WO2018092623A1

WO2018092623A1 - Resin composition, molded article, and method for producing molded article

Info

Publication number: WO2018092623A1
Application number: PCT/JP2017/039902
Authority: WO
Inventors: 佐藤　和哉; 加藤　智則; 中村　仁
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2016-11-18
Filing date: 2017-11-06
Publication date: 2018-05-24
Also published as: TWI752111B; KR102392296B1; KR20190077333A; TW201829617A

Abstract

Provided are: a resin composition having excellent oxygen barrier properties and excellent impact resistance; a molded article using the resin composition; and a method for producing a molded article. The resin composition contains 3-17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3-5.0 wt%, and 1-15 parts by weight of a compound represented by general formula (1) below, with respect to 100 parts by weight of a polyamide resin composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, wherein 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine and 70 mol% or more of the dicarboxylic acid-derived structural unit is derived from an α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms. In general formula (1), R¹ is a C1-10 alkyl group, R² is a C2-12 alkyl group, and n is an integer of 1-3.

Description

RESIN COMPOSITION, MOLDED ARTICLE, AND METHOD FOR PRODUCING MOLDED ARTICLE

The present invention relates to a resin composition, a molded product, and a method for producing the molded product. In particular, the present invention relates to a resin composition capable of providing a molded article having excellent oxygen barrier properties and impact resistance.

Polyamide resins are widely used in various applications because of their excellent chemical resistance and heat resistance.
For example, Patent Document 1 discloses a blow molding polyamide comprising a polyamide containing at least an amine-terminated polyamide having a ratio of terminal amino group to terminal carboxyl group: the latter = 100: 0 to 50:50 and a modified polyolefin. A composition is disclosed. Furthermore, it is described that the amine-terminated polyamide is polyamide 11 or polyamide 12, and that the modified polyolefin is an epoxy-modified, acid anhydride-modified or carboxylic acid-modified polyolefin. Furthermore, it is described that such a polyamide composition is excellent in IZOD impact strength.

JP 2001-302908 A

However, when the inventor examined the above-mentioned Patent Document 1, it was found that although the impact resistance was high, the oxygen barrier property was insufficient.
Moreover, even if a polyamide resin having excellent oxygen barrier properties is used, there is a problem if it is inferior in impact resistance.
An object of the present invention is to solve such problems, and is a resin composition excellent in oxygen barrier properties and excellent in impact resistance, and a molded article and a molding using the resin composition. It aims at providing the manufacturing method of goods.

As a result of investigations by the present inventors under the above-mentioned problems, a general formula (1) is added to a predetermined xylylenediamine-based polyamide resin together with an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight. It was found that a compounded product having excellent oxygen barrier properties and a significantly improved impact resistance can be obtained by blending the compound represented by the formula, and the present invention was completed. . Specifically, the above problem has been solved by the following means <1>, preferably <2> to <14>.
<1> Consists of structural units derived from diamine and structural units derived from dicarboxylic acid, 70 mol% or more of structural units derived from diamine are derived from xylylenediamine, and 70 mol% or more of structural units derived from dicarboxylic acid is carbon 3 to 17 parts by weight of an acid-modified polyolefin having an acid modification rate of 0.3 to 5.0% by weight with respect to 100 parts by weight of a polyamide resin derived from α, ω-linear aliphatic dicarboxylic acid of several 4 to 20; And a resin composition comprising 1 to 15 parts by weight of a compound represented by the following general formula (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 xylylenediamine contains at least one of metaxylylenediamine and paraxylylenediamine.
<3> The resin composition according to <1> or <2>, wherein the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms includes at least one of sebacic acid and adipic acid.
<4> 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, <1> to The resin composition as described in any one of <3>.
<5> The resin composition according to any one of <1> to <4>, wherein the acid-modified polyolefin includes at least one of maleic acid-modified polyolefin and maleic anhydride-modified polyolefin.
<6> In the polyamide resin, 70 mol% or more of the structural unit derived from dicarboxylic acid is 10 to 90 parts by weight of the polyamide resin derived from adipic acid, and 70 mol% or more of the structural unit derived from dicarboxylic acid is converted to sebacic acid. The resin composition according to any one of <1> to <5>, comprising the derived polyamide resin in a proportion of 90 to 10 parts by weight.
<7> The resin composition according to any one of <1> to <6>, which is a coating material for the core material.
<8> A molded product 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 from the resin composition according to any one of <1> to <5>.
<10> The molded article according to <9>, further including a second coating layer mainly composed of an aliphatic polyamide resin in contact with the coating layer.
<11> The molded article according to <10>, wherein the aliphatic polyamide resin is polyamide 12.
<12> 70 mol% or more of the structural unit derived from dicarboxylic acid 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 which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived The molded article according to <10> or <11>, wherein the polyamide resin contains 90 to 10 parts by weight of 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 article, comprising coating a core material with the resin composition according to any one of <1> to <7>.

