal carboxyl group of the aliphatic polyester with the imino ether compound having a specific structure. Thereby, a polyester film and a molded article with high hydrolysis resistance can be obtained. Furthermore, according to the present invention, generation of volatilized gas in the production process can be suppressed, and the thickening of the resin composition can also be suppressed. Therefore, the production suitability and processing when forming a polyester film or a molded product from the aliphatic polyester resin composition Stability can be increased.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Imino ether compound)
The resin composition of the present invention contains an imino ether compound represented by the following general formula (1).

In general formula (1), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ³ represents an alkyl group represented by the following general formula (2) or an aryl group represented by the following general formula (3), and R ¹¹ , R ¹² and R ¹³ are each independently Represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ² , R ³ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring. However, when R ³ is represented by the following general formula (2), the bond formed by at least one of R ¹¹ to R ¹³ and at least one of R ³¹ to R ³³ is a bond having two or more linking atoms.

In the general formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. R ³¹ , R ³² and R ³³ may be connected to each other to form a ring. In General Formula (3), R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. N represents an integer of 0 to 5. In general formulas (2) and (3), * represents a position bonded to a nitrogen atom.

In the general formula (1), the alkyl group represented by R ² is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R ² may be linear or branched. Further, the alkyl group represented by R ² may be a cycloalkyl group. Examples of the alkyl group represented by R ² include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, n-pentyl group, Examples thereof include a sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, and a cyclohexyl group. Of these, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, and a cyclohexyl group are more preferable.
The alkyl group represented by R ² may further have a substituent. Examples of the substituent include the alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amide group, hydroxyl group, ester group, ether group, and aldehyde group. The number of carbon atoms of the alkyl group represented by R ² may indicate the number of carbon that does not contain a substituent group.

The aryl group represented by R ² is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group represented by R ² include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable. The aryl group represented by R ² may further have a substituent. In addition, as said substituent, said substituent can be illustrated similarly, However, As long as reaction of an imino ether group and a carboxyl group can be advanced, a substituent in particular is not restrict | limited. The number of carbon atoms of the aryl group represented by R ² is the number of carbon atoms not including a substituent.

The alkoxy group represented by R ² is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms. Is particularly preferred. The alkoxy group represented by R ² may be linear, branched or cyclic. Preferable examples of the alkoxy group represented by R ² include a group in which —O— is linked to the terminal of the alkyl group represented by R ² . The alkoxy group represented by R ² may further have a substituent. In addition, as said substituent, said substituent can be illustrated similarly, However, As long as reaction of an imino ether group and a carboxyl group can be advanced, a substituent in particular is not restrict | limited. The number of carbon atoms of the alkoxy group represented by R ^2, indicate the number of carbon that does not contain a substituent group.

R ³ represents an alkyl group represented by the general formula (2) or an aryl group represented by the general formula (3). In the general formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. When R ³¹ , R ³² and R ³³ are substituents, they may be linked to each other to form a ring. Examples of the substituent include the alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amide group, hydroxyl group, ester group, ether group, and aldehyde group. R ³¹ , R ³² and R ³³ may be all hydrogen atoms or the same substituent or different substituents. Further, the alkyl group represented by the general formula (2) may be linear or branched. Further, the alkyl group represented by the general formula (2) may be a cycloalkyl group.
In the general formula (3), R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. When n is 2 or more, R ⁴¹ may be the same or different. In addition, as a substituent, said substituent can be illustrated similarly. N is more preferably from 0 to 3, and further preferably from 0 to 2.

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The alkyl group and aryl group can be exemplified similarly an alkyl group and aryl group R ² can be taken.

R ² , R ³ , R ¹¹ , R ¹² and R ¹³ are preferably not bonded to form a ring, but R ² , R ³ , R ¹¹ , R ¹² and R ¹³ are bonded to each other to form a ring. May be. For example, when R ³ is represented by the above general formula (3), R ⁴¹ and at least one of R ¹¹ to R ¹³ may combine to form a ring, and a benzene ring and R ¹¹ to R ¹³ A ring containing any of the above may form a condensed ring. When R ³ is represented by the general formula (3), it is preferable that R ⁴¹ and at least one of R ¹¹ to R ¹³ are not bonded to form a ring.
However, when R ³ is represented by the general formula (2), the bond formed by at least one of R ¹¹ to R ¹³ and at least one of R ³¹ to R ³³ is a bond having two or more linking atoms. When R ³ is represented by the above general formula (2), the bond formed by one of R ¹¹ to R ¹³ and one of R ³¹ to R ³³ is a bond having two or more linking atoms, and a double bond A bond is preferred. When R ³ is represented by the general formula (2), it is preferable that at least one of R ¹¹ to R ¹³ and at least one of R ³¹ to R ³³ are not bonded to form a ring.

General formula (1) may include a repeating unit. In this case, at least one of R ² , R ³ or R ¹¹ to R ¹³ is a repeating unit, and this repeating unit preferably includes an imino ether part.

In addition, the imino ether compound used in the present invention is preferably represented by the following general formula (4).

In general formula (4), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5.

In the general formula (4), R ² , R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (1), and preferred ranges are also the same. Moreover, in General formula (4), ^R41 is the same as that in General formula (3), and its preferable range is also the same. N is preferably 0 to 3, more preferably 0 to 2.

The imino ether compound used in the present invention is preferably represented by the following general formula (5).

In general formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ and R ⁴¹ each independently represent a substituent. When a plurality of R ²¹ and R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5, and m represents an integer of 0 to 5.

In the general formula (5), R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (1), and preferred ranges are also the same. In the general formula (5), R ⁴¹ is the same as that in the general formula (3), and the preferred range is also the same. ^{Incidentally,} it is possible to illustrate the same substituents as ^{R 41} in the ^{R 21} also, the general formula (3).

In the general formula (5), n is preferably 0 to 3, and more preferably 0 to 2. Further, m is preferably 0 to 3, and more preferably 0 to 2.

The imino ether compound used in the present invention is preferably represented by the following general formula (6).

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ¹ represents an alkylene part which may have a substituent, a cycloalkylene part which may have a substituent, or a substituent at the bond terminal to the carbon atom. The p-valent group which is the arylene part which may have or the alkoxylene part which may have a substituent is represented.

