JP6761206B2 - Polyglycolic acid resin composition - Google Patents

Description

The present invention relates to a polyglycolic acid resin composition, and more specifically, a polyglycolic acid resin composition containing a crystal nucleating agent composed of an amide compound, a polyglycolic acid resin molded product obtained from the resin composition, and the resin. The present invention relates to a laminated body including a layer made of a molded body.

From the viewpoint of protecting the natural environment, research on aliphatic polyesters that can be biodegradable in the natural environment is being vigorously conducted. Among them, polyglycolic acid resin has biocompatibility, is easily hydrolyzable, has high gas barrier properties, and has excellent mechanical properties. Therefore, sheets, films, packaging containers, bottles, and medical treatments can be used alone or in combination with other resins. It is expected to be used as a part such as sutures and molding materials.
However, since the polyglycolic acid resin has a slow crystallization rate, it has a drawback that it softens at a temperature equal to or higher than the glass transition point (Tg) when it is not sufficiently crystallized. Further, the crystallinity of the polyglycolic acid resin is improved by heat treatment (annealing) at a predetermined temperature in the mold during injection molding, but the crystallinity is slow, so that the molding cycle is poor and the productivity is low. There is a problem in. Furthermore, when crystallization is performed using only the polyglycolic acid resin, spherulites having a size equal to or larger than the wavelength of light that causes light scattering grows, which impairs the appearance (opaqueness) and mechanical properties of the molded product. It causes.

In order to solve these problems, a method of adding a crystal nucleating agent to a polyglycolic acid resin is being studied. The crystal nucleating agent becomes a primary crystal nuclei of a crystalline polymer, promotes crystal growth, miniaturizes the spherulite size, and promotes crystallization.
So far, as crystal nucleating agents for polyglycolic acid resins, carbon-based fillers, talc, kaolin, barium sulfate, aromatic carboxylic acid metal salts, etc. (Patent Document 1), graphite, hydroxyapatite, high melting point amide compounds, etc. (Patent). Document 2), carboxylic acid derivative (Patent Document 3) and the like are disclosed.

Japanese Unexamined Patent Publication No. 2008-260902 International Publication No. 2011/024653 Pamphlet International Publication No. 2014/07734 Pamphlet

As described above, various crystal nucleating agents have been proposed to increase the crystallization rate of the polyglycolic acid resin, but in recent years, in order to realize higher molding processability and heat resistance of the polyglycolic acid resin. In addition, a more effective crystal nucleating agent is desired.
Therefore, according to the present invention, the crystallization rate is faster than that of the polyglycolic acid resin to which a crystal nucleating agent suitable for promoting the crystallization of the polyglycolic acid resin is added, and higher molding processability and heat resistance can be improved. An object of the present invention is to provide a polyglycolic acid resin composition, a polyglycolic acid resin molded body obtained by crystallizing the polyglycolic acid resin composition, and a laminate having a layer made of the polyglycolic acid resin molded body. To do.

As a result of diligent studies to achieve the above object, the present inventors have been able to promote the crystallization of the polyglycolic acid resin by adding a specific amide compound as a crystal nucleating agent to the polyglycolic acid resin. I found it possible.

