JP2015183022A - polyester amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester amide compound exhibiting sufficient oxygen absorption performance and also having no generation of discomfort odor.SOLUTION: There is provided a polyester amide compound comprising: a polyhydric carboxylic acid unit of 25 to 49.995 mol%; a polyhydric alcohol unit of 25 to 49.995 mol%; and a specified structural unit of 0.1 to 50 mol%, in which the polyhydric carboxylic acid unit, provided that the polyhydric carboxylic acid unit is defined as 100 mol%, comprises a specified aromatic dicarboxylic acid unit of 70 to 99.99 mol%, and a unit selected from a specified sulfophthalic acid unit and a specified sulfophthalic acid metal salt unit by 0.01 to 30.0 mol%, and the polyhydric alcohol unit, when the polyhydric alcohol unit is defied as 100 mol%, comprises a specified aliphatic diol unit by 70 mol% or higher.

Description

  The present invention relates to a polyesteramide compound (including a polyesteramide resin and a polyesteramide oligomer) that exhibits oxygen absorption performance, and a polyesteramide composition containing the polyesteramide compound.

Conventionally, a metal can, a glass bottle, or a container or a molded body made of a thermoplastic resin has been used as a packaging material for pharmaceuticals, beverages, foods, chemicals, and the like. Containers and molded articles made of thermoplastic resins are superior in terms of light weight, moldability, packaging productivity such as heat sealing, and cost, and are used in large quantities. Among thermoplastic resins, a type of polyester that has ethylene terephthalate as the main repeating unit (hereinafter abbreviated as PET) is mechanical performance, melt stability, solvent resistance, aroma retention, transparency, and recycling. And is widely used for films, sheets, hollow containers and the like. Furthermore, since PET has a relatively good oxygen barrier property, when it is applied to beverage bottles that are stored refrigerated, it can exhibit sufficient storage performance of the contents.
However, in recent years, there has been a demand for reducing the environmental burden due to mass production of plastics and an increase in the amount of waste, and containers using PET tend to be thinner and lighter. Since thinning and lightening cause deterioration of the oxygen barrier property of the container, in order to achieve thinning and lightening while maintaining the storage performance of the container made of PET, a method for increasing the oxygen barrier property of the container Is required.

As a method for suppressing oxygen permeation from the outside of a container made of PET, a method of combining a material having better oxygen barrier properties than PET with PET is known. For example, a container having a multilayer structure can be produced by laminating a layer having excellent oxygen barrier properties, such as at least one layer of polymetaxylylene adipamide, ethylene-vinyl alcohol copolymer, polyacrylonitrile or aluminum foil, with a PET layer. Moreover, the method of manufacturing a container from the layer formed by melt-blending the above-mentioned thermoplastic resin excellent in oxygen barrier property and PET is mentioned (refer patent document 1 and 2). However, this method can not only completely block a small amount of oxygen entering from the outside of the container, but also cannot prevent deterioration of contents due to oxygen remaining in the container.
Another method includes coating a thermosetting resin excellent in oxygen barrier property on the inside or outside of a container made of PET, or depositing an inorganic oxide (see Patent Documents 3 and 4). However, this method also cannot completely block a small amount of oxygen entering from the outside of the container, and if an external force such as an impact or bending is applied to the container, a thermosetting resin film or an inorganic oxidation film is applied. There is a problem that cracks occur in the material vapor-deposited film and the oxygen barrier property is greatly lowered.

As a method for completely blocking a small amount of oxygen entering from outside the container, a method for imparting an oxygen absorbing function to the container itself is known. According to this method, not only the entry of oxygen from the outside of the container can be prevented, but also the oxygen remaining in the container can be removed, so that the storability of the contents stored in the container can be significantly improved. it can.
As a means for achieving this method, a method of adding an oxygen absorbent to the thermoplastic resin constituting the container may be mentioned. For example, Patent Documents 5 and 6 describe an oxygen-absorbing multilayer body and an oxygen-absorbing film in which an oxygen absorbent composed of iron powder or the like is dispersed in a resin. Patent Document 7 describes a packaging oxygen trapping barrier that uses polyamide added with a metal catalyst such as cobalt as an oxygen absorber and absorbs oxygen inside and outside the container. Patent Document 8 describes a container using an oxygen absorption layer containing an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt in a gas barrier resin. Still another method includes a method of producing a container from oxygen-absorbing PET obtained by copolymerizing a compound that exhibits an oxygen-absorbing function with PET. For example, Patent Document 9 describes a container using a copolyester composed of a polyester segment and an oxygen-scavenging polyolefin segment.

JP-A 61-108542 Japanese Patent Laid-Open No. 62-181336 JP-A-5-345383 JP 2004-026225 A JP-A-2-72851 Japanese Patent Laid-Open No. 4-90848 Japanese Patent No. 2991437 JP 2005-111468 A Special table 2001-501559 gazette

  The oxygen-absorbing multilayer body and oxygen-absorbing film in which an oxygen absorbent such as iron powder is dispersed in the resin exhibit excellent oxygen absorption performance, but the resin is colored black by the oxygen absorbent such as iron powder and becomes opaque. For this reason, there is a restriction in use that it cannot be used in the field of packaging that requires transparency.

  Those using oxygen-absorbing polyamides containing transition metals such as cobalt and oxygen-absorbing resin compositions composed of ethylenically unsaturated compounds are relatively transparent, so they can be used in packaging containers that require transparency. Although it has the advantage that it can be applied, the resin composition is colored depending on the type of the transition metal catalyst, which is not preferable. Further, these resin compositions exhibit an oxygen absorption function on the principle that the resin is oxidized and deteriorated by the transition metal catalyst. In the oxygen absorbing material using a xylylene group-containing polyamide as a polyamide, the generation of radicals due to the extraction of hydrogen atoms from the methylene chain adjacent to the arylene group of the polyamide resin by transition metal atoms, and the addition of oxygen molecules to the radicals Since it occurs by each reaction such as generation of peroxy radicals and extraction of hydrogen atoms by peroxy radicals, as the oxygen absorption proceeds, the polymer main chain undergoes a rapid decomposition reaction, and the container is colored yellow, and the mechanical strength is increased. There is a problem of greatly decreasing in a short period of time.

  In addition, even in an oxygen absorbing material using an ethylenically unsaturated compound, a rapid decomposition reaction accompanying an oxygen absorbing function expressed by a transition metal catalyst occurs. When an ethylenically unsaturated compound is incorporated in the polymer main chain, it has the disadvantage that the mechanical strength decreases due to rapid decomposition of the polymer main chain, as in the case of the polyamide described above, and a large amount of ketones and aldehydes that cause off-flavors. Therefore, there is a limit to the packaging materials that can be used. When an ethylenically unsaturated compound is dispersed in a polymer that does not oxidize, a decrease in mechanical strength is suppressed, but it is inevitable that ketones and aldehydes that also cause off-flavors are generated in large quantities.

  In any case, the oxygen scavenging resin composition composed of the above-mentioned thermoplastic resin is essential to add a transition metal such as cobalt as an oxidation catalyst, and in order to be used as a container for storing food and beverages. Therefore, it is necessary to design a container for preventing the elution of the oxidation catalyst. Further, it is of course necessary to devise measures for preventing the elution of the decomposition products that are generated suddenly. In reality, the containers that can use these and their uses are very limited.

  The subject of this invention is providing the polyesteramide compound and polyesteramide composition which can express sufficient oxygen absorption performance.

［前記一般式（Ｉ）中、Ｒ¹は置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表す。前記一般式（ＩＩ）中、Ａｒはスルホ基で置換されていないアリーレン基を表す。前記一般式（ＩＩＩ）及び（ＩＩＩ’）中、Ｒ²は置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表し、ｍは０〜３の整数を表し、Ｍは金属元素を表し、ｎは１〜５の整数を表す。それぞれのＲ²は、同じであっても、異なっていてもよい。前記一般式（ＩＶ）中、Ｘは炭素数２〜２０のアルキレン基を表す。］
＜２＞前記一般式（Ｉ）におけるＲ¹が、置換もしくは無置換の炭素数１〜６のアルキル基又は置換もしくは無置換の炭素数６〜１０のアリール基である、上記＜１＞に記載のポリエステルアミド化合物。
＜３＞前記一般式（ＩＩ）で表される芳香族ジカルボン酸単位が、イソフタル酸単位、テレフタル酸単位及び２，６−ナフタレンジカルボン酸単位からなる群から選ばれる少なくとも１種を合計で７０モル％以上含む、上記＜１＞又は＜２＞に記載のポリエステルアミド化合物。
＜４＞前記一般式（ＩＩＩ）又は（ＩＩＩ’）におけるＭが、リチウム、ナトリウム、カリウム、マグネシウム、カルシウムから選ばれる１種である、上記＜１＞〜＜３＞のいずれかに記載のポリエステルアミド化合物。
＜５＞前記一般式（ＩＩＩ）で表されるスルホフタル酸単位及び下記一般式（ＩＩＩ’）で表されるスルホフタル酸金属塩単位が、下記一般式（ＩＩＩａ）で表されるスルホイソフタル酸単位及び下記一般式（ＩＩＩ’ａ）で表されるスルホイソフタル酸単位である、上記＜１＞〜＜４＞のいずれかに記載のポリエステルアミド化合物。

［前記一般式（ＩＩＩａ）及び（ＩＩＩ’ａ）中、Ｒ²、ｍ、Ｍ及びｎは、それぞれ前記一般式（ＩＩＩ）又は（ＩＩＩ’）におけるＲ²、ｍ、Ｍ及びｎと同じである。］
＜６＞前記一般式（ＩＩＩａ）又は（ＩＩＩ’ａ）におけるｍが０である、上記＜５＞に記載のポリエステルアミド化合物。
＜７＞前記一般式（ＩＶ）で表される脂肪族ジオール単位が、エチレングリコール単位、１，３−プロパンジオール単位及び１，４−ブタンジオール単位からなる群から選ばれる少なくとも１種を合計で７０モル％以上含む、上記＜１＞〜＜６＞のいずれかに記載のポリエステルアミド化合物。
＜８＞極限粘度が０．４ｄｌ／ｇ以上１．５ｄｌ／ｇ以下である、上記＜１＞〜＜７＞のいずれかに記載のポリエステルアミド化合物。
＜９＞極限粘度が０．１ｄｌ／ｇ以上０．４ｄｌ／ｇ未満である、上記＜１＞〜＜７＞のいずれかに記載のポリエステルアミド化合物。
＜１０＞上記＜１＞〜＜９＞のいずれかに記載のポリエステルアミド化合物を含むポリエステルアミド組成物。 The present invention provides the following polyesteramide compounds and polyesteramide compositions.
<1> 25 to 49.995 mol% of polyvalent carboxylic acid units;
25 to 49.995 mol% of polyhydric alcohol units;
A polyesteramide compound containing 0.1 to 50 mol% of a structural unit represented by the following general formula (I),
When the polyvalent carboxylic acid unit is 100 mol% of the polyvalent carboxylic acid unit,
The aromatic dicarboxylic acid unit represented by the following general formula (II) is represented by 70 to 99.99 mol%, and the sulfophthalic acid unit represented by the following general formula (III) and the following general formula (III ′). Including 0.01 to 30.0 mol% in total of units selected from metal units of sulfophthalic acid,
A polyesteramide compound, wherein the polyhydric alcohol unit contains 70 mol% or more of an aliphatic diol unit represented by the following general formula (IV) when the polyhydric alcohol unit is 100 mol%.

