TWI752111B - Resin composition, molded article, and method for producing the molded article - Google Patents

Abstract

The present invention provides a resin composition having excellent oxygen barrier properties and excellent impact resistance, a molded article using the resin composition, and a method for producing the molded article. A resin composition containing 3 to 17 parts by weight of an acid-modified polyolefin with an acid modification rate of 0.3 to 5.0 wt % and 1 to 15 parts by weight of the following general formula (1 ), the polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and more than 70 mol% of the structural unit derived from diamine is derived from xylene diamine, derived from diamine More than 70 mol% of the structural units of the carboxylic acid are derived from α,ω-straight-chain aliphatic dicarboxylic acids with 4 to 20 carbon atoms; in the general formula (1), R ¹ is an alkyl group with 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.

Description

Resin composition, molded article, and method for producing the molded article

The present invention relates to a resin composition, a molded product, and a method for producing the molded product. In particular, it relates to a resin composition that can provide molded articles with excellent oxygen barrier properties and impact resistance.

Polyamide resins are widely used in various applications because they are excellent in chemical resistance, heat resistance, and the like. For example, Patent Document 1 discloses a polyamide composition for blow molding composed of a polyamide and a modified polyolefin, and the polyamide contains at least a terminal amine group and a terminal carboxyl group in the ratio of the former: the latter=100: 0~50: 50 amine-terminated polyamide. It is further described that the amine-terminated polyamide is polyamide 11 or polyamide 12, and the modified polyolefin is epoxy-modified, acid-anhydride-modified or carboxylic acid-modified polyolefin. It is also described that such a polyamide composition has excellent IZOD impact strength. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-302908

THE PROBLEM TO BE SOLVED BY THE INVENTION However, the inventors of the present invention conducted studies on the above-mentioned Patent Document 1, and found that although the impact resistance is high, the oxygen barrier properties are not satisfactory. In addition, even if a polyamide resin having excellent oxygen barrier properties is used, there is a problem of poor impact resistance. In order to solve this problem, the present invention aims to provide a resin composition having excellent oxygen barrier properties and excellent impact resistance, a molded article using the resin composition, and a method for producing the molded article. [Means of Solving Problems]

通式(1)中，R¹ 為碳數1~10之烷基，R² 為碳數2~12之烷基，n為1~3之整數。 ＜2＞ 如＜1＞之樹脂組成物，其中，該亞二甲苯二胺含有間亞二甲苯二胺及對亞二甲苯二胺中之至少一者。 ＜3＞ 如＜1＞或＜2＞之樹脂組成物，其中，該碳數4~20之α,ω-直鏈脂肪族二羧酸含有癸二酸及己二酸中之至少一者。 ＜4＞ 如＜1＞~＜3＞中任一項之樹脂組成物，其中，該通式(1)表示之化合物與該酸改性率為0.3~5.0重量%之酸改性聚烯烴之重量比為3：10~16：10。 ＜5＞ 如＜1＞~＜4＞中任一項之樹脂組成物，其中，該酸改性聚烯烴含有馬來酸改性聚烯烴及馬來酸酐改性聚烯烴中之至少1種。 ＜6＞ 如＜1＞~＜5＞中任一項之樹脂組成物，其中，該聚醯胺樹脂中，相對於10~ 90重量份之來自二羧酸之構成單元之70莫耳%以上係來自己二酸之聚醯胺樹脂， 以90~10重量份之比例含有來自二羧酸之構成單元之70莫耳%以上係來自癸二酸之聚醯胺樹脂。 ＜7＞ 如＜1＞~＜6＞中任一項之樹脂組成物，係芯材之被覆材料。 ＜8＞ 一種成形品，係將如＜1＞~＜7＞中任一項之樹脂組成物予以成形而成。 ＜9＞ 一種成形品，含有芯材與該芯材之被覆層，該被覆層由如＜1＞~＜5＞中任一項之樹脂組成物形成。 ＜10＞ 如＜9＞之成形品，更具有接觸該被覆層之將脂肪族聚醯胺樹脂作為主成分之第2被覆層。 ＜11＞ 如＜10＞之成形品，其中，該脂肪族聚醯胺樹脂為聚醯胺12。 ＜12＞ 如＜10＞或＜11＞之成形品，其中，構成該被覆層之聚醯胺樹脂中，相對於10~90重量份之來自二羧酸之構成單元之70莫耳%以上係來自己二酸之聚醯胺樹脂，以90~10重量份之比例含有來自二羧酸之構成單元之70莫耳%以上係來自癸二酸之聚醯胺樹脂。 ＜13＞ 如＜9＞~＜12＞中任一項之成形品，其中，該芯材為光導波路或連續中空體。 ＜14＞ 一種成形品之製造方法，包括將芯材利用如＜1＞~＜7＞中任一項之樹脂組成物予以被覆之步驟。 [發明之效果]Based on the above problems, the inventors of the present application have conducted studies and found that by blending the compound represented by the general formula (1) with an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight to a predetermined diethylene oxide Among the toluenediamine-based polyamide resins, a molded article having excellent oxygen barrier properties and significantly improved impact resistance can be obtained, and the present invention has been completed. Specifically, the above-mentioned problems are solved by the following means <1>, preferably by means of <2> to <14>. <1> A resin composition containing 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0 wt %, and 1 to 15 parts by weight of the following compounds, relative to 100 parts by weight of a polyamide resin The compound represented by the formula (1), the polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and more than 70 mol% of the structural unit derived from diamine is derived from xylene diamine , More than 70 mol% of the constituent units derived from dicarboxylic acid are derived from α,ω-straight-chain aliphatic dicarboxylic acids with 4 to 20 carbon atoms. [Chemical 1] General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3. <2> The resin composition according to <1>, wherein the xylene diamine contains at least one of m-xylene diamine and p-xylylene diamine. <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> The resin composition according to any one of <1> to <3>, wherein the compound represented by the general formula (1) and the acid-modified polyolefin having an acid modification rate of 0.3 to 5.0 wt % are combined. The weight ratio is 3:10~16:10. <5> The resin composition according to any one of <1> to <4>, wherein the acid-modified polyolefin contains at least one of maleic acid-modified polyolefin and maleic anhydride-modified polyolefin. <6> The resin composition according to any one of <1> to <5>, wherein in the polyamide resin, 70 mol % or more of the constituent units derived from dicarboxylic acid relative to 10 to 90 parts by weight It is a polyamide resin derived from adipic acid and contains more than 70 mol% of the constituent units derived from dicarboxylic acid in a proportion of 90 to 10 parts by weight. It is a polyamide resin derived from sebacic acid. <7> The resin composition according to any one of <1> to <6> is the covering material of the core material. <8> A molded article obtained by molding the resin composition according to any one of <1> to <7>. <9> A molded article comprising a core material and a coating layer of the core material, wherein the coating layer is formed of the resin composition according to any one of <1> to <5>. <10> The molded article according to <9> further has a second coating layer containing an aliphatic polyamide resin as a main component in contact with the coating layer. <11> The molded article of <10>, wherein the aliphatic polyamide resin is polyamide 12. <12> The molded article of <10> or <11>, wherein in the polyamide resin constituting the coating layer, 70 mol % or more of the constituent units derived from dicarboxylic acid relative to 10 to 90 parts by weight are The polyamide resin derived from adipic acid contains more than 70 mol% of the constituent units derived from dicarboxylic acid in a ratio of 90 to 10 parts by weight, and is a polyamide resin derived from sebacic acid. <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> A method for producing a molded product, comprising the step of coating a core material with the resin composition according to any one of <1> to <7>. [Effect of invention]

According to the present invention, a resin composition having excellent oxygen barrier properties and excellent impact resistance, a molded article using the resin composition, and a method for producing the molded article can be provided.