（式中、Ａは炭素原子数１乃至１０のアルキレン基を表し、Ｒ^１及びＲ^２はそれぞれ独立して炭素原子数１乃至６のアルキル基を表し、Ｒ^３乃至Ｒ^１０はそれぞれ独立して、水素原子、炭素原子数１乃至６のアルキル基、炭素原子数２乃至７のアシル基、炭素原子数２乃至７のアルコキシカルボニル基、アミノ基、炭素原子数１乃至６のアシルアミノ基、ヒドロキシ基、又は炭素原子数１乃至６のアルコキシ基を表す。）
第２観点として、前記Ａが炭素原子数２乃至８のアルキレン基である、第１観点のポリグリコール酸樹脂組成物に関する。
第３観点として、前記Ａが、エチレン基、トリメチレン基、テトラメチレン基及びヘキサメチレン基からなる群から選ばれる基である、第２観点のポリグリコール酸樹脂組成物に関する。
第４観点として、前記Ａがヘキサメチレン基である、第１観点乃至第３観点のうち何れか一つのポリグリコール酸樹脂組成物に関する。
第５観点として、前記Ｒ^３乃至Ｒ^１０が水素原子である、第１観点乃至第４観点のうち何れか一つのポリグリコール酸樹脂組成物に関する。
第６観点として、前記Ｒ^１及びＲ^２がメチル基である、第１観点乃至第５観点のうち何れか一つのポリグリコール酸樹脂組成物に関する。
第７観点として、前記結晶核剤の含有量が、前記ポリグリコール酸樹脂１００質量部に対して０．００１〜１０質量部である、第１観点乃至第６観点のうち何れか一つのポリグリコール酸樹脂組成物に関する。
第８観点として、第１観点乃至第７観点のうち何れか一つのポリグリコール酸樹脂組成物の結晶化物である、ポリグリコール酸樹脂成形体に関する。
第９観点として、第８観点のポリグリコール酸樹脂成形体からなる層を具備する積層体に関する。 That is, the present invention relates to a polyglycolic acid resin composition containing a polyglycolic acid resin and a crystal nucleating agent composed of an amide compound represented by the formula [1] as a first aspect.

(In the formula, A represents an alkylene group having 1 to 10 carbon atoms, R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms, and R ^{3 to} R ¹⁰ independently represent each. , Hydrogen atom, alkyl group with 1 to 6 carbon atoms, acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, amino group, acylamino group with 1 to 6 carbon atoms, hydroxy group , Or an alkoxy group having 1 to 6 carbon atoms.)
As a second aspect, it relates to the polyglycolic acid resin composition of the first aspect, wherein A is an alkylene group having 2 to 8 carbon atoms.
As a third aspect, the polyglycolic acid resin composition of the second aspect, wherein A is a group selected from the group consisting of an ethylene group, a trimethylene group, a tetramethylene group and a hexamethylene group.
As a fourth aspect, the present invention relates to a polyglycolic acid resin composition according to any one of the first to third aspects, wherein A is a hexamethylene group.
As a fifth aspect, relates to the R ³ to R ¹⁰ is a hydrogen atom, the first aspect to any one of the polyglycolic acid resin composition of the fourth aspect.
A sixth aspect relates to R ¹ and R ² are methyl groups, the first aspect to any one of the polyglycolic acid resin composition of the fifth aspect.
As a seventh aspect, the polyglycol of any one of the first to sixth aspects, wherein the content of the crystal nucleating agent is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyglycolic acid resin. The present invention relates to an acid resin composition.
As the eighth aspect, the present invention relates to a polyglycolic acid resin molded article which is a crystallized product of any one of the first to seventh aspects of the polyglycolic acid resin composition.
As a ninth aspect, the present invention relates to a laminate including a layer made of the polyglycolic acid resin molded article according to the eighth aspect.

The polyglycolic acid resin composition of the present invention has an improved crystallization promoting effect of the polyglycolic acid resin by using a specific amide compound as a crystal nucleating agent, and is excellent in molding processability and heat resistance. It is possible to provide a polyglycolic acid resin composition, a polyglycolic acid resin molded body obtained by crystallizing the polyglycolic acid resin composition, and a laminate having a layer made of the polyglycolic acid resin molded body. ..
The molded product of the present invention can be suitably used as a biodegradable material such as a bioabsorbable suture, a bioabsorbable stent, and a nerve regeneration induction tube.
The molded product of the present invention can be suitably used as a gas barrier layer for sheets, films, packaging containers, bottles, etc., and as a material for shale gas drilling.

Hereinafter, the present invention will be described in more detail.

<Polyglycolic acid resin composition>
The polyglycolic acid (hereinafter, also referred to as PGA) resin composition of the present invention is composed of a PGA resin and a crystal nucleating agent composed of an amide compound.

[PGA resin]
The PGA resin used in the present invention includes the formula [2].
-[O-CH _2- C (= O)]-[2]
Glycolic acid homopolymers consisting only of glycolic acid repeating units represented by (hereinafter, also referred to as PGA homopolymers, including ring-opening polymers of glycolide, which is a bimolecular cyclic ester of glycolic acid), said glycolic acid repeating. Examples thereof include polyglycolic acid copolymers containing units (hereinafter, also referred to as PGA copolymers). Such PGA resins may be used alone or in combination of two or more.

