JP3593828B2 - Polyamide resin composition for inner layer of laminated bottle and laminated bottle - Google Patents

Description

（式中、Ｒ¹ は２価の炭化水素残基、Ｒ² およびＲ³ は１価の炭化水素基、Ｒ⁴およびＲ⁵ は水素原子または１価の炭化水素基を示す）
前記一般式（Ｉ）で表されるビスアミド化合物としては、例えば、エチレンジアミン、プロピレンジアミン、ブチレンジアミン等のジアミンとステアリン酸、ヘキサン酸、オクタン酸等の脂肪酸との反応によって得られるアルキレンビス脂肪酸アミドがある。
【００２４】
また、前記一般式（ＩＩ）で表されるビスアミド化合物としては、例えば、メチルアミン、エチルアミン、ブチルアミン等のアルキルアミンとテレフタル酸、コハク酸、アジピン酸等のジカルボン酸との反応によって得られる。これらのビスアミド化合物は一種のみ用いても良く、また、二種以上を組み合わせて使用しても良い。
【００２５】
また、本発明に用いる脂肪酸金属塩（Ｃ）としては、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸カルシウム、ステアリン酸アルミニウム、オレイン酸カリウム、酢酸ナトリウム、酢酸カリウム等から選ばれる１種以上であるが、中でも炭素原子数１５以上の脂肪酸の金属塩が好ましい。これらの脂肪酸金属塩も、一種のみ用いても良く、二種以上を組み合わせて使用しても良い。
【００２６】
また本発明においては、ビスアミド化合物（Ｂ）と脂肪酸金属塩（Ｃ）を組み合わせて使用しても良い。
【００２７】
ビスアミド化合物あるいは脂肪酸金属塩の配合量は、ポリアミド１００重量部に対し、０．０１重量部〜５重量部が好ましく、さらに好ましくは０．１重量部〜３重量部である。この配合量が少なすぎると十分な剥離性が得られず、配合量が多すぎると成形時に内側層に穴空き等が発生しやすくなり好ましくない。そして、最も好ましい配合量は０．５〜２重量部である。
【００２８】
ビスアミド化合物あるいは脂肪酸金属塩を添加する方法としては、重合時に添加する方法、あるいはペレットにドライブレンドで添加する方法、ペレットとビスアミド化合物あるいは脂肪酸金属塩を押出し機を用いて溶融混練する方法のいずれでも構わない。最終的にブロ−成形されたポリアミド樹脂中にビスアミド化合物あるいは脂肪酸金属塩が含有されていれば有効であり、本発明はこれらの添加方法に束縛されるものではない。
【００２９】
上記ポリアミド樹脂を積層剥離ボトルに成形する方法としては、上記ポリアミド樹脂組成物を内側層に用い、ポリアミド以外の熱可塑性樹脂または熱可塑性樹脂組成物を外側層として、当業界で一般的な積層剥離ボトルの成形方法、例えばブロ−成形で行うことができる。また、積層ボトルでは、内側層と外側層の間に中間層を設けることも任意である。
【００３０】
ポリアミド以外の熱可塑性樹脂としては、ポリオレフィン、ポリエステル、ポリ塩化ビニル、ポリカーボネートなどが挙げられるが、中でもポリオレフィンが好ましい。
【００３１】
また、本発明では、必要に応じて本発明のポリアミド樹脂に、酸化防止剤、耐熱剤、可塑剤、無機充填剤、その他の添加剤、その他の樹脂を配合することも可能であり、その結果、更に付加価値の高い積層剥離ボトルを得ることも可能である。
【００３２】
【実施例】
以下に、実施例を挙げて本発明を具体的に説明する。
【００３３】
（１）融点の測定
示差走査熱量計（ＤＳＣ）を用いて、試料重量１０ｍｇ、昇温速度２０℃／分でポリアミドの融点を測定した。
【００３４】
（２）積層剥離ボトルの剥離性
外側層にポリエチレンを用い、内側層にポリアミド樹脂組成物を用いて、共押出しブロ−成形により外側層の厚さ１．５ｍｍ、内側層の厚さ０．２ｍｍである図１に示した積層剥離ボトルを成形した。図１（ａ）、（ｂ）において、１は外側層、２は内側層、３は大気導入孔である。
【００３５】
尚、大気導入孔３については図２に示したように、ボトル口部から吸引パッド４´を有する可撓性パイプ４を挿入し、吸引パッド４´を内側層２の内側に当接させた状態で吸引を行ない、外側層と内側層を強制的に剥離させる。得られた剥離部分に対して、外側層からドリル５で穿孔し、大気導入孔を設けた。
【００３６】
このようにして製造された積層剥離ボトルに、市販のシャンプ−を充填してボトル口に内側層内に大気を侵入させない構造になっているポンプディスペンサ−を装填して、内容物を少量ずつ注出する実験を行ない、剥離性等の評価を行なった。また、内容物の注出が終了した後、該ボトルを切断して内側層の収縮性を確認した。
【００３７】
実施例１