According to the present invention, it is possible to provide a resin composition having excellent oxygen barrier properties and excellent impact resistance, a molded product using the resin composition, and a method for producing the molded product.

It is the schematic which shows the evaluation method of the adhesiveness of an Example.

Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

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, and 70 of the structural unit derived from dicarboxylic acid. The acid modification rate is 100 parts by weight of a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter sometimes referred to as “XD polyamide resin”). It contains 3 to 17 parts by weight of 0.3 to 5.0% by weight of acid-modified polyolefin and 1 to 15 parts by weight of a compound represented by the following general formula (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.
By setting it as such a structure, the resin composition (molded article) excellent in oxygen barrier property and excellent in impact resistance is obtained. Furthermore, a resin composition having excellent coverage can be obtained.
That is, it is known that the XD polyamide resin is excellent in oxygen barrier properties. However, the impact resistance is not always sufficient. In the present invention, surprisingly, the impact resistance is remarkably improved by blending the acid-modified polyolefin into the XD polyamide resin and further blending the compound represented by the general formula (1). Is a successful one. That is, in order to improve the impact resistance of the polyamide resin, blending the acid-modified polyolefin has been performed so far. However, as a result of studies by the present inventors, it has been found that there are cases where sufficient impact resistance cannot be ensured only by blending acid-modified polyolefin into XD polyamide resin. In the present invention, the acid modification rate of the acid-modified polyolefin is within a predetermined range, and by blending the compound represented by the general formula (1), the impact resistance has been significantly improved. It is. In particular, it is extremely surprising that the impact resistance is remarkably improved by blending the compound represented by the general formula (1).
Furthermore, in the present invention, improvement in coverage can also be achieved. For this reason, the resin composition of this invention can be preferably used also for a coating material.
Details of the present invention will be described below.

<XD polyamide resin>
The polyamide resin (XD 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 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and dicarboxylic acid More than 70 mol% of the derived structural units are derived from α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

The XD-based polyamide resin preferably contains at least 80 mol%, more preferably 90 mol%, more preferably 95 mol%, and still more preferably 98 mol% of diamine-derived structural units at least of xylylenediamine. Preferably, at least 80 mol%, more preferably 90 mol% or more, still more preferably 95 mol% or more, and even more preferably 98 mol% or more of the structural unit derived from one dicarboxylic acid has 4 carbon atoms. Derived from at least one of ˜20 α, ω-linear aliphatic dicarboxylic acids.

That is, xylylenediamine, which is a raw material for 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. .
Furthermore, from the viewpoint of coatability, the xylylenediamine is preferably composed of 30 to 100 mol% metaxylylenediamine and 0 to 70 mol% paraxylylenediamine, and 60 to 100 mol% metaxylylenediamine and More preferably, it consists of 0 to 40 mol% paraxylylenediamine, and more preferably 70 to 100 mol% metaxylylenediamine and 0 to 30 mol% paraxylylenediamine.
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 metaxylylenediamine. By setting it as such a structure, coverage is improved more effectively.