[In the general formula (I), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. In the general formula (II), Ar represents an arylene group not substituted with a sulfo group. In the general formulas (III) and (III ′), R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, m represents an integer of 0 to 3, and M represents a metal element. , N represents an integer of 1-5. Each R ² may be the same or different. In the general formula (IV), X represents an alkylene group having 2 to 20 carbon atoms. ]
<2> R ¹ in the general formula (I) is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms having 1 to 6 carbon atoms, according to the <1> Polyester amide compound.
<3> The aromatic dicarboxylic acid unit represented by the general formula (II) is a total of 70 mol of at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit and a 2,6-naphthalenedicarboxylic acid unit. % Or more of the polyesteramide compound according to <1> or <2>.
<4> The polyester according to any one of <1> to <3>, wherein M in the general formula (III) or (III ′) is one selected from lithium, sodium, potassium, magnesium, and calcium. Amide compounds.
<5> The sulfophthalic acid unit represented by the general formula (III) and the sulfophthalic acid metal salt unit represented by the following general formula (III ′) are a sulfoisophthalic acid unit represented by the following general formula (IIIa) and The polyesteramide compound according to any one of <1> to <4>, which is a sulfoisophthalic acid unit represented by the following general formula (III′a).

[In the general formula (IIIa) and ^{(III'a), R 2, m} , M and n are the same as R ^2, m, M and n in each of the general formulas (III) or (III ') . ]
<6> The polyesteramide compound according to <5>, wherein m in the general formula (IIIa) or (III′a) is 0.
<7> The aliphatic diol unit represented by the general formula (IV) is a total of at least one selected from the group consisting of an ethylene glycol unit, a 1,3-propanediol unit, and a 1,4-butanediol unit. The polyesteramide compound according to any one of <1> to <6>, which is contained in an amount of 70 mol% or more.
<8> The polyesteramide compound according to any one of <1> to <7>, wherein the intrinsic viscosity is 0.4 dl / g or more and 1.5 dl / g or less.
<9> The polyesteramide compound according to any one of <1> to <7>, wherein the intrinsic viscosity is 0.1 dl / g or more and less than 0.4 dl / g.
<10> A polyesteramide composition comprising the polyesteramide compound according to any one of <1> to <9>.

  The polyesteramide compound and the polyesteramide composition of the present invention are excellent in oxygen absorption performance. Therefore, for example, the polyesteramide compound and the polyesteramide composition of the present invention are suitable for use as an oxygen absorbent by filling a sachet or the like. More preferable usage forms of the polyesteramide compound and the polyesteramide composition of the present invention include use in packaging materials and packaging containers. Packaging materials and packaging containers using the polyesteramide compound or the polyesteramide composition of the present invention can exhibit sufficient oxygen absorption performance, do not generate unpleasant odors, and store the contents in a good state. it can.

［前記一般式（Ｉ）中、Ｒ¹は置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表す。前記一般式（ＩＩ）中、Ａｒはスルホ基で置換されていないアリーレン基を表す。前記一般式（ＩＩＩ）及び（ＩＩＩ’）中、Ｒ²は置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表し、ｍは０〜３の整数を表し、Ｍは金属元素を表し、ｎは１〜５の整数を表す。それぞれのＲ²は、同じであっても、異なっていてもよい。前記一般式（ＩＶ）中、Ｘは炭素数２〜２０のアルキレン基を表す。］ 1. Polyesteramide Compound The polyesteramide compound of the present invention comprises a polyhydric carboxylic acid unit of 25 to 49.995 mol%, a polyhydric alcohol unit of 25 to 49.995 mol%, and a tertiary hydrogen-containing carboxylic acid unit (preferably A structural unit represented by formula (I)) 0.1 to 50 mol%, and the polyvalent carboxylic acid unit is 100 mol% when the polyvalent carboxylic acid unit is 100 mol% The aromatic dicarboxylic acid unit represented by the following general formula (II) is represented by 70 to 99.99 mol%, and the sulfophthalic acid unit represented by the following general formula (III) and the following general formula (III ′). A total of 0.01 to 30.0 mol% of units selected from sulfophthalic acid metal salt units, and the polyhydric alcohol unit comprises 100 mol% of the polyhydric alcohol unit. When, including aliphatic diol unit represented by the following general formula (IV) 70 mol% or more, a polyester amide compound.

[In the general formula (I), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. In the general formula (II), Ar represents an arylene group not substituted with a sulfo group. In the general formulas (III) and (III ′), R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, m represents an integer of 0 to 3, and M represents a metal element. , N represents an integer of 1-5. Each R ² may be the same or different. In the general formula (IV), X represents an alkylene group having 2 to 20 carbon atoms. ]

  However, the sum of the polyvalent carboxylic acid unit, the polyhydric alcohol unit, and the tertiary hydrogen-containing carboxylic acid unit shall not exceed 100 mol%. The polyesteramide compound of the present invention may further contain a structural unit other than those described above as long as the effects of the present invention are not impaired.

The polyesteramide compound of the present invention includes a polyesteramide resin and a polyesteramide oligomer.
The “polyesteramide resin” of the present invention means a polymer having an intrinsic viscosity of 0.4 dl / g or more in the polyesteramide compound of the present invention. Polyesteramide resin is a material that can be molded independently, and can be processed into packaging materials and packaging containers. If necessary, other resins and additives may be added to and mixed with the polyesteramide resin of the present invention, and the polyesteramide composition thus obtained may be molded. The polyesteramide resin of the present invention exhibits sufficient oxygen absorption performance, does not generate unpleasant odor, and has very good transparency.
The “polyesteramide oligomer” of the present invention means a polymer having an intrinsic viscosity of less than 0.4 dl / g in the polyesteramide compound of the present invention. Polyesteramide oligomers are materials that cannot normally be molded by themselves. In general, an oligomer often refers to a polymer having a number average molecular weight of 1000 or less, but the polyesteramide oligomer of the present invention includes not only such a general oligomer but also a number average molecular weight of less than 10,000. Polymers can also be included.

  The polyesteramide oligomer of the present invention is suitable for filling into a sachet or the like and used as an oxygen absorbent. Further, the polyesteramide oligomer of the present invention can be suitably used as a resin raw material or a resin additive. When the polyesteramide oligomer of the present invention is used as a resin raw material, the polyesteramide oligomer and other resin raw materials can be copolymerized to obtain a copolymer resin, and the copolymer resin is molded to form a packaging material or a packaging container. Can be processed. When the polyesteramide oligomer of the present invention is used as a resin additive, a polyesteramide composition obtained by adding a polyesteramide oligomer to a resin can be molded into a packaging material or a packaging container. At this time, sufficient oxygen absorption performance can be expressed without deteriorating the transparency and mechanical strength of the resin. The copolymer resin or polyesteramide composition obtained by using the polyesteramide oligomer of the present invention exhibits sufficient oxygen absorption performance and does not generate an unpleasant odor.

  In the polyesteramide compound of the present invention, the content of the tertiary hydrogen-containing carboxylic acid unit is 0.1 to 50 mol%. If the content of the tertiary hydrogen-containing carboxylic acid unit is less than 0.1 mol%, sufficient oxygen absorption performance is not exhibited. On the other hand, if the content of the tertiary hydrogen-containing carboxylic acid unit exceeds 50 mol%, the tertiary hydrogen content is too high, so that the physical properties such as gas barrier properties and mechanical properties of the polyesteramide compound are deteriorated. When the contained carboxylic acid is an amino acid, the peptide bond is continuous, so that the heat resistance is not sufficient, and a cyclic product consisting of a dimer of amino acids is formed, which inhibits polymerization. The content of the tertiary hydrogen-containing carboxylic acid unit is preferably 0.2 mol% or more, more preferably 1 mol% or more, and preferably 45 mol from the viewpoint of oxygen absorption performance and the properties of the polyesteramide compound. % Or less, more preferably 40 mol% or less.

  In the polyesteramide compound of the present invention, the content of the polycarboxylic acid unit is 25 to 49.995 mol%, preferably 30 to 49.995 mol%, from the viewpoint of oxygen absorption performance and the properties of the compound to be formed. is there. Similarly, in the polyesteramide compound of the present invention, the content of polyhydric alcohol units is 25 to 49.995 mol%, preferably 30 to 49.995 mol%.

［前記一般式（Ｉ）中、Ｒ¹は置換基を表す。前記一般式（Ｉａ）中、Ｒ^1aは置換基を表し、Ａ¹及びＡ²はそれぞれ独立に単結合又は２価の連結基を表す。ただし、Ａ¹及びＡ²がともに単結合である場合を除く。］ 1-1.3 Grade Hydrogen-containing Carboxylic Acid Unit The tertiary hydrogen-containing carboxylic acid unit in the present invention has at least one amino group and one carboxyl group from the viewpoint of polymerization of the polyesteramide compound. Specific examples include structural units represented by the following general formula (I) or (Ia).

[In the general formula (I), R ¹ represents a substituent. In the general formula (Ia), R ^1a represents a substituent, and A ¹ and A ² each independently represent a single bond or a divalent linking group. However, the case where both A ¹ and A ² are single bonds is excluded. ]

  The polyesteramide compound of the present invention contains a tertiary hydrogen-containing carboxylic acid unit. By containing such a tertiary hydrogen-containing carboxylic acid unit as a copolymerization component, the polyesteramide compound of the present invention can exhibit excellent oxygen absorbability.

In the present invention, the mechanism by which the polyesteramide compound having a tertiary hydrogen-containing carboxylic acid unit exhibits good oxygen absorption performance has not yet been clarified, but is estimated as follows. In a compound that can constitute a tertiary hydrogen-containing carboxylic acid unit, an electron-withdrawing group and an electron-donating group are bonded to the same carbon atom. It is considered that a very stable radical is generated by a phenomenon called a stabilized captodative effect. That is, the carboxyl group is an electron withdrawing group, and the carbon to which the adjacent tertiary hydrogen is bonded becomes electron deficient (δ ⁺ ), so the tertiary hydrogen also becomes electron deficient (δ ⁺ ), Dissociates to form radicals. When oxygen and water are present here, it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.

In the general formulas (I) and (Ia), R ¹ and R ^1a each represent a substituent. Examples of the substituent represented by R ¹ and R ^1a in the present invention include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (1 to 15, preferably 1 to 6 carbon atoms). Linear, branched or cyclic alkyl groups having atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl) An alkenyl group (a linear, branched or cyclic alkenyl group having 2 to 10, preferably 2 to 6 carbon atoms, such as a vinyl group, an allyl group), an alkynyl group (2 to 10, preferably 2 to Alkynyl group having 6 carbon atoms, for example, ethynyl group, propargyl group), aryl group (6-16, preferably 6-10 carbon atoms) For example, a phenyl group, a naphthyl group), a heterocyclic group (5- to 6-membered aromatic or non-aromatic heterocyclic compound obtained by removing one hydrogen atom, preferably 1 to 12, Is a monovalent group having 2 to 6 carbon atoms, such as 1-pyrazolyl group, 1-imidazolyl group, 2-furyl group, cyano group, hydroxyl group, nitro group, alkoxy group (1-10, preferably A linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, such as a methoxy group or an ethoxy group, an aryloxy group (6 to 12, preferably an aryloxy group having 6 to 8 carbon atoms) A phenoxy group), an acyl group (formyl group, 2-10, preferably an alkylcarbonyl group having 2-6 carbon atoms, or 7-12, preferably 7-9 carbon atoms. Having an arylcarbonyl group, for example, an acetyl group, a pivaloyl group, a benzoyl group), an amino group (amino group, an alkylamino group having 1-10, preferably 1-6 carbon atoms, 6-12, preferably An anilino group having 6 to 8 carbon atoms, or a heterocyclic amino group having 1 to 12, preferably 2 to 6 carbon atoms (for example, an amino group, a methylamino group, an anilino group), a mercapto group, An alkylthio group (an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group), an arylthio group (6 to 12, preferably 6 to 8 carbon atoms) An arylthio group, such as a phenylthio group, a heterocyclic thio group (2-10, preferably a heterocyclic thio group having 1-6 carbon atoms, such as 2- Down zone benzothiazolylthio group), an imido group (2 to 10, preferably an imido group having 4 to 8 carbon atoms, for example, N- succinimido group, N- phthalimido group).

