KR102392296B1 - Resin composition, molded article and manufacturing method of molded article - Google Patents

Resin composition, molded article and manufacturing method of molded article Download PDF

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KR102392296B1
KR102392296B1 KR1020197010473A KR20197010473A KR102392296B1 KR 102392296 B1 KR102392296 B1 KR 102392296B1 KR 1020197010473 A KR1020197010473 A KR 1020197010473A KR 20197010473 A KR20197010473 A KR 20197010473A KR 102392296 B1 KR102392296 B1 KR 102392296B1
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acid
resin composition
weight
derived
polyamide resin
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KR1020197010473A
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KR20190077333A (en
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카즈야 사토
토모노리 카토
진 나카무라
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미쯔비시 가스 케미칼 컴파니, 인코포레이티드
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/34—Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
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    • B29C48/76—Venting, drying means; Degassing means
    • B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
    • B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
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Abstract

산소배리어성이 우수하고, 또한, 내충격성이 우수한 수지 조성물, 그리고, 상기 수지 조성물을 이용한 성형품 및 성형품의 제조방법의 제공. 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 3~17중량부, 및, 하기 일반식(1)로 표시되는 화합물을 1~15중량부 포함하는, 수지 조성물;

Figure 112019037335319-pct00010

일반식(1) 중, R1은, 탄소수 1~10의 알킬기이며, R2는, 탄소수 2~12의 알킬기이며, n은 1~3의 정수이다.A resin composition having excellent oxygen barrier properties and excellent impact resistance, and a molded article and a method for manufacturing a molded article using the resin composition. It is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 70 mol% or more of the structural unit derived from dicarboxylic acid has 4 carbon atoms Based on 100 parts by weight of the polyamide resin derived from α,ω-linear aliphatic dicarboxylic acid of ~20, 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight, and the following general formula ( A resin composition comprising 1 to 15 parts by weight of the compound represented by 1);
Figure 112019037335319-pct00010

In general formula (1), R< 1 > is a C1-C10 alkyl group, R< 2 > is a C2-C12 alkyl group, and n is an integer of 1-3.

Description

수지 조성물, 성형품 및 성형품의 제조방법Resin composition, molded article and manufacturing method of molded article

본 발명은, 수지 조성물, 성형품 및 성형품의 제조방법에 관한 것이다. 특히, 산소배리어성 및 내충격성이 우수한 성형품을 제공가능한 수지 조성물에 관한 것이다.The present invention relates to a resin composition, a molded article, and a method for producing a molded article. In particular, it relates to a resin composition capable of providing a molded article having excellent oxygen barrier properties and impact resistance.

폴리아미드수지는, 내약품성, 내열성 등이 우수한 점에서, 각종 용도로 널리 이용되고 있다.BACKGROUND ART Polyamide resins have excellent chemical resistance, heat resistance, and the like, and are therefore widely used for various purposes.

예를 들어, 특허문헌 1에는, 말단아미노기와 말단카르복실기의 비율이, 전자:후자=100:0~50:50인 아민말단폴리아미드를 적어도 포함하는 폴리아미드와 변성 폴리올레핀으로 이루어진 블로우성형용 폴리아미드 조성물이 개시되어 있다. 나아가, 아민말단폴리아미드가 폴리아미드11 또는 폴리아미드12인 것, 변성 폴리올레핀이, 에폭시변성, 산무수물변성 또는 카르본산변성 폴리올레핀인 것이 기재되어 있다. 나아가, 이러한 폴리아미드 조성물이, IZOD충격강도가 우수한 것도 기재되어 있다.For example, in Patent Document 1, a polyamide for blow molding composed of a polyamide containing at least an amine-terminated polyamide in which the ratio of terminal amino groups and terminal carboxyl groups is the former: the latter = 100:0 to 50:50 and a modified polyolefin. A composition is disclosed. Further, it is described that the amine-terminated polyamide is polyamide 11 or polyamide 12, and that the modified polyolefin is epoxy-modified, acid anhydride-modified or carboxylic acid-modified polyolefin. Furthermore, it is also described that such a polyamide composition is excellent in IZOD impact strength.

일본특허공개 2001-302908호 공보Japanese Patent Laid-Open No. 2001-302908

그러나, 본 발명자가 상기 특허문헌 1에 대하여 검토한 결과, 내충격성이 높으나, 산소배리어성이 불충분한 것을 알 수 있었다.However, as a result of the present inventor examining the said patent document 1, although impact resistance was high, it turned out that oxygen barrier property is inadequate.

또한, 산소배리어성이 우수한 폴리아미드수지를 이용해도, 내충격성이 뒤떨어지면 문제이다.Moreover, even if a polyamide resin excellent in oxygen barrier properties is used, it is a problem if the impact resistance is poor.

본 발명은, 이러한 과제를 해결하는 것을 목적으로 하는 것으로서, 산소배리어성이 우수하고, 또한, 내충격성이 우수한 수지 조성물, 그리고, 상기 수지 조성물을 이용한 성형품 및 성형품의 제조방법을 제공하는 것을 목적으로 한다.The present invention, as an object of solving these problems, is excellent in oxygen barrier properties, and also excellent in impact resistance to provide a resin composition, and a molded article and a method for manufacturing a molded article using the resin composition for the purpose of providing do.

상기 과제하에, 본 발명자가 검토를 행한 결과, 소정의 자일릴렌디아민계 폴리아미드수지에, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀과 함께, 일반식(1)로 표시되는 화합물을 배합함으로써, 산소배리어성이 우수한 성형품으로서, 또한, 내충격성이 현격하게 향상된 성형품이 얻어지는 것을 발견하고, 본 발명을 완성하기에 이르렀다. 구체적으로는, 하기 수단<1>에 의해, 바람직하게는 <2>~<14>에 의해, 상기 과제는 해결되었다.As a result of studies conducted by the present inventor under the above subject, a compound represented by the general formula (1) is blended with an acid-modified polyolefin having an acid-modified rate of 0.3 to 5.0 wt% in a predetermined xylylenediamine-based polyamide resin. By doing so, it was discovered that a molded article having excellent oxygen barrier properties and significantly improved impact resistance can be obtained, and the present invention has been completed. Specifically, by the following means <1>, Preferably, the said subject was solved by <2> - <14>.

<1> 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 3~17중량부, 및, 하기 일반식(1)로 표시되는 화합물을 1~15중량부 포함하는, 수지 조성물;<1> Consists of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and 70 mol% or more of the structural unit derived from dicarboxylic acid Based on 100 parts by weight of the polyamide resin derived from the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight, and A resin composition containing 1 to 15 parts by weight of the compound represented by the general formula (1);

일반식(1)General formula (1)

[화학식 1][Formula 1]

Figure 112019037335319-pct00001
Figure 112019037335319-pct00001

일반식(1) 중, R1은, 탄소수 1~10의 알킬기이며, R2는, 탄소수 2~12의 알킬기이며, n은 1~3의 정수이다.In general formula (1), R< 1 > is a C1-C10 alkyl group, R< 2 > is a C2-C12 alkyl group, and n is an integer of 1-3.

<2> 상기 자일릴렌디아민이, 메타자일릴렌디아민 및 파라자일릴렌디아민의 적어도 일방을 포함하는, <1>에 기재된 수지 조성물.<2> The resin composition according to <1>, wherein the xylylenediamine contains at least one of meta-xylylenediamine and para-xylylenediamine.

<3> 상기 탄소수 4~20의 α,ω-직쇄지방족 디카르본산이, 세바스산 및 아디프산의 적어도 일방을 포함하는, <1> 또는 <2>에 기재된 수지 조성물.<3> The resin composition according to <1> or <2>, wherein the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains at least one of sebacic acid and adipic acid.

<4> 상기 일반식(1)로 표시되는 화합물과, 상기 산변성률이 0.3~5중량%의 산변성 폴리올레핀의 중량비가 3:10~16:10인, <1>~<3> 중 어느 하나에 기재된 수지 조성물.<4> Any of <1> to <3>, wherein the weight ratio of the compound represented by the general formula (1) to the acid-modified polyolefin having an acid modification rate of 0.3 to 5% by weight is 3:10 to 16:10 The resin composition as described in one.

<5> 상기 산변성 폴리올레핀이, 말레산변성 폴리올레핀 및 무수말레산변성 폴리올레핀의 적어도 1종을 포함하는, <1>~<4> 중 어느 하나에 기재된 수지 조성물.<5> The resin composition according to any one of <1> to <4>, wherein the acid-modified polyolefin contains at least one of a maleic acid-modified polyolefin and a maleic anhydride-modified polyolefin.

<6> 상기 폴리아미드수지가, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는, <1>~<5> 중 어느 하나에 기재된 수지 조성물.<6> 70 mol% of the structural unit derived from dicarboxylic acid relative to 10 to 90 parts by weight of the polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid The resin composition according to any one of <1> to <5>, wherein the above contains the polyamide resin derived from sebacic acid in a proportion of 90 to 10 parts by weight.

<7> 심재의 피복재료인, <1>~<6> 중 어느 하나에 기재된 수지 조성물.<7> The resin composition according to any one of <1> to <6>, which is a coating material for a core material.

<8> <1>~<7> 중 어느 하나에 기재된 수지 조성물을 성형하여 이루어진 성형품.<8> A molded article obtained by molding the resin composition according to any one of <1> to <7>.

<9> 심재와, 상기 심재의 피복층을 포함하고, 상기 피복층이 <1>~<5> 중 어느 하나에 기재된 수지 조성물로부터 형성되는 성형품.<9> A molded article comprising a core material and a coating layer of the core material, wherein the coating layer is formed from the resin composition according to any one of <1> to <5>.

<10> 추가로, 상기 피복층에 접하는, 지방족 폴리아미드수지를 주성분으로 하는 제2 피복층을 갖는, <9>에 기재된 성형품.<10> The molded article according to <9>, further comprising a second coating layer containing an aliphatic polyamide resin as a main component, which is in contact with the coating layer.

<11> 상기 지방족 폴리아미드수지가 폴리아미드12인, <10>에 기재된 성형품.<11> The molded article according to <10>, wherein the aliphatic polyamide resin is polyamide 12.

<12> 상기 피복층을 구성하는 폴리아미드수지가 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는, <10> 또는 <11>에 기재된 성형품.<12> With respect to 10 to 90 parts by weight of the polyamide resin in which the polyamide resin constituting the coating layer is derived from adipic acid in an amount of 70 mol% or more of the constituent units derived from dicarboxylic acid, the amount of the constituent units derived from dicarboxylic acid is The molded article according to <10> or <11>, wherein 70 mol% or more contains the polyamide resin derived from sebacic acid in a proportion of 90 to 10 parts by weight.

<13> 상기 심재가, 광도파로 또는 연속중공체인, <9>~<12> 중 어느 하나에 기재된 성형품.<13> The molded article according to any one of <9> to <12>, wherein the core material is an optical waveguide or a continuous hollow body.

<14> 심재를, <1>~<7> 중 어느 하나에 기재된 수지 조성물로 피복하는 것을 포함하는, 성형품의 제조방법.<14> A method for producing a molded article, comprising coating a core material with the resin composition according to any one of <1> to <7>.

본 발명에 의해, 산소배리어성이 우수하고, 또한, 내충격성이 우수한 수지 조성물, 그리고, 상기 수지 조성물을 이용한 성형품 및 성형품의 제조방법을 제공 가능해졌다.ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the resin composition excellent in oxygen barrier property and excellent in impact resistance, and a molded article using the said resin composition, and the manufacturing method of a molded article.

도 1은 실시예의 접착성의 평가방법을 나타내는 개략도이다.BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the evaluation method of adhesiveness of an Example.

이하에 있어서, 본 발명의 내용에 대하여 상세히 설명한다. 한편, 본 명세서에 있어서 「~」란 그 전후에 기재되는 수치를 하한값 및 상한값으로서 포함하는 의미로 사용된다.Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

본 발명의 수지 조성물은, 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소원자수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지(이하, 「XD계 폴리아미드수지」라고 하기도 한다) 100중량부에 대하여, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 3~17중량부, 및, 하기 일반식(1)로 표시되는 화합물을 1~15중량부 포함하는 것을 특징으로 한다.The resin composition of the present invention is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, Based on 100 parts by weight of a polyamide resin derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter also referred to as “XD-based polyamide resin”) 70 mol% or more, the acid modification rate is 3 to 17 parts by weight of an acid-modified polyolefin of 0.3 to 5.0% by weight, and 1 to 15 parts by weight of a compound represented by the following general formula (1).

일반식(1)General formula (1)

[화학식 2][Formula 2]

Figure 112019037335319-pct00002
Figure 112019037335319-pct00002

일반식(1) 중, R1은, 탄소수 1~10의 알킬기이며, R2는, 탄소수 2~12의 알킬기이며, n은 1~3의 정수이다.In general formula (1), R< 1 > is a C1-C10 alkyl group, R< 2 > is a C2-C12 alkyl group, and n is an integer of 1-3.

이러한 구성으로 함으로써, 산소배리어성이 우수하고, 또한, 내충격성이 우수한 수지 조성물(성형품)이 얻어진다. 나아가, 피복성이 우수한 수지 조성물이 얻어진다.By setting it as such a structure, the resin composition (molded article) excellent in oxygen barrier property and also excellent in impact resistance is obtained. Furthermore, the resin composition excellent in coating property is obtained.

즉, XD계 폴리아미드수지는, 산소배리어성이 우수한 것이 알려져 있다. 그러나, 내충격성에 대해서는 반드시 충분하다고는 할 수 없었다. 본 발명에서는, XD계 폴리아미드수지에, 산변성 폴리올레핀을 배합하고, 추가로, 상기 일반식(1)로 표시되는 화합물을 배합함으로써, 놀랍게도, 내충격성을 현격히 향상시키는 것에 성공한 것이다. 즉, 폴리아미드수지의 내충격성을 향상하기 위해, 산변성 폴리올레핀을 배합하는 것은 지금까지도 행해지고 있었다. 그러나, 본 발명자가 검토한 결과, XD계 폴리아미드수지에, 산변성 폴리올레핀을 배합한 것만으로는, 충분한 내충격성을 확보하지 못하는 경우가 있는 것을 알 수 있었다. 그리고, 본 발명에서는, 산변성 폴리올레핀의 산변성률을 소정의 범위로 하고, 또한, 일반식(1)로 표시되는 화합물을 배합함으로써, 내충격성을 현저히 향상시키는 것에 성공한 것이다. 특히, 일반식(1)로 표시되는 화합물을 배합함으로써, 내충격성이 현저히 향상되는 것은 매우 놀라운 일이다.That is, it is known that XD-based polyamide resins are excellent in oxygen barrier properties. However, the impact resistance was not necessarily sufficient. In the present invention, by blending the acid-modified polyolefin with the XD-based polyamide resin and further blending the compound represented by the general formula (1), surprisingly, it has succeeded in remarkably improving the impact resistance. That is, in order to improve the impact resistance of a polyamide resin, mix|blending of acid-modified polyolefin has been performed until now. However, as a result of the inventor's examination, it turned out that sufficient impact resistance may not be ensured only by mix|blending an acid-modified polyolefin with an XD-type polyamide resin. And in this invention, it succeeded in making the acid-modification rate of an acid-modified polyolefin into a predetermined range, and further improving impact resistance remarkably by mix|blending the compound represented by General formula (1). In particular, it is very surprising that the impact resistance is remarkably improved by blending the compound represented by the general formula (1).