In the general formula (6), R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (1), and preferred ranges are also the same. Moreover, in General formula (6), ^R41 is the same as that in General formula (3), and its preferable range is also the same. N is preferably 0 to 3, more preferably 0 to 2.

In General Formula (6), L ¹ may have an alkylene part that may have a substituent, a cycloalkylene part that may have a substituent, or a substituent at the terminal of the bond with the carbon atom. A p-valent group which is an arylene part or an alkoxylene part which may have a substituent is represented. p represents an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of the divalent group include an alkylene group that may have a substituent, a cycloalkylene group that may have a substituent, an arylene group that may have a substituent, and a substituent. And an alkoxylene group which may be used. In addition, the bond terminal to the carbon atom has an alkylene part which may have a substituent, a cycloalkylene part which may have a substituent, an arylene part which may have a substituent, or a substituent. A partial structure, such as —SO ₂ —, —CO—, a substituted or unsubstituted alkylene part, a substituted or unsubstituted alkenylene part, an alkynylene part, a substituted or unsubstituted phenylene part, And a group containing at least one selected from a substituted or unsubstituted biphenylene moiety, a substituted or unsubstituted naphthylene moiety, —O—, —S— and —SO—.
Preferably, for example, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, ethylene, n-butylene, substituted or unsubstituted cyclohexylene, substituted or unsubstituted —C ₆ H ₁₀ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₁₀ -CH ₂ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₅ -C (CH ₃ ) ₂ -C ₆ H _5- Substituted, unsubstituted —C ₆ H ₅ —CH ₂ —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —C (O) —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —S—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —SO ₂ —C ₆ H ₅ — , Substituted or unsubstituted _{-C 6 H 5 -C (CF 3} ) 2 -C 6 H 5 -, substituted or unsubstituted _{-C 6 H 5 -NHC (O)} -C 6 H 5 -, substituted or unsubstituted _-C 6 H ₅ —O—C ₆ H ₅ —C (CH ₃ ) ₂ —C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —C (O ) —C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —SO ₂ —C ₆ H ₅ —O—C ₆ H ₅ —, substituted Alternatively, unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —S—C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O— (C ₆ H _{5 ) 2 -O-C 6 H 5} -, substituted or unsubstituted _{-C 6 H 5 -O-C 6} H 5 -C (CF 3) 2 -C 6 H 5 -O-C 6 H 5 -, I And the like.
Specific examples of the trivalent group include, for example, a group obtained by removing one hydrogen atom from those having a substituent among the groups listed as examples of the divalent group.
Specific examples of the tetravalent group include, for example, a group obtained by removing two hydrogen atoms from those having a substituent among the groups listed as examples of the divalent group.

In the present invention, by setting p to 2 to 4, a compound having two or more imino ether moieties in one molecule can be obtained, and a more excellent end-capping effect can be exhibited. Furthermore, by using a compound having two or more imino ether moieties in one molecule, the imino ether value (total molecular weight / number of functional groups of imino ether) can be lowered, and the imino ether compound and the terminal carboxyl group of the polyester can be efficiently produced. Can be reacted.

The imino ether compound used in the present invention is preferably represented by the following general formula (7).

In general formula (7), R ² has an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. P represents an integer of 2 to 4, and L ² represents an arylene moiety that may have a substituent, or a cycloalkylene moiety that may have a substituent, at the bond terminal to the nitrogen atom. Represents a p-valent group.

In the general formula (7), R ² , R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (1), and preferred ranges are also the same.

In General Formula (7), L ² represents a p-valent group whose bond terminal to the nitrogen atom is an arylene part that may have a substituent or a cycloalkylene part that may have a substituent. To express. L ² is preferably a p-valent group whose bond terminal to the nitrogen atom is an arylene moiety that may have a substituent. p represents an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ² include an arylene group which may have a substituent and a cycloalkylene group which may have a substituent. The bond terminal to the nitrogen atom is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, and as a partial structure, —SO ₂ —, —CO—, Substituted or unsubstituted alkylene part, substituted or unsubstituted alkenylene part, alkynylene part, substituted or unsubstituted phenylene part, substituted or unsubstituted biphenylene part, substituted or unsubstituted naphthylene part, -O-, -S- And a group containing at least one selected from —SO—.
Preferably, for example, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted cyclohexylene, substituted or unsubstituted —C ₆ H ₁₀ —C ₆ H ₁₀ — Substituted or unsubstituted —C ₆ H ₁₀ —CH ₂ —C ₆ H ₁₀ —, substituted or unsubstituted —C ₆ H ₅ —C (CH ₃ ) ₂ —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —CH ₂ —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —C (O) —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O— C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —S—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —SO ₂ —C ₆ H ₅ —, substituted or unsubstituted -C ₆ H ₅ -C (CF ₃ ) ₂ —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —NHC (O) —C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ — C (CH ₃ ) ₂ —C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —C (O) —C ₆ H ₅ —O— C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —SO ₂ —C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —S—C ₆ H ₅ —O—C ₆ H ₅ —, substituted or unsubstituted —C ₆ H ₅ —O— (C ₆ H ₅ ) ₂ —O—C ₆ H ₅ -, Substituted or unsubstituted —C ₆ H ₅ —O—C ₆ H ₅ —C (CF ₃ ) ₂ —C ₆ H ₅ —O—C ₆ H ₅ —, and the like.

The imino ether compound used in the present invention is preferably represented by the following general formula (8).

In general formula (8), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ³ represents a p-valent group in which the bond terminal to the oxygen atom is an alkylene part. However, in the alkylene part of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.

In the general formula (8), R ² are each as agreed in the general formula (1), and preferred ranges are also the same. Moreover, in General formula (8), ^R41 is the same as that in General formula (3), and its preferable range is also the same. N is preferably 0 to 3, more preferably 0 to 2.

In General Formula (8), L ³ represents a p-valent group in which the bond terminal to the oxygen atom is an alkylene part. In the alkylene part of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent. p represents an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ³ include an alkylene group. In addition, the bond terminal to the oxygen atom is an alkylene moiety, and the partial structure includes —SO ₂ —, —CO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, substituted or unsubstituted And a group containing at least one selected from a substituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, —O—, —S— and —SO—.
Preferably, for example, ethylene, n-butylene, substituted or unsubstituted —CH ₂ —C (CH ₃ ) ₂ —CH ₂ —, substituted or unsubstituted —CH ₂ —C ₆ H ₅ —CH ₂ —, etc. Is mentioned.