Among these functional groups, those having a hydrogen atom may be further substituted with the above groups, for example, an alkyl group substituted with a hydroxyl group (for example, hydroxyethyl group), an alkyl group substituted with an alkoxy group (For example, methoxyethyl group), an alkyl group substituted with an aryl group (for example, benzyl group), an aryl group substituted with an alkyl group (for example, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples include 2-methylphenoxy group), but are not limited thereto.
In addition, when a functional group is further substituted, the carbon number mentioned above shall not include the carbon number of the further substituent. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. The following description of the number of carbon atoms shall be similarly understood unless otherwise specified.

In the general formula (Ia), A ¹ and A ² each represent a single bond or a divalent linking group. However, the case where both A ¹ and A ² are single bonds is excluded. Examples of the divalent linking group include a linear, branched or cyclic alkylene group (C1-C12, preferably C1-C4 alkylene group such as a methylene group or ethylene group), an aralkylene group (carbon number). Examples thereof include aralkylene groups having 7 to 30 carbon atoms, preferably 7 to 13 carbon atoms, such as benzylidene groups, arylene groups (arylene groups having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms such as phenylene groups), and the like. These may further have a substituent, and examples of the substituent include the functional groups exemplified above as substituents represented by R ¹ and R ^1a . Examples thereof include, but are not limited to, an arylene group substituted with an alkyl group (for example, a xylylene group).

  It is preferable that the polyesteramide compound of this invention contains at least 1 type of the structural unit represented by the said general formula (I) or (Ia). Among these, from the viewpoint of improving the availability of raw materials and oxygen absorption, a carboxylic acid unit having tertiary hydrogen on the α-carbon (carbon atom adjacent to the carboxyl group) is more preferable, and is represented by the general formula (I). The structural unit is particularly preferred.

R ¹ in the general formula (I) is as described above. Among them, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferable, and a substituted or unsubstituted carbon number of 1 to 6 is preferable. And a substituted or unsubstituted aryl group having 6 to 10 carbon atoms is more preferable, and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group are particularly preferable.
Specific examples of preferable R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, hydroxymethyl group, 1 Examples thereof include, but are not limited to, -hydroxyethyl group, mercaptomethyl group, methylsulfanylethyl group, phenyl group, naphthyl group, benzyl group, 4-hydroxybenzyl group. Among these, a methyl group, an ethyl group, and a benzyl group are more preferable.

Compounds that can constitute the structural unit represented by the general formula (I) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine, 2 -Although alpha-amino acids, such as phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, proline, can be illustrated, it is not limited to these.
Moreover, as a compound which can comprise the structural unit represented by the said general formula (Ia), (beta) -amino acids, such as 3-aminobutyric acid, can be illustrated, However, It is not limited to these.
These may be any of D-form, L-form and racemate, or allo-form. Moreover, these can be used individually or in combination of 2 or more types.

  Among these, α-amino acids having tertiary hydrogen in the α carbon are particularly preferable from the viewpoints of availability of raw materials and oxygen absorption improvement. Among α-amino acids, alanine is most preferable from the viewpoints of ease of supply, inexpensive price, ease of polymerization, and low yellowness (YI) of the polymer. Since alanine has a relatively low molecular weight and a high copolymerization rate per 1 g of the polyesteramide compound of the present invention, the oxygen absorption performance per 1 g of the polyesteramide compound is good.

  Further, the purity of the compound that can constitute the tertiary hydrogen-containing carboxylic acid unit is 95% or more from the viewpoint of the influence on the polymerization such as the delay of the polymerization rate and the influence on the quality such as the yellowness of the polymer. Preferably, it is 98.5% or more, more preferably 99% or more. Further, sulfate ions and ammonium ions contained as impurities are preferably 500 ppm or less, more preferably 200 ppm or less, and still more preferably 50 ppm or less.

1-2. Polyvalent carboxylic acid unit The polyvalent carboxylic acid unit in the polyesteramide compound of the present invention is an aromatic dicarboxylic acid unit represented by the general formula (II) when the polyvalent carboxylic acid unit is 100 mol%. 70 to 99.99 mol%, and a unit selected from the sulfophthalic acid unit represented by the general formula (III) and the sulfophthalic acid metal salt unit represented by the following general formula (III ′) in total 0.01 Contains ~ 30.0 mol%. By including the sulfophthalic acid unit or the metal salt unit of sulfophthalic acid, the polyamide compound of the present invention exhibits excellent oxygen absorption performance, and can further improve the transparency of a molded article using the same.

1-2-1. Aromatic dicarboxylic acid unit From the viewpoint of imparting appropriate heat resistance and oxygen barrier properties, the polyvalent carboxylic acid unit in the polyesteramide compound of the present invention, when the polyvalent carboxylic acid unit is 100 mol%, The aromatic dicarboxylic acid unit represented by the general formula (II) is 70 to 99.99 mol%, preferably 80 to 99.95 mol%, more preferably 90 to 99.93 mol% in the polyvalent carboxylic acid unit. Including.
In terms of this, when the polyesteramide compound of the present invention contains 25 mol% of polyvalent carboxylic acid units, the aromatic dicarboxylic acid units represented by the general formula (II) in the polyesteramide compound of the present invention The content is 17.5 to 24.9975 mol%, preferably 20 to 24.9875 mol%, more preferably 22.5 to 24.9825 mol%. In addition, when the polyesteramide compound of the present invention contains 49.995 mol% of polyvalent carboxylic acid units, the aromatic dicarboxylic acid unit represented by the general formula (II) in the polyesteramide compound of the present invention is contained. The amount is 34.9965-49.9900005 mol%, preferably 39.996-49.9700025 mol%, more preferably 44.9955-49.9600035 mol%.

In the general formula (II), Ar represents an arylene group not substituted with a sulfo group. That is, the aromatic dicarboxylic acid unit represented by the general formula (II) includes a sulfophthalic acid unit represented by the general formula (III) and a sulfophthalic acid metal salt unit represented by the following general formula (III ′). Is not included. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
Compounds that can constitute the aromatic dicarboxylic acid unit represented by the general formula (II) include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis ( Examples include p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, and ester-forming derivatives thereof. However, it is not limited to these. These can be used alone or in combination of two or more.
The aromatic dicarboxylic acid unit represented by the general formula (II) includes at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit in the aromatic dicarboxylic acid unit. The total content is preferably not less than 50 mol%, and the content is preferably not less than 70 mol%, more preferably not less than 80 mol%, still more preferably not less than 90 mol%, and preferably not more than 100 mol%. It is.

1-2-2. Sulfophthalic acid unit and sulfophthalic acid metal unit The polyvalent carboxylic acid unit in the polyesteramide compound of the present invention is 100 mol% from the viewpoint of oxygen absorption and the transparency of the molded product. Sometimes, the unit selected from the sulfophthalic acid unit represented by the general formula (III) and the sulfophthalic acid metal salt unit represented by the general formula (III ′) in a total of 0.01 to 30.0 mol%, Preferably it is 0.01-15.0 mol%, More preferably, it is 0.03-12.0 mol%, More preferably, it is 0.05-10.0 mol%, More preferably, it is 0.08-8.0 mol % Is included.
In terms of this, when the polyesteramide compound of the present invention contains 25 mol% of polyvalent carboxylic acid units, the sulfophthalic acid unit represented by the general formula (III) in the polyesteramide compound of the present invention and the general The total content of units selected from the metal unit of sulfophthalic acid salt represented by the formula (III ′) is 0.0025 to 7.5 mol%, preferably 0.0025 to 3.75 mol%, more preferably 0. .0075 to 3 mol%, more preferably 0.0125 to 2.5 mol%, still more preferably 0.02 to 2 mol%. In the case where the polyesteramide compound of the present invention contains 49.995 mol% of a polycarboxylic acid unit, the sulfophthalic acid unit represented by the general formula (III) in the polyesteramide compound of the present invention and the general formula The total content of units selected from the metal salt unit of sulfophthalic acid represented by (III ′) is 0.0049995 to 14.9985 mol%, preferably 0.0049995 to 7.49925 mol%, more preferably 0.8. It is 0499985-5.9994 mol%, More preferably, it is 0.0249975-4.9995 mol%, More preferably, it is 0.039996-3.9996 mol%.

In the general formula (III ′), M is a metal atom. n is the valence of M and is an integer of 1 to 5.
Examples of the metal atom of M include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as beryllium, magnesium, calcium and strontium. Among these, alkali metals are preferable, sodium or lithium is preferable, and sodium is more preferable. In addition, when n is 2 or more, it can be cross-linked with another unit (for example, a sulfo group in another sulfophthalic acid unit or a sulfophthalic acid metal salt unit) via M.

In the general formulas (III) and (III ′), R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and m is an integer of 0 to 3. When m is 2 or 3, each R ² may be the same or different.
As said alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group etc. are mentioned, for example. Among these, a C1-C6 alkyl group is preferable and a C1-C4 alkyl group is more preferable.
Examples of the aryl group include a phenyl group and a naphthyl group. Among these, an aryl group having 6 to 12 carbon atoms is preferable, and a phenyl group is more preferable.
Examples of the substituent that the alkyl group and aryl group may have include, for example, a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, an alkyl group, an alkenyl group, an aryl group, a cyano group, a hydroxyl group, a nitro group, and an alkoxy group. Group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group and the like. Among these groups, those having a hydrogen atom may be further substituted with the above-described substituents.

Specific examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, hydroxymethyl group, 1- Examples thereof include a hydroxyethyl group, a mercaptomethyl group, a methylthioethyl group, a phenyl group, a naphthyl group, a biphenyl group, a benzyl group and a 4-hydroxybenzyl group, and among them, a methyl group, an ethyl group and a benzyl group are preferable.

  The sulfophthalic acid unit represented by the general formula (III) or the sulfophthalic acid metal salt unit represented by the general formula (III ′) includes a phthalic acid structure in which two —CO— are bonded to the ortho position, and a meta position. And an isophthalic acid structure bonded to the para position, and an isophthalic acid structure is preferable. That is, the sulfophthalic acid unit represented by the general formula (III) and the sulfophthalic acid metal salt unit represented by the following general formula (III ′) are the sulfoisophthalic acid unit represented by the following general formula (IIIa) and A sulfoisophthalic acid metal salt unit represented by the general formula (III′a) is preferred.

［前記一般式（ＩＩＩａ）及び（ＩＩＩ’ａ）中、Ｒ²、ｍ、Ｍ及びｎは、それぞれ前記一般式（ＩＩＩ）又は（ＩＩＩ’）におけるＲ²、ｍ、Ｍ及びｎと同じである。］

[In the general formula (IIIa) and ^{(III'a), R 2, m} , M and n are the same as R ^2, m, M and n in each of the general formulas (III) or (III ') . ]

Preferable R ² is as described above. As the sulfophthalic acid unit or the metal salt unit of sulfophthalic acid, m = 0, that is, the benzene ring is not substituted by R ² , each represented by the following general formula (IIIb) And a sulfoisophthalic acid metal salt unit represented by the following general formula (III′b).