나아가 본 발명에서는, 피복성의 향상도 달성 가능하다. 이 때문에, 본 발명의 수지 조성물은, 피복재료에도 바람직하게 이용할 수 있다.Furthermore, in this invention, the improvement of coatability is also achievable. For this reason, the resin composition of this invention can be used suitably also for a coating material.

이하, 본 발명의 상세에 대하여, 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, the detail of this invention is demonstrated.

<XD계 폴리아미드수지><XD-based polyamide resin>

본 발명에서 이용하는 폴리아미드수지(XD계 폴리아미드수지)는, 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래한다.The polyamide resin (XD-based polyamide resin) used in the present invention is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and at least 70 mol% of the structural unit derived from diamine is derived from xylylenediamine, , 70 mol% or more of the constituent units derived from dicarboxylic acid are derived from α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

XD계 폴리아미드수지는, 디아민유래의 구성단위의, 바람직하게는 80몰% 이상, 보다 바람직하게는 90몰% 이상, 더욱 바람직하게는 95몰% 이상, 한층 바람직하게는 98몰% 이상이, 자일릴렌디아민의 적어도 1종에서 유래하고, 디카르본산유래의 구성단위의, 바람직하게는 80몰% 이상, 보다 바람직하게는 90몰% 이상, 더욱 바람직하게는 95몰% 이상, 한층 바람직하게는 98몰% 이상이, 탄소수가 4~20의 α,ω-직쇄지방족 디카르본산의 적어도 1종에서 유래한다.The XD-based polyamide resin is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more of the structural units derived from diamine, Derived from at least one type of xylylenediamine, preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably, of the structural unit derived from dicarboxylic acid. 98 mol% or more originates in at least 1 sort(s) of C4-C20 alpha, omega-linear aliphatic dicarboxylic acid.

즉, XD계 폴리아미드수지의 원료인 자일릴렌디아민은, 산소배리어성의 관점에서 메타자일릴렌디아민 및 파라자일릴렌디아민의 적어도 일방을 포함하는 것이 바람직하고, 메타자일릴렌디아민을 적어도 포함하는 것이 보다 바람직하다.That is, the xylylenediamine, which is a raw material of the XD-based polyamide resin, preferably contains at least one of metaxylylenediamine and paraxylylenediamine from the viewpoint of oxygen barrier properties, and more preferably contains at least metaxylylenediamine. Do.

또한 피복성의 관점에서, 자일릴렌디아민이, 30~100몰%의 메타자일릴렌디아민과 0~70몰%의 파라자일릴렌디아민으로 이루어진 것이 바람직하고, 60~100몰%의 메타자일릴렌디아민과 0~40몰%의 파라자일릴렌디아민으로 이루어진 것이 보다 바람직하고, 70~100몰%의 메타자일릴렌디아민과 0~30몰%의 파라자일릴렌디아민으로 이루어진 것이 더욱 바람직하다.In addition, from the viewpoint of coating properties, it is preferable that xylylenediamine consists of 30-100 mol% meta-xylylenediamine and 0-70 mol% para-xylylenediamine, and 60-100 mol% meta-xylylenediamine and 0 It is more preferably composed of ~40 mol% of para-xylylenediamine, and more preferably composed of 70-100 mol% of meta-xylylenediamine and 0-30 mol% of para-xylylenediamine.

본 발명에서 이용하는 자일릴렌디아민은, 바람직하게는 90몰% 이상, 보다 바람직하게는 95몰% 이상, 더욱 바람직하게는 98몰% 이상이 메타자일릴렌디아민이다. 이러한 구성으로 함으로써, 피복성이 보다 효과적으로 향상된다.The xylylenediamine used in the present invention is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98 mol% or more of meta-xylylenediamine. By setting it as such a structure, coatability improves more effectively.

XD계 폴리아미드수지의 원료디아민으로서 이용할 수 있는 자일릴렌디아민 이외의 디아민으로는, 테트라메틸렌디아민, 펜타메틸렌디아민, 2-메틸펜탄디아민, 헥사메틸렌디아민, 헵타메틸렌디아민, 옥타메틸렌디아민, 노나메틸렌디아민, 데카메틸렌디아민, 도데카메틸렌디아민, 2,2,4-트리메틸-헥사메틸렌디아민, 2,4,4-트리메틸헥사메틸렌디아민 등의 지방족 디아민, 1,3-비스(아미노메틸)시클로헥산, 1,4-비스(아미노메틸)시클로헥산, 1,3-디아미노시클로헥산, 1,4-디아미노시클로헥산, 비스(4-아미노시클로헥실)메탄, 2,2-비스(4-아미노시클로헥실)프로판, 비스(아미노메틸)데칼린, 비스(아미노메틸)트리시클로데칸 등의 지환식 디아민, 비스(4-아미노페닐)에테르, 파라페닐렌디아민, 비스(아미노메틸)나프탈렌 등의 방향환을 갖는 디아민 등을 예시할 수 있고, 1종 또는 2종 이상을 혼합하여 사용할 수 있다.Examples of diamines other than xylylenediamine that can be used as the raw material diamine of the XD-based polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nonamethylenediamine. , aliphatic diamines such as decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1 ,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl) ) having an aromatic ring such as alicyclic diamines such as propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane, bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene Diamine etc. can be illustrated, and it can use 1 type or in mixture of 2 or more types.

디아민으로서, 자일릴렌디아민 이외의 디아민을 이용하는 경우는, 디아민유래의 구성단위의 30몰% 이하이며, 바람직하게는 1~25몰%, 특히 바람직하게는 5~20몰%의 비율로 이용한다.When using a diamine other than xylylenediamine as the diamine, it is 30 mol% or less of the structural unit derived from diamine, preferably 1 to 25 mol%, and particularly preferably 5 to 20 mol%.

XD계 폴리아미드수지의 원료디카르본산으로서 이용하는 탄소수 4~20의 α,ω-직쇄지방족 디카르본산으로는, 탄소수 6~16의 α,ω-직쇄지방족 디카르본산이 바람직하고, 탄소수 6~10의 α,ω-직쇄지방족 디카르본산이 더욱 바람직하다. 탄소수 4~20의 α,ω-직쇄지방족 디카르본산으로는, 예를 들어 석신산, 글루타르산, 피멜린산, 수베르산, 아젤라산, 아디프산, 세바스산, 운데칸이산, 도데칸이산 등의 지방족 디카르본산을 예시할 수 있고, 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 이들 중에서도 폴리아미드수지의 융점이 성형가공하기에 적절한 범위가 됨으로써, 아디프산 및 세바스산의 적어도 일방을 포함하는 것이 바람직하다.As the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms used as the raw material dicarboxylic acid for the XD-based polyamide resin, α,ω-straight chain aliphatic dicarboxylic acid having 6 to 16 carbon atoms is preferable, and the carbon number is 6 to 10 α,ω-linear aliphatic dicarboxylic acid is more preferred. Examples of α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelinic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, dode Aliphatic dicarboxylic acids, such as candianic acid, can be illustrated, and it can use 1 type or in mixture of 2 or more types. Among these, the polyamide resin preferably contains at least one of adipic acid and sebacic acid because the melting point of the polyamide resin falls within an appropriate range for molding.

또한, 탄소수 4~20의 α,ω-직쇄지방족 디카르본산으로서, 아디프산을 이용하면, 보다 산소배리어성이 우수한 수지 조성물이 얻어진다.In addition, when adipic acid is used as the α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, a resin composition more excellent in oxygen barrier properties can be obtained.

또한, 탄소수 4~20의 α,ω-직쇄지방족 디카르본산으로서, 세바스산을 이용하면, 보다 내충격성이 우수한 수지 조성물이 얻어진다.In addition, when sebacic acid is used as the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, a resin composition more excellent in impact resistance can be obtained.

또한, 탄소수 4~20의 α,ω-직쇄지방족 디카르본산으로서, 아디프산과 세바스산의 양방을 이용하면, 지방족 폴리아미드수지와의 접착성이 향상된 수지 조성물이 얻어진다. 이러한 폴리아미드수지(XD6/XD10)에 있어서, 아디프산 성분과 세바스산 성분의 몰비는, 10:90~90:10인 것이 바람직하고, 30:70~90:10인 것이 보다 바람직하고, 50:50~80:20인 것이 더욱 바람직하다.Further, when both adipic acid and sebacic acid are used as the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, a resin composition with improved adhesion to the aliphatic polyamide resin can be obtained. In this polyamide resin (XD6/XD10), the molar ratio of the adipic acid component and the sebacic acid component is preferably 10:90 to 90:10, more preferably 30:70 to 90:10, 50 :50-80:20 is more preferable.

상기 탄소수 4~20의 α,ω-직쇄지방족 디카르본산 이외의 디카르본산 성분으로는, 이소프탈산, 테레프탈산, 오르토프탈산 등의 프탈산 화합물, 1,2-나프탈렌디카르본산, 1,3-나프탈렌디카르본산, 1,4-나프탈렌디카르본산, 1,5-나프탈렌디카르본산, 1,6-나프탈렌디카르본산, 1,7-나프탈렌디카르본산, 1,8-나프탈렌디카르본산, 2,3-나프탈렌디카르본산, 2,6-나프탈렌디카르본산, 2,7-나프탈렌디카르본산과 같은 이성체 등의 나프탈렌디카르본산 등을 예시할 수 있고, 1종 또는 2종 이상을 혼합하여 사용할 수 있다.Examples of the dicarboxylic acid components other than the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, and 1,3-naphthalene. Dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2 Naphthalenedicarboxylic acid such as isomers such as ,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid may be exemplified, and one type or a mixture of two or more types may be used. can be used

디카르본산 성분으로서, 탄소수 4~20의 α,ω-직쇄지방족 디카르본산 이외의 디카르본산을 이용하는 경우는, 성형가공성, 배리어성의 점에서, 테레프탈산, 이소프탈산을 이용하는 것이 바람직하다. 테레프탈산, 이소프탈산의 비율은, 바람직하게는 디카르본산유래의 구성단위의 30몰% 이하이며, 보다 바람직하게는 1~30몰%, 특히 바람직하게는 5~20몰%의 범위이다.When using dicarboxylic acids other than α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms as the dicarboxylic acid component, it is preferable to use terephthalic acid or isophthalic acid from the viewpoints of molding processability and barrier properties. The proportion of terephthalic acid and isophthalic acid is preferably 30 mol% or less of the structural unit derived from dicarboxylic acid, more preferably 1 to 30 mol%, and particularly preferably 5 to 20 mol%.

한편, 여기서, 「디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성된다」는 것은, XD계 폴리아미드수지를 구성하는 아미드결합이 디카르본산과 디아민의 결합에 의해 형성되어 있는 것을 말한다. 또한, XD계 폴리아미드수지는, 디카르본산유래의 구성단위와, 디아민유래의 구성단위 이외에, 말단기 등의 다른 부위를 포함한다. 나아가, 디카르본산과 디아민의 결합에서 유래하지 않는 아미드결합을 갖는 반복단위나 미량의 불순물 등이 포함되는 경우도 있을 것이다. 구체적으로는, XD계 폴리아미드수지는, 디아민성분, 디카르본산 성분 이외에도, 폴리아미드수지를 구성하는 성분으로서, 본 발명의 효과를 손상시키지 않는 범위에서 ε-카프로락탐이나 라우로락탐 등의 락탐류, 아미노카프론산, 아미노운데칸산 등의 지방족 아미노카르본산류도 공중합성분으로서 사용할 수 있다. 본 발명에서는, XD계 폴리아미드수지의, 바람직하게는 90중량% 이상이, 보다 바람직하게는 95중량% 이상이 디아민유래의 구성단위 또는 디카르본산유래의 구성단위이다.On the other hand, here, "composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid" means that the amide bond constituting the XD-based polyamide resin is formed by the bond between dicarboxylic acid and diamine. . In addition, the XD-based polyamide resin contains other sites such as terminal groups in addition to the structural unit derived from dicarboxylic acid and the structural unit derived from diamine. Furthermore, there may be cases where a repeating unit having an amide bond that is not derived from the bond between dicarboxylic acid and diamine or a trace amount of impurities may be included. Specifically, the XD-based polyamide resin is a component constituting the polyamide resin in addition to the diamine component and dicarboxylic acid component, and is a lactam such as ε-caprolactam and laurolactam within the range that does not impair the effects of the present invention. Aliphatic aminocarboxylic acids, such as amino acids, aminocaproic acid, and aminoundecanoic acid, can also be used as the copolymerization component. In the present invention, preferably 90% by weight or more, more preferably 95% by weight or more of the XD-based polyamide resin is a structural unit derived from diamine or a structural unit derived from dicarboxylic acid.

본 발명에서 이용하는 XD계 폴리아미드수지는, 수평균 분자량(Mn)이 6,000~30,000인 것이 바람직하고, 보다 바람직하게는 8,000~28,000이며, 더욱 바람직하게는 9,000~26,000이다. 이러한 범위이면, 성형가공성이 보다 양호해진다.The XD-based polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000 to 30,000, more preferably 8,000 to 28,000, and still more preferably 9,000 to 26,000. If it is such a range, moldability will become more favorable.

한편, 여기서 말하는 수평균 분자량(Mn)은, 폴리아미드수지의 말단아미노기농도[NH2](μ당량/g)와 말단카르복실기농도[COOH](μ당량/g)로부터, 다음 식으로 산출된다.On the other hand, the number average molecular weight (Mn) here is calculated from the terminal amino group concentration [NH 2 ] (μ equivalent/g) and the terminal carboxyl group concentration [COOH] (μ equivalent/g) of the polyamide resin by the following formula.

수평균 분자량(Mn)=2,000,000/([COOH]+[NH2])Number average molecular weight (Mn)=2,000,000/([COOH]+[NH 2 ])

XD계 폴리아미드수지의 제조방법은, 일본특허공개 2014-173196호 공보의 단락 0052~0053의 기재를 참작할 수 있고, 이들 내용은 본 명세서에 편입된다.For the manufacturing method of XD-type polyamide resin, Paragraph 0052 - 0053 of Unexamined-Japanese-Patent No. 2014-173196 can be considered into consideration, and these content is integrated in this specification.