The content of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit.

通式(1)中，R¹ 為碳數1~10之烷基，R² 為碳數2~12之烷基，n為1~3之整數。 藉由成為如此之構成，可獲得氧氣阻隔性優異且耐衝擊性優異的樹脂組成物(成形品)。且可獲得被覆性優異的樹脂組成物。 亦即，已知XD系聚醯胺樹脂其氧氣阻隔性優異。但難說其耐衝擊性必定令人滿意。本發明中，藉由在XD系聚醯胺樹脂中摻合酸改性聚烯烴，並進一步摻合上述通式(1)表示之化合物，出乎意料地成功顯著改善了耐衝擊性。亦即，為了改善聚醯胺樹脂之耐衝擊性，至今為止進行了酸改性聚烯烴的摻合。但，本案發明人等進行研究的結果，發現只是在XD系聚醯胺樹脂中摻合酸改性聚烯烴的話，有時會有無法確保充分的耐衝擊性的情況。然後，本發明藉由將酸改性聚烯烴之酸改性率設定為預定之範圍，且摻合通式(1)表示之化合物，成功地顯著改善了耐衝擊性。特別是藉由摻合通式(1)表示之化合物，耐衝擊性極度出乎意料地得到了顯著改善。 進一步，本發明中亦可達成被覆性的提升。因此，本發明之樹脂組成物也可理想地使用於被覆材料。 以下，針對本發明之詳細內容進行說明。The resin composition of the present invention is characterized in that the acid modification ratio of 3 to 17 parts by weight is 0.3 to 5.0 per 100 parts by weight of the polyamide resin (hereinafter, sometimes referred to as "XD-based polyamide resin"). % by weight of acid-modified polyolefin, and 1 to 15 parts by weight of the compound represented by the following general formula (1), the polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, derived from More than 70 mol % of the constituent units of diamines are derived from xylene diamine, and more than 70 mol % of the constituent units of dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. carboxylic acid. [Chemical 2] General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3. With such a configuration, a resin composition (molded article) excellent in oxygen barrier properties and excellent in impact resistance can be obtained. And a resin composition excellent in coatability can be obtained. That is, XD-based polyamide resins are known to be excellent in oxygen barrier properties. But it is difficult to say that its impact resistance must be satisfactory. In the present invention, by blending the acid-modified polyolefin with the XD-based polyamide resin, and further blending the compound represented by the above-mentioned general formula (1), the impact resistance was unexpectedly successfully improved significantly. That is, in order to improve the impact resistance of polyamide resins, blending of acid-modified polyolefins has hitherto been performed. However, as a result of studies conducted by the inventors of the present invention, it was found that sufficient impact resistance may not be ensured in some cases by simply blending an acid-modified polyolefin with an XD-based polyamide resin. Then, the present invention succeeded in significantly improving impact resistance by setting the acid modification rate of the acid-modified polyolefin to a predetermined range and blending the compound represented by the general formula (1). In particular, by blending the compound represented by the general formula (1), the impact resistance is surprisingly significantly improved. Furthermore, in the present invention, the coverage can also be improved. Therefore, the resin composition of the present invention can also be suitably used for a coating material. Hereinafter, the details of the present invention will be described.

<XD-based polyamide resin> 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 the structure derived from diamine is composed of More than 70 mol % of the units are derived from xylene diamine, and more than 70 mol % of the constituent units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

For the XD series polyamide resin, the constituent units derived from diamine are preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and more preferably 98 mol%. At least 1 mol% or more are derived from at least one of xylene diamine, and the constituent units derived from dicarboxylic acid are preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more , and more preferably 98 mol% or more are derived from at least one of α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

That is, from the viewpoint of oxygen barrier properties, the xylene diamine which is the raw material of the XD series polyamide resin preferably contains at least one of m-xylene diamine and p-xylylene diamine, and at least m-xylene diamine is contained. Xylenediamine is more preferred. Further considering the coverage point of view, xylene diamine should be composed of 30~100 mol% of xylene diamine and 0~70 mol% of p-xylene diamine, and 60~100 mol% of p-xylene diamine. The better composition is between 0-40 mol% of p-xylene diamine and 0-40 mol % of p-xylene diamine, which is composed of between 70-100 mol % of p-xylene diamine and 0-30 mol % of p-xylene diamine Toluenediamine constitutes particularly preferred. The xylene diamine used in the present invention is preferably more than 90 mol %, more preferably more than 95 mol %, especially preferably more than 98 mol % is m-xylene diamine. By having such a configuration, the coverage is more effectively improved.

Diamines other than xylylenediamine that can be used as the raw material diamine for XD-based polyamide resins include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, and hexamethylenediamine. Methylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, deca methylene diamine, lauryl diamine, 2,2,4-trimethyl-hexamethylene diamine, 2, Aliphatic diamines such as 4,4-trimethylhexamethylenediamine; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane 3-Diaminocyclohexane, 1,4-Diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminocyclohexyl)propane Alicyclic diamines such as methyl)decalin, bis(aminomethyl)tricyclodecane, etc.; bis(4-aminophenyl)ether, p-phenylenediamine, bis(aminomethyl)naphthalene, etc. As for the diamine etc. which have an aromatic ring, 1 type may be used and 2 or more types may be mixed and used for it. When a diamine other than xylene diamine is used as the diamine, the proportion of the constituent units derived from the diamine is 30 mol% or less, preferably 1-25 mol%, and particularly preferably 5-20 mol% use.

The α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms used as the raw material dicarboxylic acid of the XD series polyamide resin is preferably α,ω-linear aliphatic dicarboxylic acid having 6 to 16 carbon atoms. The acid is preferably an α,ω-straight-chain aliphatic dicarboxylic acid having 6 to 10 carbon atoms. α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, for example, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, tenacic acid Aliphatic dicarboxylic acids such as monoalkanedioic acid and dodecanedioic acid may be used alone or in combination of two or more. Among these, at least one of adipic acid and sebacic acid is preferably contained in consideration of the melting point of the polyamide resin in a range suitable for molding. Furthermore, when adipic acid is used as the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, a resin composition having more excellent oxygen barrier properties can be obtained. Furthermore, when sebacic acid is used as the α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, a resin composition having more excellent impact resistance can be obtained. Further, if both adipic acid and sebacic acid are used as α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms, a resin with improved adhesion to aliphatic polyamide resins can be obtained. composition. In such a polyamide resin (XD6/XD10), the molar ratio of the adipic acid component and the sebacic acid component is preferably 10:90~90:10, more preferably 30:70~90:10, and 50: 50~80: 20 is preferred.