［前記一般式（ＩＩＩ’ｂ）中、Ｍ及びｎは、それぞれ前記一般式（ＩＩＩ’）におけるＭ及びｎと同じである。］

[In the general formula (III′b), M and n are the same as M and n in the general formula (III ′), respectively. ]

  The position of the sulfo group in the sulfoisophthalic acid unit or the metal salt unit of sulfoisophthalic acid can be 2, 4, 5, or 6, but is preferably substituted at the 5-position, and represented by the following general formula (IIIc) A 5-sulfoisophthalic acid unit represented by the following general formula (III′c) is preferable.

［前記一般式（ＩＩＩ’ｃ）中、Ｍ及びｎは、それぞれ前記一般式（ＩＩＩ’）におけるＭ及びｎと同じである。］

[In the general formula (III′c), M and n are the same as M and n in the general formula (III ′), respectively. ]

  Examples of the compound that can constitute the 5-sulfoisophthalic acid unit or the 5-sulfoisophthalic acid metal salt unit represented by the general formula (IIIc) or (III′c) in the polyesteramide compound of the present invention include 5 -Sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, bis (5-sulfoisophthalic acid) calcium, 5-sodium sulfoisophthalic acid dimethyl, 5-sodium sulfoisophthalic acid Examples include diethyl.

1-2-3. Other Polycarboxylic Acid Units The polyesteramide compound of the present invention is an aromatic dicarboxylic acid unit represented by the general formula (II) and the general formula (III) as long as the effects of the present invention are not impaired. It may have a polyvalent carboxylic acid unit (abbreviated as “other polyvalent carboxylic acid unit”) other than the sulfophthalic acid unit represented and the sulfophthalic acid metal salt unit represented by the following general formula (III ′). .
Examples of the compound that can constitute the other polyvalent carboxylic acid unit include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, trivalent or higher polyvalent carboxylic acid, anhydrides of these acids, alkyl esters, and the like. However, it is not limited to these.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, citraconic acid, 2-methylsuccinic acid, itaconic acid And glutaconic acid. Examples of alicyclic dicarboxylic acids include cyclohexane dicarboxylic acids and decalin dicarboxylic acids. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.

1-3. Polyhydric alcohol unit The polyhydric alcohol unit in the polyesteramide compound of the present invention has the above general formula (IV) when the polyhydric alcohol unit is 100 mol% from the viewpoint of imparting flexibility necessary as a packaging material. In the polyhydric alcohol unit, and the content is preferably 80 mol% or more, more preferably 90 mol% or more, and preferably 100 mol%. % Or less.
In terms of this, when the polyesteramide compound of the present invention contains 25 mol% of polyhydric alcohol units, the content of the aliphatic diol unit represented by the general formula (IV) in the polyesteramide compound of the present invention Is 17.5 mol% or more, preferably 20 mol% or more, more preferably 22.5 mol% or more, and preferably 25 mol% or less. When the polyesteramide compound of the present invention contains 49.995 mol% of polyhydric alcohol units, the content of the aliphatic diol unit represented by the general formula (IV) in the polyesteramide compound of the present invention is , 34.9965 mol% or more, preferably 39.996 mol% or more, more preferably 44.9955 mol% or more, and preferably 49.9995 mol% or less.

In the general formula (IV), X represents an alkylene group having 2 to 20 carbon atoms. The alkylene group preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, and may be linear, branched or cyclic.
Examples of the compound that can constitute the aliphatic diol unit represented by the general formula (IV) include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, 2 carbon atoms such as 2,3-butanediol, 1,5-pentadiol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol -20 aliphatic diols and ester-forming derivatives thereof can be exemplified, but are not limited thereto. These can be used alone or in combination of two or more.
Among these, the aliphatic diol unit represented by the general formula (IV) includes at least one selected from the group consisting of an ethylene glycol unit, a 1,3-propanediol unit, and a 1,4-butanediol unit. The total content of the group diol units is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.

Examples of the compound that can constitute a polyhydric alcohol unit other than the aliphatic diol unit represented by the general formula (IV) include hydrogenated bisphenol A, aromatic diol, and trivalent or higher polyhydric alcohol. However, it is not limited to these.
Examples of the aromatic diol include hydroquinone, resorcin, bisphenol A, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone, and the like. Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, and trimethylolpropane.

1-4. The degree of polymerization of the polyesteramide compound As for the degree of polymerization of the polyesteramide compound of the present invention, the intrinsic viscosity is used as an index because its use is close to that of a polyester resin. The intrinsic viscosity of the polyesteramide compound of the present invention is preferably 0.1 dl / g or more and 1.5 dl / g or less.
When the polyesteramide compound of the present invention is a polyesteramide resin, the intrinsic viscosity is preferably 0.4 to 1.5 dl / g, more preferably from the viewpoint of molding processability and mechanical properties, strength, odor and the like of the molded body. Is 0.5 to 1.2 dl / g, more preferably 0.6 to 1.0 dl / g. However, when the polyesteramide resin of the present invention is used as an additive or modifier for other thermoplastic resins, it is not limited to this range.
When the polyesteramide compound of the present invention is a polyesteramide oligomer, the intrinsic viscosity is preferably 0.1 dl / g or more and less than 0.4 dl / g, more preferably from the viewpoints of handleability, reactivity and thermal stability. It is 0.15-0.35 dl / g, More preferably, it is 0.15-0.3 dl / g.
In addition, intrinsic viscosity is calculated | required by the method as described in an Example. The limiting viscosity can be controlled within the above range by appropriately setting the polymerization time, the amount of catalyst, the degree of vacuum during polymerization, and the like.

2. Process for Producing Polyesteramide Compound The polyesteramide compound of the present invention comprises a polyvalent carboxylic acid component capable of constituting the polyvalent carboxylic acid unit, a polyhydric alcohol component capable of constituting the polyhydric alcohol unit, and the tertiary hydrogen. It can be produced by polycondensation with a tertiary hydrogen-containing carboxylic acid component that can constitute the containing carboxylic acid unit, and the degree of polymerization can be controlled by adjusting polycondensation conditions and the like. A small amount of monoamine, monoalcohol or monocarboxylic acid may be added as a molecular weight modifier during polycondensation.

There is no restriction | limiting in particular in the polycondensation method of the polyesteramide compound of this invention, A conventionally well-known method is applicable. For example, the methyl ester of a polyvalent carboxylic acid component, a polyhydric alcohol component and, if necessary, the above-mentioned copolymerization component are reacted in the presence of a transesterification catalyst to distill off the produced methanol, and then transesterify it. After transesterification by adding a catalyst and proceeding polycondensation, by directly reacting a polyvalent carboxylic acid component and a polyhydric alcohol component and, if necessary, the above-mentioned copolymerization component, the water formed is esterified, Examples thereof include a melt polymerization method such as a direct esterification method in which a polymerization catalyst is added to promote polycondensation, and a solution polymerization method. In order to efficiently produce the polyesteramide compound of the present invention, it is preferable to employ a direct esterification method from the viewpoint of the reactivity of the constituent components.
The timing of adding the tertiary hydrogen-containing carboxylic acid component in the direct esterification method may be at any stage of the polycondensation step. From the viewpoint of ensuring that the tertiary hydrogen-containing carboxylic acid component is incorporated into the polymer, polymerization is performed. The tertiary hydrogen-containing carboxylic acid component is preferably added at the stage of esterification of the polyvalent carboxylic acid component and the polyhydric alcohol component, or at the stage of adding the polycondensation catalyst to the low polymerization degree product. Can be added.

2-1. Catalysts and additives In the production of polyesteramide compounds, transesterification catalysts, esterification catalysts, etherification inhibitors, polymerization catalysts used for polymerization, various stabilizers such as heat stabilizers, light stabilizers, polymerization regulators, etc. Also conventionally known ones can be used.

  Examples of the transesterification catalyst and the esterification catalyst include compounds such as manganese, cobalt, zinc, titanium, and calcium. An amine compound etc. are illustrated as an etherification inhibitor.

  Examples of the polymerization catalyst include compounds containing germanium, antimony, titanium, aluminum and the like. Examples of the compound containing germanium include amorphous germanium dioxide, crystalline germanium dioxide, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, germanium phosphite, and the amount used is a polyesteramide compound. The germanium atom concentration in the inside is preferably set to 5 to 150 ppm, more preferably 10 to 100 ppm, and still more preferably 15 to 70 ppm.

  Examples of the compound containing antimony include antimony trioxide, antimony acetate, antimony tartrate, antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony. The antimony atom concentration is preferably set to be 10 to 400 ppm, more preferably 20 to 350 ppm, and still more preferably 30 to 300 ppm.

  Compounds containing titanium include tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetraalkyl titanates such as tetra-n-butyl titanate and their partial hydrolysates, titanyl oxalate, titanyl ammonium oxalate, oxalate Examples include titanyl sodium titanate, potassium titanyl oxalate, titanyl calcium oxalate, titanyl oxalate compounds such as titanyl strontium oxalate, trimellitic acid titanium, titanium sulfate, titanium chloride, etc. The amount used is titanium in the polyesteramide compound The atomic concentration is preferably set to 0.5 to 300 ppm, more preferably 1 to 200 ppm, and still more preferably 3 to 100 ppm.

  Compounds containing aluminum include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate and aluminum oxalate, oxides, inorganic acid salts such as aluminum hydroxide, aluminum chloride, aluminum hydroxide chloride and aluminum carbonate, aluminum Examples include aluminum alkoxides such as methoxide and aluminum ethoxide, aluminum xylate compounds such as aluminum acetylacetonate and aluminum acetylacetate, organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysates thereof. The amount used is preferably set to be 1 to 400 ppm as the aluminum atom concentration in the polyesteramide compound, more preferably A ～300Ppm, more preferably from 5 to 200 ppm.

  In the production of the polyesteramide compound of the present invention, an alkali metal compound or an alkaline earth metal compound may be used. Examples of the alkali metal compound or alkaline earth metal compound include alkali metal or alkaline earth metal carboxylates and alkoxides. The amount used is preferably set to be 0.1 to 200 ppm as an alkali metal or alkaline earth metal atom concentration in the polyesteramide compound, more preferably 0.5 to 150 ppm, and still more preferably 1 ~ 100 ppm.

  In the production of the polyesteramide compound of the present invention, one or more kinds of phosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof can be used as a heat stabilizer. For example, phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, phosphorous acid , Phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, and the like. The amount used is preferably set to be 1 to 200 ppm as the phosphorus atom concentration in the polyesteramide compound, more preferably 2 to 150 ppm, and even more preferably 3 to 100 ppm.

  In the production of the polyesteramide compound of the present invention, a higher alcohol such as lauryl alcohol can be added to adjust the weight average molecular weight. For the purpose of improving physical properties, a polyhydric alcohol such as glycerin may be added. In addition, you may add the additive mentioned later.

2-2. Step for increasing the degree of polymerization The polyesteramide compound produced by the above polymerization method can be used as it is, but may further undergo a step for increasing the degree of polymerization. Further examples of the step of increasing the degree of polymerization include reactive extrusion in an extruder and solid phase polymerization. As a heating device used in solid-phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer are provided. A conical heating device can be preferably used, but a known method and device can be used without being limited thereto. In particular, when solid-phase polymerization of a polyesteramide compound is performed, a heating device of a rotating drum type among the above-described devices can seal the inside of the system and easily proceed with polycondensation in a state where oxygen that causes coloring is removed. Therefore, it is preferably used.

3. Polyesteramide Composition The polyesteramide composition of the present invention is a composition containing the polyesteramide compound of the present invention. The polyesteramide composition of the present invention is a mixture obtained by adding and mixing various additives and various resins to the polyesteramide resin and polyesteramide oligomer of the present invention. The polyesteramide oligomer may react with the added additive or resin.