본 발명에 있어서는, XD계 폴리아미드수지의 융점은, 150~350℃인 것이 바람직하고, 180~300℃인 것이 보다 바람직하고, 180~280℃인 것이 더욱 바람직하다.In this invention, it is preferable that it is 150-350 degreeC, as for melting|fusing point of XD-type polyamide resin, it is more preferable that it is 180-300 degreeC, It is still more preferable that it is 180-280 degreeC.

한편, 본 발명에 있어서의 융점이란, DSC(시차주사열량측정)법에 의해 관측되는 승온시의 흡열피크의 피크탑의 온도이다. 구체적으로는, 융점의 측정은, 시마즈제작소사(SHIMADZU CORPORATION)제 「DSC-60」을 이용하고, 시료량은 약 1mg으로 하고, 분위기가스로는 질소를 30mL/분으로 흘리고, 승온속도는 10℃/분의 조건으로 실온으로부터 예상되는 융점 이상의 온도까지 가열하고 용융시킨 폴리아미드수지를, 드라이아이스로 급랭하고, 10℃/분의 속도로 융점 이상의 온도까지 재차 승온했을 때에 관측되는 흡열피크의 피크탑의 온도를 측정함으로써 행할 수 있다.In addition, melting|fusing point in this invention is the temperature of the peak top of the endothermic peak at the time of temperature rise observed by DSC (differential scanning calorimetry) method. Specifically, the melting point was measured using "DSC-60" manufactured by SHIMADZU CORPORATION, the sample amount was about 1 mg, nitrogen was flowed as an atmospheric gas at 30 mL/min, and the temperature increase rate was 10 ° C/min. The peak top of the endothermic peak observed when the polyamide resin heated and melted from room temperature to a temperature higher than the expected melting point under the condition of It can be carried out by measuring the temperature.

본 발명의 수지 조성물이, XD계 폴리아미드수지를 2종 이상 포함하는 경우의 폴리아미드수지의 융점은, 상기의 DSC측정시에 가장 상온측에서 관측되는 흡열피크의 피크탑의 온도의 값으로 한다.When the resin composition of the present invention contains two or more XD-based polyamide resins, the melting point of the polyamide resin is the temperature of the peak top of the endothermic peak most observed at room temperature in the above DSC measurement. .

본 발명의 수지 조성물에 있어서의 XD계 폴리아미드수지의 비율은, 50중량% 이상이며, 60중량% 이상인 것이 바람직하고, 70중량% 이상인 것이 더욱 바람직하고, 80중량% 이상으로 할 수도 있다.The proportion of the XD-based polyamide resin in the resin composition of the present invention is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and may be 80% by weight or more.

본 발명의 수지 조성물은, XD계 폴리아미드수지를, 1종만 포함할 수도 있고, 2종 이상 포함할 수도 있다. 2종 이상 포함하는 경우, 합계량이 상기 범위가 되는 것이 바람직하다.The resin composition of this invention may contain only 1 type, and may contain 2 or more types of XD-type polyamide resin. When 2 or more types are included, it is preferable that a total amount becomes the said range.

<다른 폴리아미드수지><Other polyamide resins>

본 발명의 수지 조성물은, 상기 XD계 폴리아미드수지 이외의 폴리아미드수지를 포함할 수도 있다. 이러한 다른 폴리아미드수지로는, 폴리아미드4, 폴리아미드6, 폴리아미드11, 폴리아미드12, 폴리아미드46, 폴리아미드66, 폴리아미드610, 폴리아미드612, 폴리헥사메틸렌테레프탈아미드(폴리아미드6T), 폴리헥사메틸렌이소프탈아미드(폴리아미드6I), 폴리아미드66/6T, 폴리아미드9T, 폴리아미드9MT, 폴리아미드6I/6T 등을 들 수 있다.The resin composition of the present invention may contain a polyamide resin other than the XD-based polyamide resin. Such other polyamide resins include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T). , polyhexamethylene isophthalamide (polyamide 6I), polyamide 66/6T, polyamide 9T, polyamide 9MT, polyamide 6I/6T, and the like.

본 발명의 수지 조성물에 있어서의, 다른 폴리아미드수지의 함유량은, 배합하는 경우, XD계 폴리아미드수지 100중량부에 대하여, 1~50중량부가 바람직하고, 5~40중량부가 보다 바람직하다.In the resin composition of the present invention, the content of the other polyamide resin is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the XD-based polyamide resin when blending.

또한, 본 발명의 수지 조성물은, XD계 폴리아미드수지 이외의 다른 폴리아미드수지를 실질적으로 포함하지 않는 구성으로 할 수도 있다. 실질적으로 포함하지 않는다는 것은, 본 발명의 수지 조성물에 포함되는 폴리아미드수지 중, 다른 폴리아미드수지의 비율이, XD계 폴리아미드수지의 5중량% 이하인 것을 말하고, 3중량% 이하인 것이 바람직하고, 1중량% 이하인 것이 더욱 바람직하다.Further, the resin composition of the present invention may have a configuration substantially free of polyamide resins other than the XD-based polyamide resin. Substantially free means that among the polyamide resins contained in the resin composition of the present invention, the ratio of other polyamide resins is 5% by weight or less of the XD-based polyamide resin, preferably 3% by weight or less, and 1 It is more preferably not more than weight %.

<산변성 폴리올레핀><Acid-modified polyolefin>

본 발명의 수지 조성물은, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 포함한다.The resin composition of this invention contains the acid-modified polyolefin whose acid-modification rate is 0.3 to 5.0 weight%.

상기 산변성률의 하한값은, 0.4중량% 이상이 바람직하고, 0.5중량% 이상이 보다 바람직하고, 0.6중량% 이상이 더욱 바람직하고, 0.8중량% 이상이 한층 바람직하고, 0.9중량% 이상이 보다 한층 바람직하다. 이러한 범위로 함으로써, 내충격성을 보다 효과적으로 향상시킬 수 있다. 한편, 상기 산변성률의 상한값으로는, 4.0중량% 이하가 바람직하고, 3.0중량% 이하가 보다 바람직하고, 2.5중량% 이하가 더욱 바람직하고, 1.8중량% 이하가 한층 바람직하다. 이러한 범위로 함으로써, 본 발명의 수지 조성물을 피복재료(성형품의 피복층)로서 이용할 때, 용융신장이 양호해지고, 피복층의 두께를 보다 균일하게 할 수 있다.The lower limit of the acid modification rate is preferably 0.4 wt% or more, more preferably 0.5 wt% or more, still more preferably 0.6 wt% or more, still more preferably 0.8 wt% or more, and still more preferably 0.9 wt% or more. desirable. By setting it as such a range, impact resistance can be improved more effectively. On the other hand, as an upper limit of the said acid modification rate, 4.0 weight% or less is preferable, 3.0 weight% or less is more preferable, 2.5 weight% or less is still more preferable, and 1.8 weight% or less is still more preferable. By setting it as such a range, when using the resin composition of this invention as a coating material (coating layer of a molded article), melt elongation becomes favorable and the thickness of a coating layer can be made more uniform.

한편, 본 발명에 있어서의 산유도체에 의한 변성률은, 후술하는 실시예에 기재된 방법으로 측정된다.On the other hand, the rate of denaturation by the acid derivative in the present invention is measured by the method described in Examples to be described later.

본 발명에서 이용하는 산변성 폴리올레핀은, 폴리올레핀을 산변성하여 얻어진다. 산변성이란, 산유도체를 폴리올레핀에 어떠한 형태로 반응시키는 것을 말한다. 구체적으로는, 본 발명에서 이용하는 산변성 폴리올레핀은, 산유도체를, 폴리올레핀의 주쇄에 그래프트하거나, 폴리올레핀의 주쇄에 산유도체를 편입시킴으로써 얻어진다. 본 발명에서는, 폴리올레핀은, 폴리올레핀의 주쇄에 산유도체가 그래프트한 그래프트중합체인 것이 바람직하다.The acid-modified polyolefin used in the present invention is obtained by acid-modifying polyolefin. Acid modification refers to reacting an acid derivative with polyolefin in any form. Specifically, the acid-modified polyolefin used in the present invention is obtained by grafting an acid derivative to the main chain of the polyolefin or incorporating the acid derivative into the main chain of the polyolefin. In the present invention, the polyolefin is preferably a graft polymer in which an acid derivative is grafted onto the main chain of the polyolefin.

산유도체로는, 산 또는 산무수물인 것이 바람직하고, 불포화카르본산 또는 불포화카르본산의 무수물인 것이 바람직하고, 불포화카르본산의 무수물인 것이 보다 바람직하다. 불포화카르본산은, 불포화디카르본산인 것이 바람직하고, 불포화카르본산의 무수물도, 불포화디카르본산의 무수물인 것이 바람직하다.As an acid derivative, it is preferable that it is an acid or an acid anhydride, It is preferable that it is an unsaturated carboxylic acid or an anhydride of unsaturated carboxylic acid, It is more preferable that it is an anhydride of unsaturated carboxylic acid. It is preferable that unsaturated carboxylic acid is unsaturated dicarboxylic acid, and it is preferable that the anhydride of unsaturated carboxylic acid is also an anhydride of unsaturated dicarboxylic acid.

산유도체로는, 말레산, 무수말레산, 이타콘산, 무수이타콘산, 5-노보넨-2,3-디카르본산, 5-노보넨-2,3-디카르본산무수물, 엔딕산, 무수엔딕산, 시트라콘산, 무수시트라콘산, 1-부텐-3,4-디카르본산, 1-부텐-3,4-디카르본산무수물이 더욱 바람직하고, 말레산 및 무수말레산이 한층 바람직하고, 무수말레산이 보다 한층 바람직하다.As acid derivatives, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, endic acid, anhydride Endic acid, citraconic acid, citraconic anhydride, 1-butene-3,4-dicarboxylic acid, and 1-butene-3,4-dicarboxylic acid anhydride are more preferable, and maleic acid and maleic anhydride are still more preferable. , maleic anhydride is still more preferable.

상기 공중합체를 산유도체로 변성하는 방법은, 공지의 기술로 행할 수 있고, 특별히 제한은 없으나, 예를 들어, 산유도체와 상기 공중합체의 원료인 단량체를 공중합하는 방법, 산유도체를 상기 공중합체에 그래프트시키는 방법 등을 이용할 수 있다. 한편, 본 발명에 있어서의 수지 조성물에서는, XD계 폴리아미드수지가 산변성 폴리올레핀과 결합해 있는 경우도 있을 것이다.The method for modifying the copolymer into an acid derivative can be carried out by a known technique, and there is no particular limitation. For example, a method of copolymerizing an acid derivative and a monomer that is a raw material of the copolymer, and an acid derivative with the copolymer A method of grafting to , etc. can be used. On the other hand, in the resin composition of the present invention, there may be cases in which the XD-based polyamide resin is bonded to the acid-modified polyolefin.

상기 산변성 폴리올레핀은, 에틸렌유래의 구성단위와 탄소수 3~20의 α-올레핀유래의 구성단위를 포함하는 공중합체를 산변성하여 이루어진 것이 바람직하다. 이러한 구성으로 함으로써, 내충격성이 보다 효과적으로 향상된다.The acid-modified polyolefin is preferably formed by acid-modifying a copolymer comprising ethylene-derived structural units and α-olefin-derived structural units having 3 to 20 carbon atoms. By setting it as such a structure, impact resistance improves more effectively.

탄소수 3~20의 α-올레핀으로는, 탄소수 3~10의 α-올레핀이 바람직하고, 탄소수 3~8의 α-올레핀이 보다 바람직하고, 탄소수 3~5의 α-올레핀이 더욱 바람직하고, 탄소수 3 또는 4의 α-올레핀이 한층 바람직하다. 탄소수 3~20의 α-올레핀의 구체예로는, 프로필렌, 1-부텐, 1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-노넨, 1-데센, 1-운데센, 1-도데센, 1-트리데센, 1-테트라데센, 1-펜타데센, 1-헥사데센, 1-헵타데센, 1-옥타데센, 1-노나데센, 1-에이코센, 3-메틸-1-부텐, 3-메틸-1-펜텐, 3-에틸-1-펜텐, 4-메틸-1-펜텐, 4-메틸-1-헥센, 4,4-디메틸-1-헥센, 4,4-디메틸-1-펜텐, 4-에틸-1-헥센, 3-에틸-1-헥센, 9-메틸-1-데센, 11-메틸-1-도데센 및 12-에틸-1-테트라데센이 예시되고, 프로필렌 및 1-부텐이 바람직하다.The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, still more preferably an α-olefin having 3 to 5 carbon atoms, further preferably an α-olefin having 3 to 5 carbon atoms. 3 or 4 ?-olefins are still more preferred. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 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-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1- Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene are exemplified, and propylene and 1-butene are preferred.

상기 에틸렌유래의 구성단위와 탄소수 3~20의 α-올레핀유래의 구성단위를 포함하는 공중합체는, 탄소수 3~20의 α-올레핀유래의 반복단위를 1종만 포함할 수도 있고, 2종 이상 포함할 수도 있다. 상기 공중합체는, 랜덤중합체여도, 블록중합체여도 된다. 상기 공중합체는, 탄소수 3~20의 α-올레핀유래의 구성단위를 전체구성단위의 6~25몰%의 비율로 포함하는 것이 바람직하고, 보다 바람직하게는 8~22몰%, 더욱 바람직하게는 10~20몰%이다. 이러한 구성으로 함으로써, 내충격성이 보다 효과적으로 향상된다.The copolymer including the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms may include only one type of repeating unit derived from α-olefin having 3 to 20 carbon atoms, or includes two or more types. You may. A random polymer or a block polymer may be sufficient as the said copolymer. The copolymer preferably contains a structural unit derived from an α-olefin having 3 to 20 carbon atoms in a proportion of 6 to 25 mol% of the total structural unit, more preferably 8 to 22 mol%, still more preferably 10 to 20 mol%. By setting it as such a structure, impact resistance improves more effectively.

또한, 상기 공중합체는, 에틸렌유래의 구성단위를, 전체구성단위의 94~75몰%의 비율로 포함하는 것이 바람직하고, 보다 바람직하게는 92~78몰%, 더욱 바람직하게는, 90~80몰%이다.In addition, the copolymer preferably contains ethylene-derived structural units in a ratio of 94 to 75 mol% of the total structural units, more preferably 92 to 78 mol%, still more preferably 90 to 80 is mole %.

나아가, 상기 공중합체는, 에틸렌유래의 구성단위 및 탄소수 3~20의 α-올레핀유래의 구성단위 이외의 다른 구성단위를 포함할 수도 있다. 본 발명에서 이용하는 산변성 폴리올레핀이, 다른 구성단위를 포함하는 경우, 상기 공중합체의 전체구성단위의 10몰% 이하의 범위인 것이 바람직하다.Furthermore, the copolymer may include other structural units other than ethylene-derived structural units and α-olefin-derived structural units having 3 to 20 carbon atoms. When the acid-modified polyolefin used in the present invention includes other structural units, it is preferably in the range of 10 mol% or less of the total structural units of the copolymer.