ε−カプロラクタムとヘキサメチレンジアミン・アジピン酸塩の水溶液を常法により重合して、融点が２０７℃である６／６６共重合ポリアミドペレットを得た。このポリアミドの２２７℃、剪断速度１０ｓｅｃ^−１の条件での溶融粘度は２３０００ポイズであった。このポリアミドペレット１００重量部にエチレンビスステアリルアミド１．０重量部を単軸押出機により溶融混練したものを用いて前記の方法で積層剥離ボトルを成形し、内容物を注出する実験を行なった。
【００３８】
その結果、外側層と内側層の剥離性は良好であり、外側層の変形は発生しなかった。また、内側層もほぼ完全に収縮して内容物の残量もほとんど認められなかった。
【００３９】
実施例２
ε−カプロラクタムとヘキサメチレンジアミン・アジピン酸の水溶液を常法により重合して、融点が２０７℃である６／６６共重合ポリアミドペレットを得た。このポリアミドペレット１００重量部にステアリン酸カルシウム１．０重量部を単軸押出機により溶融混練したものを用いて前記の方法で積層剥離ボトルを成形し、内容物を注出する実験を行なった。評価結果を表１に示す。
【００４０】
実施例３
ε−カプロラクタムとω−ラウロラクタムの水溶液を、常法により重合して、融点が１３５℃である６／１２共重合ポリアミドペレットを得た。このポリアミドの１５５℃、剪断速度１０ｓｅｃ^−１の条件での溶融粘度は２１０００ポイズであった。このポリアミドペレット１００重量部にエチレンビスステアリルアミド１．０重量部を単軸押出機により溶融混練したものを用いて前記の方法で積層剥離ボトルを成形し、内容物を注出する実験を行なった。評価結果を表１に示す。
【００４１】
実施例４
ε−カプロラクタムとω−ラウロラクタムの水溶液を、常法により重合して、融点が１３５℃である６／１２共重合ポリアミドペレットを得た。このポリアミドの１５５℃、剪断速度１０ｓｅｃ^−１の条件での溶融粘度は２１０００ポイズであった。このポリアミドペレット１００重量部にステアリン酸カルシウム１．０重量部を単軸押出機により溶融混練したものを用いて前記の方法で積層剥離ボトルを成形し、内容物を注出する実験を行なった。評価結果を表１に示す。実施例５、６
表１に示すポリアミドに、表１に示す添加量のエチレンビスステアリルアミドを単軸押出機で溶融混練し、このポリアミドペレットを用いて実施例１と同じ方法で抽出の実験を行った。評価結果を表１に示す。
【００４２】
【表１】

比較例１および実施例７〜１０
表２に示す単一組成のポリアミドおよび共重合ポリアミドに、第２表に示す添加量のエチレンビスステアリルアミドを単軸押出機で溶融混練し、このポリアミドペレットを用いて、実施例１と同じ方法で注出の実験を行なった。
【００４３】
【表２】

融点が２０７℃である６／６６共重合ポリアミド（ビスアミド無添加）では、注出の際、外側層に変形は発生しないものの、外側層と内側層が剥離する時には剥離音が生じた。また、内側層が完全に収縮しないため、内容物が完全に注出できなかった（比較例１）。
【００４４】
融点が２０７℃である６／６６共重合にポリアミドにエチレンビスステアリルアミドを０．０７重量部添加した場合には、注出の際、外側層に変形は発生しないものの、外側層と内側層が剥離する時には剥離音が生じた。また、内側層が完全に収縮しないため、内容物が若干残ったが実用的には耐え得るものであった （実施例７）。
【００４５】
融点が２０７℃である６／６６共重合ポリアミドにエチレンビスステアリルアミドを６．０重量部添加した場合では、積層剥離ボトル成形後のボトルの内側層に小さな穴が発生したため、外側層と内側層の間に内容物が漏れたが実用的には耐え得るものであった（実施例８）。
【００４６】
融点が２１５℃である６／６６共重合ポリアミドにエチレンビスステアリルアミドを１．０重量部添加した場合、注出の際、外側層に変形は発生しないものの、外側層と内側層が剥離する時には剥離音が生じた。また、内側層が完全に収縮しないため、内容物が若干残ったが実用的には耐え得るものであった（実施例９）。
【００４７】
融点が２２５℃であるポリアミド−６にエチレンビスステアリルアミドを１．０重量部添加した場合も、注出の際、外側層に変形は発生しないものの、外側層と内側層が剥離する時には剥離音が生じた。また、内側層が完全に収縮しないため、内容物が若干残ったが実用的には耐え得るものであった（実施例１８）。
【００４８】
【発明の効果】
以上のように本発明のポリアミド樹脂組成物を内側層に使用した積層剥離ボトルは、優れた剥離性を有し、内容物の減少に伴い内側層のみが変形し、外側層は変形が起こらず、内側層が内容物に忠実に収縮するために内容物が完全に使い切れる。
【図面の簡単な説明】
【図１】（ａ）は本発明の積層ボトルを示す一部断面説明図、（ｂ）はその要部拡大断面図である。