3-1. Additives The polyesteramide compound of the present invention is a lubricant, crystallization nucleating agent, anti-whitening agent, matting agent, heat stabilizer, weathering stabilizer, ultraviolet absorber, plasticizer, flame retardant depending on the required performance. Further, additives such as an antistatic agent, an anti-coloring agent, an antioxidant, and an impact resistance improving material may be added to form a polyesteramide composition. These additives can be added as necessary within a range not impairing the effects of the present invention.

  For mixing the polyesteramide compound of the present invention and the additive, a conventionally known method can be used, but dry mixing that is low in cost and does not receive heat history is preferably performed. For example, the polyester amide compound and said additive are put into a tumbler, and the method of mixing by rotating is mentioned. Further, in the present invention, in order to prevent classification of the polyesteramide compound and additive after dry mixing, a method is adopted in which a viscous liquid is attached to the polyesteramide compound as a spreading agent, and then the additive is added and mixed. You can also. Examples of the spreading agent include a surfactant and the like, but a known one can be used without being limited thereto.

3-1-1. Anti-whitening agent In the polyesteramide composition of the present invention, it is preferable to add a diamide compound and / or a diester compound to the polyesteramide compound as a suppression of whitening after hydrothermal treatment or after a long period of time. The diamide compound and / or diester compound is effective in suppressing whitening due to precipitation of oligomers. A diamide compound and a diester compound may be used alone or in combination.

  The diamide compound used in the present invention is preferably a diamide compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms. When the aliphatic dicarboxylic acid has 8 or more carbon atoms and the diamine has 2 or more carbon atoms, a whitening prevention effect can be expected. In addition, when the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diamine has 10 or less carbon atoms, uniform dispersion in the polyesteramide composition is good. The aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred. One kind of diamide compound may be used, or two or more kinds may be used in combination.

Examples of the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Examples of the diamine include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, and bis (aminomethyl) cyclohexane. A diamide compound obtained by combining these is preferred.
A diamide compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine mainly composed of ethylenediamine, or a diamide compound obtained from an aliphatic dicarboxylic acid mainly consisting of montanic acid and a diamine having 2 to 10 carbon atoms A diamide compound obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine is particularly preferable.

The diester compound used in the present invention is preferably a diester compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms. When the aliphatic dicarboxylic acid has 8 or more carbon atoms and the diol has 2 or more carbon atoms, an effect of preventing whitening can be expected. Further, when the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diol has 10 or less carbon atoms, uniform dispersion in the polyesteramide composition is good. The aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred. One type of diester compound may be used, or two or more types may be used in combination.
Examples of the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30). Examples of the diol include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol. A diester compound obtained by combining these is preferred.
Particularly preferred is a diester compound obtained from an aliphatic dicarboxylic acid mainly composed of montanic acid and a diol mainly composed of ethylene glycol and / or 1,3-butanediol.

  In the present invention, the addition amount of the diamide compound and / or diester compound is 0.005 to 0.5 parts by mass, preferably 0.05 to 0.5 parts by mass, particularly preferably 100 parts by mass of the polyesteramide compound. It is 0.12-0.5 mass part. Addition of 0.005 parts by mass or more with respect to 100 parts by mass of the polyesteramide compound and use in combination with the crystallization nucleating agent can be expected to produce a synergistic effect for preventing whitening. Moreover, it becomes possible to keep the cloudiness of the molded object obtained by shape | molding the polyesteramide composition of this invention low that the addition amount is 0.5 mass part or less with respect to 100 mass parts of polyesteramide.

3-1-2. Crystallization nucleating agent From the viewpoint of improving transparency, it is preferable to add a crystallization nucleating agent to the polyesteramide composition of the present invention. In addition to improving transparency, it is also effective for whitening due to crystallization after hydrothermal treatment or after a long period of time. By adding a crystallization nucleating agent to the polyester amide compound, the spherulite size can be reduced to visible light. It can be suppressed by setting it to 1/2 or less of the wavelength. In addition, when a diamide compound and / or a diester compound and a crystallization nucleating agent are used in combination, whitening suppression far superior to the degree expected from each whitening suppression effect can be obtained due to their synergistic effect.

  Examples of inorganic crystallization nucleating agents used in the present invention include glass fillers (glass fibers, pulverized glass fibers (milled fibers), glass flakes, glass beads, etc.), calcium silicate fillers (wollastonite). Etc.), mica, talc (powder talc and granular talc with rosin as binder), kaolin, potassium titanate whisker, boron nitride, layered silicate clay, nanofiller, carbon fiber, etc., usually thermoplastic resin These may be used in combination, and two or more of these may be used in combination. The maximum diameter of the inorganic crystallization nucleating agent is preferably 0.01 to 5 μm. In particular, powder talc having a particle size of 3.0 μm or less is preferable, powder talc having a particle size of about 1.5 to 3.0 μm is more preferable, and powder talc having a particle size of 2.0 μm or less is particularly preferable. In addition, granular talc using rosin as a binder in this powdered talc is particularly preferable because the dispersed state in the polyesteramide composition is good. Organic crystallization nucleating agents include crystallization nucleating agents, capsules consisting of bilayer films of micro to nano level size, bis (benzylidene) sorbitol-based or phosphorus-based transparent crystal nucleating agents, rosinamide-based Gelling agents and the like are preferable, and bis (benzylidene) sorbitol crystallization nucleating agents are particularly preferable.

  The addition amount of the crystallization nucleating agent is preferably 0.005 to 2.0 parts by mass, more preferably 0.01 to 1.5 parts by mass with respect to 100 parts by mass of the polyesteramide compound. By adding these at least one crystallization nucleating agent to the polyesteramide compound in combination with the diamide compound and / or diester compound, a synergistic effect of preventing whitening can be obtained. In particular, the inorganic crystallization nucleating agent such as talc is 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the polyesteramide compound, and the organic crystallization nucleating agent such as bis (benzylidene) sorbitol crystallization nucleating agent is It is particularly preferable to use 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polyesteramide compound.

  The bis (benzylidene) sorbitol-based crystallization nucleating agent is selected from bis (benzylidene) sorbitol and bis (alkylbenzylidene) sorbitol, and is a condensation product (diacetal compound) produced by acetalization reaction of sorbitol and benzaldehyde or alkyl-substituted benzaldehyde. And can be conveniently prepared by various synthetic methods known in the art. Here, the alkyl may be linear or cyclic, and may be saturated or unsaturated. A common synthesis method uses the reaction of 1 mole of D-sorbitol with about 2 moles of aldehyde in the presence of an acid catalyst. The reaction temperature varies widely depending on the characteristics (melting point, etc.) of the aldehyde used as the starting material for the reaction. The reaction medium may be an aqueous medium or a non-aqueous medium. One preferred method that can be used to prepare the diacetals used in the present invention is described in US Pat. No. 3,721,682. Although this disclosure is limited to benzylidene sorbitols, the bis (alkylbenzylidene) sorbitols used in the present invention can also be conveniently prepared by the methods described therein.

  Specific examples of the bis (benzylidene) sorbitol crystallization nucleating agent (diacetal compound) include bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (n-propylbenzylidene) sorbitol, bis (p -Isopropylbenzylidene) sorbitol, bis (p-isobutylbenzylidene) sorbitol, bis (2,4-dimethylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (2,4,5-trimethylbenzylidene) sorbitol, Examples thereof include bis (2,4,6-trimethylbenzylidene) sorbitol, bis (4-biphenylbenzylidene) sorbitol and the like.

  Examples of alkyl-substituted benzaldehydes suitable for preparing bis (benzylidene) sorbitol-based crystallization nucleating agents include p-methylbenzaldehyde, n-propylbenzaldehyde, p-isopropylbenzaldehyde, 2,4-dimethylbenzaldehyde, 3,4 -Dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 4-biphenylbenzaldehyde.

  When a crystallization nucleating agent such as talc, mica, or clay is added to the polyesteramide compound, the crystallization speed is accelerated twice or more as compared with the polyesteramide compound without addition. There is no problem in injection molding applications that require a high molding cycle, but in deep drawn cups formed from stretched films and sheets, if the crystallization speed is too fast, the film or sheet cannot be stretched due to crystallization, and breakage occurs. Or formability such as unevenness of elongation is extremely reduced. However, bis (benzylidene) sorbitol-based crystallization nucleating agent does not accelerate the crystallization rate even when added to a polyesteramide compound, so it is used for applications such as deep drawn cups formed from stretched films and sheets. Is preferred.

  Furthermore, it has been found that the bis (benzylidene) sorbitol-based crystallization nucleating agent not only suppresses whitening but also improves oxygen barrier properties when added to a polyesteramide compound. It is particularly preferable to use a crystallization nucleating agent of bis (benzylidene) sorbitol (A) that can obtain both effects of suppressing whitening and improving oxygen barrier properties.

  The polyesteramide composition of the present invention can be used as a gas barrier layer to which a layered silicate is added, improving not only the oxygen barrier property of the molded product but also the barrier property against other gases such as carbon dioxide gas. Can do.

  The layered silicate is a 2-octahedral or 3-octahedral layered silicate having a charge density of 0.25 to 0.6. Examples of the 2-octahedral type include montmorillonite, beidellite, and the like. Examples of the octahedron type include hectorite and saponite. Among these, montmorillonite is preferable.

  The layered silicate is preferably obtained by expanding an interlayer of the layered silicate by previously bringing an organic swelling agent such as a polymer compound or an organic compound into contact with the layered silicate. As the organic swelling agent, a quaternary ammonium salt can be preferably used. Preferably, a quaternary ammonium salt having at least one alkyl group or alkenyl group having 12 or more carbon atoms is used.

  Specific examples of organic swelling agents include trimethyl dodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, trimethyl alkyl decyl ammonium salt, trimethyl alkyl decyl ammonium salt; trimethyl octadecenyl ammonium salt Trimethylalkenylammonium salts such as trimethyloctadecadienylammonium salt; triethylalkylammonium salts such as triethyldodecylammonium salt, triethyltetradecylammonium salt, triethylhexadecylammonium salt, triethyloctadecylammonium salt; tributyldodecylammonium salt, tributyltetradecyl Ammonium salt, tributyl hexadecyl ammonium salt, tri Tributylalkylammonium salts such as tiloctadecylammonium salt; dimethyldialkylammonium salts such as dimethyldidodecylammonium salt, dimethylditetradecylammonium salt, dimethyldihexadecylammonium salt, dimethyldioctadecylammonium salt, dimethylditallowammonium salt; dimethyl Dioctadecenyl ammonium salt, dimethyl dialkenyl ammonium salt such as dimethyl dioctadecadienyl ammonium salt; diethyl didodecyl ammonium salt, diethyl ditetradecyl ammonium salt, diethyl dihexadecyl ammonium salt, diethyl dioctadecyl ammonium salt, etc. Diethyl dialkyl ammonium salt; dibutyl didodecyl ammonium salt, dibutyl ditetradecyl ammonium salt, dibu Dibutyl dialkyl ammonium salts such as rudihexadecyl ammonium salt and dibutyl dioctadecyl ammonium salt; Methyl benzyl dialkyl ammonium salts such as methyl benzyl dihexadecyl ammonium salt; Dibenzyl dialkyl ammonium salts such as dibenzyl dihexadecyl ammonium salt; Tridodecyl Trialkylmethylammonium salts such as methylammonium salt, tritetradecylmethylammonium salt, trioctadecylmethylammonium salt; trialkylethylammonium salts such as tridodecylethylammonium salt; trialkylbutylammonium salts such as tridodecylbutylammonium salt; 4-amino-n-butyric acid, 6-amino-n-caproic acid, 8-aminocaprylic acid, 10-aminodecanoic acid, 12-aminodode Examples include ω-amino acids such as canic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. In addition, hydroxyl group and / or ether group-containing ammonium salts, among them, methyl dialkyl (PAG) ammonium salt, ethyl dialkyl (PAG) ammonium salt, butyl dialkyl (PAG) ammonium salt, dimethyl bis (PAG) ammonium salt, diethyl bis (PAG) ) Ammonium salt, dibutyl bis (PAG) ammonium salt, methyl alkyl bis (PAG) ammonium salt, ethyl alkyl bis (PAG) ammonium salt, butyl alkyl bis (PAG) ammonium salt, methyl tri (PAG) ammonium salt, ethyl tri (PAG) ammonium Salt, butyltri (PAG) ammonium salt, tetra (PAG) ammonium salt (wherein alkyl is carbon number such as dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc.) A quaternary ammonium containing at least one alkylene glycol residue such as a polyalkylene glycol residue, preferably a polyethylene glycol residue or a polypropylene glycol residue having 20 or less carbon atoms). Salts can also be used as organic swelling agents. Among them, trimethyldodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, dimethyl didodecyl ammonium salt, dimethyl ditetradecyl ammonium salt, dimethyl dihexadecyl ammonium salt, dimethyl dioctadecyl ammonium salt, dimethyl A ditallow ammonium salt is preferred. These organic swelling agents can be used alone or as a mixture of a plurality of types.