Dicarboxylic acid components other than the above-mentioned α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms can be exemplified by phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid; 1, 2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid Acids, naphthalene dicarboxylic acids such as isomers such as 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, etc. can be used One type, or two or more types may be used in combination.

When a dicarboxylic acid other than α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component, terephthalic acid, isophthalic acid, and isophthalic acid are preferably used in view of moldability and barrier properties. formic acid. The ratio of terephthalic acid and isophthalic acid is preferably below 30 mol % of the constituent units derived from dicarboxylic acid, more preferably 1-30 mol %, particularly preferably 5-20 mol % .

In addition, "consisting of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid" here means that the amide bond constituting the XD-based polyamide resin is formed by the combination of dicarboxylic acid and diamine. Moreover, XD-type polyamide resin contains other parts, such as a terminal group, in addition to the structural unit derived from dicarboxylic acid and the structural unit derived from diamine. Furthermore, a repeating unit having an amide bond not derived from the bond between a dicarboxylic acid and a diamine, a trace amount of impurities, and the like may be contained. Specifically, in the range which does not impair the effect of the present invention, as a component constituting the polyamide resin, in addition to the diamine component and the dicarboxylic acid component, ε-caprolactone may be used in the XD-based polyamide resin. Lactamides such as amide and lauryl lactamide; aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid are used as copolymerization components. In the present invention, the content of the XD-based polyamide resin is preferably 90% by weight or more, more preferably 95% by weight or more is a structural unit derived from a diamine or a structural unit derived from a dicarboxylic acid.

The XD series polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000-30,000, more preferably 8,000-28,000, and particularly preferably 9,000-26,000. Within such a range, the formability becomes more favorable.

In addition, the number average molecular weight (Mn) referred to here _{is calculated by the following formula from the terminal amine group concentration [NH 2} ] (μ equivalent/g) and the terminal carboxyl group concentration [COOH] (μ equivalent/g) of the polyamide resin . Number average molecular weight (Mn)=2,000,000/([COOH]+[NH ₂ ])

Regarding the production method of the XD-based polyamide resin, the descriptions of paragraphs 0052 to 0053 of JP 2014-173196 A can be referred to, and the contents are incorporated herein by reference.

In the present invention, the melting point of the XD series polyamide resin is preferably 150-350°C, more preferably 180-300°C, and particularly preferably 180-280°C. In addition, the melting point in this invention is the peak top temperature of the endothermic peak part at the time of temperature rise observed by DSC (differential scanning calorimetry) method. Specifically, the melting point can be measured by using "DSC-60" manufactured by Shimadzu Corporation (SHI MADZU CORPORATION), in a sample size of about 1 mg, nitrogen gas is introduced as an ambient gas at 30 mL/min, and the temperature increase rate is 10°C Under the condition of /min, heat from room temperature to a temperature above the expected melting point to melt the polyamide resin, use dry ice to rapidly cool the molten polyamide resin, and heat it again at a rate of 10°C/min to a temperature above the melting point. The temperature was measured by measuring the peak top temperature of the endothermic peak observed at this time. The melting point of the polyamide resin when the resin composition of the present invention contains two or more XD-based polyamide resins is the value of the peak top temperature of the endothermic peak observed on the highest temperature side in the aforementioned DSC measurement.

The ratio 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. The resin composition of the present invention may contain only one type of XD-based polyamide resin, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above-mentioned range.

<Other polyamide resins> The resin composition of the present invention may contain polyamide resins other than the above-mentioned XD-based polyamide resins. 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 Amine 9MT, polyamide 6I/6T, etc. The content of other polyamide resins in the resin composition of the present invention, in the case of blending, is preferably 1-50 parts by weight, 5-40 parts by weight, relative to 100 parts by weight of XD series polyamide resins. good. Moreover, the resin composition of this invention may be a structure which does not contain substantially other polyamide resin other than XD type polyamide resin. Substantially not contained means that in the polyamide resin contained in the resin composition of the present invention, the proportion of other polyamide resins is 5% by weight or less of the XD series polyamide resin, preferably 3% by weight or less, which is 1 wt% or less is particularly preferred.

<Acid-modified polyolefin> The resin composition of the present invention contains an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight. The lower limit of the acid modification rate is preferably 0.4% by weight or more, more preferably 0.5% by weight or more, more preferably 0.6% by weight or more, still more preferably 0.8% by weight or more, and still more preferably 0.9% by weight or more. By setting it within such a range, impact resistance can be improved more effectively. On the other hand, the upper limit of the acid modification rate is preferably 4.0 wt % or less, more preferably 3.0 wt % or less, more preferably 2.5 wt % or less, and even more preferably 1.8 wt % or less. When the resin composition of the present invention is used as a covering material (a covering layer of a molded article) within such a range, the melt stretching becomes favorable, and the thickness of the covering layer can be made more uniform. In addition, the modification rate by the acid derivative in this invention was measured by the method described in the Example mentioned later.

The acid-modified polyolefin used in the present invention is obtained by acid-modifying the polyolefin. Acid modification refers to reacting an acid derivative with a polyolefin in some way. 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 obtained by grafting an acid derivative to the main chain of the polyolefin. The acid derivative is preferably an acid or an acid anhydride, preferably an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, and more preferably an unsaturated carboxylic acid anhydride. The unsaturated carboxylic acid is preferably an unsaturated dicarboxylic acid, and the unsaturated carboxylic acid anhydride is also preferably an unsaturated dicarboxylic acid anhydride. The acid derivatives are maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, endobicyclic -[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid), endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid anhydride, citraconic acid, Citraconic anhydride, 1-butene-3,4-dicarboxylic acid, 1-butene-3,4-dicarboxylic acid anhydride are particularly preferred, maleic acid and maleic anhydride are particularly preferred, maleic anhydride is particularly preferred good. The method of modifying the above-mentioned copolymer with an acid derivative can be carried out by a known technique without particular limitation. The method of grafting the compound to the above-mentioned copolymer, etc. In addition, in the resin composition of the present invention, the XD-based polyamide resin may be combined with the acid-modified polyolefin.