Examples of diamines other than xylylenediamine that can be used as raw material diamines for XD-based polyamide resins 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) propa , Alicyclic diamines such as bis (aminomethyl) decalin and bis (aminomethyl) tricyclodecane, diamines having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, and bis (aminomethyl) naphthalene Can be used, and one kind or a mixture of two or more kinds can be used.
When a diamine other than xylylenediamine is used as the diamine, it is used in an amount of 30 mol% or less, preferably 1 to 25 mol%, particularly preferably 5 to 20 mol% of the structural unit derived from the diamine.

The α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms used as the raw material dicarboxylic acid of the XD polyamide resin is preferably an α, ω-linear aliphatic dicarboxylic acid having 6 to 16 carbon atoms. More preferred are 6 to 10 α, ω-linear aliphatic dicarboxylic acids. Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. An aliphatic dicarboxylic acid can be illustrated and it can use 1 type or in mixture of 2 or more types. Among these, it is preferable that at least one of adipic acid and sebacic acid is contained since the melting point of the polyamide resin is in an appropriate range for molding.
Further, 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.
Further, 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.
Furthermore, 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 having improved adhesion to the aliphatic polyamide resin can be obtained. In such a polyamide resin (XD6 / XD10), the molar ratio of the adipic acid component to the sebacic acid component is preferably 10:90 to 90:10, and more preferably 30:70 to 90:10. 50:50 to 80:20 is more preferable.

Examples of the dicarboxylic acid component 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 and orthophthalic 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, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Examples include isomers such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and the like, and one kind or a mixture of two or more kinds can be used.

When a dicarboxylic acid other than an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component, terephthalic acid or isophthalic acid is preferably used from the viewpoint of moldability and barrier properties. . The proportion of terephthalic acid and isophthalic acid is preferably 30 mol% or less, more preferably 1 to 30 mol%, particularly preferably 5 to 20 mol% of the structural unit derived from dicarboxylic acid.

Here, “consisting of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid” means that the amide bond constituting the XD-based polyamide resin is formed by a bond between the dicarboxylic acid and the diamine. Moreover, XD type polyamide resin contains other site | parts, such as a terminal group, in addition to the structural unit derived from dicarboxylic acid and the structural unit derived from diamine. Furthermore, there may be a case where a repeating unit having an amide bond that is not derived from a bond between a dicarboxylic acid and a diamine, a trace amount of impurities, and the like are included. Specifically, the XD polyamide resin is a component constituting the polyamide resin in addition to the diamine component and the dicarboxylic acid component, and lactams such as ε-caprolactam and laurolactam, aminocapron as long as the effects of the present invention are not impaired. Aliphatic aminocarboxylic acids such as acids and aminoundecanoic acids can also be used as copolymerization components. In the present invention, 90% by weight or more, more preferably 95% by weight or more of the XD polyamide resin is a structural unit derived from diamine or a structural unit derived from dicarboxylic acid.

The XD 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, still more preferably 9,000 to 26,000. When it is in such a range, the moldability becomes better.

The number average molecular weight (Mn) here is calculated by the following formula 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. Is done.
Number average molecular weight (Mn) = 2,000,000 / ([COOH] + [NH ₂ ])

The description of paragraphs 0052 to 0053 of JP-A No. 2014-173196 can be referred to for the production method of the XD-based polyamide resin, and the contents thereof are incorporated in the present specification.

In the present invention, the melting point of the XD type polyamide resin is preferably 150 to 350 ° C., more preferably 180 to 300 ° C., and further preferably 180 to 280 ° C.
In the present invention, the melting point is the temperature at the peak top of the endothermic peak at the time of temperature rise observed by the 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 at 30 mL / min as the atmospheric gas, and the heating rate was 10 Observed when polyamide resin heated and melted from room temperature to a temperature above the expected melting point under the condition of ° C / min is rapidly cooled with dry ice and heated again to a temperature above the melting point at a rate of 10 ° C / min. This can be done by measuring the temperature at the peak top of the endothermic peak.
The melting point of the polyamide resin in the case where the resin composition of the present invention contains two or more types of XD polyamide resins is the temperature at the peak top of the endothermic peak observed on the highest temperature side during the DSC measurement.

The ratio of the XD 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 80% by weight or more. You can also.
The resin composition of the present invention may contain only one type of XD polyamide resin or two or more types. When 2 or more types are included, the total amount is preferably within the above range.