The molecular weight per iminoether part of the iminoether compound is preferably 1000 or less, more preferably 750 or less, and even more preferably 500 or less. By setting the molecular weight per imino ether part within this range, it is possible to seal the terminal carboxylic acid group of the polyester with a low addition amount.

The molecular weight of the whole imino ether compound is preferably 280 or more, and more preferably 300 or more. By setting the molecular weight of the imino ether within this range, volatilization can be more effectively suppressed.

The imino ether compound is preferably a bifunctional or higher functional compound, and more preferably a bifunctional, trifunctional or tetrafunctional compound from the viewpoint of ease of synthesis. Here, the functional number represents the number of imino ether parts contained in the compound, and the bifunctional imino ether compound means a compound containing two imino ether parts. By making the iminoether compound a bifunctional or higher compound, the end-capping effect can be further enhanced.

Although the preferable specific example of General formula (1) is shown below, this invention is not limited to this.

(Chemical modification method of aliphatic polyester terminal carboxyl group)
Chemical modification of the aliphatic polyester terminal carboxyl group can be performed by mixing the imino ether compound represented by the general formula (1) and the aliphatic polyester in a molten state. When the imino ether compound and the aliphatic polyester are reacted at 100 to 350 ° C., the imino ether group reacts with the terminal carboxyl group of the aliphatic polyester to form a carboxylic acid ester as shown in the following reaction scheme. Moreover, since the imino ether compound represented by the general formula (1) becomes an amide compound by reacting with the terminal carboxyl group of the aliphatic polyester, the aliphatic polyester and the general formula (1) are represented in the resin composition. When the imino ether compound is reacted, an amide compound is also included.

The reaction of a compound having a carboxylic acid group such as an imino ether compound and an aliphatic polyester can be carried out at a reaction temperature of 100 to 350 ° C. to chemically modify the terminal carboxyl group of the polyester. The reaction temperature is selected according to the melting point (Tm) of the aliphatic polyester used, and is preferably (Tm + 5) ° C. to (Tm + 100) ° C., more preferably (Tm + 10) ° C. to (Tm + 80) ° C. When it is higher than (Tm + 5) ° C., the aliphatic polyester is completely melted and the surface becomes good. On the other hand, when the temperature is lower than (Tm + 100) ° C., the aliphatic polyester is not thermally decomposed and the hydrolysis resistance is improved.
For example, in the case of polylactic acid, it is preferably 175 ° C. to 270 ° C., more preferably 180 ° C. to 250 ° C. An example of satisfying these temperature ranges is to react at 200 ° C. In the case of polybutylene succinate, 120 ° C. to 215 ° C. is preferable, and 125 ° C. to 195 ° C. is more preferable. An example of satisfying these temperature ranges is to react at 160 ° C. In the case of polyglycolic acid, it is preferably 230 ° C. to 325 ° C., more preferably 235 ° C. to 305 ° C. An example of satisfying these temperature ranges is to react at 250 ° C.

The reaction rate between the imino ether compound represented by the general formula (1) and the terminal carboxyl group of the aliphatic polyester is preferably 0.1 to 99%, more preferably 1 to 90%. More preferably, it is ˜80%. By setting the reaction rate within the above range, the hydrolysis resistance can be sufficiently improved. Furthermore, by making a reaction rate into the said range, it can suppress that the produced | generated amide compound elutes from a polyester film, and can make the surface shape of a polyester film more favorable.

Conventionally, carboxylic acid is esterified by reacting oxazoline or oxazine with carboxylic acid of polyethylene terephthalate. It is known that a ring-opening reaction occurs when oxazoline or oxazine is used as a terminal blocking agent. It is also known that self-condensation proceeds as a side reaction simultaneously with the ring-opening reaction.

The self-condensation accompanied by the ring-opening reaction as described above is considered to be caused by the high nucleophilicity of the amide group of the alkylamide generated by the ring-opening reaction. On the other hand, the chain compounds of the imino ethers of the present invention are not self-condensed, and those of cyclic compounds are not highly nucleophilic in the aromatic amide obtained by the esterification reaction. It is thought that there is nothing. Thereby, it can suppress that an imino ether compound gelatinizes in an aliphatic polyester resin.

(Aliphatic polyester)
The resin composition of the present invention contains the above-described imino ether compound and an aliphatic polyester. The aliphatic polyester that can be used in the present invention is not particularly limited, but an aliphatic polyester obtained by polycondensation of an aliphatic dicarboxylic acid and an aliphatic dialcohol can be used. Especially, what has biodegradability is preferable and it is more preferable to use plant-derived aliphatic polyester.

Aliphatic polyesters include polylactic acid resin, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polyglycolic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid and hydroxybutyric acid / hydroxyvaleric acid It is preferably at least one selected from a coalescence, and more preferably at least one selected from a polylactic acid resin, polybutylene succinate and polyglycolic acid. One aliphatic polyester may be used alone, or two or more aliphatic polyesters may be used in combination. Two or more kinds of copolymers of these aliphatic polyesters may be used.

Aliphatic polyester is a material with low hydrolysis resistance. In particular, polylactic acid-based resins are easily hydrolyzed in a humid heat environment. However, the hydrolysis resistance of the aliphatic polyester can be improved by sealing the terminal carboxyl group of the aliphatic polyester with the specific imino ether compound described above. Moreover, when kneading | mixing a resin composition or forming a film and a molded article from a resin composition, generation | occurrence | production of volatilization gas can be suppressed and the work safety | security in a manufacturing process can be improved.

In the present invention, the weight average molecular weight (Mw) of the aliphatic polyester is preferably 10,000 or more, more preferably 30000 or more, and particularly preferably 60000 or more. As the weight average molecular weight of the aliphatic polyester, a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent can be used.