【図２】本発明の積層ボトルの大気導入孔の形成方法を示す説明図である。
【符号の説明】
１…外側層
２…内側層
３…大気導入孔
４…可撓性パイプ
５…ドリル[0001]
[Industrial applications]
The present invention relates to a polyamide resin composition used for the inner layer of a laminated bottle, and more specifically, has excellent releasability, and only the inner layer is deformed and the outer layer is deformed as the content decreases. The present invention relates to a polyamide resin composition used for the inner layer of a laminated peeling bottle in which the contents are completely used up because the inner layer shrinks faithfully to the contents, and a laminated bottle using the same.
[0002]
[Prior art]
BACKGROUND ART Conventionally, a laminated bottle in which an outer layer and an inner layer of a laminated bottle are freely peeled and only the inner layer is deformed and the outer layer is not deformed is known. For example, JP-A-4-339759 discloses an outer layer. It is described that in a laminated bottle composed of at least two layers of a layer and an inner layer, the outer layer and the inner layer are made detachable, and the outer layer and the inner layer are bonded at the mouth.
[0003]
Japanese Unexamined Patent Publication No. 6-345069 discloses a laminated peelable bottle in which the outer layer and the inner layer can be peeled off, wherein the material of the inner layer has a higher melting point than the material of the outer layer, and the flexural modulus is 10,000 kg / cm ^2. It is described that it is made of a synthetic resin material in the range of ５０50,000 kg / cm ² and forms an air introduction hole in an outer layer.
[0004]
[Problems to be solved by the invention]
However, although the laminated bottle described in JP-A-4-339759 uses nylon for the inner layer, the releasability is not sufficient, and the laminated bottle described in JP-A-6-345069 has a content. Even if it does not decrease, there are problems that peeling starts, and the inner layer does not shrink faithfully to the contents, so that the contents cannot be used up to the end.