  In this invention, what added 0.5-8 mass parts of layered silicate processed with the organic swelling agent with respect to 100 mass parts of polyesteramide compounds is used preferably, More preferably, it is 1-6 mass parts, More preferably Is 2-5 parts by mass. If the amount of layered silicate added is less than 0.5 parts by mass, the effect of improving gas barrier properties is small, which is not preferable. On the other hand, if it is more than 8 parts by mass, the gas barrier layer becomes cloudy and the transparency of the container is impaired, which is not preferable.

  In the polyesteramide composition, the layered silicate is preferably uniformly dispersed without locally agglomerating. Here, the uniform dispersion means that the layered silicate is separated into a flat plate in the polyesteramide composition, and 50% or more of them have an interlayer distance of 5 nm or more. Here, the interlayer distance refers to the distance between the centers of gravity of the flat objects. The larger the distance, the better the dispersion state, the better the appearance such as transparency, and the better the gas barrier properties such as oxygen and carbon dioxide.

3-1-3. Anti-gelling / fish eye reducing agent In the polyesteramide composition of the present invention, the polyesteramide compound is selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate and derivatives thereof. It is preferred to add one or more carboxylates. Examples of the derivative include 12-hydroxystearic acid metal salts such as calcium 12-hydroxystearate, magnesium 12-hydroxystearate, and sodium 12-hydroxystearate. By adding the carboxylates, it is possible to prevent the gelation of the polyesteramide compound that occurs during the molding process and to reduce fish eyes in the molded body, thereby improving the suitability of the molding process.

  The addition amount of the carboxylates is preferably 400 to 10,000 ppm, more preferably 800 to 5000 ppm, and still more preferably 1000 to 3000 ppm as the concentration in the polyesteramide composition. If it is 400 ppm or more, thermal degradation of the polyesteramide compound can be suppressed and gelation can be prevented. Moreover, if it is 10,000 ppm or less, a polyesteramide composition will not produce a molding defect, and neither coloring nor whitening will occur. If carboxylate salts, which are basic substances, are present in the molten polyesteramide compound, it is presumed that the modification of the polyesteramide compound with heat is delayed and the formation of a gel that is considered to be the final modified product is suppressed. The carboxylates described above are excellent in handling properties, and among them, metal stearate is preferable because it is inexpensive and has an effect as a lubricant, and can stabilize the molding process. Furthermore, there is no particular limitation on the shape of the carboxylate salt, but when the powder and the smaller particle size are dry-mixed, it is easy to uniformly disperse in the polyesteramide composition. Is preferably 0.2 mm or less.

3-1-4. Antioxidant It is preferable that the polyesteramide composition of the present invention contains an antioxidant from the viewpoint of controlling oxygen absorption performance and suppressing deterioration of mechanical properties. Examples of the antioxidant include copper-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and thio-based antioxidants. Antioxidants and phosphorus antioxidants are preferred.

  Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4′-butylidenebis (3-methyl). -6-tert-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio)- 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-butylphenol), N, N′-hexamethylenebis (3,5-di-t -Butyl-4-hydroxy-hydroxycinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium, tris- (3,5-di-t-butyl-4) -Hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol , Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylene- Bis- (4-ethyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O -Cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-te Raoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3′-bis- (4′-hydroxy-3′-T-butylphenyl) butyric acid] glycol ester, 1,3, 5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, d-α-tocopherol, etc. It is done. These can be used alone or as a mixture thereof. Specific examples of commercially available hindered phenol compounds include Irganox 1010 and Irganox 1098 manufactured by BASF (both are trade names).

  Specific examples of phosphorus antioxidants include triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol Examples thereof include organic phosphorus compounds such as diphosphite, tetra (tridecyl-4,4′-isopropylidenediphenyl) diphosphite, and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. These can be used alone or as a mixture thereof.

  The content of the antioxidant in the polyesteramide composition can be used without particular limitation as long as it does not impair the various performances of the composition, but from the viewpoint of controlling oxygen absorption performance and suppressing deterioration of mechanical properties, the present invention. Preferably it is 0.001-3 mass parts with respect to 100 mass parts of the polyesteramide compound, More preferably, it is 0.01-1 mass part.

3-1-5. Impact resistance improving material In the amide composition containing the polyester amide of the present invention, an impact resistance improving material may be added to improve impact resistance, film pinhole resistance and flexibility. Examples of impact resistance improvers include polyolefins, polyamide elastomers, hydrogenated products of styrene-butadiene copolymer resins, ionomers, ethylene-ethyl acrylate copolymer resins, ethylene-ethyl acrylate copolymer resins modified with maleic anhydride, ethylene -Methacrylic acid copolymer resin, nylon 6,66,12, nylon 12, nylon 12 elastomer, ethylene-propylene copolymer elastomer, polyester elastomer and the like can be added. The addition amount of the impact resistance improving material is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and particularly preferably 2 to 3% by mass. When the amount added is large, transparency and gas barrier properties are lowered. If the amount added is small, impact resistance, pinhole resistance and flexibility of the film are not improved so much.

3-2. Resin The polyesteramide compound of the present invention may be mixed with various resins depending on the required use and performance to form a polyesteramide composition. Although it does not specifically limit as resin which can be mixed with the polyesteramide compound of this invention, It is preferable that it is at least 1 sort (s) chosen from the group which consists of polyolefin, polyester, polyamide, polyvinyl alcohol, and plant origin resin.
Among these, in order to effectively exhibit the oxygen absorption effect, a blend with a resin having high oxygen barrier properties such as polyester, polyamide and polyvinyl alcohol is preferable, a blend with polyester is more preferable, and a blend with PET Is more preferable.

  For mixing the polyesteramide compound of the present invention and the resin, a conventionally known method can be used, but melt mixing is preferable. When the polyesteramide compound of the present invention and a resin are melt-mixed to produce desired pellets and molded articles, they can be melt-blended using an extruder or the like. The extruder may be a single-screw or twin-screw extruder, but a twin-screw extruder is preferred from the viewpoint of mixing properties. As the screw to be melted, a known screw such as a so-called nylon or polyolefin, a slow compression type, a rapid compression type, a single flight, a double flight, or the like can be used, but is not limited thereto.

3-2-1. Polyolefin Specific examples of polyolefin include olefin homopolymers such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene -Copolymers of ethylene and α-olefins such as polybutene-1 copolymers and ethylene-cyclic olefin copolymers; ethylene-α, β-unsaturated carboxylic acid copolymers, ethylene-α, β-unsaturated Other carboxylic acid ester copolymers, ionic cross-linked products of ethylene-α, β-unsaturated carboxylic acid copolymers, ethylene-vinyl acetate copolymers, parts of ethylene-vinyl acetate copolymers or other saponified products Ethylene copolymers; graft modification of these polyolefins with acid anhydrides such as maleic anhydride And graft-modified polyolefin, and the like.

3-2-2. Polyester The polyester comprises one or two or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof and one or two or more selected from polyhydric alcohols containing glycol, or Those consisting of hydroxycarboxylic acids and their ester-forming derivatives, or those consisting of cyclic esters.

  Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutane Examples include dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, and the like. Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, Diphenic acid, , 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4, Aromatic dicarboxylics exemplified by 4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like Acids or ester-forming derivatives thereof, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid Including metal sulfonate groups Aromatic dicarboxylic acids or their lower alkyl ester derivatives.

  Among the above dicarboxylic acids, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferable in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be copolymerized as necessary. .

  As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.

  As glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethyl Aliphatic glycols exemplified by tylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β- Hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol Examples thereof include aromatic glycols exemplified by C, 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and the like.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component. Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like. Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

  Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides and the like.

  The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.

  The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component. A polyester containing 80 mol% or more is preferable, and a polyester containing 90 mol% or more is more preferable. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.

  Examples of the naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.

  The polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more. The alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.

  The copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propane. It is preferably at least one selected from the group consisting of diol and 2-methyl-1,3-propanediol from the viewpoint of achieving both transparency and moldability, and is particularly preferably isophthalic acid, diethylene glycol, neopentyl glycol, 1 More preferred is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.

  A preferred example of the polyester used in the present invention is a polyester whose main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and still more preferably an ethylene terephthalate unit. A linear polyester containing 80 mol% or more is preferable, and a linear polyester containing 90 mol% or more of ethylene terephthalate units is particularly preferable.

  Another preferred example of the polyester used in the present invention is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, more preferably 70 mol% or more of ethylene-2,6-naphthalate unit. It is a linear polyester, more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferable is a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units. Polyester.

  Other preferable examples of the polyester used in the present invention include linear polyesters containing 70 mol% or more of propylene terephthalate units, linear polyesters containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexanedimethylene terephthalate. A linear polyester containing 70 mol% or more of units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  In particular, the composition of the entire polyester is a combination of terephthalic acid / isophthalic acid // ethylene glycol, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol, and terephthalic acid // ethylene glycol / neopentyl glycol. It is preferable in order to satisfy both properties and moldability. Needless to say, a small amount (5 mol% or less) of diethylene glycol generated by dimerization of ethylene glycol may be included in the esterification (transesterification) reaction or polycondensation reaction.

  Other preferable examples of the polyester used in the present invention include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. This polyglycolic acid may be copolymerized with other components such as lactide.

3-2-3. Polyamides that can be used in the present invention include polyamides whose main constituent units are units derived from lactams or aminocarboxylic acids, and aliphatic polyamides whose main constituent units are units derived from aliphatic diamines and aliphatic dicarboxylic acids. A partially aromatic polyamide whose main constituent unit is a unit derived from an aliphatic diamine and an aromatic dicarboxylic acid, a partially aromatic polyamide whose main constituent unit is a unit derived from an aromatic diamine and an aliphatic dicarboxylic acid, and the like As necessary, monomer units other than the main structural unit may be copolymerized.

  Examples of the lactam or aminocarboxylic acid include lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid. .

  As the aliphatic diamine, an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used. Furthermore, an alicyclic diamine may be used. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples include aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.