상기 공중합체의 구체예로는, 에틸렌/프로필렌 공중합체, 에틸렌/부텐-1 공중합체, 에틸렌/헥센-1 공중합체, 에틸렌/프로필렌/디시클로펜타디엔 공중합체, 에틸렌/프로필렌/5-에틸리덴-2-노보넨 공중합체가 예시된다.Specific examples of the copolymer include ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/hexene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene A -2-norbornene copolymer is exemplified.

본 발명에서 이용하는 산변성 폴리올레핀의 시판품으로는, 미쯔이화학제 타프머(상품명, 그래프트 중합체), 듀퐁제 푸사본드(상품명), 다우제 Amplify(상품명) 등을 들 수 있다.Examples of commercially available acid-modified polyolefins used in the present invention include Mitsui Chemical Taffmer (trade name, graft polymer), DuPont Fusabond (trade name), Dow Amplify (trade name), and the like.

본 발명의 수지 조성물은, XD계 폴리아미드수지 100중량부에 대하여, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 3~17중량부를 포함한다. 산변성 폴리올레핀의 배합량의 하한값은, XD계 폴리아미드수지 100중량부에 대하여, 4중량부 이상이 바람직하고, 5중량부 이상이 보다 바람직하고, 6중량부 이상이 더욱 바람직하고, 7중량부 이상이 한층 바람직하고, 9중량부 이상이 보다 한층 바람직하다. 산변성 폴리올레핀의 배합량의 상한값은, XD계 폴리아미드수지 100중량부에 대하여, 16중량부 이하가 바람직하다. 이러한 범위로 함으로써, 본 발명의 효과가 보다 효과적으로 달성된다.The resin composition of the present invention contains 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight based on 100 parts by weight of the XD-based polyamide resin. The lower limit of the compounding amount of the acid-modified polyolefin is preferably 4 parts by weight or more, more preferably 5 parts by weight or more, still more preferably 6 parts by weight or more, and 7 parts by weight or more with respect to 100 parts by weight of the XD-based polyamide resin. This is still more preferable, and 9 parts by weight or more is still more preferable. As for the upper limit of the compounding quantity of an acid-modified polyolefin, 16 weight part or less is preferable with respect to 100 weight part of XD-type polyamide resins. By setting it as such a range, the effect of this invention is achieved more effectively.

본 발명의 수지 조성물은, 산변성 폴리올레핀을 1종만 포함할 수도 있고, 2종 이상 포함할 수도 있다. 2종 이상 포함하는 경우, 합계량이 상기 범위가 되는 것이 바람직하다.The resin composition of this invention may contain only 1 type, and may contain 2 or more types of acid-modified polyolefin. When 2 or more types are included, it is preferable that a total amount becomes the said range.

한편, 본 발명의 수지 조성물은, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀 이외의 다른 폴리올레핀을 포함할 수도 있으나, 실질적으로 다른 폴리올레핀을 포함하지 않는 편이 바람직하다. 실질적으로 포함하지 않는다는 것은, 본 발명의 수지 조성물에 포함되는 폴리올레핀 중, 다른 폴리올레핀의 양이 5중량% 이하인 것을 말한다.On the other hand, the resin composition of the present invention may contain other polyolefins other than the acid-modified polyolefin having an acid-modified rate of 0.3 to 5.0% by weight, but it is preferably substantially free of other polyolefins. Not substantially included means that the amount of other polyolefins is 5 wt% or less among polyolefins contained in the resin composition of the present invention.

<다른 열가소성 수지><Other thermoplastic resins>

본 발명의 수지 조성물은, 상기 폴리아미드수지, 다른 폴리아미드수지, 및, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀 이외의 기타 열가소성 수지를 포함할 수도 있다. 구체적으로는, 폴리페닐렌에테르수지, 폴리스티렌수지, 열가소성 폴리에스테르수지, 폴리아세탈수지, 폴리우레탄수지, 폴리유산계 수지, 폴리페닐렌설파이드수지 등을 들 수 있다.The resin composition of the present invention may contain the above polyamide resin, other polyamide resins, and other thermoplastic resins other than the acid-modified polyolefin having an acid-modified rate of 0.3 to 5.0% by weight. Specific examples include polyphenylene ether resins, polystyrene resins, thermoplastic polyester resins, polyacetal resins, polyurethane resins, polylactic acid-based resins, and polyphenylene sulfide resins.

본 발명의 수지 조성물에 있어서의 다른 열가소성 수지의 비율은, 배합하는 경우, 수지성분의 5~20중량%의 범위내에서 배합하는 것이 바람직하다. 또한, 다른 열가소성 수지를 실질적으로 포함하지 않는 구성으로 할 수도 있다. 실질적으로 포함하지 않는다는 것은, 본 발명의 수지 조성물에 포함되는 수지성분 중, 다른 열가소성 수지의 양이 5중량% 이하인 것을 말한다.When mix|blending, it is preferable to mix|blend the ratio of the other thermoplastic resin in the resin composition of this invention within the range of 5 to 20 weight% of a resin component. Moreover, it can also be set as the structure which does not contain another thermoplastic resin substantially. Substantially not included means that the amount of the other thermoplastic resin among the resin components included in the resin composition of the present invention is 5 wt% or less.

<일반식(1)로 표시되는 화합물><Compound represented by general formula (1)>

본 발명의 수지 조성물은, 일반식(1)로 표시되는 화합물을 포함한다.The resin composition of this invention contains the compound represented by General formula (1).

일반식(1)General formula (1)

[화학식 3][Formula 3]

Figure 112019037335319-pct00003
Figure 112019037335319-pct00003

일반식(1) 중, R1은, 탄소수 1~10의 알킬기이며, R2는, 탄소수 2~12의 알킬기이며, n은 1~3의 정수이다.In general formula (1), R< 1 > is a C1-C10 alkyl group, R< 2 > is a C2-C12 alkyl group, and n is an integer of 1-3.

일반식(1)로 표시되는 화합물에 있어서, OH기의 부분은, 오르토위치, 파라위치, 메타위치 중 어느 것으로 치환될 수도 있으나, 파라위치 또는 오르토위치가 바람직하고, 파라위치가 보다 바람직하다.In the compound represented by the general formula (1), the portion of the OH group may be substituted with any of the ortho, para, and meta positions, but the para position or ortho position is preferable, and the para position is more preferable.

일반식(1)로 표시되는 화합물에 있어서, n은 1 또는 2가 바람직하고, 1이 더욱 바람직하다.In the compound represented by general formula (1), 1 or 2 is preferable and, as for n, 1 is more preferable.

일반식(1)에 있어서의 R1로 표시되는 알킬기의 탄소수의 하한값은, 2 이상인 것이 바람직하고, 3 이상인 것이 보다 바람직하고, 4 이상인 것이 더욱 바람직하고, 5 이상인 것이 한층 바람직하다. R1로 표시되는 알킬기의 탄소수의 상한값은, 9 이하인 것이 바람직하고, 8 이하인 것이 보다 바람직하고, 7 이하인 것이 더욱 바람직하고, 6 이하인 것이 한층 바람직하다. R1로서의 알킬기는, 직쇄 또는 분지알킬기가 바람직하고, 직쇄알킬기가 보다 바람직하다. 이러한 구성으로 함으로써, 내충격성이 보다 향상되는 경향이 있다.It is preferable that it is 2 or more, and, as for the lower limit of carbon number of the alkyl group represented by R< 1 > in General formula (1), it is more preferable that it is 3 or more, It is more preferable that it is 4 or more, It is still more preferable that it is 5 or more. It is preferable that it is 9 or less, and, as for the upper limit of carbon number of the alkyl group represented by R< 1 >, it is more preferable that it is 8 or less, It is more preferable that it is 7 or less, It is still more preferable that it is 6 or less. A straight-chain or branched alkyl group is preferable, and, as for the alkyl group as R< 1 >, a straight-chain alkyl group is more preferable. By setting it as such a structure, there exists a tendency for impact resistance to improve more.

일반식(1)로 표시되는 화합물에 있어서, R2로 표시되는 알킬기의 탄소수의 하한값은, 3 이상인 것이 바람직하고, 5 이상인 것이 보다 바람직하고, 6 이상인 것이 더욱 바람직하고, 7 이상인 것이 한층 바람직하다. R2로 표시되는 알킬기의 탄소수의 상한값은, 11 이하인 것이 바람직하고, 10 이하인 것이 보다 바람직하고, 9 이하인 것이 더욱 바람직하다. R2로서의 알킬기는, 직쇄 또는 분지알킬기가 바람직하고, 직쇄알킬기가 보다 바람직하다. 이러한 구성으로 함으로써, 내충격성이 보다 향상되는 경향이 있다.In the compound represented by the general formula (1), the lower limit of the number of carbon atoms in the alkyl group represented by R 2 is preferably 3 or more, more preferably 5 or more, still more preferably 6 or more, and still more preferably 7 or more. . It is preferable that it is 11 or less, and, as for the upper limit of carbon number of the alkyl group represented by R< 2 >, it is more preferable that it is 10 or less, It is still more preferable that it is 9 or less. A straight-chain or branched alkyl group is preferable, and, as for the alkyl group as R< 2 >, a straight-chain alkyl group is more preferable. By setting it as such a structure, there exists a tendency for impact resistance to improve more.

또한, 본 발명에서는, 일반식(1)로 표시되는 화합물에 있어서, R2를 구성하는 탄소수가, R1을 구성하는 탄소수보다, 2 이상 큰 것이 바람직하고, 2~4 큰 것이 보다 바람직하다. 이러한 구성으로 함으로써, 내충격성이 보다 향상되는 경향이 있다.Moreover, in this invention, in the compound represented by General formula (1), it is preferable that carbon number which comprises R< 2 > is 2 or more larger than carbon number which comprises R< 1 >, and it is more preferable that it is 2-4 larger. By setting it as such a structure, there exists a tendency for impact resistance to improve more.

이하에, 일반식(1)로 표시되는 화합물의 예를 든다. 그러나, 본 발명이 이것들로 한정되지 않는 것은 물론이다.Below, the example of the compound represented by General formula (1) is given. However, it goes without saying that the present invention is not limited to these.

[화학식 4][Formula 4]

Figure 112019037335319-pct00004
Figure 112019037335319-pct00004

본 발명의 수지 조성물은, XD계 폴리아미드수지 100중량부에 대하여, 일반식(1)로 표시되는 화합물을 1~15중량부 포함한다. 일반식(1)로 표시되는 화합물의 하한값으로는, 4중량부 이상이 바람직하고, 5중량부 이상이 보다 바람직하고, 6중량부 이상이 더욱 바람직하고, 7중량부 이상이 한층 바람직하다. 또한, 상한값으로는, 14중량부 이하가 바람직하다.The resin composition of the present invention contains 1 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the XD-based polyamide resin. As a lower limit of the compound represented by General formula (1), 4 weight part or more is preferable, 5 weight part or more is more preferable, 6 weight part or more is still more preferable, 7 weight part or more is still more preferable. Moreover, as an upper limit, 14 weight part or less is preferable.

일반식(1)로 표시되는 화합물은, 1종만일 수도 있고, 2종 이상일 수도 있다. 2종 이상 포함하는 경우, 합계량이 상기 범위인 것이 바람직하다.One type may be sufficient as the compound represented by General formula (1), and 2 or more types may be sufficient as it. When 2 or more types are included, it is preferable that a total amount is the said range.

본 발명의 수지 조성물은, 일반식(1)로 표시되는 화합물과, 산변성률이 0.3~5중량%의 산변성 폴리올레핀의 중량비가, 3:10~16:10인 것이 바람직하고, 3:10~13:10이 보다 바람직하고, 4:10~13:10이 더욱 바람직하고, 5:10~13:10이 한층 바람직하다. 이러한 범위로 함으로써, 산소배리어성과 내충격성을 밸런스 좋게, 보다 향상시킬 수 있다.In the resin composition of the present invention, the weight ratio of the compound represented by the general formula (1) and the acid-modified polyolefin having an acid modification rate of 0.3 to 5% by weight is preferably 3:10 to 16:10, 3:10 -13:10 are more preferable, 4:10-13:10 are still more preferable, and 5:10-13:10 are still more preferable. By setting it as such a range, oxygen barrier property and impact resistance can be improved more with good balance.

<다른 첨가제><Other additives>

나아가, 본 발명의 목적·효과를 손상시키지 않는 범위에서, 본 발명의 수지 조성물에는, 충전제, 산화방지제, 열안정제 등의 안정제, 내가수분해성 개량제, 내후안정제, 염소제, 자외선흡수제, 핵제, 가소제, 분산제, 난연제, 대전방지제, 착색방지제, 겔화방지제, 착색제, 이형제, 활제 등의 첨가제 등을 첨가할 수 있다. 이들 상세는, 일본특허 제4894982호 공보의 단락 0130~0155의 기재를 참작할 수 있고, 이들 내용은 본 명세서에 편입된다.Further, within the scope not impairing the object and effect of the present invention, the resin composition of the present invention contains fillers, antioxidants, stabilizers such as heat stabilizers, hydrolysis resistance improving agents, weathering stabilizers, chlorine agents, ultraviolet absorbers, nucleating agents, and plasticizers. , a dispersant, a flame retardant, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a colorant, a releasing agent, and an additive such as a lubricant may be added. These details can consider description of Paragraph 0130 - 0155 of Unexamined-Japanese-Patent No. 4894982, and these content is integrated in this specification.

한편, 일반식(1)로 표시되는 화합물은, 수지 조성물의 가소제로서 이용되는 것도 있는데, 본 발명의 수지 조성물에서는, 일반식(1)로 표시되는 화합물 이외의 가소제를 실질적으로 포함하지 않는 구성으로 하는 것이 바람직하다. 실질적으로 포함하지 않는다는 것은, 예를 들어, 본 발명의 수지 조성물에 있어서, 다른 가소제의 함유량이, 일반식(1)로 표시되는 화합물의 중량의 0.1중량% 이하인 것을 말한다. 다른 가소제로는, 일본특허공개 H7-11131호 공보의 단락 0039에 기재된 가소제나 일본특허공개 2001-302908호 공보의 단락 0031에 기재된 가소제가 예시된다.On the other hand, the compound represented by the general formula (1) may be used as a plasticizer in the resin composition, but in the resin composition of the present invention, a plasticizer other than the compound represented by the general formula (1) is substantially not included. It is preferable to do Not containing substantially means that, for example, in the resin composition of this invention, content of another plasticizer is 0.1 weight% or less of the weight of the compound represented by General formula (1). As another plasticizer, the plasticizer of Paragraph 0039 of Unexamined-Japanese-Patent No. H7-11131, and the plasticizer of Paragraph 0031 of Unexamined-Japanese-Patent No. 2001-302908 are illustrated.