The aliphatic polyester used in the present invention is preferably a polylactic acid resin. The polylactic acid resin is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component. The polylactic acid-based resin may be a copolymerized polylactic acid copolymerized with a monomer component having other ester forming ability. Other copolymer components include isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, etc. Arocyclic dicarboxylic acids such as aromatic dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, succinic acid, 3,3 -Aliphatic dicarboxylic acids such as diethyl succinic acid, glutaric acid, 2,2-dimethyl glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydro Dicarboxylic acids derived from hydroxycarboxylic acids such as civaleric acid, hydroxypropionic acid, hydroxycaproic acid, hydroxybenzoic acid, and ester-forming derivatives thereof, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, Aliphatic diols such as octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, 2,2-bis (4- From aromatic diols such as β-hydroxyethoxyphenyl) sulfone, low molecular weight polyalkylene glycols such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol Guide is the diol, glycerin, compounds or derivatives thereof containing a plurality of hydroxyl groups in the molecule such as pentaerythritol. In addition, it is preferable that the ratio for which the polymer chain derived from another polymerizable monomer occupies the copolymer whole quantity is 50 mol% or less in conversion of a monomer. Furthermore, it is especially preferable that it is 20 mol% or less. Further, the arrangement pattern of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

The molecular weight and molecular weight distribution of the polylactic acid-based resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight (Mw) is preferably 10,000 or more, more preferably 30000 or more, 60,000 or more is particularly preferable. As the weight average molecular weight of the polylactic acid-based resin, a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent can be used.

Commercially available products may be used as the polylactic acid resin. Examples of the marketed products include the Lacia (registered trademark) series manufactured by Mitsui Chemicals.

In the present invention, the content of the aliphatic polyester in the resin composition is not particularly limited, but is preferably 10 to 99.9% by mass based on the total amount of the resin composition. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. The aliphatic polyester may contain 1 type or 2 types or more, and when it contains 2 types or more, it is preferable that the total amount becomes the said range.

(Resin composition)
The resin composition of the present invention contains the aliphatic polyester and the imino ether compound described above. In addition, unless the resin composition of this invention is contrary to the meaning of this invention, it does not refuse containing compounds other than the imino ether compound mentioned above. For example, a carbodiimide compound, a ketene imine compound, an epoxy compound, an oxazoline compound, and the like can be used in combination. However, the content of the imino ether compound contained in the resin composition of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, with respect to the organic compound other than the polyester, More preferably, it is 90 mass% or more.

The imino ether compound represented by the general formula (1) is contained in an amount of 0.05 to 10% by mass with respect to the total mass of the aliphatic polyester and the imino ether compound represented by the general formula (1). It is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, and particularly preferably 0.1 to 1% by mass. By making content of the iminoether compound represented by General formula (1) into the said range, since the hydrolysis resistance of a resin composition can be improved more, it is preferable. Moreover, the polyester film and molded article with which coloring was suppressed can be formed by making content of the imino ether compound represented by General formula (1) into the said range. In addition, 1 type, or 2 or more types may be contained for the imino ether compound. When 2 or more types are included, the total amount is preferably within the above range.

(Additive)
Furthermore, within the range that does not impair the effects of the present invention, the resin composition of the present invention includes various additives such as plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, Inorganic fine particles and organic compounds may be added as necessary as flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, sequestering agents, ion exchangers, or coloring pigments. Good. Color pigments include carbon black, titanium oxide, zinc oxide, barium sulfate, iron oxide, and other inorganic pigments, as well as cyanine, styrene, phthalocyanine, anthraquinone, perinone, isoindolinone, and quinophthalone. Organic pigments such as quinocridone and thioindigo can be used. Similarly, modifiers such as various inorganic particles such as calcium carbonate, silica, silicon nitride, clay, talc, kaolin, and zirconium acid, and particles such as crosslinked polymer particles and various metal particles can also be used. Furthermore, waxes, silicone oils, various surfactants, various fluororesins, polyphenylene sulfides, polyamides, polyacrylates such as ethylene / acrylate copolymers, methyl methacrylate polymers, various rubbers, ionomers, polyurethanes And small amounts of other polymers such as thermoplastic elastomers.

(Other polyester)
The resin composition of the present invention may contain a polyester other than the aliphatic polyester (hereinafter referred to as other polyester).

Other polyesters are not limited, but saturated polyesters are preferable. By using a saturated polyester, a polyester film that is superior in terms of mechanical strength as compared with a film using an unsaturated polyester can be obtained.

The saturated polyester is preferably a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. As the linear saturated polyester, for example, those described in JP-A-2009-155479 and JP-A-2010-235824 can be appropriately used.

The above-mentioned linear saturated polyester is produced, for example, by subjecting an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative to an esterification reaction or a transesterification reaction, and then a polycondensation reaction. Can do. Moreover, the carboxylic acid value and intrinsic viscosity of the polyester can be controlled by selecting the raw material and reaction conditions. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization catalyst during these reactions.

As the polymerization catalyst, Al-based, Sb-based, Ge-based, and Ti-based compounds are preferably used from the viewpoint of keeping the carboxyl group content below a predetermined range, and Ti-based compounds are particularly preferable. In the case of using a Ti compound, an embodiment in which polymerization is performed by using the Ti compound as a catalyst in the range of 1 to 30 ppm, more preferably 3 to 15 ppm is preferable. When the ratio of the Ti compound is within the above-described range, the terminal carboxyl group can be adjusted to a preferable range, and the hydrolysis resistance of the polyester film can be kept low.

For example, Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 3997756, Japanese Patent No. 3996866, Japanese Patent No. 3997866, Japanese Patent No. 3996871, The methods described in Japanese Patent No. 4000086, Japanese Patent No. 4053837, Japanese Patent No. 4127119, Japanese Patent No. 4134710, Japanese Patent No. 4159154, Japanese Patent No. 4269704, Japanese Patent No. 431538, and the like can be applied.

The polyester is preferably solid-phase polymerized after polymerization. Thereby, a preferable carboxylic acid value can be achieved. Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time and then sent out), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time). Specifically, solid phase polymerization is described in Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392, Japanese Patent No. 4167159, etc. The method can be applied.

The temperature of the solid phase polymerization is preferably 170 to 240 ° C, more preferably 180 to 230 ° C, and further preferably 190 to 220 ° C. The solid phase polymerization time is preferably 5 to 100 hours, more preferably 10 to 75 hours, and further preferably 15 to 50 hours. The solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.

Specific examples of the linear saturated polyester include polyethylene terephthalate (PET), polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), and polyethylene-2,6-naphthalate. Among these, polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferable from the viewpoint of the balance between mechanical properties and cost, and polyethylene terephthalate is more particularly preferable.