  Moreover, as said aliphatic dicarboxylic acid, linear aliphatic dicarboxylic acid and alicyclic dicarboxylic acid are preferable, and also linear aliphatic dicarboxylic acid which has a C4-C12 alkylene group is especially preferable. Examples of such linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer Examples thereof include acids and functional derivatives thereof. Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

  Examples of the aromatic diamine include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene, and the like.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. It is done.

Specific polyamides include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 4, 6, polyamide 6, 6, polyamide 6, 10, polyamide 6T, polyamide 9T, polyamide 6IT, polymetaxylylene azide. Pamide (Polyamide MXD6), Isophthalic acid copolymer polymetaxylylene adipamide (Polyamide MXD6I), Polymetaxylylene sebamide (Polyamide MXD10), Polymetaxylylene decanamide (Polyamide MXD12), Poly 1,3-bis Examples include aminocyclohexane adipamide (polyamide BAC6) and polyparaxylylene sebacamide (polyamide PXD10). More preferable polyamides include polyamide 6, polyamide MXD6, and polyamide MXD6I.

  Further, as a copolymerization component of the polyamide, a polyether having at least one terminal amino group or a terminal carboxyl group and a number average molecular weight of 2000 to 20000, or an organic carboxylate of the polyether having the terminal amino group, or An amino salt of a polyether having a terminal carboxyl group can also be used. Specific examples include bis (aminopropyl) poly (ethylene oxide) (polyethylene glycol having a number average molecular weight of 2000 to 20000).

  The partially aromatic polyamide may contain a structural unit derived from a polybasic carboxylic acid having 3 or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range.

  The polyamide is basically a conventionally known melt polycondensation method in the presence of water or a melt polycondensation method in the absence of water, or a polyamide obtained by these melt polycondensation methods. It can be manufactured by a method or the like. The melt polycondensation reaction may be performed in one step or may be performed in multiple steps. These may be comprised from a batch-type reaction apparatus, and may be comprised from the continuous-type reaction apparatus. The melt polycondensation step and the solid phase polymerization step may be operated continuously or may be operated separately.

3-2-4. Polyvinyl alcohol Specific examples of polyvinyl alcohol include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer and a portion thereof, or a completely saponified product. Further, the modified product may be used.

3-2-5. Plant-derived resin Specific examples of the plant-derived resin include an overlapping portion with the above resin, but are not particularly limited, and examples thereof include aliphatic polyester-based biodegradable resins other than various known petroleum materials. Examples of the aliphatic polyester-based biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES), and the like. And polyalkylene alkanoates.

3-3. Metal In addition, in the polyesteramide compound of the present invention, when further oxygen absorption performance is required in addition to the oxygen absorption effect, Group VIII metal of the periodic table such as iron, cobalt, nickel, etc .; copper, silver, etc. One or more metal atoms selected from Group I metals such as tin, titanium, zirconium; Group V metals such as vanadium; Group VI metals such as chromium; Group VII metals such as manganese. Can be added as a compound or metal complex before the start of the polycondensation reaction, during the reaction, or during extrusion. Among these metal atoms, a group VIII metal atom is preferable from the viewpoint of oxygen absorption ability, and a cobalt atom is more preferable.

In the present invention, a compound containing a metal atom (hereinafter referred to as a metal catalyst compound) is preferably used to add and mix the metal atom into the polyesteramide compound. The metal catalyst compound is used in the form of a low-valent inorganic acid salt, organic acid salt or complex salt of the metal atom.
Examples of inorganic acid salts include halides such as chloride and bromide, sulfur oxyacid salts such as sulfates, nitrogen oxyacid salts such as nitrates, phosphorus oxyacid salts such as phosphates, and silicates. . On the other hand, examples of the organic acid salt include a carboxylate, a sulfonate, a phosphonate, and the like. The carboxylate is suitable for the purpose of the present invention, and specific examples thereof include acetic acid, propionic acid, isopropylate. On acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecane Acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, lindelic acid, tuzuic acid, petroceric acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, Examples include transition metal salts such as sulfamic acid and naphthenic acid.

  Also, metal complexes with β-diketone or β-keto acid ester can be used. Examples of the β-diketone or β-keto acid ester include acetylacetone, ethyl acetoacetate, 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, Acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis (4-methyl) Benzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane , Dibenzoylmethane, bis (4-chlorobenzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) methane, butanoylacetone, distearoylmethane, Acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane, dipivaloylmethane, and the like can be used.

Among these, carboxylate, halide, and acetylacetonate complex containing the metal atom are preferable because the oxygen absorption function is good.
One or more of the metal catalyst compounds can be added, but those containing cobalt as a metal atom are particularly excellent in oxygen absorption function and are preferably used. Cobalt stearate (II) or cobalt acetate (II) is particularly preferred because it is solid or powdery and has excellent handleability during melt mixing.

  The concentration of the metal atom added to the polyesteramide compound is not particularly limited, but it is preferably in the range of 1 to 1000 ppm, more preferably 1 to 700 ppm with respect to 100 parts by mass of the polyesteramide compound. If the addition amount of the metal atom is 1 ppm or more, in addition to the oxygen absorption effect of the polyesteramide compound of the present invention, the oxygen absorption function is sufficiently developed and the effect of improving the oxygen barrier property of the packaging material is obtained. The method for adding the metal catalyst compound to the polyesteramide compound is not particularly limited, and can be added by any method.

3-4. Oxidizing organic compound The polyesteramide composition of the present invention may further contain an oxidizing organic compound.
Oxidizing organic compounds are organic compounds that are oxidized automatically in the presence of oxygen or in the presence of any one of catalyst, heat, light, moisture, etc., and hydrogen can be easily extracted. Those having active carbon atoms that can be used in the following are preferred. Specific examples of such activated carbon atoms include those containing a carbon atom adjacent to a carbon-carbon double bond, a tertiary carbon atom having a carbon side chain attached thereto, and an active methylene group.
For example, vitamin C and vitamin E are also examples of oxidizing organic compounds. In addition, polymers such as polypropylene that have tertiary hydrogen that is easily oxidized to molecules, polymers that have a carbon-carbon double bond in the molecule, such as butadiene, isoprene, and cyclohexanone, and polymers that consist of or contain them. Is also mentioned as an example of an oxidizing organic compound. Among these, from the viewpoint of oxygen absorption capacity and processability, compounds and polymers having a carbon-carbon double bond are preferred, compounds containing a carbon-carbon double bond having 4 to 20 carbon atoms, and units derived therefrom. An oligomer or polymer containing is more preferred.

  Examples of the compound containing a carbon-carbon double bond having 4 to 20 carbon atoms include conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1, Chain non-conjugated dienes such as 4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene Cyclic such as 2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene, etc. Non-conjugated dienes; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene Down-5-norbornene, trienes such as 2-propenyl-2,2-norbornadiene and chloroprene.

These compounds are incorporated in the form of a homopolymer, a random copolymer, a block copolymer or the like alone, in combination of two or more kinds, or in combination with other monomers.
Monomers used in combination include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1- Examples include decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. In addition, monomers such as styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl acetate, methyl methacrylate, and ethyl acrylate can be used. It is.

  Specific examples of the oligomer or polymer containing a unit derived from a compound containing a carbon-carbon double bond having 4 to 20 carbon atoms include polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), Natural rubber, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), ethylene-propylene-diene rubber (EPDM), and the like can be mentioned, but are not limited to these examples. The carbon-carbon double bond in the polymer is not particularly limited, and may be present in the main chain in the form of a vinylene group or may be present in the side chain in the form of a vinyl group.

In the oligomer or polymer containing a unit derived from a compound containing the above-mentioned carbon-carbon double bond, a carboxylic acid group, a carboxylic acid anhydride group, or a hydroxyl group is introduced with a molecule, or the above-described functional group. It is preferably blended with a modified oligomer or polymer. Monomers used to introduce these functional groups include carboxylic acid groups, carboxylic anhydride groups, carboxylate groups, carboxylic acid ester groups, carboxylic acid amide groups, carbonyl groups, hydroxyl groups, and other functional groups. And an ethylenically unsaturated monomer having a group.
As these monomers, it is preferable to use unsaturated carboxylic acids or derivatives thereof, and specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, etc. α, β-unsaturated carboxylic acid, unsaturated carboxylic acid such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydroanhydride Examples include α, β-unsaturated carboxylic acid anhydrides such as phthalic acid and unsaturated carboxylic acid anhydrides such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride.

  Acid modification of an oligomer or polymer containing a unit derived from a compound containing a carbon-carbon double bond is produced by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof to the oligomer or polymer by a method known per se. However, it can also be produced by random copolymerization of the aforementioned compound containing a carbon-carbon double bond and an unsaturated carboxylic acid or derivative thereof.

  The preferable content of the oxidizing organic compound is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and still more preferably from the viewpoint of oxygen absorption performance and transparency in the polyesteramide composition. 0.5-5 mass%.

4). Use of Polyesteramide Compound and Polyesteramide Composition The polyesteramide compound and the polyesteramide composition of the present invention can be used for any application that requires oxygen barrier properties and oxygen absorption performance. For example, the polyesteramide compound of the present invention may be filled alone in a sachet or the like and used as an oxygen absorbent.
Representative examples of the polyesteramide compound and the polyesteramide composition of the present invention include, but are not limited to, molded materials such as packaging materials and packaging containers. The polyesteramide compound or the polyesteramide composition of the present invention can be used after being processed as at least a part of the molded product. For example, the polyesteramide compound or the polyesteramide composition of the present invention can be used as at least part of a film-like or sheet-like packaging material, and can also be used in bottles, trays, cups, tubes, flat bags, standing pouches, etc. It can be used as at least a part of packaging containers such as various pouches. The structure of the packaging material or the molded body of the packaging container may be a single-layer structure of a layer made of the polyesteramide compound or the polyesteramide composition of the present invention, or a layer made of the layer and another thermoplastic resin. It may be a multilayer structure combining these. Preferable specific examples of the multilayer structure include a PET layer / polyester amide compound or a layer / PET layer comprising a polyester amide composition. The thickness of the layer comprising the polyesteramide compound or polyesteramide composition of the present invention is not particularly limited, but preferably has a thickness of 1 μm or more.

There are no particular limitations on the method for producing a molded product such as a packaging material or packaging container, and any method can be used. For example, for forming a film-like or sheet-like packaging material or tube-shaped packaging material, a polyesteramide compound or a polyesteramide composition melted through a T die, a circular die, etc. is extruded from an attached extruder. can do. In addition, the film-form molded object obtained by the above-mentioned method can also be processed into a stretched film by extending | stretching this. A bottle-shaped packaging container can be obtained by injecting a melted polyesteramide compound or a polyesteramide composition into a mold from an injection molding machine, producing a preform, and then heating to a stretching temperature and blow-stretching. it can.
Also, containers such as trays and cups are manufactured by injecting a melted polyesteramide compound or polyesteramide composition into a mold from an injection molding machine, or forming a sheet-like packaging material such as vacuum forming or pressure forming. It can be obtained by molding by the method. The packaging material and the packaging container can be manufactured through various methods regardless of the above-described manufacturing method.

  The packaging material and packaging container obtained by using the polyesteramide compound and the polyesteramide composition of the present invention are suitable for storing and storing various articles. Store and store various items such as beverages, seasonings, cereals, liquids and solid processed foods that require aseptic filling or heat sterilization, chemicals, liquid daily necessities, pharmaceuticals, semiconductor integrated circuits, and electronic devices be able to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  The component composition, intrinsic viscosity, and melting point of the polyesteramide compounds and polyester compounds obtained in Examples and Comparative Examples were measured by the following methods. Further, the amount of oxygen absorbed was measured by the following method.