<수지 조성물의 특성><Characteristics of the resin composition>

본 발명의 수지 조성물은, ISO다목적시험편(두께: 4mm)으로 성형하고, ISO 179 1eA에 따라서 측정한 샤르피충격값이, 상기 수지 조성물로부터, 일반식(1)로 표시되는 화합물을 제외한 수지 조성물을 ISO다목적시험편(두께: 4mm)에 성형하고, ISO 179 1eA에 따라서 측정한 샤르피충격값보다 높은 것이 바람직하고, 1.5배 이상 높은 것이 보다 바람직하고, 2.0배 이상 높은 것이 더욱 바람직하고, 3.0배 이상 높은 것이 한층 바람직하다. 상기 배율은 높은 편이 바람직하나, 4.0배 이하, 더 나아가 3.7배 이하일 수도 있다. 여기서의, 샤르피충격값은, 실시예에 기재된 방법에 따라서 측정된다.The resin composition of the present invention is molded into an ISO multi-purpose test piece (thickness: 4 mm), and the Charpy impact value measured in accordance with ISO 179 1eA is, from the resin composition, a resin composition excluding the compound represented by the general formula (1). It is molded into an ISO multipurpose test piece (thickness: 4 mm) and is preferably higher than the Charpy impact value measured in accordance with ISO 179 1eA, more preferably 1.5 times or more, still more preferably 2.0 times or more, and 3.0 times or more higher more preferably. The magnification is preferably higher, but may be 4.0 times or less, and further, 3.7 times or less. Here, the Charpy impact value is measured according to the method described in Examples.

<수지 조성물의 바람직한 실시형태><Preferred embodiment of resin composition>

본 발명의 수지 조성물의 바람직한 실시형태로서, 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.3~5중량%의 산변성 폴리올레핀을 6~17중량부, 및, 일반식(1)로 표시되는 화합물을 4~15중량부 포함하는, 수지 조성물을 들 수 있다.As a preferred embodiment of the resin composition of the present invention, it is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and derived from dicarboxylic acid. Based on 100 parts by weight of the polyamide resin derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 70 mol% or more of the constituent units of - 17 weight part and the resin composition containing 4-15 weight part of compounds represented by General formula (1) are mentioned.

본 발명의 수지 조성물의 보다 바람직한 실시형태로서, 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.6~5중량%의 산변성 폴리올레핀을 6~17중량부, 및, 일반식(1)로 표시되는 화합물을 4~15중량부 포함하는, 수지 조성물을 들 수 있다.As a more preferred embodiment of the resin composition of the present invention, it is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and dicarboxylic acid With respect to 100 parts by weight of the polyamide resin derived from α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 70 mol% or more of the derived structural unit contains an acid-modified polyolefin having an acid modification rate of 0.6 to 5% by weight. The resin composition containing 6-17 weight part and 4-15 weight part of compounds represented by General formula (1) is mentioned.

본 발명의 수지 조성물의 특히 바람직한 실시형태로서, 디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.6~5중량%의 산변성 폴리올레핀을 6~17중량부, 및, 일반식(1)로 표시되는 화합물을 4~15중량부 포함하고, 일반식(1)에 있어서, R1이 탄소수 3~10의 알킬기이며, R2가 탄소수 5~12의 알킬기인, 수지 조성물을 들 수 있다.As a particularly preferred embodiment of the resin composition of the present invention, it is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and dicarboxylic acid With respect to 100 parts by weight of the polyamide resin derived from α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 70 mol% or more of the derived structural unit contains an acid-modified polyolefin having an acid modification rate of 0.6 to 5% by weight. 6 to 17 parts by weight, and 4 to 15 parts by weight of the compound represented by the general formula (1), in the general formula (1), R 1 is an alkyl group having 3 to 10 carbon atoms, and R 2 is 5 carbon atoms The resin composition which is a -12 alkyl group is mentioned.

또한, 본 발명의 수지 조성물의 다른 일실시형태(「블렌드의 실시형태」라고 하기도 한다)로서, 본 발명의 수지 조성물에 있어서, 상기 폴리아미드수지가, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는, 수지 조성물이 예시된다. 이러한 구성으로 함으로써, 지방족 폴리아미드수지(특히, 폴리아미드12 및 폴리아미드11)와의 접착성을 보다 향상시킬 수 있다. 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지와 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지의 블렌드비율은, 10~90중량부에 대하여, 90~10중량부인 것이 바람직하고, 30~80중량부에 대하여, 20~70중량부인 것이 보다 바람직하고, 50~80중량부에 대하여, 20~50중량부인 것이 더욱 바람직하다. 본 실시형태에 있어서는, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지와 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지의 합계가, 본 발명의 수지 조성물에 포함되는 폴리아미드수지의 90중량% 이상을 차지하는 것이 바람직하고, 95중량% 이상을 차지하는 것이 보다 바람직하다. 블렌드의 실시형태에 있어서도, 더욱, 상기 바람직한 실시형태를 만족시키는 것이 바람직하다.Further, as another embodiment of the resin composition of the present invention (also referred to as "embodiment of blend"), in the resin composition of the present invention, the polyamide resin is 70 mol% of the structural unit derived from dicarboxylic acid. With respect to 10 to 90 parts by weight of the polyamide resin derived from adipic acid, 70 mol% or more of the structural unit derived from dicarboxylic acid contains 90 to 10 parts by weight of the polyamide resin derived from sebacic acid. , a resin composition is exemplified. By setting it as such a structure, adhesiveness with an aliphatic polyamide resin (especially polyamide 12 and polyamide 11) can be improved more. The blend ratio of the polyamide resin in which at least 70 mol% of the constituent units derived from dicarboxylic acid is derived from adipic acid and the polyamide resin in which at least 70 mol% of the constituent units derived from dicarboxylic acid is derived from sebacic acid is 10 With respect to -90 weight part, it is preferable that it is 90-10 weight part, With respect to 30-80 weight part, it is more preferable that it is 20-70 weight part, With respect to 50-80 weight part, it is still more preferable that it is 20-50 weight part. Do. In the present embodiment, 70 mol% or more of the structural unit derived from dicarboxylic acid is a polyamide resin derived from adipic acid, and 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from sebacic acid. It is preferable that the sum total of occupies 90 weight% or more of the polyamide resin contained in the resin composition of this invention, and it is more preferable that it occupies 95 weight% or more. Also in embodiment of blend, it is further more preferable to satisfy the said preferable embodiment.

<수지 조성물의 제조방법><Method for producing resin composition>

수지 조성물의 제조방법으로는, 임의의 방법을 채용할 수 있다. 예를 들어, 폴리아미드수지와, 산변성 폴리올레핀과, 일반식(1)로 표시되는 화합물과, 필요에 따라 배합되는 다른 성분을 V형 블렌더 등의 혼합수단을 이용하여 혼합하고, 일괄 블렌드품을 조제한 후, 벤트부착 압출기로 용융혼련하여 펠릿화하는 방법을 들 수 있다. 혹은, 2단계 연입법으로서, 미리, 충전제 이외의 성분 등을, 충분히 혼합 후, 벤트부착 압출기로 용융혼련하여 펠릿을 제조한 후, 그 펠릿과 충전제를 혼합 후, 벤트부착 압출기로 용융혼련하는 방법을 들 수 있다.Arbitrary methods can be employ|adopted as a manufacturing method of a resin composition. For example, the polyamide resin, the acid-modified polyolefin, the compound represented by the general formula (1), and other components to be blended as needed are mixed using a mixing means such as a V-type blender, and a batch blend product is obtained. After preparation, the method of melt-kneading with a vent extruder and pelletizing is mentioned. Alternatively, as a two-step continuous method, after sufficiently mixing components other than the filler in advance, melt-kneading with a vented extruder to prepare pellets, the pellet and the filler are mixed, followed by melt-kneading with a vented extruder can be heard

상기 서술한 블렌드의 실시형태에 있어서는, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지와, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지와, 산변성 폴리올레핀과, 일반식(1)로 표시되는 화합물과, 필요에 따라 배합되는 다른 성분을 V형 블렌더 등의 혼합수단을 이용하여 혼합하고, 일괄블렌드하는 것이 예시된다. 또한, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지와, 산변성 폴리올레핀과, 일반식(1)로 표시되는 화합물과, 필요에 따라 배합되는 다른 성분을 용융혼련하여 얻은 펠릿과, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지와, 산변성 폴리올레핀과, 일반식(1)로 표시되는 화합물과, 필요에 따라 배합되는 다른 성분을 용융혼련하여 얻은 펠릿을 드라이블렌드할 수도 있다.In the above-described embodiment of the blend, 70 mol% or more of the structural units derived from dicarboxylic acid are the polyamide resin derived from adipic acid, and 70 mol% or more of the structural units derived from dicarboxylic acid are from sebacic acid. It is exemplified that the derived polyamide resin, the acid-modified polyolefin, the compound represented by the general formula (1), and other components to be blended as necessary are mixed using a mixing means such as a V-type blender and blended together. . In addition, 70 mol% or more of the structural unit derived from dicarboxylic acid is a polyamide resin derived from adipic acid, an acid-modified polyolefin, a compound represented by the general formula (1), and other components blended as necessary. Pellets obtained by melt-kneading, a polyamide resin derived from sebacic acid at least 70 mol% of the constituent units derived from dicarboxylic acid, an acid-modified polyolefin, and a compound represented by the general formula (1) are blended as needed It is also possible to dry blend the pellets obtained by melt-kneading other components to be used.

나아가, 충전제 이외의 성분 등을, V형 블렌더 등으로 충분히 혼합한 것을 미리 조정해두고, 이 혼합물을 벤트부착 이축압출기의 제1 슈트로부터 공급하고, 충전제는 압출기 도중의 제2 슈트로부터 공급하여 용융혼련, 펠릿화하는 방법을 들 수 있다.Furthermore, ingredients other than the filler are sufficiently mixed with a V-type blender or the like, and this mixture is supplied from the first chute of the vented twin screw extruder, and the filler is supplied from the second chute in the middle of the extruder and melted The method of kneading|mixing and pelletizing is mentioned.

압출기의 혼련존의 스크류구성은, 혼련을 촉진하는 엘리먼트를 상류측에, 승압능력이 있는 엘리먼트를 하류측에 배치하는 것이 바람직하다.As for the screw configuration of the kneading zone of the extruder, it is preferable to arrange the element for promoting kneading on the upstream side and the element having the pressure-increasing ability on the downstream side.

혼련을 촉진하는 엘리먼트로는, 순차이동 니딩디스크엘리먼트, 직교 니딩디스크엘리먼트, 광폭 니딩디스크엘리먼트, 및 순차이동 믹싱스크류엘리먼트 등을 들 수 있다.Examples of the element for promoting kneading include a sequential kneading disk element, an orthogonal kneading disk element, a wide kneading disk element, and a sequentially moving mixing screw element.

용융혼련에 있어서의 가열온도는, 수지의 융점에 따라 190~350℃의 범위로부터 적당히 선택할 수 있다. 온도가 지나치게 높으면 분해가스가 발생하기 쉽고, 불투명화의 원인이 되는 경우가 있다. 이 때문에, 전단발열 등을 고려한 스크류구성을 선정하는 것이 바람직하다. 또한, 혼련시나, 후행정의 성형시의 분해를 억제하는 관점에서, 산화방지제나 열안정제를 사용하는 것이 바람직하다.The heating temperature in melt-kneading can be appropriately selected from the range of 190 to 350°C depending on the melting point of the resin. When the temperature is too high, decomposition gas is likely to be generated, which may cause opacification. For this reason, it is preferable to select a screw configuration in consideration of shear heat generation and the like. In addition, from the viewpoint of suppressing decomposition at the time of kneading or molding of the post-stroke, it is preferable to use an antioxidant or a heat stabilizer.

<성형품><Molded article>

본 발명의 성형품은, 본 발명의 수지 조성물을 성형하여 이루어진다. 성형방법으로는, 종래 공지의 성형방법을 채용할 수 있다. 구체적으로는, 사출성형, 블로우성형, 압출성형, 압축성형, 진공성형, 프레스성형, 다이렉트블로우성형, 회전성형, 샌드위치성형 및 이색성형 등의 성형방법을 예시할 수 있다.The molded article of this invention is formed by shape|molding the resin composition of this invention. As a shaping|molding method, a conventionally well-known shaping|molding method is employable. Specifically, molding methods such as injection molding, blow molding, extrusion molding, compression molding, vacuum molding, press molding, direct blow molding, rotational molding, sandwich molding, and dichroic molding can be exemplified.

본 발명의 성형품은, 섬유, 실, 로프, 튜브, 호스, 필름, 시트, 각종 성형재료, 각종 부품, 완성품에 널리 이용된다. 이용분야에 대해서는 특별히 정하는 것은 아니나, 자동차 등 수송기부품, 일반기계부품, 정밀기계부품, 전자·전기기기부품, OA기기부품, 건재·주택설비관련부품, 의료장치, 레저스포츠용품, 유희구, 의료품, 식품포장용 필름 등의 일용품, 방위 및 항공우주제품 등에 널리 이용된다.The molded article of the present invention is widely used for fibers, threads, ropes, tubes, hoses, films, sheets, various molding materials, various parts, and finished products. The field of use is not specifically defined, but transportation equipment parts such as automobiles, general machinery parts, precision machinery parts, electronic and electric equipment parts, OA equipment parts, building materials and housing equipment related parts, medical devices, leisure sports goods, entertainment equipment, medical products, It is widely used in daily necessities such as food packaging film, defense and aerospace products.

<피복재료로서의 이용><Use as a covering material>

본 발명의 수지 조성물은 특히, 내충격성에 더하여, 피복성도 우수한 점에서, 피복재료로서 바람직하게 이용된다. 본 발명의 수지 조성물이 피복재료로서 이용되는 경우의 성형품으로는, 심재와, 심재의 피복층을 포함하고, 피복층이 본 발명의 수지 조성물로부터 형성되는 성형품이 예시된다.The resin composition of the present invention is particularly preferably used as a coating material in addition to impact resistance and excellent coating properties. As a molded article in the case where the resin composition of this invention is used as a coating material, it contains a core material and the coating layer of a core material, The molded article in which the coating layer is formed from the resin composition of this invention is illustrated.