The other polyester may be a homopolymer or a copolymer. Further, polyester may be blended with a small amount of other types of resins such as polyimide. Moreover, as polyester, you may use crystalline polyester which can form anisotropy at the time of melt film forming.

The weight average molecular weight (Mw) of other polyesters is preferably from 5,000 to 100,000, more preferably from 8,000 to 80,000, particularly preferably from 12,000 to 60,000, from the viewpoints of heat resistance and viscosity. As the weight average molecular weight, a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent can be used.

The resin composition of the present invention may not contain other polyesters, but when other polyesters are contained, the content of other polyesters is 0.01 to 10 with respect to the total mass of the aliphatic polyester. The content is preferably mass%, more preferably 0.01 to 5 mass%. Another polyester may contain 1 type (s) or 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.

(Polyester film)
The present invention also relates to a polyester film containing the above-described resin composition.

The polyester film of the present invention is preferably stretched and more preferably biaxially stretched. That is, the polyester film of the present invention is preferably a biaxially oriented film. Especially, it is especially preferable compared with extending | stretching of tubular etc. that it is plane biaxially stretched, and it is more especially preferable that it is biaxially stretched sequentially. The biaxially stretched polyester film is stretched in the longitudinal direction (MD: Machine Direction) (hereinafter also referred to as “longitudinal stretching”) and in the width direction (TD: Transverse Direction) (hereinafter also referred to as “lateral stretching”). It is a film that has been applied. Each of the longitudinal stretching and the lateral stretching may be performed once, may be performed a plurality of times, and may be stretched longitudinally and laterally at the same time.

The terminal carboxyl group content in the polyester film (the carboxylic acid value of the polyester, hereinafter also referred to as AV) is preferably 30 eq / ton or less, more preferably 20 eq / ton or less, and particularly preferably 16 eq / ton or less with respect to the polyester. And more particularly preferably 15 eq / ton or less. When the carboxyl group content is 25 eq / ton or less, it is possible to maintain the hydrolysis resistance and heat resistance of the polyester film by combining with the imino ether compound, and it is possible to suppress a decrease in strength when the moisture and heat age. . The terminal carboxyl group content in the polyester can be adjusted by polymerization catalyst species, polymerization time, and film forming conditions (film forming temperature and time). The carboxyl group content is H.264. A. Pohl, Anal. Chem. 26 (1954) 2145, and can be measured by a titration method. Specifically, the polyester is dissolved in benzyl alcohol at 205 ° C., a phenol red indicator is added, and titrated with a solution of sodium hydroxide in water / methanol / benzyl alcohol to determine the carboxylic acid value (eq / ton) can be calculated.

The terminal hydroxyl group content in the polyester film is preferably 120 eq / ton or less, more preferably 90 eq / ton or less, based on the polyester. When the upper layer is provided, the lower limit of the hydroxyl group content is preferably 20 eq / ton or more from the viewpoint of adhesion. The hydroxyl group content in the polyester can be adjusted by the polymerization catalyst species, the polymerization time, and the film forming conditions (film forming temperature and time). As the terminal hydroxyl group content, a value measured by ¹ H-NMR using a deuterated hexafluoroisopropanol solvent can be used.

The thickness of the polyester film of the present invention varies depending on the application. For example, 25 to 300 μm is preferable, and 120 to 300 μm is more preferable. When the thickness is 25 μm or more, sufficient mechanical strength is obtained, and when the thickness is 300 μm or less, a merit in cost can be obtained.

Furthermore, the polyester film of the present invention may be subjected to various surface treatments for the purpose of improving printability, laminate suitability, coating suitability, and the like. Examples of the surface treatment include corona discharge treatment, plasma treatment, flame treatment, and acid treatment, and any method can be used, and continuous treatment is possible. In addition, the corona discharge treatment can be exemplified as the most preferable in view of easy installation of the apparatus in the existing film forming equipment and the simplicity of the treatment.

The polyester film of the present invention may be laminated with other layers. For example, a laminate may be provided by providing a coating layer containing at least one functional group selected from COOH, OH, SO ₃ H, NH ₂ and a salt thereof.

(Molding)
The resin composition of the present invention can form a film or sheet as described above. Furthermore, the resin composition of the present invention can be molded into fibers and various molded products from a molten / solution state. By using the resin composition of the present invention, various molded articles can have sufficiently high heat resistance and hydrolysis resistance, and can be used in a wider field than before. For example, in the textile field, it can be applied to clothing use, fishing lines, fishing nets, laver nets, vegetation-protecting nonwoven fabrics, civil engineering nets, sandbags, seedling pots, agricultural materials or draining bags. Further, the film or sheet can be applied to a packaging film, an agricultural and horticultural film, a shopping bag, a garbage bag or a compost bag. As molded articles, it can be applied to containers and tableware such as beverage and cosmetic bottles, disposable cups, trays, knives, forks, and spoons, flower pots, nurseries, home appliances, OA equipment casings, mechanical parts, and automobile parts.

The resin composition of the present invention is preferably used in the fiber and film fields among the above. In the fiber and film fields, the volume specific surface area is large and sufficient hydrolysis resistance is required. However, fibers and films using the resin composition of the present invention are suitable because they have sufficient hydrolysis resistance. . When the fiber composition is used from the resin composition of the present invention, it can be dyed at a high temperature with an aqueous dispersion solution of the dye, and can be dyed in a dark or vivid color without impairing the tear strength of the fabric. . In addition, when the fiber is used underwater for fishery materials such as fishing nets, practically necessary and sufficient strength can be exhibited by appropriately sealing the carboxyl group ends. Furthermore, the fiber and film containing the resin composition of the present invention are rich in aging stability, and can exhibit the original performance without deterioration even after a long period of time after production. In addition, when the fiber or film is used or processed, stable strength properties and durability can be exhibited even when exposed to various dry heat conditions and high temperature atmospheres.

The fiber containing the resin composition of the present invention can be used as a multifilament, monofilament, staple fiber, tow or spunbond. In particular, when used as a multifilament, the strength is preferably 3.0 cN / dtex or more, more preferably 4.0 cN / dtex or more from a practical viewpoint. Moreover, 9.0 cN / dtex or less is preferable from a viewpoint of obtaining a yarn by an industrial yarn-making process with less fluff and yarn breakage.