[0005]
As described above, the conventional technology has excellent peelability, and as the content decreases, only the inner layer shrinks faithfully to the content, and the outer layer does not deform. Did not.
[0006]
It is an object of the present invention to have an excellent peeling property, only the inner layer is deformed as the content is reduced, the outer layer is not deformed, and the inner layer shrinks faithfully to the content, so that the content is completely It is an object of the present invention to provide a polyamide resin composition used for the inner layer of a laminated peeling bottle that can be used up and a laminated bottle using it.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive research to develop a laminated release bottle and a resin composition therefor that have excellent release properties, only the inner layer is deformed as the content is reduced, and the outer layer is not deformed. As a result of the repetition, the present invention has been made as follows.
[0008]
(1) The polyamide resin is selected from the group consisting of (B) a bisamide compound and / or (C) sodium stearate, potassium stearate, calcium stearate, aluminum stearate, potassium oleate, sodium acetate, and potassium acetate. A polyamide resin composition for a laminated bottle inner layer, comprising one or more fatty acid metal salts.
[0009]
(2) The compound according to (1), wherein the compounding amount of the (B) bisamide compound and / or (C) the fatty acid metal salt is 0.01 to 5 parts by weight based on 100 parts by weight of the polyamide resin (A). A) A polyamide resin composition for a laminated bottle inner layer according to the above.
[0010]
(3) The polyamide resin composition for a laminated bottle inner layer according to the above (1) or (2), wherein the polyamide (A) is a copolymer polyamide.
[0011]
(4) The polyamide resin composition for a laminated bottle inner layer according to (3), wherein the copolymerized polyamide has a nylon 6 component as a copolymerized component.
[0012]
(5) (B) wherein the bisamide compound is characterized in that the aliphatic Bisuami de (1) to (4) laminated bottle inner layer polyamide resin composition according to any one of.
[0013]
(6) The polyamide resin composition according to any one of the above (1) to (5), wherein the (C) aliphatic metal salt is a metal salt of a fatty acid having 15 or more carbon atoms. .
[0014]
(7) A laminated bottle, wherein the polyamide resin composition according to (1) is used for an inner layer, and a thermoplastic resin or a thermoplastic resin composition other than polyamide is used for an outer layer.
[0015]
(8) The laminated bottle according to (7), wherein the thermoplastic resin is at least one resin selected from polyolefin, polyester, polyvinyl chloride, polyphenylene sulfide, and polycarbonate.
[0016]
(9) The polyamide resin (A) is selected from the group consisting of (B) a bisamide compound and / or (C) sodium stearate, potassium stearate, calcium stearate, aluminum stearate, potassium oleate, sodium acetate, and potassium acetate. A laminated bottle, characterized in that a polyamide resin composition containing one or more fatty acid metal salts is used as an inner layer, and a thermoplastic resin or a thermoplastic resin composition other than the polyamide resin is used as an outer layer, and these are blow-molded. Production method.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
The polyamide (A) used in the present invention is not particularly limited as long as it is a polyamide, but preferably has a melting point of 210 ° C. or lower, more preferably 190 ° C. or lower.
[0018]
When the melting point is 210 ° C. or less, when this is used inside the laminated bottle, the releasability of the outer layer and the inner layer is good, and when the content decreases, the inner layer shrinks faithfully to the content. It is preferred.
[0019]
The polyamide having the above melting point is not particularly limited, but is preferably a copolymerized polyamide from the viewpoint of the property that the inner layer shrinks faithfully to the contents, and particularly preferably a copolymer having a polyamide-6 structure.
[0020]
Specific examples of such a copolymerized polyamide include polyamide-6 / 66, polyamide-6 / 12, polyamide-6 / 610, polyamide-6 / 6T (terephthalic acid component), polyamide-6 / 66/12, and polyamide. And polymerized polyamides such as -6/66/610 and polyamide-6 / 66/610/12.
[0021]
Although the molecular weight of the polyamide is not particularly limited, from the viewpoint of blow moldability, the melt viscosity at a temperature 20 ° C. higher than the melting point of the polyamide and a shear rate of 10 sec ⁻¹ is 8,000 to 200,000 poise. Is preferred.