The above acid-modified polyolefin is preferably obtained by acid-modifying a copolymer containing a constituent unit derived from ethylene and a constituent unit derived from an α-olefin having 3 to 20 carbon atoms. By adopting such a configuration, the impact resistance is more effectively improved. The α-olefin with a carbon number of 3 to 20 is preferably an α-olefin with a carbon number of 3 to 10, preferably an α-olefin with a carbon number of 3 to 8, and an α-olefin with a carbon number of 3 to 5. Alpha-olefins of 3 or 4 are even more preferred. Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. ene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-Nadecene, 1-Eicosene, 3-Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene ene, 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, preferably propylene and 1-butene. The above-mentioned copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms may contain only one repeating unit derived from an α-olefin having 3 to 20 carbon atoms, or may contain two or more types. . The above-mentioned copolymer may be a random polymer or a block polymer. The above-mentioned copolymer preferably contains the constituent units derived from α-olefins having 3 to 20 carbon atoms in a ratio of 6 to 25 mol % of the total constituent units, more preferably 8 to 22 mol %, particularly preferably 10 to 20 mol % %. By adopting such a configuration, the impact resistance is more effectively improved. Furthermore, the above-mentioned copolymer preferably contains the constituent units derived from ethylene in a ratio of 94 to 75 mol % of all constituent units, more preferably 92 to 78 mol %, and still more preferably 90 to 80 mol %. Furthermore, the above-mentioned copolymer may contain other structural units other than the structural unit derived from ethylene and the structural unit derived from the α-olefin having 3 to 20 carbon atoms. When the acid-modified polyolefin used in the present invention contains other structural units, it is preferably in the range of 10 mol % or less of all the structural units of the above-mentioned copolymer. Specific examples of the above-mentioned copolymers include: ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/hexene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5 - Ethylene-2-norbornene copolymer.

Commercially available acid-modified polyolefins used in the present invention include Tafmer (trade name, graft polymer) manufactured by Mitsui Chemicals, Fusabond (trade name) manufactured by DuPont, Amplify (trade name) manufactured by Dow, and the like.

The resin composition of the present invention contains 3 to 17 parts by weight of an acid-modified polyolefin with an acid modification rate of 0.3 to 5.0% by weight relative to 100 parts by weight of the XD-based polyamide resin. The lower limit of the blending amount of the acid-modified polyolefin is preferably 4 parts by weight or more, more preferably 5 parts by weight or more, more preferably 6 parts by weight or more, and 7 parts by weight relative to 100 parts by weight of the XD series polyamide resin. It is more preferable that it is more than 9 parts by weight, and it is more preferable that it is 9 parts by weight or more. The upper limit of the blending amount of the acid-modified polyolefin is preferably 16 parts by weight or less with respect to 100 parts by weight of the XD-based polyamide resin. By setting it within such a range, the effect of this invention can be achieved more effectively. The resin composition of the present invention may contain only one type of acid-modified polyolefin, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above-mentioned range. In addition, the resin composition of the present invention may contain other polyolefins other than the acid-modified polyolefin with an acid modification rate of 0.3 to 5.0% by weight, and it is preferable that the other polyolefins are not substantially contained. Not substantially contained means that the content of other polyolefins in the polyolefin contained in the resin composition of the present invention is 5% by weight or less.

<Other thermoplastic resins> The resin composition of the present invention may contain the above-mentioned polyamide resins, other polyamide resins, and thermoplastic resins other than the acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight. Specifically, polyphenylene ether resin, polystyrene resin, thermoplastic polyester resin, polyacetal resin, polyurethane resin, polylactic acid-based resin, polyphenylene sulfide resin, etc. can be mentioned. The proportion of other thermoplastic resins in the resin composition of the present invention, if blended, is preferably blended within the range of 5 to 20% by weight of the resin component. Moreover, the structure which does not contain other thermoplastic resins substantially may be sufficient. Not substantially contained means that the amount of other thermoplastic resins in the resin component contained in the resin composition of the present invention is 5% by weight or less.

通式(1)中，R¹ 為碳數1~10之烷基，R² 為碳數2~12之烷基，n為1~3之整數。<The compound represented by the general formula (1)> The resin composition of the present invention contains the compound represented by the general formula (1). [Chemical 3] General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.

In the compound represented by the general formula (1), part of the OH group can be substituted at any position among ortho, para and meta positions, preferably para position or ortho position, more preferably para position. In the compound represented by the general formula (1), n is preferably 1 or 2, more preferably 1.

^{The lower limit of the carbon number of the alkyl group represented by R 1} in the general formula (1) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. The upper limit of the carbon number of the alkyl group represented by R ¹ is preferably 9 or less, more preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less. The alkyl group as R ¹ is preferably a straight-chain or branched alkyl group, more preferably a straight-chain alkyl group. With such a configuration, the impact resistance tends to be further improved. In the compound represented by the general formula (1), ^{the lower limit of the carbon number of the alkyl group represented by R 2} is preferably 3 or more, more preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more. The upper limit of the carbon number of the alkyl group represented by R ² is preferably 11 or less, more preferably 10 or less, and particularly preferably 9 or less. The alkyl group as R ² is preferably a straight-chain or branched alkyl group, more preferably a straight-chain alkyl group. With such a configuration, the impact resistance tends to be further improved. In addition, in the present invention, in the compound represented by the general formula (1), the number of carbon atoms ^{constituting R 2} is preferably larger by 2 or more, more preferably 2 to 4 larger than the number of carbon atoms ^{constituting R 1 .} With such a configuration, the impact resistance tends to be further improved.

Examples of the compound represented by the general formula (1) are listed below. However, it goes without saying that the present invention is not limited to these. [hua 4]

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. The lower limit of the compound represented by the general formula (1) is preferably 4 parts by weight or more, more preferably 5 parts by weight or more, more preferably 6 parts by weight or more, and even more preferably 7 parts by weight or more. Moreover, the upper limit is preferably 14 parts by weight or less. The compound represented by the general formula (1) may be only one type or two or more types. When two or more kinds are contained, the total amount is preferably within the above-mentioned range.

As far as the resin composition of the present invention is concerned, 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 5.0 wt % is preferably 3:10 to 16:10, which is 3 : 10~13:10 is better, 4:10~13:10 is better, 5:10~13:10 is better. By setting it within such a range, the oxygen barrier property and impact resistance can be well balanced and further improved.

<Other additives> Further, in the range that does not impair the purpose and effect of the present invention, fillers, antioxidants, stabilizers such as thermal stabilizers, hydrolysis resistance improvers, weather resistance additives can be added to the resin composition of the present invention. Stabilizers, matting agents, UV absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, coloration inhibitors, gelation inhibitors, colorants, mold release agents, lubricants and other additives Wait. The details of these can be referred to the descriptions in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, which are incorporated herein by reference.

Further, the compound represented by the general formula (1) may be used as a plasticizer for the resin composition, and the resin composition of the present invention is preferably configured to substantially contain no plasticizers other than the compound represented by the general formula (1). Not substantially contained means that, for example, in the resin composition of the present invention, the content of other plasticizers is 0.1% by weight or less of the weight of the compound represented by the general formula (1). As other plasticizers, the plasticizer described in paragraph 0039 of Japanese Patent Laid-Open No. 7-11131 and the plasticizer described in paragraph 0031 of Japanese Patent Application Laid-Open No. 2001-302908 can be exemplified.