<Other polyamide resins>
The resin composition of the present invention may contain a polyamide resin other than the XD polyamide resin. Examples of 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 isophthalate. Examples include ramid (polyamide 6I), polyamide 66 / 6T, polyamide 9T, polyamide 9MT, polyamide 6I / 6T, and the like.
The content of the other polyamide resin in the resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the XD polyamide resin.
Moreover, the resin composition of this invention can also be set as the structure which does not contain other polyamide resins other than XD type polyamide resin substantially. “Substantially free” means that the ratio of the other polyamide resin in the polyamide resin contained in the resin composition of the present invention is 5% by weight or less of the XD-based polyamide resin, and 3% by weight or less. It is preferable that the content is 1% by weight or less.

<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, still more preferably 0.6% by weight or more, still more preferably 0.8% by weight or more. 9% by weight or more is even more preferable. By setting it as 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% by weight or less, more preferably 3.0% by weight or less, further preferably 2.5% by weight or less, and even more preferably 1.8% by weight or less. . By setting it as such a range, when the resin composition of the present invention is used as a coating material (a coating layer of a molded product), the melt elongation becomes good and the thickness of the coating layer can be made more uniform. .
In addition, the modification | denaturation rate by the acid derivative in this invention is measured by the method as described in the Example mentioned later.

The acid-modified polyolefin used in the present invention is obtained by acid-modifying a polyolefin. Acid modification refers to reacting an acid derivative with polyolefin in some form. Specifically, the acid-modified polyolefin used in the present invention can be obtained by grafting an acid derivative onto 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 onto the main chain of the polyolefin.
The acid derivative is preferably an acid or an acid anhydride, preferably an unsaturated carboxylic acid or an anhydride of an unsaturated carboxylic acid, and more preferably an anhydride of an unsaturated carboxylic acid. The unsaturated carboxylic acid is preferably an unsaturated dicarboxylic acid, and the unsaturated carboxylic acid anhydride is also preferably an unsaturated dicarboxylic acid anhydride.
Examples of the acid derivatives include maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, endic acid, and endic anhydride Acid, citraconic acid, citraconic anhydride, 1-butene-3,4-dicarboxylic acid, 1-butene-3,4-dicarboxylic acid anhydride is more preferred, maleic acid and maleic anhydride are more preferred, and maleic anhydride is preferred. Even more preferred.
The method of modifying the copolymer with an acid derivative can be performed by a known technique, and is not particularly limited. For example, a method of copolymerizing an acid derivative and a monomer that is a raw material of the copolymer A method of grafting an acid derivative onto the above copolymer can be used. In the resin composition of the present invention, the XD polyamide resin may be bonded to the acid-modified polyolefin.

The acid-modified polyolefin is preferably obtained by acid-modifying a copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. By setting it as such a structure, impact resistance improves more effectively.

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, More preferred are α-olefins having 3 or 4 carbon atoms. 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 Pyrene and 1-butene are preferred.
The copolymer containing the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms may contain only one type of repeating unit derived from α-olefin having 3 to 20 carbon atoms. Two or more kinds may be included. The copolymer may be a random polymer or a block polymer. The copolymer preferably contains structural units derived from α-olefins having 3 to 20 carbon atoms in a proportion of 6 to 25 mol%, more preferably 8 to 22 mol%, still more preferably 10%, based on the total structural units. ˜20 mol%. By setting it as such a structure, impact resistance improves more effectively.
The copolymer preferably contains ethylene-derived structural units in a proportion of 94 to 75 mol%, more preferably 92 to 78 mol%, and still more preferably 90 to 80 mol% of the total structural units. It is.

Further, the copolymer may contain other structural units other than the structural unit derived from ethylene and the structural unit derived from 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 the total structural units of the copolymer.
Specific examples of the above copolymer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / hexene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / A 5-ethylidene-2-norbornene copolymer is exemplified.

Examples of commercially available acid-modified polyolefins used in the present invention include Mitsui Chemicals Tuffmer (trade name, graft polymer), DuPont Husabond (trade name), Dow Amplify (trade name), and the like.