피복의 대상이 되는 심재로는, 얇고, 장척상의 재료로서, 표면에 본 발명의 수지 조성물을 피복할 수 있는 것이면, 특별히 정하는 것은 아니나, 공지의 것을 널리 채용할 수 있다. 예를 들어, 금속선이나, 광케이블 등의 광도파로, 파이프 및 튜브 등의 연속중공체 등이 예시된다. 본 발명의 심재의 형상의 일례로서, 평균직경 50μm~1cm(바람직하게는, 평균직경 50μm~8mm)로서, 50cm 이상의 길이인 것이 예시된다. 이러한 심재는, 연속중공체일 수도 있는 것은 물론이다.The core material to be coated is not particularly defined as long as it is a thin, elongated material that can coat the surface of the resin composition of the present invention, but a known material can be widely adopted. For example, an optical waveguide, such as a metal wire or an optical cable, continuous hollow bodies, such as a pipe and a tube, etc. are illustrated. As an example of the shape of the core material of this invention, as an average diameter of 50 micrometers - 1 cm (preferably, an average diameter of 50 micrometers - 8 mm), a length of 50 cm or more is illustrated. It goes without saying that such a core material may be a continuous hollow body.

피복층의 평균두께로는, 100μm~1mm가 예시되고, 200μm~800μm가 바람직하다.As an average thickness of a coating layer, 100 micrometers - 1 mm are illustrated, and 200 micrometers - 800 micrometers are preferable.

또한, 본 발명의 수지 조성물은, 산소배리어성도 우수한 점에서, 상온분위기하에서 이용될 수 있는 성형품의 피복층으로서 적합하다. 상온분위기하의 예로는, 예를 들어 100℃ 이상, 더 나아가 120℃ 이상의 온도를 말하고, 상한은 특별히 정하지 않으나, 예를 들어 140℃ 이하이다. 본 발명에서는, 폴리메틸메타크릴레이트(PMMA)로부터 구성되는 직경 5mm의 심재에, 본 발명의 수지 조성물을 평균두께가 500μm가 되도록 피복하고, 상기 상온분위기하 240시간에 있어서도, YI값(옐로우인덱스값)의 변화가 5를 초과하여 변화하지 않는 것이 바람직하다. 여기서의, YI값의 측정은, 후술하는 실시예에 기재된 방법에 따른다.Further, the resin composition of the present invention is also excellent in oxygen barrier properties, and therefore is suitable as a coating layer for a molded article that can be used in a room temperature atmosphere. Examples of the ambient temperature atmosphere include, for example, 100° C. or higher, further, 120° C. or higher, and the upper limit is not particularly determined, but is, for example, 140° C. or lower. In the present invention, the resin composition of the present invention is coated on a core material having a diameter of 5 mm composed of polymethyl methacrylate (PMMA) so that the average thickness is 500 μm, and the YI value (yellow index value) does not change by more than 5. Here, the YI value is measured according to the method described in Examples to be described later.

본 발명의 성형품으로서의 광도파로는, 심재를 본 발명의 수지 조성물로 피복한 것이 예시된다.Examples of the optical waveguide as a molded article of the present invention include those in which a core material is coated with the resin composition of the present invention.

본 발명의 성형품이 광도파로인 경우, 심재는, 광전송 등의 기능을 잃지 않는 것이면 되고, PMMA(폴리메틸메타크릴레이트), 유리 등이 예시된다.When the molded article of the present invention is an optical waveguide, the core material may be any material that does not lose functions such as light transmission, and examples thereof include PMMA (polymethyl methacrylate) and glass.

심재의 피복에 있어서, 심재의 표면에 수지 조성물을 피복할 수도 있고, 심재의 표면에 클래드층 등의 임의의 층을 마련한 후, 상기 클래드층 등의 표면에 본 발명의 수지 조성물을 피복할 수도 있다. 본 발명의 바람직한 실시형태로서, 심재의 표면에 클래드층을 갖고, 상기 클래드층의 표면에 본 발명의 수지 조성물로부터 형성되는 층을 갖는 광도파로가 예시된다. 클래드층으로는, 불소수지가 예시된다. 클래드층으로서의 불소수지의 상세는, 일본특허공개 2007-071929호 공보의 단락 0041 및 0042의 기재, 그리고, 일본특허공개 2003-084148호 공보의 단락 0048의 기재를 참작할 수 있고, 이들 내용은 본 명세서에 편입된다.In coating the core material, the resin composition may be coated on the surface of the core material, or an arbitrary layer such as a cladding layer may be provided on the surface of the core material, and then the surface of the cladding layer or the like may be coated with the resin composition of the present invention. . As a preferred embodiment of the present invention, an optical waveguide having a cladding layer on the surface of a core and a layer formed from the resin composition of the present invention on the surface of the cladding layer is exemplified. As the cladding layer, a fluororesin is exemplified. For the details of the fluororesin as the cladding layer, the description of paragraphs 0041 and 0042 of Japanese Patent Application Laid-Open No. 2007-071929 and the description of paragraph 0048 of Japanese Patent Application Laid-Open No. 2003-084148 can be considered. incorporated into the specification.

광화이버케이블은, 사용형태에 따라서는, 폴리아미드12 등의 지방족 폴리아미드수지제의 커넥터와 접속되는 경우가 있다. 이 때문에, 본 발명의 수지 조성물도 지방족 폴리아미드수지와의 접착성이 요구되는 경우가 있다. 지방족 폴리아미드수지와의 접착성의 관점에서는, 본 발명의 수지 조성물은, 상기 블렌드의 실시형태인 것이 바람직하다.An optical fiber cable may be connected to a connector made of an aliphatic polyamide resin, such as polyamide 12, depending on the mode of use. For this reason, also in the resin composition of this invention, adhesiveness with an aliphatic polyamide resin may be requested|required. From the viewpoint of adhesiveness with the aliphatic polyamide resin, the resin composition of the present invention is preferably the embodiment of the blend described above.

또한, 본 발명의 성형품의 일실시형태로서, 심재와, 상기 심재의 피복층(제1 피복층)을 포함하고, 제1 피복층이 본 발명의 수지 조성물로부터 형성되고, 다시, 제1 피복층에 접하는, 지방족 폴리아미드수지(바람직하게는 폴리아미드11 및 폴리아미드12의 적어도 1종, 보다 바람직하게는 폴리아미드12)를 주성분으로 하는 제2 피복층을 갖는 성형품이 예시된다. 제1 피복층은, 본 발명의 수지 조성물로부터 형성된다. 특히, 수지 조성물에 포함되는 폴리아미드수지가 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는 것이 바람직하다.Further, as an embodiment of the molded article of the present invention, an aliphatic comprising a core material and a coating layer (first coating layer) of the core material, wherein the first coating layer is formed from the resin composition of the present invention and again in contact with the first coating layer A molded article having a second coating layer mainly composed of a polyamide resin (preferably at least one of polyamide 11 and polyamide 12, more preferably polyamide 12) is exemplified. A 1st coating layer is formed from the resin composition of this invention. In particular, with respect to 10 to 90 parts by weight of the polyamide resin in which the polyamide resin contained in the resin composition is 70 mol% or more of the constituent units derived from dicarboxylic acid derived from adipic acid, 70 of the constituent units derived from dicarboxylic acid It is preferable that the mol% or more contains the polyamide resin derived from sebacic acid in a ratio of 90 to 10 parts by weight.

여기서, 지방족 폴리아미드수지를 주성분으로 한다는 것은, 제2 피복층에 포함되는 성분 중, 가장 함유량이 많은 수지성분이 지방족 폴리아미드수지인 것을 말하고, 제2 피복층에 포함되는 수지성분의 80중량% 이상이 지방족 폴리아미드수지인 것이 바람직하다.Here, the aliphatic polyamide resin as the main component means that the resin component with the highest content among the components included in the second coating layer is the aliphatic polyamide resin, and 80% by weight or more of the resin component included in the second coating layer It is preferable that it is an aliphatic polyamide resin.

제2 피복층은, 제1 피복층의 외층일 수도 있고, 제1 피복층의 내층일 수도 있다. 바람직하게는, 제2 피복층은, 제1 피복층의 외층인 것이 바람직하다. 이러한 외층을 마련함으로써, 내황산성이 우수한 성형품이 얻어진다. 또한, 제1 피복층의 외층으로서, 제2 피복층을 마련하는 경우, 제1 피복층의 내층으로 해도, 지방족 폴리아미드수지를 주성분으로 하는 피복층을 마련해도 된다.The second coating layer may be an outer layer of the first coating layer or an inner layer of the first coating layer. Preferably, it is preferable that the 2nd coating layer is an outer layer of the 1st coating layer. By providing such an outer layer, a molded article excellent in sulfuric acid resistance is obtained. Moreover, when providing a 2nd coating layer as an outer layer of a 1st coating layer, you may provide the coating layer which has an aliphatic polyamide resin as a main component as an inner layer of a 1st coating layer.

제2 피복층에는, 지방족 폴리아미드수지 이외의 폴리아미드수지, 변성 폴리올레핀, 기타 열가소성 수지, 각종 첨가제, 유리섬유 등의 강화제를 배합해도 된다. 이들 상세는, 국제공개 WO2015/022818호 팜플렛의 단락 0018~0025의 기재를 참작할 수 있고, 이들 내용은 본 명세서에 편입된다. 또한, 제1 피복층과 제2 피복층의 층구성 및 성형방법에 대해서는, 국제공개 WO2015/022818호 팜플렛의 단락 0051~0054의 기재를 참작할 수 있고, 이들 내용은 본 명세서에 편입된다.In the second coating layer, a reinforcing agent such as a polyamide resin other than an aliphatic polyamide resin, a modified polyolefin, other thermoplastic resins, various additives, and glass fiber may be blended. For these details, the description of paragraphs 0018 to 0025 of the international publication WO2015/022818 pamphlet can be considered into consideration, and these contents are incorporated herein by reference. In addition, about the layer structure of a 1st coating layer and a 2nd coating layer, and a shaping|molding method, Paragraph 0051 - 0054 of International Publication WO2015/022818 pamphlet can be considered into consideration, and these contents are incorporated herein.

실시예Example

이하에 실시예를 들어 본 발명을 더욱 구체적으로 설명한다. 이하의 실시예에 나타내는 재료, 사용량, 비율, 처리내용, 처리순서 등은, 본 발명의 취지를 일탈하지 않는 한, 적당히, 변경할 수 있다. 따라서, 본 발명의 범위는 이하에 나타내는 구체예로 한정되는 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, amounts of use, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<폴리아미드수지(MXD6)의 합성><Synthesis of polyamide resin (MXD6)>

아디프산 8.9kg에 차아인산나트륨일수화물 0.3g 및 아세트산나트륨 0.1g을 첨가하고, 반응캔내에서 0.1MPaA에 있어서 170℃에서 가열하고 용융한 후, 내용물을 교반하면서, 메타자일릴렌디아민(미쯔비시가스화학사제) 8.3kg을 2시간에 걸쳐 서서히 적하하고, 온도를 250℃까지 상승시켰다. 온도상승 후, 1시간에 걸쳐 압력을 0.08MPaA까지 완만하게 저하시키고, 0.5시간 유지하였다. 반응종료 후, 내용물을 스트랜드상으로 취출하고, 펠릿타이저로 펠릿화하여, 15kg의 펠릿을 얻었다. 얻어진 펠릿을 열매가열의 외투를 갖는 텀블러(회전식의 진공조)에 투입하고, 감압상태(0.5~10Torr)에 있어서 200℃에서 1시간 가열을 계속함으로써, 얻어진 펠릿의 고상중합을 행하여, 폴리아미드수지(MXD6)를 얻었다. 얻어진 MXD6의 융점은 237℃였다.After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 8.9 kg of adipic acid, heating at 170° C. at 0.1 MPaA in a reaction can and melting, while stirring the contents, metaxylylenediamine (Mitsubishi Gas) Chemical company make) 8.3 kg was dripped gradually over 2 hours, and the temperature was raised to 250 degreeC. After the temperature rise, the pressure was gently lowered to 0.08 MPaA over 1 hour, and maintained for 0.5 hour. After completion of the reaction, the contents were taken out in the form of strands and pelletized with a pelletizer to obtain 15 kg of pellets. The obtained pellets are put into a tumbler (rotary vacuum chamber) having a heat medium heating coat, and heating is continued at 200° C. under reduced pressure (0.5 to 10 Torr) for 1 hour, solid-state polymerization of the obtained pellets is performed, and polyamide resin (MXD6) was obtained. The obtained MXD6 had a melting point of 237°C.

<폴리아미드수지(MP6)의 합성><Synthesis of polyamide resin (MP6)>

아디프산 8.9kg에 차아인산나트륨일수화물 0.3g 및 아세트산나트륨 0.1g을 첨가하고, 반응캔내에서 0.1MPaA에 있어서 170℃에서 가열하고 용융한 후, 내용물을 교반하면서, 자일릴렌디아민(파라자일릴렌디아민과 메타자일릴렌디아민의 몰비가 3:7인 혼합디아민, 미쯔비시가스화학사제) 8.3kg을 2시간에 걸쳐 서서히 적하하고, 온도를 270℃까지 상승시켰다. 온도상승 후, 1시간에 걸쳐 압력을 0.08MPaA까지 완만하게 저하시키고, 0.5시간 유지하였다. 반응종료 후, 내용물을 스트랜드상으로 취출하고, 펠릿타이저로 펠릿화하여, 15kg의 펠릿을 얻었다. 얻어진 펠릿을 열매가열의 외투를 갖는 텀블러(회전식의 진공조)에 투입하고, 감압상태(0.5~10Torr)에 있어서 200℃에서 1시간 가열을 계속함으로써, 얻어진 펠릿의 고상중합을 행하여, 폴리아미드수지(MP6)를 얻었다. 얻어진 MP6의 융점은 융점 254℃였다.After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 8.9 kg of adipic acid, heating at 170° C. at 0.1 MPaA in a reaction can to melt, and stirring the contents, xylylenediamine (paraxylylene) 8.3 kg of mixed diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a molar ratio of diamine and metaxylylenediamine of 3:7 was gradually added dropwise over 2 hours, and the temperature was raised to 270°C. After the temperature rise, the pressure was gently lowered to 0.08 MPaA over 1 hour, and maintained for 0.5 hour. After completion of the reaction, the contents were taken out in the form of strands and pelletized with a pelletizer to obtain 15 kg of pellets. The obtained pellets are put into a tumbler (rotary vacuum chamber) having a heat medium heating coat, and heating is continued at 200° C. under reduced pressure (0.5 to 10 Torr) for 1 hour, solid-state polymerization of the obtained pellets is performed, and polyamide resin (MP6) was obtained. The obtained MP6 had a melting point of 254°C.