(1) Component composition
The component composition of the copolymer was quantified using ¹ H-NMR (400 MHz, manufactured by JEOL Ltd., trade name: JNM-AL400, measurement mode: NON ( ¹ H)). Specifically, a 5% by mass solution of a polyesteramide compound and a polyester compound was prepared using trifluoroacetic acid-d as a solvent, and ¹ H-NMR measurement was performed.

(2) Intrinsic viscosity 0.5 g of the polyesteramide compound or polyester compound is dissolved by heating in 120 g of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (mass ratio = 6: 4), and after filtration, up to 25 ° C. A sample for measurement was prepared by cooling. The measurement was performed at 25 ° C. using a capillary viscometer automatic measuring device (trade name: SS-300-L1 manufactured by Shibayama Kagaku Seisakusho Co., Ltd.).

(3) Melting point Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), DSC measurement (differential scanning calorimetry) was performed in a nitrogen stream at a heating rate of 10 ° C./min. (Tm) was determined.

(4) Oxygen absorption amount 2 g of the pulverized sample was placed in a 25 cm × 18 cm three-side sealed bag made of an aluminum foil laminated film together with cotton containing 10 ml of water, and sealed so that the air amount in the bag was 400 ml. . The humidity in the bag was 100% RH (relative humidity). After 28 days storage at 40 ° C., the oxygen concentration in the bag was measured with an oxygen concentration meter (trade name: LC-700F, manufactured by Toray Engineering Co., Ltd.), and the oxygen absorption amount (cc / g) was determined from this oxygen concentration. Calculated. The higher the value, the better the oxygen absorption performance.

Example 1
(Polymeramide compound polymerization)
In the esterification reactor, terephthalic acid (TPA), isophthalic acid (IPA), 5-sodium sulfoisophthalic acid (Na-SIPA), ethylene glycol (EG) and DL-alanine (DL-Ala) in the amounts shown in Table 1 The esterification reaction was performed for 3 hours at about 240 ° C. and about 0.3 MPa with stirring. This reaction product was transferred to a polycondensation tank, and tetrabutyl organotitanate (TBT) was charged as a catalyst. Excess ethylene glycol was distilled out of the system while stirring and heating in a polycondensation tank under nitrogen flow, and then polycondensation was performed under the reaction conditions shown in Table 1 to obtain a polyesteramide compound.

In the ¹ H-NMR chart of the polyesteramide compound 1 obtained in Example 1, an absorption peak (peak a) derived from hydrogen of the methyl group of DL-alanine appeared around 1.4 ppm. Further, an absorption peak (peak b) derived from hydrogen of the methylene group of ethylene glycol appeared in the vicinity of 4.7 ppm. Further, an absorption peak (peak c) derived from hydrogen at the 4-position of the aromatic ring of terephthalic acid, isophthalic acid and 5-sodiumsulfoisophthalic acid appeared in the vicinity of 7.7 to 8.2 ppm. In the vicinity of 8.4 to 8.7 ppm, absorption peaks (peak d) derived from hydrogen at the 3rd and 6th positions of the aromatic ring of 5-sodium sulfoisophthalic acid appeared.

The amount of DL-alanine units in the polyesteramide compound is calculated by the integrated intensity ratio of each peak and the following formula.

The amount of 5-sodium sulfoisophthalic acid unit in the polyesteramide compound is calculated from the integrated intensity ratio of each peak and the following formula.

From the above calculation, it was identified that the polyesteramide compound obtained in Example 1 contained 2.90 mol% of DL-alanine units. The molar fraction of each structural unit in the polyesteramide compound obtained in Example 1 is the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit / DL-Ala unit = 48.55 / 48.50 / 0. .05 / 2.90 (mol%) was identified.
Also in the other Examples and Comparative Examples, the component compositions of the prepared polyesteramide compound and the polyester compound were quantified by the same method.

Example 2
The same as in Example 1 except that the charged amount of DL-alanine was changed to 6 mol, the maximum reached resin temperature was changed to 255 ° C., and the charged amount of 5-sodium sulfoisophthalic acid was changed to 0.1 mol. A polyesteramide compound was obtained by this method. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit / DL-Ala unit = 47.15 / 47.06 / 0.09 / 5. .70 (mol%).

Example 3
The amount of terephthalic acid charged was changed to 48.6 mol, 5-sodium sulfoisophthalic acid was changed to 5-lithium sulfoisophthalic acid (Li-SIPA), the amount charged was changed to 0.3 mol, and DL -The polyester amide compound was obtained by the method similar to Example 1 except having changed the preparation amount of alanine to 12 mol, changing the highest achieved resin temperature to 250 degreeC, and changing reaction time to 4 hours. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Li-SIPA unit / DL-Ala unit = 44.65 / 44.38 / 0.27 / 10. .70 (mol%).

Example 4
A polyesteramide compound was obtained in the same manner as in Example 3 except that the charged amount of DL-alanine was changed to 20 mol. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Li-SIPA unit / DL-Ala unit = 41.65 / 41.40 / 0.25 / 16. .70 (mol%).

Example 5
A polyesteramide compound was obtained in the same manner as in Example 2, except that the amount of DL-alanine charged was changed to 30 mol, the maximum resin temperature was changed to 250 ° C., and the reaction time was changed to 4 hours. . The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit / DL-Ala unit = 38.45 / 38.37 / 0.08 / 23. .10 (mol%).

Example 6
A polyesteramide compound was obtained in the same manner as in Example 5 except that the charged amount of DL-alanine was changed to 40 mol. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit / DL-Ala unit = 35.70 / 35.63 / 0.07 / 28. .60 (mol%).

Example 7
A polyesteramide compound was obtained in the same manner as in Example 3 except that DL-alanine was changed to DL-2-aminobutyric acid (DL-AABA). The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG units / TPA units and IPA units / Li-SIPA units / DL-AABA units = 44.65 / 44.38 / 0.27 / 10. .70 (mol%).

Example 8
A polyesteramide compound was obtained in the same manner as in Example 3 except that DL-alanine was changed to DL-phenylalanine (DL-Phe). The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Li-SIPA unit / DL-Phe unit = 44.65 / 44.38 / 0.27 / 10. .70 (mol%).

Example 9
A polyesteramide compound was obtained in the same manner as in Example 3 except that the amount of tetrabutyl organotitanate added was changed to 50 ppm and the reaction time was changed to 2 hours. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Li-SIPA unit / DL-Ala unit = 44.65 / 44.38 / 0.27 / 10. .70 (mol%).

Example 10
A polyesteramide compound was obtained in the same manner as in Example 3 except that tetrabutyl organotitanate was changed to 150 ppm, the maximum reached resin temperature was changed to 265 ° C., and the reaction time was changed to 5 hours. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Li-SIPA unit / DL-Ala unit = 44.65 / 44.38 / 0.27 / 10. .70 (mol%).

Comparative Example 1
(Polymer compound polymerization)
In the esterification reaction tank, the amounts of terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol shown in Table 1 were charged, and after sufficient nitrogen substitution, at about 240 ° C. and about 0.3 MPa with stirring. The esterification reaction was performed for 3 hours. The reaction product was transferred to a polycondensation tank, and after adding the catalyst shown in Table 1, excess ethylene glycol was distilled out of the system while heating under stirring and nitrogen flow, and then the reaction shown in Table 1 Polycondensation was performed under conditions to obtain a polyester compound. The mole fraction of each structural unit in the obtained polyester compound was the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit = 50.00 / 49.90 / 0.10 (mol%).

Comparative Example 2
The same method as in Example 2 except that DL-alanine was changed to 2-aminoisobutyric acid (AIB) having no hydrogen at the α-position, the addition amount was changed to 12 mol, and the reaction time was changed to 4 hours. A polyesteramide compound was obtained. The molar fraction of each structural unit in the obtained polyesteramide compound is the sum of EG unit / TPA unit and IPA unit / Na-SIPA unit / AIB unit = 44.65 / 44.56 / 0.09 / 10.70. (Mol%).

The polyester compound not copolymerized with α-amino acid did not exhibit oxygen absorption performance (Comparative Example 1). Further, even a polyesteramide compound copolymerized with 2-aminoisobutyric acid, which is an α-amino acid having no tertiary hydrogen, did not show oxygen absorption performance (Comparative Example 2).
In contrast, polyesteramide compounds (polyesteramide resins and polyesteramide oligomers) copolymerized with α-amino acids having tertiary hydrogen can exhibit sufficient oxygen absorption performance and generate unpleasant odors. (Examples 1 to 10).

  The polyesteramide compound and the polyesteramide composition of the present invention are excellent in oxygen absorption performance. By using the polyesteramide compound or the polyesteramide composition of the present invention for packaging materials and packaging containers, sufficient oxygen absorption performance is exhibited, unpleasant odor is not generated, and the contents are stored in a good state. The packaging material and packaging container which can be provided can be provided.

Claims (10)

25 to 49.995 mol% of polyvalent carboxylic acid units;
25 to 49.995 mol% of polyhydric alcohol units;
A polyesteramide compound containing 0.1 to 50 mol% of a structural unit represented by the following general formula (I),
When the polyvalent carboxylic acid unit is 100 mol% of the polyvalent carboxylic acid unit,
The aromatic dicarboxylic acid unit represented by the following general formula (II) is represented by 70 to 99.99 mol%, and the sulfophthalic acid unit represented by the following general formula (III) and the following general formula (III ′). Including 0.01 to 30.0 mol% in total of units selected from metal units of sulfophthalic acid,
A polyesteramide compound, wherein the polyhydric alcohol unit contains 70 mol% or more of an aliphatic diol unit represented by the following general formula (IV) when the polyhydric alcohol unit is 100 mol%.

[In the general formula (I), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. In the general formula (II), Ar represents an arylene group not substituted with a sulfo group. In the general formulas (III) and (III ′), R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, m represents an integer of 0 to 3, and M represents a metal element. , N represents an integer of 1-5. Each R ² may be the same or different. In the general formula (IV), X represents an alkylene group having 2 to 20 carbon atoms. ] The polyesteramide compound according to claim 1, wherein R ¹ in the general formula (I) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. .   The aromatic dicarboxylic acid unit represented by the general formula (II) contains at least 70 mol% in total of at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit. The polyesteramide compound according to claim 1 or 2.   The polyesteramide compound according to any one of claims 1 to 3, wherein M in the general formula (III ') is one selected from lithium, sodium, potassium, magnesium, and calcium. The sulfophthalic acid unit represented by the general formula (III) and the sulfophthalic acid metal salt unit represented by the following general formula (III ′) are the sulfoisophthalic acid unit represented by the following general formula (IIIa) and the following general formula. The polyesteramide compound according to any one of claims 1 to 4, which is a sulfoisophthalic acid metal salt unit represented by (III'a).

[In the general formula (IIIa) and ^{(III'a), R 2, m} , M and n are the same as R ^2, m, M and n in each of the general formulas (III) or (III ') . ]   The polyesteramide compound according to claim 5, wherein m in the general formula (IIIa) or (III'a) is 0.   70 mol% in total of at least one selected from the group consisting of ethylene glycol units, 1,3-propanediol units and 1,4-butanediol units as the aliphatic diol units represented by the general formula (IV) The polyesteramide compound according to any one of claims 1 to 6, comprising the above.   The polyesteramide compound according to any one of claims 1 to 7, having an intrinsic viscosity of 0.4 dl / g or more and 1.5 dl / g or less.   The polyesteramide compound according to any one of claims 1 to 7, which has an intrinsic viscosity of 0.1 dl / g or more and less than 0.4 dl / g.   The polyesteramide composition containing the polyesteramide compound in any one of Claims 1-9.