[0022]
The bisamide compound (B) used in the present invention is not particularly limited, but is preferably an aliphatic bisamide, and particularly preferably a bisamide compound represented by the following general formula (I) or (II).
[0023]
Embedded image

(Wherein, R ¹ represents a divalent hydrocarbon residue, R ² and R ³ represent a monovalent hydrocarbon group, and R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon group.)
The bisamide compound represented by the general formula (I), for example, ethylenediamine Mi emissions, propylene diamine, diamine and stearic acid, such as butylene diamine, hexanoic acid, alkylene bis fatty acids obtained by reaction with fatty acids such as octanoic acid There are amides.
[0024]
The bisamide compound represented by the general formula (II) is obtained, for example, by reacting an alkylamine such as methylamine, ethylamine and butylamine with a dicarboxylic acid such as terephthalic acid, succinic acid and adipic acid . One of these bisamide compounds may be used alone, or two or more thereof may be used in combination.
[0025]
The fatty acid metal salt (C) used in the present invention is at least one selected from sodium stearate, potassium stearate, calcium stearate, aluminum stearate, potassium oleate, sodium acetate, potassium acetate, and the like. Among them, metal salts of fatty acids having 15 or more carbon atoms are preferable. These fatty acid metal salts may be used alone or in combination of two or more.
[0026]
In the present invention, the bisamide compound (B) and the fatty acid metal salt (C) may be used in combination.
[0027]
The compounding amount of the bisamide compound or the fatty acid metal salt is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polyamide. If the amount is too small, sufficient releasability cannot be obtained, and if the amount is too large, holes or the like are likely to be formed in the inner layer during molding, which is not preferable. And the most preferable compounding amount is 0.5 to 2 parts by weight.
[0028]
As a method of adding the bisamide compound or the fatty acid metal salt, any of a method of adding at the time of polymerization, a method of adding to the pellets by dry blending, and a method of melt-kneading the pellets and the bisamide compound or the fatty acid metal salt using an extruder are used. I do not care. It is effective if a bisamide compound or a fatty acid metal salt is finally contained in the blow-molded polyamide resin, and the present invention is not limited to these addition methods.
[0029]
As a method of molding the above-mentioned polyamide resin into a laminated peeling bottle, the above-mentioned polyamide resin composition is used for an inner layer, and a thermoplastic resin or a thermoplastic resin composition other than polyamide is used as an outer layer, and a general method of laminating and peeling in the art. It can be performed by a bottle molding method, for example, blow molding. In the laminated bottle, it is also optional to provide an intermediate layer between the inner layer and the outer layer.
[0030]
Examples of the thermoplastic resin other than polyamide include polyolefin, polyester, polyvinyl chloride, and polycarbonate. Among them, polyolefin is preferable.
[0031]
In the present invention, if necessary, the polyamide resin of the present invention, an antioxidant, a heat-resistant agent, a plasticizer, an inorganic filler, other additives, it is also possible to mix other resins, as a result In addition, it is possible to obtain a laminated peeling bottle having higher added value.
[0032]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0033]
(1) Measurement of Melting Point Using a differential scanning calorimeter (DSC), the melting point of the polyamide was measured at a sample weight of 10 mg and a heating rate of 20 ° C./min.
[0034]
(2) Releasability of a laminated release bottle Using polyethylene for the outer layer and a polyamide resin composition for the inner layer, co-extrusion blow molding to form an outer layer having a thickness of 1.5 mm and an inner layer having a thickness of 0.2 mm. The laminated release bottle shown in FIG. 1A and 1B, reference numeral 1 denotes an outer layer, 2 denotes an inner layer, and 3 denotes an air introduction hole.
[0035]
As shown in FIG. 2, a flexible pipe 4 having a suction pad 4 ′ was inserted from the mouth of the bottle into the air introduction hole 3, and the suction pad 4 ′ was brought into contact with the inside of the inner layer 2. Suction is performed in the state, and the outer layer and the inner layer are forcibly peeled off. The obtained peeled portion was perforated with a drill 5 from the outer layer to provide an air introduction hole.