<폴리아미드수지(MXD10)의 합성><Synthesis of polyamide resin (MXD10)>

세바스산 10.00kg에 차아인산나트륨일수화물 7.7g 및 아세트산나트륨 4.0g을 첨가하고, 반응캔내에서 0.1MPaA에 있어서 170℃에서 가열하고 용융한 후, 내용물을 교반하면서, 메타자일릴렌디아민 6.69kg을 2시간에 걸쳐 서서히 적하하고, 온도를 250℃까지 상승시켰다. 온도상승 후, 1시간에 걸쳐 압력을 0.08MPaA까지 완만하게 저하시키고, 0.5시간 유지하였다. 반응종료 후, 내용물을 스트랜드상으로 취출하고, 펠릿타이저로 펠릿화하여, 폴리아미드수지(MXD10)의 펠릿 15kg을 얻었다. 얻어진 MXD10의 융점은 190℃였다.After adding 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate to 10.00 kg of sebacic acid, heating and melting at 170° C. at 0.1 MPaA in a reaction can, while stirring the contents, 6.69 kg of metaxylylenediamine 2 It was dripped gradually over time, and the temperature was raised to 250 degreeC. After the temperature rise, the pressure was gently lowered to 0.08 MPaA over 1 hour, and maintained for 0.5 hour. After completion of the reaction, the contents were taken out in the form of strands and pelletized with a pelletizer to obtain 15 kg of polyamide resin (MXD10) pellets. Melting point of the obtained MXD10 was 190 degreeC.

<폴리아미드수지(MP10)의 합성><Synthesis of polyamide resin (MP10)>

세바스산 10.00kg에 차아인산나트륨일수화물 7.7g 및 아세트산나트륨 4.0g을 첨가하고, 반응캔내에서 0.1MPaA에 있어서 170℃에서 가열하고 용융한 후, 내용물을 교반하면서, 자일릴렌디아민(파라자일릴렌디아민과 메타자일릴렌디아민의 몰비가 3:7인 혼합디아민, 미쯔비시가스화학사제) 6.68kg을 2시간에 걸쳐 서서히 적하하고, 온도를 250℃까지 상승시켰다. 온도상승 후, 1시간에 걸쳐 압력을 0.08MPaA까지 완만하게 저하시키고, 0.5시간 유지하였다. 반응종료 후, 내용물을 스트랜드상으로 취출하고, 펠릿타이저로 펠릿화하여, 폴리아미드수지(MP10)의 펠릿 15kg을 얻었다. 얻어진 MP10의 융점은 215℃였다.After adding 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate to 10.00 kg of sebacic acid, heating at 170° C. at 0.1 MPaA in a reaction can to melt, and stirring the contents, xylylenediamine (paraxylylenediamine Mixed diamine having a molar ratio of 3:7 to metaxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6.68 kg was slowly added dropwise over 2 hours, and the temperature was raised to 250°C. After the temperature rise, the pressure was gently lowered to 0.08 MPaA over 1 hour, and maintained for 0.5 hour. After completion of the reaction, the contents were taken out in the form of strands and pelletized with a pelletizer to obtain 15 kg of polyamide resin (MP10) pellets. The obtained MP10 had a melting point of 215°C.

<기타 폴리아미드수지><Other polyamide resins>

PA12: 폴리아미드12, 다이셀·에보닉사제, 품번: X7393PA12: polyamide 12, manufactured by Daicel Evonik, part number: X7393

<산변성 폴리올레핀><Acid-modified polyolefin>

타프머MH5020: 무수말레산변성률 1.0중량%, 미쯔비시화학사제, α-올레핀의 탄소수 4Tapmer MH5020: maleic anhydride modified rate 1.0% by weight, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin having 4 carbon atoms

타프머MH5010: 무수말레산변성률 0.5중량%, 미쯔비시화학사제, α-올레핀의 탄소수 4Tapmer MH5010: maleic anhydride modified rate 0.5% by weight, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin having 4 carbon atoms

타프머MH5040: 무수말레산변성률 2.0중량%, 미쯔비시화학사제, α-올레핀의 탄소수 4Tapmer MH5040: maleic anhydride modified rate 2.0% by weight, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin having 4 carbon atoms

타프머DF610: 무수변성 폴리올레핀, 미쯔비시화학사제, α-올레핀의 탄소수 4Taffmer DF610: Anhydrous modified polyolefin, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin having 4 carbon atoms

ZeMacE60: 무수말레산변성률 50중량%, Vertellus사제, α-올레핀의 탄소수 0ZeMacE60: Maleic anhydride modified rate 50% by weight, manufactured by Vertellus, 0 carbon number of α-olefin

<산변성률의 측정><Measurement of acid denaturation rate>

시료(산변성 폴리올레핀) 0.15g에 30mL의 자일렌을 첨가하여 100℃에서 가열하고, 시료를 용해시켰다. 시료용해 후, 에탄올 2mL와 지시약(페놀프탈레인액)을 첨가하고, 적정액으로서 0.1규정의 수산화칼륨의 메탄올용액을 이용하여 중화적정을 행하였다. 시료를 첨가하지 않고 마찬가지로 적정한 것을 블랭크로 하고, 하기 식으로부터 산유도체에 의한 변성률을 산출하였다.30 mL of xylene was added to 0.15 g of the sample (acid-modified polyolefin) and heated at 100° C. to dissolve the sample. After dissolving the sample, 2 mL of ethanol and an indicator (phenolphthalein solution) were added, and neutralization titration was performed using a methanol solution of 0.1 N potassium hydroxide as a titrant. Without adding a sample, a similarly titrated one was used as a blank, and the rate of denaturation by the acid derivative was calculated from the following formula.

산유도체에 의한 변성률(중량%)=(A-B)×f×100/C/2/1000000×D×100Modification rate by acid derivative (% by weight) = (A-B) × f × 100/C/2/1000000 × D × 100

(A: 적정량(mL), B: 블랭크적정량(mL), f: 적정액의 팩터, C: 시료량(g), D: 산유도체유닛의 분자량).(A: titration amount (mL), B: blank titration amount (mL), f: titrant factor, C: sample amount (g), D: molecular weight of acid derivative unit).

상기에서 이용한 적정액의 팩터f는 1.005이다.The factor f of the titrant used above is 1.005.

<일반식(1)로 표시되는 화합물><Compound represented by general formula (1)>

HD-PB: p-하이드록시안식향산헥실데실, 카오주식회사제, 엑세팔 HD-PBHD-PB: p-hydroxybenzoate hexyldecyl, manufactured by Kao Corporation, Exepal HD-PB

EH-PB: p-하이드록시안식향산에틸헥실, 도쿄카세이공업주식회사로부터 입수EH-PB: ethylhexyl p-hydroxybenzoate, obtained from Tokyo Kasei Industrial Co., Ltd.

EH-OB: o-하이드록시안식향산에틸헥실, 도쿄카세이공업주식회사로부터 입수EH-OB: o-hydroxybenzoate ethylhexyl, obtained from Tokyo Kasei Industrial Co., Ltd.

실시예 1Example 1

표 1에 나타낸 폴리아미드수지, 산변성 폴리올레핀 및 일반식(1)로 표시되는 화합물을 표 1에 나타낸 양(중량부)이 되도록 칭량하여, 텀블러로 블렌드하고, 이축압출기(도시바기계사제, TEM37BS)의 근원으로부터 투입하고, 용융하여 압출하고, 스트랜드를 네트벨트로 공랭한 후에 펠릿타이징하여, 폴리아미드수지 조성물펠릿을 제작하였다. 압출기의 압출온도는, 폴리아미드수지의 융점+20℃로 설정하였다.The polyamide resin shown in Table 1, the acid-modified polyolefin, and the compound represented by the general formula (1) were weighed so as to be the amount (parts by weight) shown in Table 1, blended with a tumbler, and a twin-screw extruder (Toshiba Machinery Co., Ltd., TEM37BS) The polyamide resin composition pellets were prepared by pouring in from the source, extruding by melting, and cooling the strands in air with a net belt, followed by pelletizing. The extrusion temperature of the extruder was set to the melting point of the polyamide resin + 20°C.

<피복체의 제작><Production of the covering material>

직경 5mm의 PMMA로부터 형성된 심재에 대하여, 1대의 압출기와 크로스헤드를 구비한 수지피복장치로 PMMA심재에 대하여, 상기에서 얻어진 폴리아미드수지 조성물펠릿의 용융물을 이용하여 피복하였다. 압출기의 온도는 폴리아미드수지의 융점+20℃로 설정하였다. 피복층의 평균두께는 500μm, 얻어진 피복체의 평균직경 6mm, 길이는 1m였다.A core material formed from PMMA having a diameter of 5 mm was coated with a melt of the polyamide resin composition pellets obtained above with respect to the PMMA core material by a resin coating device equipped with one extruder and a crosshead. The temperature of the extruder was set to the melting point of the polyamide resin + 20°C. The average thickness of the coating layer was 500 µm, the average diameter of the obtained coating body was 6 mm, and the length was 1 m.

<산소배리어성 평가><Evaluation of oxygen barrier properties>

상기에서 얻어진 피복체의 양 말단을 스웨지로크로 봉지하고, 130℃로 설정한 오븐에 240시간 정치하였다. 시험 후에 피복층을 제거하여 심재만을 취출하고, 시험 후의 심재를 5mm 길이의 펠릿형상으로 절삭하고, JIS K 7373에 준거하여 YI값을 측정하였다. 시험전후의 YI값의 차(ΔYI)가 5 이하인 것을 ○, 5를 초과한 것을 ×로 하였다. 산소배리어성이 높은 것일수록, 심재까지 산소가 투과하지 않고, 낮은 YI값을 유지할 수 있다.Both ends of the covering body obtained above were sealed with a swage lock, and left still in an oven set at 130°C for 240 hours. After the test, the coating layer was removed, only the core material was taken out, the core material after the test was cut into pellets with a length of 5 mm, and the YI value was measured in accordance with JIS K 7373. The difference (ΔYI) between the YI values before and after the test was 5 or less, and the value exceeding 5 was ×. Oxygen does not permeate to the core material, and a low YI value can be maintained, so that oxygen barrier property is high.

YI값의 측정에는, 색차측정장치(일본전색공업(주)제, 「Z-Σ80 Color Measuring System」)를 사용하였다.For the measurement of the YI value, a color difference measuring apparatus ("Z-Sigma 80 Color Measuring System" manufactured by Nippon Denko Industries Co., Ltd.) was used.

<내충격성 평가><Impact resistance evaluation>

상기에서 얻어진 폴리아미드수지 조성물펠릿을, 사출성형기(스미토모중기계공업(주)제, 형식 「SE130DU-HP」)를 이용하여, 실린더온도를 폴리아미드수지의 융점+20℃로 하고, 금형온도 130℃, 성형사이클 55초의 조건으로 사출성형하고, ISO다목적시험편(두께: 4mm)을 성형하였다. 얻어진 ISO다목적시험편에 대하여 ISO 179 1eA에 준거하여 샤르피충격값을 측정하였다.The polyamide resin composition pellets obtained above were subjected to an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model “SE130DU-HP”), the cylinder temperature was set to the melting point of the polyamide resin + 20°C, and the mold temperature was 130 ℃, injection molding was carried out under the conditions of a molding cycle of 55 seconds, and an ISO multipurpose test piece (thickness: 4 mm) was molded. For the obtained ISO multipurpose test piece, the Charpy impact value was measured in accordance with ISO 179 1eA.

<피복성 평가><Evaluation of coating properties>

상기에서 얻어진 피복체(길이 1m)로부터, 길이 10cm의 샘플을 잘라냈다. 길이 10cm의 샘플에 대하여, 피복층의 두께를 심재의 단면에 있어서의 둘레방향으로 디지털마이크로스코프, Anmo Electronics사제를 이용하여 측정하였다. 이하와 같이 평가하였다.A sample with a length of 10 cm was cut out from the covering body (length 1 m) obtained above. With respect to the sample of 10 cm in length, the thickness of the coating layer was measured in the circumferential direction in the cross section of the core material using a digital microscope and Anmo Electronics company make. It evaluated as follows.

○: 피복층의 두께가 400μm 이하가 되는 개소가 보이지 않았다.(circle): The location used as 400 micrometers or less in thickness of a coating layer was not seen.

×: 피복층의 두께가 400μm 이하가 되는 개소가 보였다.x: The location from which the thickness of a coating layer would be 400 micrometers or less was seen.

<실시예 2~12 및 비교예 2~7><Examples 2 to 12 and Comparative Examples 2 to 7>

실시예 1에 있어서, 표 1~표 3에 나타낸 바와 같이, 폴리아미드수지, 산변성 폴리올레핀, 일반식(1)로 표시되는 화합물의 배합량 및 종류를 변경하고, 다른 것은 마찬가지로 행하였다.In Example 1, as shown in Tables 1 to 3, the compounding amount and type of the polyamide resin, the acid-modified polyolefin, and the compound represented by the general formula (1) were changed, and the rest were similarly performed.

한편, 내충격성 평가에 대하여, 파괴되지 않은 경우는, NB라고 나타냈다.On the other hand, about impact resistance evaluation, the case where it was not destroyed was shown as NB.

비교예 5에서는, 증점이 현저하며, 압출성형할 수 없었다.In Comparative Example 5, the thickening was remarkable and extrusion molding was not possible.

<비교예 1><Comparative Example 1>

폴리아미드수지로서, PA12를 이용한 것 외는 실시예 1과 마찬가지로 행하여 평가하였다.The evaluation was carried out in the same manner as in Example 1 except that PA12 was used as the polyamide resin.

<실시예 13~15><Examples 13-15>

표 4에 나타낸 중량비율이 되도록, 각 실시예에서 얻어진 폴리아미드수지 조성물펠릿을 드라이블렌드하였다. 실시예 1과 마찬가지로 성형하고, 산소배리어성, 샤르피충격값 및 피복성을 평가하였다. 또한, 이하의 방법으로, 폴리아미드12(PA12)와의 접착성을 평가하였다. 실시예 2에 대해서도, PA12와의 접착성을 평가하고, 실시예 13~15와 함께, 표 4에 나타냈다.The polyamide resin composition pellets obtained in each example were dry blended so as to have the weight ratios shown in Table 4. It was molded in the same manner as in Example 1, and the oxygen barrier property, the Charpy impact value, and the coating property were evaluated. Moreover, the adhesiveness with polyamide 12 (PA12) was evaluated by the following method. Also about Example 2, adhesiveness with PA12 was evaluated, and it showed in Table 4 together with Examples 13-15.

<PA12와의 접착성 평가><Evaluation of adhesion with PA12>

폴리아미드수지 조성물펠릿을 사출성형기(스미토모중기계공업(주)제, 형식 「SE130DU-HP」)를 이용하여, 실린더온도를 폴리아미드수지의 융점+20℃로 하고, 금형온도 130℃, 성형사이클 120초의 조건으로 사출성형하여, 폭 55mm, 길이 110mm, 두께 3mm의 시험편(후술하는 도 1에 있어서, 1로 나타낸다)을 성형하였다. 마찬가지로, 폴리아미드12 펠릿(제조원: 알케마사, 품번: AZM30 T6LD)에 대해서도, 실린더온도를 (240)℃로 하고, 금형온도 (80)℃, 성형사이클 (120)초의 조건으로 사출성형하고, 폭 55mm, 길이 110mm, 두께 3mm의 시험편(후술하는 도 1에 있어서, 2라고 나타낸다)을 성형하였다.Using an injection molding machine (Sumitomo Heavy Industries, Ltd., model "SE130DU-HP") for polyamide resin composition pellets, the cylinder temperature was set to the melting point of the polyamide resin + 20 °C, the mold temperature was 130 °C, and the molding cycle was Injection molding was carried out under the conditions of 120 seconds, and a test piece having a width of 55 mm, a length of 110 mm, and a thickness of 3 mm (indicated by 1 in FIG. 1 to be described later) was molded. Similarly, for polyamide 12 pellets (manufacturer: Alkema Corporation, part number: AZM30 T6LD), the cylinder temperature was set to (240) °C, the mold temperature was (80) °C, and the molding cycle was (120) seconds. A test piece of 55 mm, 110 mm in length, and 3 mm in thickness (shown as 2 in FIG. 1 to be described later) was molded.