<Characteristics of the resin composition> The resin composition of the present invention is formed into an ISO multi-purpose test piece (thickness: 4 mm), and the Charpy impact value measured in accordance with ISO 1791eA is preferably compared with the resin composition obtained from the resin. Composition The resin composition after removing the compound represented by the general formula (1) is formed into an ISO multi-purpose test piece (thickness: 4mm), and the Charpy impact value measured in accordance with ISO 179 1e A is higher, preferably more than 1.5 times higher , more than 2.0 times higher is better, and more than 3.0 times higher is even better. The above-mentioned magnification is preferably higher, and may be 4.0 times or less, and further may be 3.7 times or less. The Charpy impact value here is measured according to the method described in the examples.

<Preferable Embodiment of Resin Composition> Preferred embodiments of the resin composition of the present invention include the following resin compositions: containing an acid modification rate of 6 to 17 parts by weight with respect to 100 parts by weight of the polyamide resin It is 0.3~5.0 wt% of acid-modified polyolefin and 4~15 wt% of the compound represented by general formula (1). The polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid Composition, more than 70 mol% of the structural units derived from diamines are derived from xylene diamine, and more than 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-straight-chain aliphatics with 4 to 20 carbon atoms. family of dicarboxylic acids. More preferred embodiments of the resin composition of the present invention include the following resin compositions: containing 6 to 17 parts by weight of acid modified with an acid modification rate of 0.6 to 5% by weight relative to 100 parts by weight of the polyamide resin Polyolefin, and 4 to 15 parts by weight of the compound represented by the general formula (1), the polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70% of the structural unit derived from diamine More than mol % is derived from xylene diamine, and more than 70 mol % of the structural unit derived from dicarboxylic acid is derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. A particularly preferred embodiment of the resin composition of the present invention may include the following resin compositions: an acid modification having an acid modification rate of 0.6 to 5 wt % with 6 to 17 parts by weight relative to 100 parts by weight of the polyamide resin Polyolefin and 4-15 parts by weight of the compound represented by the general formula (1), in the general formula (1), R ¹ is an alkyl group with 3 to 10 carbon atoms, and R ² is an alkyl group with a carbon number of 5 to 12, The polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and more than 70 mol% of the structural unit derived from diamine is derived from xylene diamine, which is derived from the structural unit of dicarboxylic acid. More than 70 mol% of these are derived from α,ω-straight-chain aliphatic dicarboxylic acids with 4 to 20 carbon atoms.

In addition, another embodiment of the resin composition of the present invention (sometimes referred to as a "blended embodiment") can be exemplified by the following resin compositions: As for the resin composition of the present invention, among the above-mentioned polyamide resins, With respect to 10-90 parts by weight of the polyamide resin derived from adipic acid, more than 70 mol % of the structural units derived from the dicarboxylic acid contains 70% of the structural units derived from the dicarboxylic acid in a ratio of 90 to 10 parts by weight More than mol% is derived from the polyamide resin of sebacic acid. By having such a structure, the adhesiveness with the aliphatic polyamide resin (especially with the polyamide 12 and the polyamide 11) can be further improved. Blending of a polyamide resin with more than 70 mol % of the constituent units derived from dicarboxylic acid derived from adipic acid and a polyamide resin with more than 70 mol % of the constituent units derived from dicarboxylic acid derived from sebacic acid The ratio is preferably 90-10 parts by weight relative to 10-90 parts by weight, more preferably 20-70 parts by weight relative to 30-80 parts by weight, and more preferably 20-50 parts by weight relative to 50-80 parts by weight. In this embodiment, 70 mol% or more of the constituent units derived from dicarboxylic acid are polyamide resin derived from adipic acid, and 70 mol% or more of the constituent units derived from dicarboxylic acid are polyamide resin derived from sebacic acid The total of the amine resins preferably accounts for 90% by weight or more, more preferably 95% by weight or more, of the polyamide resin contained in the resin composition of the present invention. In the blended embodiment, it is further suitable to conform to the above-mentioned preferred embodiment.

<The manufacturing method of a resin composition> Arbitrary methods can be employ|adopted for the manufacturing method of a resin composition. For example, the following method can be mentioned: using a mixing means such as a V-type blender to mix the polyamide resin, acid-modified polyolefin, the compound represented by the general formula (1), and other components to be blended as needed to prepare a one-time blend After mixing, melt kneading and pelletizing with an extruder with vent holes. Or in the case of the two-stage kneading method, the following method can be exemplified: the ingredients other than the filler are thoroughly mixed in advance, and then melt-kneaded with an extruder equipped with a vent hole to produce pellets, and then the pellets are mixed with the filler. After mixing, it is melt-kneaded with an extruder equipped with a vent hole. In the embodiment of the above-mentioned blending, 70 mol% or more of the structural units derived from dicarboxylic acid are polyamide resin derived from adipic acid, and the structure derived from dicarboxylic acid can be exemplified by mixing means such as a V-type blender. More than 70 mol% of the unit is derived from the polyamide resin of sebacic acid, acid-modified polyolefin, the compound represented by the general formula (1), and other components that are blended as needed to be mixed and blended at one time . Furthermore, polyamide resins, acid-modified polyolefins, compounds represented by the general formula (1), or compounds of which 70 mol% or more of the constituent units derived from dicarboxylic acid are derived from adipic acid may be blended as needed. Pellets obtained by melt-kneading other components, polyamide resins in which 70 mol% or more of the constituent units derived from dicarboxylic acids are derived from sebacic acid, acid-modified polyolefins, and those represented by the general formula (1). The compound and other ingredients blended as needed are melt-kneaded and the pellets are dry-blended.

Further, the following methods can be mentioned: a mixture obtained by fully mixing components other than the filler with a V-type blender or the like is prepared in advance, the mixture is supplied from the first chute of a biaxial extruder provided with a vent hole, and the mixture is The filler is supplied to the second chute in the middle of the extruder, and is melt-kneaded and pelletized. Regarding the screw structure of the kneading zone of the extruder, it is preferable to arrange the element that promotes kneading on the upstream side, and the element having the pressure increasing ability is arranged on the downstream side.

The elements for promoting kneading include forward kneading disk elements, orthogonal kneading disk elements, wide kneading disk elements, forward mixing screw elements, and the like.

The heating temperature during melt-kneading can be appropriately selected from the range of 190 to 350°C according to the melting point of the resin. If the temperature is too high, decomposition gas is easily generated, which may cause opacity. Therefore, it is preferable to select a screw configuration that takes into account shear heat generation and the like. In addition, from the viewpoint of suppressing decomposition during kneading and molding in the subsequent step, it is preferable to use an antioxidant and a thermal stabilizer.

<Molded product> The molded product of the present invention is obtained by molding the resin composition of the present invention. As the molding method, a conventionally known molding method can be used. 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 two-color molding can be exemplified. The molded article of the present invention is widely used for fibers, threads, ropes, pipes, hoses, films, sheets, various molding materials, various parts, and finished products. There are no special regulations on the field of use, but it is widely used in transportation equipment parts such as automobiles, general machine parts, precision machine parts, electronic-electrical machine parts, OA machine parts, building materials-housing equipment-related parts, medical equipment, leisure sports goods, game supplies , medical supplies, food packaging films and other daily necessities, defense and aerospace products, etc.