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 with respect to 100 parts by weight of the XD 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, further preferably 6 parts by weight or more, and more preferably 7 parts by weight or more with respect to 100 parts by weight of the XD polyamide resin. Preferably, 9 parts by weight or more is even more preferable. The upper limit of the compounding amount of the acid-modified polyolefin is preferably 16 parts by weight or less with respect to 100 parts by weight of the XD polyamide resin. By setting it as such a range, the effect of this invention is 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 2 or more types are included, the total amount is preferably within the above range.
The resin composition of the present invention may contain other polyolefins other than acid-modified polyolefins having an acid modification rate of 0.3 to 5.0% by weight, but is substantially free of other polyolefins. Is preferred. “Substantially free” means that the amount 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 resin, other polyamide resins, and other thermoplastic resins other than the acid-modified polyolefin having an acid modification 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 resins, polyphenylene sulfide resins, and the like.
The proportion of the other thermoplastic resin in the resin composition of the present invention is preferably in the range of 5 to 20% by weight of the resin component. Moreover, it can also be set as the structure which does not contain other thermoplastic resins substantially. “Substantially free” means that the amount of the other thermoplastic resin is 5 wt% or less among the resin components contained in the resin composition of the present invention.

<Compound represented by the general formula (1)>
The resin composition of this invention contains the compound represented by General formula (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.

In the compound represented by the general formula (1), the OH group portion may be substituted at any of the ortho position, para position and meta position, but the para position or ortho position is preferable, and the para position is more preferable. .
In the compound represented by the general formula (1), n is preferably 1 or 2, and more preferably 1.

The lower limit of the number of carbon atoms of the alkyl group represented by R ¹ in the general formula (1) is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, and 5 or more. It is more preferable that 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, still more preferably 7 or less, and even more preferably 6 or less. . The alkyl group as R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. By adopting 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, and 6 or more. Is more preferable, and it is more preferable that it is 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 even more preferably 9 or less. The alkyl group as R ² is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. By adopting such a configuration, the impact resistance tends to be further improved.
In the present invention, in the compound represented by the general formula (1), the number of carbon atoms constituting R ² is preferably 2 or more, and preferably 2 to 4 larger than the number of carbon atoms constituting R ^1. More preferred. By adopting such a configuration, the impact resistance tends to be further improved.

Below, the example of a compound represented by General formula (1) is given. However, it goes without saying that the present invention is not limited to these examples.

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 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, further preferably 6 parts by weight or more, and further preferably 7 parts by weight or more. Moreover, as an upper limit, 14 weight part or less is preferable.
Only 1 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, the total amount is preferably within the above range.

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 3:10 to 16:10. Is preferred, 3:10 to 13:10 is more preferred, 4:10 to 13:10 is more preferred, and 5:10 to 13:10 is even more preferred. By setting it as such a range, oxygen barrier property and impact resistance can be improved with good balance.

<Other additives>
Further, the resin composition of the present invention includes a stabilizer such as a filler, an antioxidant, a heat stabilizer, a hydrolysis resistance improver, a weather resistance stabilizer, a gloss as long as the purpose and effect of the present invention are not impaired. Additives such as quenchers, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, mold release agents, lubricants, etc. can be added. . Details of these can be referred to the description of paragraphs 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein.

In addition, although the compound represented by General formula (1) may be used as a plasticizer of a resin composition, in the resin composition of this invention, plasticizers other than the compound represented by General formula (1) It is preferable to make it the structure which does not contain substantially. “Substantially free” means that, for example, in the resin composition of the present invention, the content of the other plasticizer is 0.1% by weight or less of the weight of the compound represented by the general formula (1). Say. Examples of other plasticizers include the plasticizer described in paragraph 0039 of JP-A-7-111131 and the plasticizer described in paragraph 0031 of JP-A-2001-302908.

<Characteristics of resin composition>
The resin composition of the present invention was formed into an ISO multipurpose test piece (thickness: 4 mm), and the Charpy impact value measured according to ISO 179 1eA was excluded from the resin composition represented by the general formula (1). The resin composition is molded into an ISO multipurpose test piece (thickness: 4 mm), and is preferably higher than the Charpy impact value measured according to ISO 179 1eA, more preferably 1.5 times or more, and more preferably 2.0 times or more. Higher is more preferable, and higher by 3.0 times or more is even more preferable. The higher magnification is preferable, but it 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.