Examples of the comonomer used together with the glycolic acid monomer in the production of the PGA copolymer include lactides such as dilactide (also known as 1,4-dioxane-2,5-dione); β-propiolactone and β-butyrolactone. , Β-Pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone and other lactones; trimethylene carbonate (also known as 1,3-dioxane-2-one) and the like cyclic Carbonates; Cyclic esters such as ethylene oxalate (also known as 1,4-dioxane-2,3-dione); Cyclic ether esters such as 1,4-dioxane-2-one; 1,3-Dioxane and the like Cyclic ethers; Cyclic amides such as ε-caprolactam; Hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6-hydroxycaproic acid or alkyl esters thereof; Ethylene Examples thereof include a substantially equimolar mixture of aliphatic diols such as glycol and 1,4-butanediol and aliphatic dicarboxylic acids such as succinic acid and adipic acid or alkyl esters thereof. These comonomer may be used alone or in combination of two or more. Of these comonomer, hydroxycarboxylic acids are preferable from the viewpoint of heat resistance.

Examples of the catalyst used when the PGA resin is produced by ring-opening polymerization of glycolide include tin compounds such as tin halide and tin organic carboxylate; titanium compounds such as alkoxy titanate; and aluminum compounds such as alkoxyaluminum. Examples thereof include known ring-opening polymerization catalysts such as zirconium compounds such as zirconium acetylacetone; and antimony compounds such as antimony halide and antimony oxide.

The PGA resin can be produced by a conventionally known polymerization method, and the polymerization temperature thereof is preferably 120 to 300 ° C, more preferably 130 to 250 ° C, particularly preferably 140 to 240 ° C, and 150 to 230. ° C is most preferred. When the polymerization temperature is 120 ° C. or higher, the polymerization can be sufficiently promoted, and when the polymerization temperature is 300 ° C. or lower, the thermal decomposition of the produced resin can be further suppressed.
The polymerization time of the PGA resin is preferably 2 minutes to 50 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours. When the polymerization time is 2 minutes or more, the polymerization can be sufficiently proceeded, and when the polymerization time is 50 hours or less, a more non-colored resin can be obtained.

In the PGA resin used in the present invention, the content of the glycolic acid repeating unit represented by the formula [2] is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. 100% by mass is particularly preferable. By setting the content of the glycolic acid repeating unit to 70% by mass or more, the effects as a PGA resin such as biodegradability, hydrolyzability, gas barrier property, mechanical strength, and heat resistance can be further obtained.

The weight average molecular weight Mw of the PGA resin is preferably 30,000 to 800,000, more preferably 50,000 to 500,000. When the weight average molecular weight Mw is 30,000 or more, sufficient mechanical strength of the PGA resin molded product can be obtained, and when it is 800,000 or less, melt extrusion or injection molding can be performed more easily. The weight average molecular weight Mw is a value converted to polymethyl methacrylate measured by gel permeation chromatography (GPC).

The melt viscosity (temperature: 270 ° C., shear rate: 122sec ^-1 ) of the PGA resin is preferably 50 to 3,000 Pa · s, more preferably 100 to 2,000 Pa · s, and 100 to 1,000 Pa. -S is preferable. When the melt viscosity is 50 Pa · s or more, sufficient mechanical strength of the PGA resin molded product can be obtained, and when it is 3,000 Pa · s or less, melt extrusion or injection molding can be performed more easily.

Further, the PGA resin used in the present invention may be a blend polymer containing a PGA homopolymer or a PGA copolymer as a main component and other resins. Examples of other resins include biodegradable resins other than PGA resin, which will be described later, general-purpose thermoplastic resins, general-purpose thermoplastic engineering plastics, and the like.

Examples of biodegradable resins other than the above-mentioned PGA resin include polylactic acid (PLA), poly (3-hydroxybutyric acid) (PHB), and a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoic acid (PHBH). Polyhydroxyalkanoic acid; polyester resins such as polycaprolactone, polybutylene succinate, polybutylene succinate / adipate, polybutylene succinate / carbonate, polyethylene succinate, polyethylene succinate / adipate; polyvinyl alcohol; Modified starch; cellulose acetate; chitin; chitosan; lignin and the like.