[0036]
The laminated release bottle manufactured in this manner is filled with a commercially available shampoo, and the bottle mouth is charged with a pump dispenser having a structure that does not allow air to enter the inner layer, and the content is poured little by little. An experiment was conducted to evaluate peelability and the like. After the contents were completely poured, the bottle was cut to check the shrinkage of the inner layer.
[0037]
Example 1
An aqueous solution of ε-caprolactam and hexamethylenediamine adipate was polymerized by a conventional method to obtain 6/66 copolymer polyamide pellets having a melting point of 207 ° C. The melt viscosity of this polyamide at 227 ° C. and a shear rate of 10 sec ⁻¹ was 23,000 poise. An experiment was conducted in which a lamination release bottle was molded by the above-mentioned method using a mixture obtained by melting and kneading 1.0 part by weight of ethylenebisstearylamide with 100 parts by weight of the polyamide pellets by a single screw extruder, and the content was poured out. .
[0038]
As a result, the releasability of the outer layer and the inner layer was good, and no deformation of the outer layer occurred. Also, the inner layer shrank almost completely, and the remaining amount of the contents was hardly recognized.
[0039]
Example 2
An aqueous solution of ε-caprolactam and an aqueous solution of hexamethylenediamine / adipic acid were polymerized by a conventional method to obtain 6/66 copolymer polyamide pellets having a melting point of 207 ° C. An experiment was conducted in which a lamination release bottle was molded by the above-mentioned method using 100 parts by weight of the polyamide pellets and 1.0 part by weight of calcium stearate melt-kneaded by a single screw extruder, and the content was poured out. Table 1 shows the evaluation results.
[0040]
Example 3
An aqueous solution of ε-caprolactam and ω-laurolactam was polymerized by a conventional method to obtain 6/12 copolymerized polyamide pellets having a melting point of 135 ° C. The melt viscosity of this polyamide at 155 ° C. and a shear rate of 10 sec ⁻¹ was 21,000 poise. An experiment was conducted in which a lamination release bottle was molded by the above-mentioned method using a mixture obtained by melting and kneading 1.0 part by weight of ethylenebisstearylamide with 100 parts by weight of the polyamide pellets by a single screw extruder, and the content was poured out. . Table 1 shows the evaluation results.
[0041]
Example 4
An aqueous solution of ε-caprolactam and ω-laurolactam was polymerized by a conventional method to obtain 6/12 copolymerized polyamide pellets having a melting point of 135 ° C. The melt viscosity of this polyamide at 155 ° C. and a shear rate of 10 sec ⁻¹ was 21,000 poise. An experiment was conducted in which a lamination release bottle was molded by the above-mentioned method using 100 parts by weight of the polyamide pellets and 1.0 part by weight of calcium stearate melt-kneaded by a single screw extruder, and the content was poured out. Table 1 shows the evaluation results. Examples 5 and 6
To the polyamide shown in Table 1, ethylene bisstearyl amide in an addition amount shown in Table 1 was melt-kneaded by a single screw extruder, and an extraction experiment was performed using the polyamide pellets in the same manner as in Example 1. Table 1 shows the evaluation results.
[0042]
[Table 1]

Comparative Example 1 and Examples 7 to 10
The same method as in Example 1 was carried out using a single-screw extruder to melt-knead an ethylene bisstearylamide having the amount shown in Table 2 with a polyamide and a copolyamide having a single composition shown in Table 2 and using the polyamide pellets. The experiment of pouring was performed.
[0043]
[Table 2]

With the 6/66 copolymer polyamide having a melting point of 207 ° C. (without addition of bisamide), no deformation occurred in the outer layer upon pouring, but a peeling sound was generated when the outer layer and the inner layer were separated. In addition, since the inner layer did not completely shrink, the contents could not be completely poured out (Comparative Example 1).