<Usage as a Covering Material> Since the resin composition of the present invention has particularly excellent impact resistance and is excellent in coatability, it can be preferably used as a covering material. The molded article when the resin composition of the present invention is used as a coating material can be exemplified by a molded article including a core material and a coating layer of the core material, and the coating layer is formed of the resin composition of the present invention. The core material to be covered is not particularly limited as long as it is a thin and elongated material whose surface can be covered with the resin composition of the present invention, and known products can be widely used. For example, optical waveguides such as metal wires and optical cables, continuous hollow bodies such as pipes and tubes, and the like can be exemplified. As an example of the shape of the core material of the present invention, an average diameter of 50 μm to 1 cm (preferably an average diameter of 50 μm to 8 mm) and a length of 50 cm or more can be exemplified. Needless to say, the core material can also be a continuous hollow body. The average thickness of the coating layer can be exemplified in the range of 100 μm to 1 mm, preferably 200 μm to 800 μm. Moreover, since the resin composition of this invention is excellent also in oxygen-barrier property, it is suitable as a coating layer of the molded article which can be utilized in a high temperature environment. An example in a high temperature environment refers to, for example, a temperature of 100°C or higher, and further refers to a temperature of 120°C or higher, and the upper limit is not particularly specified, for example, it is 140°C or lower. In the present invention, the resin composition of the present invention is coated with a core material of 5 mm in diameter made of polymethyl methacrylate (PMMA) so that the average thickness is 500 μm, and even if it is left to stand for 240 hours in the aforementioned high temperature environment, The change in YI value (yellow index value) should still not change by more than 5. The YI value here was measured according to the method described in the following Examples.

As the optical waveguide of the molded article of the present invention, a core material can be exemplified by coating a core material with the resin composition of the present invention. When the molded article of the present invention is an optical waveguide, the core material may be one that does not lose functions such as light transmission, and examples thereof include PMMA (polymethyl methacrylate), glass, and the like. When coating the core material, the surface of the core material may be coated with a resin composition, 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 of the present invention composition. A preferred embodiment of the present invention can be exemplified by an optical waveguide having a cladding layer on the surface of the core material, and a layer formed of the resin composition of the present invention on the surface of the cladding layer. As the coating layer, a fluororesin can be exemplified. For details of the fluororesin used as the coating layer, reference can be made to the descriptions in paragraphs 0041 and 0042 of JP-A No. 2007-071929 and the description in paragraph 0048 of JP-A-2003-084148, which are incorporated herein by reference. middle.

Depending on the form of use, an optical fiber cable may be connected to a connector made of aliphatic polyamide resin such as polyamide 12. Therefore, the adhesiveness to the aliphatic polyamide resin is sometimes required for the resin composition of the present invention. In consideration of the adhesiveness with the aliphatic polyamide resin, the resin composition of the present invention is preferably the above-mentioned blended embodiment. Further, as an embodiment of the molded article of the present invention, a molded article including a core material and a coating layer (first coating layer) of the core material can be exemplified, and the first coating layer is formed of the resin composition of the present invention, and further has The second coating layer that is in contact with the first coating layer and contains an aliphatic polyamide resin (preferably at least one of polyamide 11 and polyamide 12, more preferably polyamide 12) as a main component. The first coating layer is formed of the resin composition of the present invention. In particular, in the polyamide resin contained in the resin composition, more than 70 mol% of the constituent units derived from dicarboxylic acid relative to 10 to 90 parts by weight are preferably polyamide resin derived from adipic acid, and 90 to 90 mol% The ratio of 10 parts by weight contains a polyamide resin derived from sebacic acid in a proportion of 70 mol% or more of the constituent units derived from dicarboxylic acid. Here, the aliphatic polyamide resin as the main component means that among the components contained in the second coating layer, the resin component with the largest content is the aliphatic polyamide resin, and the resin component contained in the second coating layer is the second coating layer. 80% by weight or more is preferably an aliphatic polyamide resin. The second coating layer may be an outer layer of the first coating layer, or may be an inner layer of the first coating layer. Preferably, the second coating layer is an outer layer of the first coating layer. By providing such an outer layer, a molded article excellent in sulfuric acid resistance can be obtained. Furthermore, when the second coating layer is provided as the outer layer of the first coating layer, a coating layer containing an aliphatic polyamide resin as a main component may be provided as an inner layer of the first coating layer. Polyamide resins other than aliphatic polyamide resins, modified polyolefins, other thermoplastic resins, various additives, and reinforcing agents such as glass fibers may be blended with the second coating layer. For the details, please refer to the descriptions in paragraphs 0018 to 0025 of International Publication No. WO2015/022818, which are incorporated herein by reference. In addition, regarding the layer structure and forming method of the 1st coating layer and the 2nd coating layer, the description of the paragraphs 0051-0054 of the international publication WO2015/022818 pamphlet can be referred to, and these contents are incorporated in this specification. [Example]

Hereinafter, the present invention will be described more specifically with reference to Examples. The materials, usage amounts, 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.

<Synthesis of polyamide resin (MXD6)> 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate were added to 8.9 kg of adipic acid, heated to 170° C. at 0.1 MPaA in a reaction tank, and then melted. While stirring the content, 8.3 kg of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was gradually added dropwise over 2 hours, and the temperature was raised to 250°C. After the temperature was raised, the pressure was gradually 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 a strand shape, and pelletized by a pelletizer to obtain pellets of 15 kg. Put the obtained pellets into a drum (rotary vacuum tank) with a heating medium heating jacket, and continue to heat at 200° C. for 1 hour in a decompressed state (0.5~10 Torr) to carry out solid-phase polymerization of the obtained pellets to obtain a polymer. Amide resin (MXD6). The melting point of the obtained MXD6 was 237°C.

<Synthesis of Polyamide Resin (MP6)> 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate were added to 8.9 kg of adipic acid, heated to 170° C. at 0.1 MPaA in a reaction tank, and then melted. While stirring the contents, slowly dropwise added xylylenediamine (a mixed diamine with a molar ratio of p-xylylenediamine and m-xylylenediamine of 3:7, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 8.3 over 2 hours. kg, and the temperature was raised to 270°C. After the temperature was raised, the pressure was gradually 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 strand form, and pelletized by a pelletizer to obtain pellets of 15 kg. Put the obtained pellets into a drum (rotary vacuum tank) with a heating medium heating jacket, and continue to heat at 200° C. for 1 hour in a decompressed state (0.5~10 Torr) to carry out solid-phase polymerization of the obtained pellets to obtain a polymer. Amide resin (MP6). The obtained MP6 had a melting point of 254°C.