Examples of the general-purpose thermoplastic resin include polyethylene (PE), polyethylene copolymer, polypropylene (PP), polypropylene copolymer, polybutylene (PB), ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer. Polystyrene resins such as coalesced (EEA), poly (4-methyl-1-pentene); polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer weight Examples thereof include polystyrene resins such as copolymers (ABS); polyvinyl chloride resins; polyurethane resins; phenol resins; epoxy resins; amino resins; unsaturated polyester resins.

Examples of the general-purpose engineering plastic include polyamide resin; polyimide resin; polycarbonate resin; polyphenylene ether resin; modified polyphenylene ether resin; polyester resin such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyacetal resin; polysulfone resin. ; Polyphenylene sulfide resin and the like can be mentioned.

[Crystal nucleating agent consisting of an amide compound]
The crystal nucleating agent used in the present invention comprises an amide compound represented by the formula [1].

In the formula [1], A represents an alkylene group having 1 to 10 carbon atoms, R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms, and R ^{3 to} R ¹⁰ are independent. Then, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an amino group, and an acylamino group having 1 to 6 carbon atoms, It represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms represented by A are methylene group, ethylene group, trimethylene group, 1-methylethylene group, propane-2,2-diyl group, tetramethylene group and 1-methyltri. Methylene group, 1,1-dimethylethylene group, butane-2,2-diyl group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2 -Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1 -Dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyltrimethylene group, 1,2,2-trimethyltri Examples include chain or branched alkylene groups such as methylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group. Be done. Of these, an alkylene group having 2 to 8 carbon atoms is preferable, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group are more preferable, and a hexamethylene group is particularly preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert. -Butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group and the like can be mentioned. Of these, a methyl group is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{3 to} R ¹⁰ include the same groups as those exemplified in R ¹ and R ² described above.

The acyl group having 2 to 7 carbon atoms represented by R ^{3 to} R ¹⁰ is a group in which a carbonyl group is bonded to an alkyl group having 1 to 6 carbon atoms, that is, an acetyl group, a propionyl group, a butyryl group, or an isobutylyl group. , Pentanoyl group, 2-methylbutanoyl group, 3-methylbutanoyl group, pivaloyl group, n-hexanoyl group, 4-methylpentanoyl group, 3,3-dimethylbutanoyl group, heptanoyle group, cyclohexanecarbonyl group, etc. Can be mentioned.

The alkoxycarbonyl group having 2 to 7 carbon atoms represented by R ^{3 to} R ¹⁰ is a group in which a carbonyl group is bonded to an alkoxy group having 1 to 6 carbon atoms, that is, a methoxycarbonyl group, an ethoxycarbonyl group, or n−. Propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group , N-hexyloxycarbonyl group, cyclohexyloxycarbonyl group and the like.

Examples of the acylamino group having 1 to 6 carbon atoms represented by R ^{3 to} R ¹⁰ include an acetamide group, a propionamide group, a butylamide group, an isobutylamide group, a pentanamide group, a 2-methylbutaneamide group, and a 3-methylbutaneamide group. Examples thereof include a group, a pivalamide group, an n-hexaneamide group, a 4-methylpentaneamide group, a 3,3-dimethylbutaneamide group, a heptaneamide group, a cyclohexanecarboxamide group and the like.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ^{3 to} R ¹⁰ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-. Examples thereof include a butoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, an n-hexyloxy group and a cyclohexyloxy group.

As the above R ^{3 to} R ¹⁰ , a hydrogen atom is preferable.

The production method of the amide compound represented by the formula [1] is not particularly limited, but a carboxylic acid or an activator thereof (acid halide, acid anhydride, acid azide, active ester, etc.) and anilins are used. , Can be easily obtained by amidation by a conventionally known method.
Specifically, for example, the method shown in the formula [3] can be mentioned.