[0044]
When 0.07 parts by weight of ethylenebisstearylamide is added to polyamide in a 6/66 copolymer having a melting point of 207 ° C., the outer layer and the inner layer are not deformed at the time of pouring, although the outer layer is not deformed. When peeling, a peeling sound was generated. In addition, since the inner layer did not completely shrink, some contents remained, but were practically durable (Example 7).
[0045]
When 6.0 parts by weight of ethylenebisstearylamide was added to 6/66 copolymer polyamide having a melting point of 207 ° C., small holes were formed in the inner layer of the bottle after the lamination release bottle was formed. Although the contents leaked during this period, it was practically durable (Example 8).
[0046]
When 1.0 part by weight of ethylenebisstearylamide is added to 6/66 copolymer polyamide having a melting point of 215 ° C., no deformation occurs in the outer layer during pouring, but when the outer layer and the inner layer are separated, Peeling noise occurred. In addition, since the inner layer did not completely shrink, some contents remained, but were practically durable (Example 9).
[0047]
When 1.0 part by weight of ethylenebisstearylamide is added to polyamide-6 having a melting point of 225 ° C., the outer layer is not deformed at the time of pouring, but a peeling sound is generated when the outer layer and the inner layer are separated. Occurred. In addition, since the inner layer did not completely shrink, some contents remained, but were practically durable (Example 18).
[0048]
【The invention's effect】
As described above, the laminated release bottle using the polyamide resin composition of the present invention for the inner layer has excellent releasability, only the inner layer is deformed as the content is reduced, and the outer layer is not deformed. The contents are completely used up because the inner layer shrinks faithfully to the contents.
[Brief description of the drawings]
FIG. 1A is a partially sectional explanatory view showing a laminated bottle of the present invention, and FIG. 1B is an enlarged sectional view of a main part thereof.
FIG. 2 is an explanatory view showing a method for forming an air introduction hole of the laminated bottle of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Outer layer 2 ... Inner layer 3 ... Air introduction hole 4 ... Flexible pipe 5 ... Drill

Claims (9)

(A) a polyamide resin and (B) a bisamide compound and / or (C) at least one member selected from the group consisting of sodium stearate, potassium stearate, calcium stearate, aluminum stearate, potassium oleate, sodium acetate, and potassium acetate A polyamide resin composition for an inner layer of a laminated bottle , wherein a fatty acid metal salt of the above is blended. 2. The laminate according to claim 1, wherein the compounding amount of (B) the bisamide compound and / or (C) the fatty acid metal salt is 0.01 to 5 parts by weight based on 100 parts by weight of (A) the polyamide resin. Polyamide resin composition for bottle inner layer. The polyamide resin composition for a laminated bottle inner layer according to claim 1 or 2, wherein the polyamide (A) is a copolymer polyamide. 4. The polyamide resin composition for a laminated bottle inner layer according to claim 3, wherein the copolymerized polyamide has a nylon 6 component as a copolymerized component. (B) a bisamide compound aliphatic claims 1-4 stacked bottles inside layer for the polyamide resin composition according to any one, characterized in that Bisuami is de. The polyamide resin composition for a laminated bottle inner layer according to any one of claims 1 to 5, wherein the (C) aliphatic metal salt is a metal salt of a fatty acid having 15 or more carbon atoms. A laminated bottle, characterized in that the polyamide resin composition according to claim 1 is used for an inner layer, and a thermoplastic resin or a thermoplastic resin composition other than polyamide is used for an outer layer. The laminated bottle according to claim 7, wherein the thermoplastic resin is at least one resin selected from polyolefin, polyester, polyvinyl chloride, polyphenylene sulfide, and polycarbonate. (A) a polyamide resin and (B) a bisamide compound and / or (C) at least one member selected from the group consisting of sodium stearate, potassium stearate, calcium stearate, aluminum stearate, potassium oleate, sodium acetate, and potassium acetate A polyamide resin composition containing a fatty acid metal salt as an inner layer and a thermoplastic resin or a thermoplastic resin composition other than the polyamide resin as an outer layer, and blow-molding these.

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