<Synthesis of polyamide resin (MXD10)> 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate were added to 10.00 kg of sebacic acid, heated to 170° C. at 0.1 MPaA in a reaction tank, and then melted. While stirring the content, 6.69 kg of m-xylenediamine was slowly added dropwise over 2 hours to raise the temperature to 250°C. After the temperature was raised, the pressure was gradually lowered to 0.08 MPaA over 1 hour and maintained for 0.5 hour. After the completion of the reaction, the contents were taken out in a strand shape, and pelletized by a pelletizer to obtain 15 kg of pellets of polyamide resin (MXD10). The melting point of the obtained MXD10 was 190°C.

<Synthesis of Polyamide Resin (MP10)> 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate were added to 10.00 kg of sebacic acid, heated to 170° C. at 0.1 MPaA in a reaction tank, and then melted. While stirring the contents, slowly dropwise added xylene diamine (a mixed diamine with a molar ratio of p-xylylene diamine and m-xylene diamine of 3:7, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6.68 over 2 hours. kg, and the temperature was raised to 250°C. After the temperature was raised, the pressure was gradually lowered to 0.08 MPaA over 1 hour and maintained for 0.5 hour. After the completion of the reaction, the contents were taken out in a strand shape, and pelletized by a pelletizer to obtain 15 kg of pellets of polyamide resin (MP10). The obtained MP10 had a melting point of 215°C.

<Other polyamide resins> PA12: Polyamide 12, manufactured by Daicel-Evonik, product number: X7393

<Acid-modified polyolefin> Tafmer MH5020: maleic anhydride modification rate of 1.0% by weight, manufactured by Mitsubishi Chemical Corporation, carbon number of α-olefin 4 Tafmer MH5010: maleic anhydride modification rate of 0.5% by weight, manufactured by Mitsubishi Chemical Corporation, α-olefin with carbon number of 4 Tafmer MH5040: maleic anhydride modification rate of 2.0% by weight, manufactured by Mitsubishi Chemical Corporation, α-olefin with carbon number of 4 Tafmer DF610: Polyolefin without acid modification, manufactured by Mitsubishi Chemical Corporation, α - Carbon number of olefin 4 ZeMac E60: Maleic anhydride modification rate of 50% by weight, manufactured by Vertellus, carbon number of α-olefin 0

<Measurement of acid modification rate> 30 mL of xylene was added to 0.15 g of the sample (acid-modified polyolefin), and the sample was heated at 100° C. to dissolve the sample. After the sample was dissolved, 2 mL of ethanol and an indicator (phenolphthalein solution) were added, and neutralization titration was performed using a methanol solution of 0.1 equivalent potassium hydroxide as a titrant. The modification rate by the acid derivative was calculated according to the following formula, using a sample that was titrated in the same manner without adding the sample as a blank. Modification rate by acid derivative (% by weight)=(AB)×f×100/C/2/1000000×D×100 (A: titration amount (mL), B: blank control titration amount (mL), f : coefficient of titrant, C: sample amount (g), D: molecular weight of acid derivative unit). The coefficient f of the titrant used above is 1.005.

<The compound represented by the general formula (1)> HD-PB: Hexyldecyl p-hydroxybenzoate, manufactured by Kao Co., Ltd., EXCEPARL HD-PB EH-PB: Ethylhexyl p-hydroxybenzoate, manufactured by Tokyo Chemical Industry Co., Ltd. Co., Ltd. obtained EH-OB: Ethylhexyl phthalate, obtained by Tokyo Chemical Industry Co., Ltd.

(Example 1) The polyamide resin, the acid-modified polyolefin, and the compound represented by the general formula (1) shown in Table 1 were weighed so as to be the amounts (parts by weight) shown in Table 1, and blended with a roller. It was mixed, added from the base of a biaxial extruder (manufactured by Toshiba Machine Co., Ltd., TEM37BS), melted and extruded, and the strands were air-cooled on a net belt and then pelletized to produce a polyamide resin. Composition pellets. The extrusion temperature of the extruder was set to the melting point of the polyamide resin + 20°C.

<Preparation of coating body> For a core material made of PMMA with a diameter of 5 mm, using a single extruder and a resin coating device with a cross head, the PMMA was treated with the melt of the polyamide resin composition pellets obtained above. The core material is coated. The temperature of the extruder was set to the melting point of the polyamide resin + 20°C. The average thickness of the covering layer was 500 μm, and the average diameter of the obtained covering body was 6 mm and the length was 1 m.

<Evaluation of Oxygen Barrier Properties> Both ends of the covering body obtained above were sealed with Swagelok, and left to stand in an oven set at 130° C. for 240 hours. After the test, the coating layer was removed, and only the core material was taken out. The core material after the test was cut into a pellet shape with a length of 5 mm, and the YI value was measured according to JIS K 7373. When the difference (ΔYI) of the YI value before and after the test was 5 or less, it was evaluated as ○, and when it exceeded 5, it was evaluated as ×. The higher the oxygen barrier, the less oxygen will penetrate into the core material, and a low YI value can be maintained. The YI value was measured using a color-difference measuring device (“Z-Σ80 Color Measuring System”, manufactured by Nippon Denshoku Industries Co., Ltd.).

<Evaluation of impact resistance> Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., type "SE130DU-HP"), set the cylinder temperature to be the melting point of the polyamide resin + 20°C, and mold at a mold temperature of 130°C. The pellets of the polyamide resin composition obtained above were injection-molded under the condition of a cycle of 55 seconds, and molded into ISO multipurpose test pieces (thickness: 4 mm). For the obtained ISO multipurpose test pieces, the Charpy impact value was measured in accordance with ISO 179 1eA.

<Evaluation of Coverability> A sample having a length of 10 cm was cut out from the cover body (1 m in length) obtained above. About the sample of length 10 cm, the thickness of the coating layer was measured in the circumferential direction of the core material cross section using a digital microscope manufactured by Anmo Electronics. And it evaluated as follows. ○: No portion where the thickness of the coating layer was 400 μm or less was observed. ×: A portion where the thickness of the coating layer was 400 μm or less was observed.

<Examples 2 to 12 and Comparative Examples 2 to 7> The blending of the polyamide resin, acid-modified polyolefin, and compound represented by the general formula (1) in Example 1 was changed as shown in Tables 1 to 3 amount and type, and other operations are performed in the same manner. In addition, regarding the impact resistance evaluation, when it is not damaged, it shows as NB. In Comparative Example 5, it was not able to be extruded due to a significant increase in viscosity.

<Comparative example 1> Except having used PA12 as a polyamide resin, it carried out similarly to Example 1, and implemented evaluation.

<Examples 13 to 15> The polyamide resin composition pellets obtained in the respective examples were dry-blended so that the weight ratios shown in Table 4 were obtained. Molding was performed in the same manner as in Example 1, and the oxygen barrier properties, the Charpy impact value, and the coating properties were evaluated. Moreover, the adhesiveness with polyamide 12 (PA12) was evaluated by the following method. About Example 2, the evaluation of the adhesiveness with PA12 was also performed, and it shows in Table 4 together with Examples 13-15.