Further, the single fiber fineness of the fiber containing the resin composition of the present invention may be selected according to the required characteristics such as the usage form, mechanical strength, biodegradation rate, etc., but is usually 0.5 dtex or more and 11111 dtex or less. . In addition, the total fineness as a multifilament is preferably 5 dtex or more and 11111 dtex or less. Furthermore, the cross-sectional shape is arbitrary, such as round, flat, hollow, Y-type, T-type, or polygonal, but a round cross-section is preferable from the viewpoint of yarn production.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

The imino ethers (1) to (8) used in Examples and Comparative Examples were synthesized by the following synthesis method.

[Synthesis Example 1]
<Synthesis of iminoether (1)>

In a 5 L three-necked flask, 600 g (2.80 mol) of triethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid ( 2.5 mmol) was added, and the mixture was stirred for 2 hours with heating under reflux. The reaction system temperature was set to 100 ° C. or lower, and the refluxed ethanol was removed with a Dean-Stark apparatus. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction mixture was cooled to room temperature, and methanol was added for crystallization to obtain 777 g of iminoether (1) (yield 95%). The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 2]
<Synthesis of iminoether (2)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid ( 2.5 mmol) was added, and the mixture was stirred for 2 hours with heating under reflux. The reaction system temperature was set to 100 ° C. or lower, and the refluxed methanol was removed with a Dean-Stark apparatus. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and methanol was added for crystallization to obtain 745 g of iminoether (2) (yield 95%). The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 3]
<Synthesis of iminoether (3)>

In a 5 L three-necked flask, trimethyl orthoacetate 338 g (2.80 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 498 g (1.28 mol), toluene 480 ml, methanesulfonic acid 0.24 g (2 0.5 mmol), and the mixture was stirred for 2 hours under reflux with heating. The reaction system temperature was set to 100 ° C. or lower, and the refluxed methanol was removed with a Dean-Stark apparatus. After confirming the completion of the reaction by TLC, the mixture was cooled to room temperature, and methanol was added for crystallization to obtain 615 g of iminoether (3) (yield 92%). The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 4]
<Synthesis of iminoether (4)>

A 5 L three-necked flask was charged with 512 g (2.80 mol) of trimethoxymethylbenzene, 310 g (1.28 mol) of 4,4′-diaminobenzanilide, 480 ml of toluene, and 0.24 g (2.5 mmol) of methanesulfonic acid, and heated to reflux. Stir for 2 hours. The reaction system temperature was set to 100 ° C. or lower, and the refluxed methanol was removed with a Dean-Stark apparatus. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and methanol was added for crystallization to obtain 504 g (yield 85%) of iminoether (4). The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 5]
<Synthesis of iminoether (5)>

A 5 L three-necked flask was charged with 512 g (2.80 mol) of trimethoxymethylbenzene, 191.8 g (1.28 mol) of 4-aminoacetanilide, 480 ml of toluene, and 0.24 g (2.5 mmol) of methanesulfonic acid. Stir for hours. The reaction system temperature was set to 100 ° C. or lower, and the refluxed methanol was removed with a Dean-Stark apparatus. After confirming the completion of the reaction by TLC, the mixture was cooled to room temperature, and methanol was added for crystallization to obtain 309 g of iminoether (5) (yield 90%). The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 6]
<Synthesis of iminoether (6)>

A 5 L three-necked flask was charged with 210 g (1.0 mol) of 4,4′-methylenebis (cyclohexylamine), 243 g (2.4 mol) of triethylamine and 1.0 L of dimethylacetamide, and 336 g (2.4 mol) of benzoyl chloride in an ice bath. Was added dropwise, and the mixture was stirred at room temperature for 1 hour. 2.0 L of 1 mol / L hydrochloric acid water was added, and the mixture was stirred for 1 hour and filtered to obtain 397 g (yield 95%) of (6-1). The obtained compound was identified by ¹ H-NMR.

To a 5 L three-necked flask, 300 g of (6-1) and 1.0 L of thionyl chloride were added and stirred at 65 ° C. for 2 hours, and then excess thionyl chloride was removed under reduced pressure. After cooling to room temperature, 1.0 ml of THF (tetrahydrofuran) was added, and 310 g (1.6 mol) of SM-28 (sodium methylate 28% methanol solution) was added dropwise in an ice bath, followed by stirring at room temperature for 1 hour. 1.5 L of ethyl acetate and 1.0 L of pure water were added for liquid separation, dried over magnesium sulfate, and concentrated to obtain a solid. Methanol 2.0L was added there, and it stirred at room temperature for 1 hour, and obtained 288 g (yield 90%) of imino ether (6) by filtering. The obtained compound was identified by ¹ H-NMR.

[Synthesis Example 7]
<Synthesis of iminoether (7)>

To a solution of 92.4 g (0.75 mol) of p-anisidine and 59 g (0.75 mol) of pyridine in 500 ml of N, N-dimethylacetamide, 50 g (0.19 mol) of trimesic acid trichloride in N, N-dimethyl was added under ice cooling. A solution of 100 ml of acetamide was added dropwise. After heating up to room temperature, it stirred for 3 hours. The reaction solution was slowly added to 5 L of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 96.8 g (97% yield) of (7-1).

(7-1) A suspension of 26.3 g (50 mmol) of thionyl chloride in 100 ml was stirred with heating under reflux for 3 hours. After confirming that the reaction system became transparent, the mixture was further stirred for 2 hours. Thionyl chloride was distilled off, 200 ml of tetrahydrofuran was added, and 21.2 g (110 mol) of sodium methoxide 28% methanol solution was added dropwise under ice cooling. The temperature of the system was raised to room temperature and stirred for 10 minutes, and then ethyl acetate / water was added for liquid separation. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography using an ethyl acetate / hexane mixed solvent as an eluent. By distilling off the solvent, 25.0 g (yield 88%) of iminoether (7) was obtained. The obtained exemplary compound was identified by ¹ H-NMR.

[Synthesis Example 8]
<Synthesis of iminoether (8)>

Benzoyl chloride 95 (0.5 mol) was slowly added to an ice-cooled solution of 46.5 g (0.5 mol) of aniline and 44 g (0.6 mol) of pyridine in 300 ml of N, N-dimethylacetamide. The temperature of the reaction system was raised to room temperature, and the completion of the reaction was confirmed by TLC. After adding 50 ml of methanol, the reaction solution was slowly added to 5 L of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 89.7 g (yield 91%) of (8-1).