In the formula [3], A and R ^{1 to} R ¹⁰ have the same meanings as described above. The X is not particularly limited as long as it is a group capable of forming an amide bond, but is not particularly limited, but is a hydroxy group; an alkoxy group such as a methoxy group or an ethoxy group; a halogen atom such as a chlorine atom or a bromine atom; an acyloxy group such as an acetoxy group; Azido group; 2,5-dioxopyrrolidine-1-yloxy group and the like. When a plurality of anilines different from each other are used, one may be reacted first and then the other may be reacted, or both may be reacted at the same time.

When the amide compound represented by these formula [1] is commercially available, a commercially available product can also be used.

The amount of the crystal nucleating agent composed of the amide compound represented by the formula [1] added is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the PGA resin. Is 0.1 to 2 parts by mass. By setting the addition amount to 0.001 part by mass or more, a sufficient crystallization rate can be obtained. Further, even if the addition amount exceeds 10 parts by mass, the crystallization rate is not further increased, so that it is economically advantageous to use it in an amount of 10 parts by mass or less.

[Other additives]
A known inorganic filler may be added to the PGA resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, silica, kaolin, clay, wolastonite, glass beads, glass flakes, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide and the like. .. The shape of these inorganic fillers may be fibrous, granular, plate-like, needle-like, spherical, or powder. These inorganic fillers can be used within 300 parts by mass with respect to 100 parts by mass of PGA resin.

A known flame retardant may be added to the PGA resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of the flame retardant include halogen-based flame retardants such as bromine and chlorine; anti-mon flame retardants such as antimon trioxide and antimon pentoxide; and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds. ; Phosphonic flame retardants such as red phosphorus, phosphate esters, ammonium polyphosphate, phosphazene; melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate / melam -Melamine-based flame retardants such as melem compound salt, melamine alkylphosphonate, melamine phenylphosphonate, melamine sulfate, and melam methanesulfonate; fluororesins such as PTFE can be mentioned. These flame retardants can be used within 200 parts by mass with respect to 100 parts by mass of PGA resin.

Further, additives generally added to the PGA resin composition of the present invention as needed, as long as the effects of the present invention are not impaired, such as end sealants, hydrolysis inhibitors, heat stabilizers, etc. Light stabilizers, heat ray absorbers, ultraviolet absorbers, antioxidants, impact improvers, plasticizers, compatibilizers, various coupling agents such as silane, titanium, and aluminum, foaming agents, antistatic agents, and release agents. Molds, lubricants, antibacterial antifungal agents, pigments, dyes, fragrances, various other fillers, other crystal nucleating agents, and other thermoplastic resins may be appropriately added.

[Method for producing polyglycolic acid resin composition]
The PGA resin composition of the present invention can be produced by mixing the PGA resin and a crystal nucleating agent composed of the amide compound. The method for mixing the crystal nucleating agent is not particularly limited. For example, a method of mixing the crystal nucleating agent with a PGA resin or a composition containing a PGA resin and another additive before molding, or a PGA resin or PGA resin at the time of molding. Examples thereof include a method of mixing a crystal nucleating agent with a composition containing the above and other additives (for example, side feed). Further, when synthesizing a PGA resin, it is also possible to produce a PGA resin composition by mixing a crystal nucleating agent with a monomer such as glycolic acid.

In the PGA resin composition of the present invention, the temperature lowering crystallization temperature (temperature at which the resin crystallizes in the process of cooling the molten resin composition) Tcc is, for example, 184 ° C. or higher at a temperature lowering rate of 20 ° C./min. Some are preferable, those having a temperature of 186 ° C. or higher are more preferable, and those having a temperature of 188 ° C. or higher are particularly preferable.

<Polyglycolic acid resin molded product>
The PGA resin molded product of the present invention is composed of the crystallized PGA resin and a crystal nucleating agent composed of the amide compound. The spherulite diameter of the PGA resin molded product of the present invention is preferably 30 μm or less, more preferably 20 μm or less. By setting the spherulite diameter to 30 μm or less, a PGA resin molded product having a smoother surface can be obtained.
Such a PGA resin molded product can be obtained, for example, by using the PGA resin composition of the present invention and crystallizing the PGA resin contained therein. The method for crystallizing the PGA resin is not particularly limited. For example, in the process of molding the PGA resin composition into a predetermined shape, the PGA resin composition may be heated to a crystallization temperature or higher and then cooled. Further, in the above process, the PGA resin composition is heated to a temperature equal to or higher than the melting point and then rapidly cooled to form an amorphous molded product, which can also be heated to crystallize.
Since the PGA resin molded product of the present invention has a small spherulite diameter and is uniform in diameter, it has excellent gas barrier properties, mechanical strength, and heat resistance.