<Preferred Embodiment of Resin Composition>
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, 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and derived from dicarboxylic acid. An acid-modified polyolefin having an acid modification rate of 0.3 to 5% by weight with respect to 100 parts by weight of a polyamide resin in which 70 mol% or more of the structural unit is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms 6 to 17 parts by weight, and 4 to 15 parts by weight of the compound represented by the general formula (1).
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, derived from dicarboxylic acid The acid modification rate is 0.6 to 5% by weight with respect to 100 parts by weight of the polyamide resin in which 70 mol% or more of the structural unit is derived from α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Examples thereof include a resin composition containing 6 to 17 parts by weight of polyolefin and 4 to 15 parts by weight of the compound represented by the general formula (1).
As a particularly preferred embodiment of the resin composition of the present invention, the resin composition 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, derived from dicarboxylic acid The acid modification rate is 0.6 to 5% by weight with respect to 100 parts by weight of the polyamide resin in which 70 mol% or more of the structural unit is derived from α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. 6 to 17 parts by weight of polyolefin and 4 to 15 parts by weight of the compound represented by the general formula (1), wherein R ¹ is an alkyl group having 3 to 10 carbon atoms in the general formula (1); ^And a resin composition in which ² is an alkyl group having 5 to 12 carbon atoms.

In another embodiment of the resin composition of the present invention (sometimes referred to as “embodiment of blend”), in the resin composition of the present invention, the polyamide resin is 70 mol of a structural unit derived from dicarboxylic acid. Resin composition containing 90 to 10 parts by weight of a polyamide resin derived from sebacic acid at 70% by mole or more of the structural unit derived from dicarboxylic acid with respect to 10 to 90 parts by weight of polyamide resin derived from adipic acid Things are illustrated. By setting it as such a structure, adhesiveness with aliphatic polyamide resin (especially polyamide 12 and polyamide 11) can be improved more. The blend ratio of the polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid and the polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from sebacic acid is 10 to 90 parts by weight. On the other hand, it is preferably 90 to 10 parts by weight, more preferably 20 to 70 parts by weight with respect to 30 to 80 parts by weight, and more preferably 20 to 50 parts by weight with respect to 50 to 80 parts by weight. Further preferred. In this embodiment, the total of the polyamide resin in which 70 mol% or more of the structural units derived from dicarboxylic acid are derived from adipic acid and the polyamide resin in which 70 mol% or more of the structural units derived from dicarboxylic acid is derived from sebacic acid is The polyamide resin contained in the resin composition of the invention preferably accounts for 90% by weight or more, and more preferably 95% by weight or more. Also in the blend embodiment, it is preferable to satisfy the above-described preferred embodiment.

<Method for producing resin composition>
Any method can be adopted as a method for producing the resin composition. For example, a polyamide resin, an acid-modified polyolefin, a 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 a batch blend product Is prepared, and then melt-kneaded with a vented extruder to form a pellet. Alternatively, as a two-stage kneading method, components other than the filler, etc., are mixed in advance and then melt-kneaded with an extruder with a vent to produce pellets, and then the pellets and filler are mixed and then extruded with a vent. The method of melt-kneading with a machine is mentioned.
In the embodiment of the blend described above, a polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid, and a polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from sebacic acid; In addition, the acid-modified polyolefin, the compound represented by the general formula (1), and other components to be blended as necessary are mixed by using a mixing means such as a V-type blender, and batch blending is exemplified. . Moreover, the polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid, the acid-modified polyolefin, the compound represented by the general formula (1), and other components blended as necessary Pellets obtained by melt kneading, a polyamide resin in which 70 mol% or more of the structural units derived from dicarboxylic acid are derived from sebacic acid, an acid-modified polyolefin, a compound represented by the general formula (1), and You may dry blend the pellet obtained by melt-kneading the other component mix | blended according to it.