<Evaluation of adhesion with PA12> Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., type "SE130DU-HP"), set the cylinder temperature to be the melting point of the polyamide resin + 20°C, and set the mold temperature to 130°C The pellets of the polyamide resin composition were injection-molded under the conditions of ℃ and molding cycle of 120 seconds, and were molded into test pieces having a width of 55 mm, a length of 110 mm, and a thickness of 3 mm (referred to as 1 in FIG. 1 described later). For polyamide 12 pellets (manufacturer: Arkema, product number: AZM30 T6LD), the cylinder temperature is also set to (240) °C, and the injection is performed at the mold temperature (80) °C and the molding cycle (120) seconds. It was formed into a test piece having a width of 55 mm, a length of 110 mm, and a thickness of 3 mm (indicated as 2 in FIG. 1 described later). As shown in Fig. 1(a), the two obtained test pieces were arranged side by side so as to be in contact with each other in the longitudinal direction (longitudinal direction), and the vibration welding tester (VWMAC-103, manufactured by BRANSON Co., Ltd.) was used at a frequency of 240 Hz. Vibration welding was performed for 2 seconds while applying a pressure of 1.5 mm in amplitude and 1 MPa to obtain a welded test piece with a thickness of 3 mm. In FIG. 1, arrow 3 represents the vibration direction. In addition, the arrow 4 shows the welding pressure direction of vibration welding. As shown in Fig. 1(b), a piece with a width of 20 mm was cut out from the obtained welded test piece, and a 3-point bending test with a distance of 64 mm between the fulcrums was carried out with the joint surface as the center. Adhesion of amine 12. Specifically, when the load at the time of fracture of the joint surface was less than 50N, it was evaluated as ×, and when it exceeded 50N, it was evaluated as ○.

【Table 1】

【Table 2】

【table 3】

【Table 4】

From the above results, it can be seen that the resin composition of the present invention can maintain excellent oxygen barrier properties and can significantly improve impact resistance (Examples 1 to 12). Furthermore, those also excellent in coatability were obtained (Examples 1 to 12). In contrast, when PA12 was used as the polyamide resin (Comparative Example 1), the impact resistance was excellent, but the oxygen barrier properties were not good. In addition, when the compound represented by the general formula (1) was not blended (Comparative Example 2), although the oxygen barrier properties were excellent, the impact resistance was remarkably poor. In Comparative Example 2, an acid-modified polyolefin known as an impact modifier was blended in the same ratio as in Examples 2, 3, etc., but the impact resistance was remarkably poor. Therefore, it turns out that the effect of this invention is an unexpected effect. On the other hand, when the compounding amount of the compound represented by the general formula (1) is too large (Comparative Example 3), although the impact resistance is excellent, the oxygen barrier properties are not good. In addition, when a polyolefin without acid modification was used (Comparative Example 4), although the oxygen barrier properties were excellent, the impact resistance was poor. And the coverage is not good. Furthermore, when a polyolefin with a high acid modification rate was used (Comparative Example 5), a significant increase in viscosity occurred, and extrusion molding was not possible. In addition, when the acid-modified polyolefin was not blended (Comparative Example 6), the oxygen barrier properties were excellent, but the impact resistance was poor. Furthermore, when the blending amount of the acid-modified polyolefin was too large (Comparative Example 7), although the impact resistance was excellent, the oxygen barrier properties were not good. And the coverage is not good.

In addition, when the constituent unit derived from dicarboxylic acid is adipic acid and the constituent unit derived from dicarboxylic acid is sebacic acid are blended as polyamide resins, excellent oxygen barrier properties, impact resistance and coating can be maintained. Polyamide resin composition with excellent adhesion to polyamide 12 (Comparison of Example 2 and Examples 13 to 15). [industrial applicability]

The resin composition of the present invention can maintain oxygen barrier properties and achieve high impact resistance, so it can be ideally used in various molded articles. Furthermore, the resin composition of the present invention also has excellent coatability. Polyamide 11 (PA11) and polyamide 12 (PA12) have conventionally been used as coating materials for optical waveguides and the like because of their excellent impact resistance and coating properties. However, when the optical waveguide is used in a high temperature environment, its oxygen barrier properties are sometimes unsatisfactory. The resin composition of the present invention has excellent oxygen barrier properties and impact resistance, and is also excellent in coating properties, so it can also be ideally used as a coating material used in a high temperature environment.

1‧‧‧The test piece formed from the pellets of the polyamide resin composition of the present invention 2‧‧‧The test piece formed from the polyamide 12 pellets 3‧‧‧The arrow indicating the vibration direction of the vibration welding tester 4‧ ‧‧Arrow indicating the direction of welding pressure of vibration welding

[Fig. 1] (a) and (b) are schematic diagrams showing a method for evaluating the adhesiveness of the examples.

Claims (12)

A resin composition containing 3 to 17 parts by weight of an acid-modified polyolefin with an acid modification rate of 0.3 to 5.0 wt % and 1 to 15 parts by weight of the following general formula (1 ), the polyamide resin is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and more than 90 mol% of the structural unit derived from diamine is derived from xylene diamine, derived from diamine. More than 90 mol% of the constituent units of the carboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms; the xylene diamine contains m-xylene diamine and p-xylylene diamine At least one of amines; the α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains at least one of sebacic acid and adipic acid;

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3. For the resin composition of claim 1, the weight ratio of the compound represented by the general formula (1) to the acid-modified polyolefin with an acid modification rate of 0.3 to 5.0 wt % is 3:10 to 16 : 10. According to the resin composition of claim 1 or 2, the acid-modified polyolefin contains at least one of maleic acid-modified polyolefin and maleic anhydride-modified polyolefin. According to the resin composition of claim 1 or 2, in the polyamide resin, more than 90 mol % of the constituent units derived from dicarboxylic acid relative to 10 to 90 parts by weight are derived from adipic acid. Polyamide resin, with The ratio of 90 to 10 parts by weight contains a polyamide resin derived from sebacic acid in a proportion of more than 90 mol% of the constituent units derived from dicarboxylic acid. For example, the resin composition of item 4 of the scope of application is the covering material of the core material. A molded product is obtained by molding the resin composition according to any one of claims 1 to 5 of the scope of the application. A molded article comprising a core material and a coating layer of the core material, the coating layer being formed of the resin composition according to any one of claims 1 to 5 of the scope of application. The molded article of claim 7 further has a second coating layer which is in contact with the coating layer and has an aliphatic polyamide resin as a main component. According to the molded article of claim 8, the aliphatic polyamide resin is polyamide 12. The molded article of claim 8 or 9, wherein in the polyamide resin constituting the coating layer, 90 mol % or more of the constituent units derived from dicarboxylic acid relative to 10 to 90 parts by weight are self-derived The polyamide resin of the diacid contains more than 90 mol% of the constituent units derived from the dicarboxylic acid in a proportion of 90 to 10 parts by weight of the polyamide resin derived from the sebacic acid. The molded product according to any one of claims 7 to 9 of the claimed scope, wherein the core material is an optical waveguide or a continuous hollow body. A method for producing a molded product, comprising the step of coating a core material with the resin composition according to any one of items 1 to 5 of the scope of the application.

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