When molding the PGA resin composition of the present invention, various molded products can be easily manufactured by using conventional molding methods such as general injection molding, blow molding, vacuum forming, and compression molding.
Further, the PGA resin has been proposed to be used for carbonated beverage bottles and the like by taking advantage of its characteristics (high gas barrier property). An injection blow is a typical molding method for this bottle.
Injection blow molding is a method in which a test tubular bottomed parison (preform) is injection-molded by injection molding, and this parison is blow-molded in a supercooled state or above the glass transition point. In detail, two more moldings are performed. It is classified into methods (hot parison method, cold parison method).
In the hot parison method, after injection molding of parison, the temperature is adjusted at a temperature below the melting point without solidification, and blow molding is performed. At this time, crystallization of the bottle occurs when the resin is cooled from the molten state, and the higher the crystallization occurs on the higher temperature side, the faster the crystallization of the resin occurs, indicating that the performance of the crystal nucleating agent is high. In the DSC measurement, the temperature-decreasing crystallization temperature Tcc is an index.
On the other hand, in the cold parison method, after injection molding of the parison, the parison is once cooled and solidified, then reheated to the glass transition point or higher, the temperature is adjusted, and then blow molding is performed. At this time, the crystallization of the bottle occurs when the resin is heated to a temperature higher than the glass transition point, and the resin crystallizes faster as the crystallization occurs on the lower temperature side, and the performance of the crystal nucleating agent is excellent. Is shown. In the DSC measurement, the temperature rise crystallization temperature (the temperature at which the resin crystallizes in the process of raising the temperature of the amorphous resin composition below the glass transition point) Tch is used as an index.
The PGA resin composition of the present invention can be suitably molded by any injection blow molding.

<Laminated body>
The laminate of the present invention includes a layer made of the PGA resin molded product of the present invention, and includes two or more layers, a layer made of the PGA resin molded product, and another layer adjacent thereto. There is no particular limitation as long as it does. Examples of the other layer adjacent to the layer made of the PGA resin molded product include a layer made of a thermoplastic resin, a layer made of paper, a layer made of an adhesive, and the like.

Examples of the thermoplastic resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polybutylene succinate, and polyethylene succinate / adipate. Polyester resins such as polylactic acid (PLA), poly3-hydroxybutyrate (PHB), polycaprolactone; polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer (EVOH) , Polyethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) and other polyolefin resins; polystyrene (PS), styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS) ), Polyethylene-based resin such as methyl methacrylate-styrene copolymer (MS); polycarbonate resin; polyvinyl chloride resin; polyvinylidene chloride resin; polyamide resin such as 6-nylon, 6,6-nylon; polyimide resin; poly Examples thereof include (meth) acrylic resins such as methyl methacrylate (PMMA); sulfide resins such as polyphenylene sulfide resins; and polyurethane resins. These thermoplastic resins may be used alone or in combination of two or more.
Among them, a polyester resin is preferable from the viewpoint of obtaining a laminate that satisfies both desired transparency and gas barrier properties according to the application, and an aromatic polyester resin in which at least one of a diol component and a dicarboxylic acid component is an aromatic compound. Is more preferable, and an aromatic polyester resin obtained from an aromatic dicarboxylic acid is particularly preferable.

In such a laminated body, the composition ratio of the layer made of the PGA resin molded product is preferably 1 to 10% on a mass basis (approximately equal to the thickness standard). By setting the composition ratio of the layer made of the PGA resin molded body to 1% by mass or more, sufficient gas barrier properties of the laminated body can be obtained. Further, when the content is 10% by mass or less, a large amount of stress is not required during blow molding, and the transparency of the laminated body can be maintained.

Specific embodiments of the laminate of the present invention include a multilayer film, a multilayer sheet, and a molded container such as a multilayer hollow container. Examples of such a laminate include those formed by coextrusion molding, co-injection molding and the like, and those formed by stretch molding by co-extrusion blow molding, co-injection blow molding and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, the devices and conditions used for the analysis of the physical properties of the sample are as follows.