(8-1) A suspension of 9.9 g (50 mmol) of thionyl chloride (400 ml) and a catalytic amount of N, N-dimethylformamide was stirred with heating under reflux for 18 hours. After confirming that the reaction system was completely dissolved, the reaction system was further stirred for 2 hours. Thereafter, thionyl chloride was distilled off to obtain 10.8 g (quant.) Of (8-2).

Sodium hydride (60%) 2.0 g (50 mmol) was dispersed in hexane, and after standing, the supernatant hexane was removed with a Pasteur pipette. This operation was repeated twice and 50 ml of tetrahydrofuran solution was added. Under ice cooling, 1.6 g (25 mmol) of ethylene glycol was added. It was visually confirmed that the generation of bubbles from the inside of the system was completed, and a tetrahydrofuran solution of ethylene dimethoxide was prepared.

(8-2) 150 ml of a tetrahydrofuran solution of 10.8 g (50 mmol) was cooled to −5 ° C., and the prepared tetrahydrofuran solution of ethylene dimethoxide was added dropwise. The temperature of the system was raised to room temperature and stirred for 30 hours, and then ethyl acetate / water was added for liquid separation. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography using an ethyl acetate / hexane mixed solvent as an eluent. By distilling off the solvent, 6.5 g (yield 62%) of iminoether (8) was obtained. The obtained exemplary compound was identified by ¹ H-NMR.

(Production and evaluation of polyester film)
Example 1
Preliminarily dried polylactic acid (PLA) (manufactured by Unitika, Terramac TE-2000) and iminoether (1) as an end-capping agent are premixed in the proportions shown in Table 1, and then a small biaxial kneading extruder After being supplied to (manufactured by Technobel) and melt-kneaded at 200 ° C., it was extruded into a strand, cooled with water, cut and pelletized.
The obtained pellets were pressed by a hot press at 190 ° C. to prepare polyester films (press films) having a thickness of 150 μm and 250 μm.

(Examples 2 to 10 and Examples 13 to 15)
A polyester film was produced in the same manner as in Example 1 except that polylactic acid and various terminal blocking agents were premixed at the ratios shown in Table 1.

(Example 11)
A polyester film was prepared in the same manner as in Example 1 except that polybutylene succinate (PBS) was used as the aliphatic polyester and melt-kneaded at 160 ° C.

Example 12
A polyester film was produced in the same manner as in Example 1 except that polyglycolic acid (PGA) was used as the aliphatic polyester and melt-kneaded at 250 ° C.

(Comparative Example 1)
A polyester film was produced in the same manner as in Example 1 except that the end-capping agent was not used.

(Comparative Example 2)
A polyester film was produced in the same manner as in Example 11 except that the end-capping agent was not used.

(Comparative Example 3)
A polyester film was produced in the same manner as in Example 12 except that the end-capping agent was not used.

(Comparative Example 4)
Preliminarily dried polylactic acid (Mitsui Chemicals, Lacia H-100) and the following carbodiimide (Rhein Chemie, Stabaxol P400) as end-capping agents were premixed in the proportions shown in Table 1, A polyester film was produced in the same manner as in Example 1 except that it was supplied to a shaft kneading extruder (manufactured by Technobel).

(Comparative Example 5)
A polyester film was produced in the same manner as in Comparative Example 4 except that tetramethylene bisoxazoline (TMBO) synthesized in Synthesis Example 9 below was used as a terminal blocking agent.

[Synthesis Example 9]
<Synthesis of TMBO>

A 5 L flask was charged with 500 g (2.47 mol) of diethyl adipate and 1500 g (9.9 mol) of ethanolamine, and ethanol produced was distilled off while stirring at 170 ° C. for 1 hour. After cooling to room temperature, benzene and methanol were added for recrystallization, and filtration was performed to obtain 471 g of TMBO-1 (yield 82%). The obtained compound was identified by ¹ H-NMR.

In a 5 L three-necked flask, 185.7 g (0.8 mol) of TMBO-1 and 1.0 L of chloroform were charged, 238 g (2.0 mol) of thionyl chloride was added dropwise in an ice bath, and the mixture was stirred at room temperature for 2 hours. After distilling off excess thionyl chloride under reduced pressure, 1.0 L of methanol was added, and 771.7 g (4.0 mol) of SM-28 was slowly added dropwise, followed by stirring at room temperature for 2 hours and at 40 ° C. for 30 hours. After cooling to room temperature and filtering, the solvent was distilled off under reduced pressure, and then 1.0 L of ethyl acetate was added and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained oily compound was purified by distillation at 128 ° C. and 133.3 Pa (1 Toll) to obtain 118 g of TMBO (yield 75%). The obtained compound was identified by ¹ H-NMR.

(Comparative Example 6)
A polyester film was produced in the same manner as in Comparative Example 4 except that the following BOXA (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the end-capping agent.

(Comparative Example 7)
A polyester film was produced in the same manner as in Comparative Example 4 except that POXA Epocross RPS (manufactured by Nippon Shokubai Co., Ltd.) was used as the end-capping agent.

(Comparative Example 8)
A polyester film was produced in the same manner as in Comparative Example 4 except that the following cyclic carbodiimide compound was used as a terminal blocking agent. Cyclic carbodiimide is a compound having a molecular weight of 516 described in Examples of Japanese Patent Application Laid-Open No. 2011-258641, and was synthesized with reference to the synthesis method described in Reference Example 2 of Japanese Patent Application Laid-Open No. 2011-258641.

(Evaluation)
<Measurement of strength retention>
Ten test pieces (size: 100 mm × 15 mm) for tensile test were collected from a polyester film having a thickness of 250 μm. Ten test pieces were subjected to a tensile test at a speed of 300 mm / min, and the average value of the tensile breaking strength was calculated and used as the tensile strength value before 80 ° C. hot water treatment. Five test pieces were immersed in deionized water heated to 80 ° C., held for 15 hours, cooled, washed, and dried to obtain test pieces after 80 ° C. hot water treatment. Using the test piece after 80 ° C. hot water treatment, a tensile test was performed at a speed of 300 mm / min, and the average value of tensile strength at break was calculated to obtain the tensile strength value after 80 ° C. hot water treatment. The strength retention was calculated by the following formula and evaluated according to the following criteria. In the following evaluation criteria, A and B are practical, and A is particularly preferable.