얻어진 2매의 시험편을, 도 1(a)에 나타낸 바와 같이 길이방향(긴 방향)이 접하도록 병렬로 배열하고, 진동융착시험기(VWMAC-103, BRANSON사제)를 이용하여, 240Hz의 진동수로, 진동폭 1.5mm, 1MPa의 압력을 첨가하면서 2초간 진동융착을 행하여, 두께 3mm의 융착시험편을 얻었다. 도 1 중, 화살표 3이 진동방향을 나타내고 있다. 또한, 화살표 4가 진동융착의 융착압력방향을 나타내고 있다.The obtained two test pieces were arranged in parallel so that the longitudinal direction (longitudinal direction) was in contact as shown in FIG. Vibration welding was performed for 2 seconds while adding a vibration width of 1.5 mm and a pressure of 1 MPa to obtain a fusion bonding test piece having a thickness of 3 mm. In FIG. 1, arrow 3 has shown the vibration direction. In addition, arrow 4 indicates the direction of the welding pressure of vibration welding.

얻어진 융착시험편으로부터 도 1(b)에 나타낸 바와 같이 폭 20mm인 것을 잘라내고, 접합면을 중심으로 하고, 지점간거리 64mm의 3점굽힘시험을 행하여, 접합면에 파단이 생겼을 때의 하중으로부터 폴리아미드12와의 접착성을 평가하였다. 구체적으로는, 접합면에 파단이 생겼을 때의 하중이 50N 미만인 것을 ×, 50N을 초과하는 것을 ○로 하였다.As shown in Fig. 1(b), a 20 mm-wide thing was cut out from the obtained fusion test piece, and a three-point bending test was performed with the joint surface as the center and a distance between points of 64 mm, and polyamide was obtained from the load when the joint surface was fractured. Adhesiveness with 12 was evaluated. Specifically, the load at the time of fracture of the joint surface was less than 50N ×, and the load exceeding 50N was defined as (circle).

[표 1][Table 1]

Figure 112019037335319-pct00005
Figure 112019037335319-pct00005

[표 2][Table 2]

Figure 112019037335319-pct00006
Figure 112019037335319-pct00006

[표 3][Table 3]

Figure 112019037335319-pct00007
Figure 112019037335319-pct00007

[표 4][Table 4]

Figure 112019037335319-pct00008
Figure 112019037335319-pct00008

상기 결과로부터 명백한 바와 같이, 본 발명의 수지 조성물은, 우수한 산소배리어성을 유지하면서, 또한, 내충격성을 현격히 향상시키는 것이 가능해졌다(실시예 1~12). 나아가, 피복성도 우수한 것이 얻어졌다(실시예 1~12).As is clear from the above results, it became possible for the resin composition of the present invention to significantly improve impact resistance while maintaining excellent oxygen barrier properties (Examples 1 to 12). Furthermore, the thing excellent also in coating property was obtained (Examples 1-12).

이에 반해, 폴리아미드수지로서 PA12를 이용한 경우(비교예 1), 내충격성은 우수하나, 산소배리어성이 뒤떨어졌었다.On the other hand, when PA12 was used as the polyamide resin (Comparative Example 1), the impact resistance was excellent, but the oxygen barrier property was inferior.

또한, 일반식(1)로 표시되는 화합물을 배합하지 않는 경우(비교예 2), 산소배리어성은 우수하였으나, 내충격성이 현격히 뒤떨어졌다. 비교예 2는, 내충격개량제로서 알려져 있는 산변성 폴리올레핀을, 실시예 2, 3 등과 동일한 비율로, 배합하고 있음에도 불구하고, 내충격성이 현격히 뒤떨어졌다. 따라서, 본 발명의 효과가 예상외의 효과인 것을 알 수 있다.Further, when the compound represented by the general formula (1) was not blended (Comparative Example 2), the oxygen barrier property was excellent, but the impact resistance was remarkably inferior. In Comparative Example 2, although the acid-modified polyolefin known as an impact modifier was blended in the same proportion as Examples 2 and 3, the impact resistance was remarkably inferior. Therefore, it can be seen that the effect of the present invention is an unexpected effect.

한편, 일반식(1)로 표시되는 화합물의 배합량이 지나치게 많은 경우(비교예 3), 내충격성은 우수하였으나, 산소배리어성이 뒤떨어졌다.On the other hand, when the compounding amount of the compound represented by the general formula (1) was too large (Comparative Example 3), the impact resistance was excellent, but the oxygen barrier property was inferior.

또한, 산변성하지 않은 폴리올레핀을 이용한 경우(비교예 4), 산소배리어성은 우수하나, 내충격성이 뒤떨어졌다. 나아가, 피복성도 뒤떨어졌다.In addition, when polyolefin not acid-modified was used (Comparative Example 4), the oxygen barrier property was excellent, but the impact resistance was inferior. Furthermore, the coating property was also inferior.

나아가, 산변성률이 높은 폴리올레핀을 이용한 경우(비교예 5), 증점이 현저하고, 압출성형을 할 수 없었다.Furthermore, when polyolefin with a high acid modification rate was used (Comparative Example 5), the thickening was remarkable and extrusion molding could not be performed.

또한, 산변성 폴리올레핀을 배합하지 않은 경우(비교예 6), 산소배리어성은 우수하나, 내충격성이 뒤떨어졌다.In addition, in the case where the acid-modified polyolefin was not blended (Comparative Example 6), the oxygen barrier property was excellent, but the impact resistance was poor.

또한, 산변성 폴리올레핀의 배합량이 지나치게 많은 경우(비교예 7), 내충격성은 우수하나, 산소배리어성이 뒤떨어졌다. 나아가, 피복성도 뒤떨어졌다.In addition, when the blending amount of the acid-modified polyolefin was too large (Comparative Example 7), the impact resistance was excellent, but the oxygen barrier property was inferior. Furthermore, the coating property was also inferior.

또한, 폴리아미드수지로서, 디카르본산유래의 구성단위가 아디프산인 것과, 디카르본산유래의 구성단위가 세바스산인 것을 블렌드한 경우, 우수한 산소배리어성, 내충격성 및 피복성을 유지하면서, 폴리아미드12와의 접착성이 우수한 폴리아미드수지 조성물이 얻어졌다(실시예 2와 실시예 13~15의 비교).In addition, as a polyamide resin, when a dicarboxylic acid-derived structural unit is adipic acid and a dicarboxylic acid-derived structural unit is sebacic acid, excellent oxygen barrier properties, impact resistance and coatability are maintained, A polyamide resin composition excellent in adhesion to polyamide 12 was obtained (comparison between Example 2 and Examples 13 to 15).

본 발명의 수지 조성물은, 산소배리어성을 유지하면서, 높은 내충격성을 달성할 수 있는 점에서, 각종 성형품에 바람직하게 이용할 수 있다.The resin composition of the present invention can be preferably used for various molded articles from the viewpoint of achieving high impact resistance while maintaining oxygen barrier properties.

나아가, 본 발명의 수지 조성물은, 피복성도 우수한 것이다. 종래부터, 폴리아미드11(PA11)이나 폴리아미드12(PA12)는, 내충격성 및 피복성이 우수하다는 특징으로부터, 광도파로 등의 피복재료로서 이용되고 있었다. 그러나, 광도파로가 상온분위기하에서 사용되는 경우, 그 산소배리어성이 불충분해지는 경우가 있었다. 본 발명의 수지 조성물은, 산소배리어성 및 내충격성이 우수하고, 또한, 피복성도 우수한 점에서, 상온분위기하에서 사용되는 피복재료로서도 바람직하게 이용된다.Furthermore, the resin composition of this invention is excellent also in coatability. Conventionally, polyamide 11 (PA11) and polyamide 12 (PA12) have been used as a coating material for optical waveguides and the like due to their excellent impact resistance and coating properties. However, when the optical waveguide is used in an atmosphere of room temperature, the oxygen barrier properties thereof may become insufficient. The resin composition of the present invention is excellent in oxygen barrier properties and impact resistance, and is also preferably used as a coating material used in a room temperature atmosphere from the viewpoint of excellent coating properties.

1 본 발명의 폴리아미드수지 조성물 펠릿으로부터 성형된 시험편1 Test piece molded from the polyamide resin composition pellets of the present invention

2 폴리아미드12 펠릿으로부터 성형된 시험편2 Specimens molded from polyamide 12 pellets

3 진동융착시험기의 진동방향을 나타내는 화살표3 Arrows indicating the direction of vibration of the vibration welding tester

4 진동융착의 융착압력방향을 나타내는 화살표4 Arrows indicating the direction of the welding pressure of vibration welding

Claims (14)

디아민유래의 구성단위와 디카르본산유래의 구성단위로부터 구성되고, 디아민유래의 구성단위의 70몰% 이상이 자일릴렌디아민에서 유래하고, 디카르본산유래의 구성단위의 70몰% 이상이 탄소수 4~20의 α,ω-직쇄지방족 디카르본산에서 유래하는 폴리아미드수지 100중량부에 대하여, 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀을 3~17중량부, 및, 하기 일반식(1)로 표시되는 화합물을 1~15중량부 포함하는, 수지 조성물;
일반식(1)
Figure 112022003097962-pct00009

일반식(1) 중, R1은, 탄소수 1~10의 알킬기이며, R2는, 탄소수 2~12의 알킬기이며, n은 1~3의 정수이다.It is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 70 mol% or more of the structural unit derived from dicarboxylic acid has 4 carbon atoms Based on 100 parts by weight of the polyamide resin derived from α,ω-linear aliphatic dicarboxylic acid of ~20, 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight, and the following general formula ( A resin composition comprising 1 to 15 parts by weight of the compound represented by 1);
General formula (1)
Figure 112022003097962-pct00009

In general formula (1), R< 1 > is a C1-C10 alkyl group, R< 2 > is a C2-C12 alkyl group, and n is an integer of 1-3. 제1항에 있어서,
상기 자일릴렌디아민이, 메타자일릴렌디아민 및 파라자일릴렌디아민의 적어도 일방을 포함하는, 수지 조성물.The method of claim 1,
The resin composition in which the said xylylene diamine contains at least one of meta-xylylene diamine and para-xylylene diamine. 제1항 또는 제2항에 있어서,
상기 탄소수 4~20의 α,ω-직쇄지방족 디카르본산이, 세바스산 및 아디프산의 적어도 일방을 포함하는, 수지 조성물.3. The method of claim 1 or 2,
The resin composition wherein the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains at least one of sebacic acid and adipic acid. 제1항 또는 제2항에 있어서,
상기 일반식(1)로 표시되는 화합물과, 상기 산변성률이 0.3~5.0중량%인 산변성 폴리올레핀의 중량비가 3:10~16:10인, 수지 조성물.3. The method of claim 1 or 2,
The weight ratio of the compound represented by the general formula (1) and the acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight is 3:10 to 16:10, the resin composition. 제1항 또는 제2항에 있어서,
상기 산변성 폴리올레핀이, 말레산변성 폴리올레핀 및 무수말레산변성 폴리올레핀의 적어도 1종을 포함하는, 수지 조성물.3. The method of claim 1 or 2,
The resin composition in which the said acid-modified polyolefin contains at least 1 sort(s) of a maleic acid-modified polyolefin and a maleic anhydride-modified polyolefin. 제1항 또는 제2항에 있어서,
상기 폴리아미드수지가, 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는, 수지 조성물.3. The method of claim 1 or 2,
In the polyamide resin, with respect to 10 to 90 parts by weight of the polyamide resin in which 70 mol% or more of the structural units derived from dicarboxylic acid are derived from adipic acid, 70 mol% or more of the structural units derived from dicarboxylic acid are seba A resin composition comprising a polyamide resin derived from Susan in an amount of 90 to 10 parts by weight. 제1항 또는 제2항에 있어서,
심재의 피복재료인, 수지 조성물.3. The method of claim 1 or 2,
The resin composition which is a coating material of a core material. 제1항 또는 제2항에 기재된 수지 조성물을 성형하여 이루어진 성형품.A molded article obtained by molding the resin composition according to claim 1 or 2. 심재와, 상기 심재의 피복층을 포함하고, 상기 피복층이 제1항 또는 제2항에 기재된 수지 조성물로부터 형성되는 성형품.A molded article comprising a core material and a coating layer of the core material, wherein the coating layer is formed from the resin composition according to claim 1 or 2. 제9항에 있어서,
추가로, 상기 피복층에 접하는, 지방족 폴리아미드수지를 주성분으로 하는 제2 피복층을 갖는, 성형품.10. The method of claim 9,
Further, the molded article has a second coating layer which is in contact with the coating layer and has an aliphatic polyamide resin as a main component. 제10항에 있어서,
상기 지방족 폴리아미드수지가 폴리아미드12인, 성형품.11. The method of claim 10,
wherein the aliphatic polyamide resin is polyamide 12. 제10항에 있어서,
상기 피복층을 구성하는 폴리아미드수지가 디카르본산유래의 구성단위의 70몰% 이상이 아디프산에서 유래하는 폴리아미드수지 10~90중량부에 대하여, 디카르본산유래의 구성단위의 70몰% 이상이 세바스산에서 유래하는 폴리아미드수지를 90~10중량부의 비율로 포함하는, 성형품.11. The method of claim 10,
70 mol% of the structural unit derived from dicarboxylic acid relative to 10 to 90 parts by weight of the polyamide resin derived from adipic acid in which the polyamide resin constituting the coating layer is 70 mol% or more of the structural unit derived from dicarboxylic acid A molded article comprising the above polyamide resin derived from sebacic acid in a proportion of 90 to 10 parts by weight. 제9항에 있어서,
상기 심재가, 광도파로 또는 연속중공체인, 성형품.10. The method of claim 9,
The molded article, wherein the core material is an optical waveguide or a continuous hollow body. 심재를, 제1항 또는 제2항에 기재된 수지 조성물로 피복하는 것을 포함하는, 성형품의 제조방법.A method for producing a molded article, comprising coating a core material with the resin composition according to claim 1 or 2.
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