(1) 5% weight loss temperature (Td _5% )
Equipment: Thermo plus TG8120 manufactured by Rigaku Co., Ltd.
Measurement conditions: Under air atmosphere Heating rate: 10 ° C / min (25-500 ° C)
(2) Differential scanning calorimetry (DSC)
Equipment: Diamond DSC manufactured by Perkin Elmer Japan Co., Ltd.

[Synthesis Example 1] Production of N ¹ , N ⁵ -bis (4-acetamide phenyl) glutaramide In a reaction flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 4-aminoacetanilide [Tokyo Kasei Kogyo Co., Ltd.] Manufactured by 3.00 g (20 mmol), triethylamine [manufactured by Tokyo Kasei Kogyo Co., Ltd.] 2.02 g (20 mmol) and N, N-dimethylacetamide 45.2 g (9 times the total mass of 4-aminoacetanilide and triethylamine) ) Was charged and cooled in an ice bath with stirring. In this solution, 1.69 g (10 mmol) of glutaryl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 15.2 g of N, N-dimethylacetamide (9 times the mass of glutaryl chloride). The mixture was slowly added dropwise and stirred for 3 hours. After adding water to the reaction mixture, the product was filtered under reduced pressure, washed with a mixed water-methanol solution (mass ratio 7: 3), and dried to obtain the target product (Compound A) as a white powder.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 342.4 ° C.

[Synthesis Example 2] Production of N ¹ , N ⁸ -bis (4-acetamidophenyl) octaneamide Synthesis except that glutalyl chloride was changed to suberoyl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] 2.11 g (10 mmol). The same procedure as in Example 1 was carried out to obtain the target product (Compound B) as a white powder.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 337.3 ° C.

[Synthesis Example 3] Production of N ¹ , N ⁴ -bis (4-acetamide phenyl) terephthalamide In a reaction flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 4-aminoacetanilide [Tokyo Kasei Kogyo Co., Ltd.] Manufactured by] 1.63 g (11 mmol), triethylamine [manufactured by Tokyo Kasei Kogyo Co., Ltd.] 1.00 g (9.9 mmol) and N, N-dimethylacetamide 23.7 g (9 based on the total mass of 4-aminoacetanilide and triethylamine) (Double amount) was charged and cooled in an ice bath with stirring. In this solution, 1.00 g (4.9 mmol) of terephthaloyl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] is dissolved in 9.0 g of N, N-dimethylacetamide (9 times the mass of terephthaloyl chloride). The solution was slowly added dropwise and stirred for 3 hours. The reaction mixture was added dropwise to 245 g of a water-methanol mixed solution (mass ratio 7: 3) (7.5 times the total mass of N, N-dimethylacetamide used), and the product was precipitated in a slurry state. The obtained slurry was filtered under reduced pressure, washed with a mixed water-methanol solution (mass ratio 7: 3), and dried to obtain the target product (Compound W) as a white powder.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 442.9 ° C.

[Synthesis Example 4] Production of N ¹ , N ⁴ -bis (4-acetylphenyl) terephthalamide 4-Aminoacetophenone [manufactured by Tokyo Chemical Industry Co., Ltd.] 1.47 g (11 mmol) was changed. Was operated in the same manner as in Synthesis Example 3 to obtain the target product (Compound X) of white powder.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 337.6 ° C.

[Synthesis Example ^{5] N} 1, N ⁴ - except that the preparation of 4-amino-acetanilide diphenyl terephthalamide was changed to aniline [Tokyo Chemical Industry Co., Ltd.] 1.01 g (11 mmol) is same procedure as Synthesis Example 3 , The target product (Compound Y) of white powder was obtained.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 285.8 ° C.

[Synthesis Example 6] Production of N ¹ , N ⁶ -diphenyl adipamide 4-Aminoacetanilide was added to aniline [manufactured by Tokyo Chemical Industry Co., Ltd.] 1.12 g (12 mmol), and the amount of triethylamine charged was 1.10 g (11 mmol). ), The terephthaloyl chloride was changed to 1.00 g (5.5 mmol) of adipoyl dichloride [manufactured by Tokyo Chemical Industry Co., Ltd.] in the same manner as in Synthesis Example 3, and the target product was a white powder. (Compound Z) was obtained.
The 5% weight loss temperature (Td _5% ) of the obtained target product was 313.1 ° C.