<Evaluation criteria>
A: Strength retention is 90% or more and 100% or less B: Strength retention is 80% or more and less than 90% C: Strength retention is 60% or more and less than 80% D: Strength retention is 0% or more and less than 60%

<Color>
The produced polyester films (thickness 150 μm and 250 μm) were visually observed and evaluated according to the following criteria. In the following evaluation criteria, A and B are practical, and A is particularly preferable.
A: Yellowness of a film having a thickness of 250 μm is equivalent to Comparative Example (1) B: Yellowness of a film having a thickness of 150 μm is equivalent to Comparative Example (1), and yellowness of a film having a thickness of 250 μm is Comparative Example (1 ) Yellower
C: The yellowness of the film having a thickness of 150 μm is yellower than that of the comparative example (1)

<Volatilization>
The presence or absence of white smoke and odor during the kneading of the resin composition was evaluated according to the following criteria. In the following evaluation criteria, A and B are practical, and A is particularly preferable.
A: White smoke, odor, none B: No white smoke, but smells C: White smoke, odor both

<Discharge stability>
The resin pressure at the time of melt kneading was evaluated according to the following criteria. A is practical in the following evaluation criteria.
A: Less than 1.0 MPa B: Less than 2.0 MPa, 1.0 MPa or more C: 2.0 MPa or more

As can be seen from Table 1, Examples 1 to 15 using a resin composition obtained by adding an imino ether compound represented by the general formula (1) as an end-capping agent to an aliphatic polyester have the strength retention of the polyester film. The rate was good and the hydrolysis resistance was excellent. In Examples 1 to 8 and Examples 11 to 15, there was no change in color of the film, and coloring was suppressed. Further, when the polyester films of Examples 1 to 15 were produced, almost no volatilized gas was generated, and the viscosity of the resin composition did not increase and the ejection stability was excellent.
On the other hand, in Comparative Examples 1 to 3 in which no end-capping agent was used, the strength retention of the polyester film was remarkably deteriorated and the hydrolysis resistance was inferior. In Comparative Examples 4 to 8, there was a color change in the film. Further, in Comparative Examples 4 to 6, white smoke and odor were generated during the production of the polyester film, and in Comparative Example 7, the hydrolysis resistance was not sufficient. In Comparative Example 8, a cyclic carbodiimide compound was used as the end-capping agent, and the generation of volatilized gas was suppressed, but there was an increase in the viscosity of the molten resin, and the discharge stability deteriorated.

According to this invention, the hydrolysis resistance of an aliphatic polyester resin composition can be improved by sealing the terminal carboxyl group of aliphatic polyester with the imino ether compound which has a specific structure. Thereby, a polyester film and a molded article with high hydrolysis resistance can be obtained. Furthermore, according to the present invention, the generation of volatilized gas in the production process can be suppressed, and the thickening of the resin composition can also be suppressed. Therefore, it is easy to form a polyester film or a molded product from the aliphatic polyester resin composition, and industrial High availability.

Claims (12)

1. A resin composition comprising an aliphatic polyester and a compound represented by the following general formula (1);
   

   

   In general formula (1), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ³ represents an alkyl group represented by the following general formula (2) or an aryl group represented by the following general formula (3), and R ¹¹ , R ¹² and R ¹³ are each independently Represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ² , R ³ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring. However, when R ³ is represented by the following general formula (2), the bond formed by at least one of R ¹¹ to R ¹³ and at least one of R ³¹ to R ³³ is a bond having two or more linking atoms.
   

   

   In the general formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. R ³¹ , R ³² and R ³³ may be connected to each other to form a ring. In General Formula (3), R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. N represents an integer of 0 to 5. In general formulas (2) and (3), * represents a position bonded to a nitrogen atom.
2. The aliphatic polyester is polylactic acid resin, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, polyglycolic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid and hydroxybutyric acid / hydroxyvaleric acid The resin composition according to claim 1, which is at least one selected from coalescence.
3. 3. The resin composition according to claim 1, wherein the aliphatic polyester is at least one selected from a polylactic acid resin, polybutylene succinate and polyglycolic acid.
4. 4. The composition according to claim 1, comprising 0.1 to 5% by mass of the compound represented by the general formula (1) with respect to the total mass of the aliphatic polyester and the compound represented by the general formula (1). The resin composition according to any one of the above.
5. The resin composition according to any one of claims 1 to 4, wherein the compound is represented by the following general formula (4):
   

   

   In general formula (4), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5.
6. The resin composition according to any one of claims 1 to 5, wherein the compound is represented by the following general formula (5):
   

   

   In general formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ and R ⁴¹ each independently represent a substituent. When a plurality of R ²¹ and R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5, and m represents an integer of 0 to 5.
7. The resin composition according to any one of claims 1 to 6, wherein the compound is represented by the following general formula (6):
   

   

   In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ¹ represents an alkylene part which may have a substituent, a cycloalkylene part which may have a substituent, or a substituent at the bond terminal to the carbon atom. The p-valent group which is the arylene part which may have or the alkoxylene part which may have a substituent is represented.
8. The resin composition according to any one of claims 1 to 7, wherein the compound is represented by the following general formula (7):
   

   

   In general formula (7), R ² has an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. P represents an integer of 2 to 4, and L ² represents an arylene moiety that may have a substituent, or a cycloalkylene moiety that may have a substituent, at the bond terminal to the nitrogen atom. Represents a p-valent group.
9. The resin composition according to any one of claims 1 to 8, wherein the compound is represented by the following general formula (8):
   

   

   In general formula (8), R ² has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁴¹ represents a substituent, and when a plurality of R ⁴¹ are present, they may be the same or different. n represents an integer of 0 to 5. P represents an integer of 2 to 4, and L ³ represents a p-valent group in which the bond terminal to the oxygen atom is an alkylene part. However, in the alkylene part of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
10. A polyester film comprising the resin composition according to any one of claims 1 to 9.
11. The polyester film according to claim 10, which is a biaxially oriented film.
12. A molded article comprising the resin composition according to any one of claims 1 to 9.