[Examples 1 and 2]
The PGA resin [Kurehax (registered trademark) manufactured by Kureha Corporation] was heated by a hot press at 270 ° C. to melt it, and then rapidly cooled with ice water. This resin was dried under reduced pressure at room temperature for 6 hours to obtain a film-like amorphous PGA resin.
Synthesis Example 1 as a crystal nucleating agent in a solution prepared by dissolving 100 parts by mass of this amorphous PGA resin in 2,000 parts by mass of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIPA). 1 part by mass of compound A or compound B obtained in 2 and 2 was added, and the mixture was stirred at room temperature (about 23 ° C.) for 30 minutes to obtain a uniform dispersion. HFIPA of the dispersion was distilled off with an evaporator to obtain a PGA resin composition containing a crystal nucleating agent.
About 1 mg was cut out from the obtained PGA resin composition, and the temperature-decreasing crystallization temperature Tcc was evaluated using DSC. The evaluation was based on the peak heat generation derived from the crystallization of PGA resin observed when the temperature was raised to 270 ° C. at a heating rate of 100 ° C./min, held for 1 minute, and then cooled at a cooling rate of 20 ° C./min. The temperature of was measured as Tcc. The larger the Tcc value, the faster the crystallization rate under the same conditions, indicating that the crystal nucleating agent has an excellent effect. The results are also shown in Table 1.

[Comparative Example 1]
The operation and evaluation were carried out in the same manner as in Example 1 except that the crystal nucleating agent was not added. The results are also shown in Table 1.

[Comparative Examples 2 to 5]
The operation and evaluation were carried out in the same manner as in Example 1 except that the compounds W, X, Y and Z obtained in Synthesis Examples 3 to 6 were used as the crystal nucleating agent. The results are also shown in Table 1.

From the results in Table 1, those using a specific amide compound as the crystal nucleating agent (Examples 1 and 2), those using no crystal nucleating agent (Comparative Example 1), and those using other amide compounds (comparison). It showed a higher Tcc as compared with Examples 2 to 5), and was confirmed to have a crystallization promoting effect. That is, by adding a specific amide compound as a crystal nucleating agent to the PGA resin, it has become possible to increase the crystallization rate of the PGA resin and provide a PGA resin composition having excellent heat resistance and molding processability. ..

Claims (9)

A polyglycolic acid resin composition containing a polyglycolic acid resin and a crystal nucleating agent composed of an amide compound represented by the formula [1].

(In the formula, A represents an alkylene group having 1 to 10 carbon atoms, R ¹ and R ² independently represent an alkyl group having 1 to 6 carbon atoms, and R ^{3 to} R ¹⁰ independently represent each. , Hydrogen atom, alkyl group with 1 to 6 carbon atoms, acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, amino group, acylamino group with 1 to 6 carbon atoms, hydroxy group , Or an alkoxy group having 1 to 6 carbon atoms.) The polyglycolic acid resin composition according to claim 1, wherein A is an alkylene group having 2 to 8 carbon atoms. The polyglycolic acid resin composition according to claim 2, wherein A is a group selected from the group consisting of an ethylene group, a trimethylene group, a tetramethylene group and a hexamethylene group. The polyglycolic acid resin composition according to any one of claims 1 to 3, wherein A is a hexamethylene group. The polyglycolic acid resin composition according to any one of claims 1 to 4, wherein R ^{3 to} R ¹⁰ are hydrogen atoms. The polyglycolic acid resin composition according to any one of claims 1 to 5, wherein R ¹ and R ² are methyl groups. The polyglycolic acid resin according to any one of claims 1 to 6, wherein the content of the crystal nucleating agent is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyglycolic acid resin. Composition. A polyglycolic acid resin molded product which is a crystallized product of the polyglycolic acid resin composition according to any one of claims 1 to 7. A laminated body including a layer made of the polyglycolic acid resin molded product according to claim 8.