Furthermore, the components other than the filler, etc., mixed sufficiently with a V-type blender, etc. are adjusted in advance, and this mixture is supplied from the first chute of the vented twin-screw extruder, and the filler is in the middle of the extruder. A method of supplying from the second chute and melt-kneading and pelletizing can be mentioned.
As for the screw configuration of the kneading zone of the extruder, it is preferable that the element that promotes kneading is arranged on the upstream side, and the element having a boosting ability is arranged on the downstream side.

Examples of elements that promote kneading include progressive kneading disc elements, orthogonal kneading disc elements, wide kneading disc elements, and progressive mixing screw elements.

The heating temperature at the time of 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 likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration that takes into account shearing heat generation and the like. Moreover, it is desirable to use an antioxidant or a heat stabilizer from the viewpoint of suppressing decomposition during kneading or molding in the subsequent process.

<Molded product>
The molded product of the present invention is formed by molding the resin composition of the present invention. As a molding method, a conventionally known molding method can be employed. Specific examples include injection molding, blow molding, extrusion molding, compression molding, vacuum molding, press molding, direct blow molding, rotational molding, sandwich molding, and two-color molding.
The molded product of the present invention is widely used for fibers, yarns, ropes, tubes, hoses, films, sheets, various molding materials, various parts, and finished products. There are no particular restrictions on the fields of use, such as transportation equipment parts such as automobiles, general machine parts, precision machine parts, electronic / electric equipment parts, OA equipment parts, building materials / household equipment-related parts, medical equipment, leisure sports equipment, playground equipment. Widely used in daily necessities such as medical products, food packaging films, defense and aerospace products.

<Use as coating material>
In particular, the resin composition of the present invention is preferably used as a coating material because it is excellent in covering properties in addition to impact resistance. As a molded product when the resin composition of the present invention is used as a coating material, a molded product including a core material and a coating layer of the core material, and the coating layer is formed from the resin composition of the present invention is exemplified. .
The core material to be coated is not particularly defined as long as it is a thin and long material and can cover the surface of the resin composition of the present invention, and widely known materials are used. it can. For example, metal wires, optical waveguides such as optical cables, and continuous hollow bodies such as pipes and tubes are exemplified. As an example of the shape of the core material of the present invention, those having 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 are exemplified. It goes without saying that such a core material may be a continuous hollow body.
Examples of the average thickness of the coating layer include 100 μm to 1 mm, preferably 200 μm to 800 μm.
Moreover, since the resin composition of the present invention is also excellent in oxygen barrier properties, it is suitable as a coating layer for molded products that can be used in a high-temperature atmosphere. As an example in a high-temperature atmosphere, for example, a temperature of 100 ° C. or higher, and further 120 ° C. or higher is used. In the present invention, a core material having a diameter of 5 mm made of polymethyl methacrylate (PMMA) is coated with the resin composition of the present invention so that the average thickness is 500 μm, and the YI value is also obtained in the high temperature atmosphere for 240 hours. It is preferable that the change in (yellow index value) does not change beyond 5. Here, the measurement of the YI value follows the method described in Examples described later.

The optical waveguide as the molded product of the present invention is exemplified by a core material coated with the resin composition of the present invention.
When the molded product of the present invention is an optical waveguide, the core material may be any material that does not lose the function of optical transmission and the like, and examples thereof include PMMA (polymethyl methacrylate) and glass.
When coating the core material, the surface of the core material may be coated with the resin composition, or after an arbitrary layer such as a cladding layer is provided on the surface of the core material, the resin of the present invention is formed on the surface of the cladding layer or the like. The composition may be coated. As a preferred embodiment of the present invention, an optical waveguide having a clad layer on the surface of the core material and a layer formed from the resin composition of the present invention on the surface of the clad layer is exemplified. An example of the clad layer is a fluororesin. Details of the fluororesin as the cladding layer can be referred to the description in paragraphs 0041 and 0042 of JP2007-071929A and the description of paragraph 0048 in JP2003-084148A, the contents of which are described in this specification. Incorporated into.

The optical fiber cable may be connected to a connector made of an aliphatic polyamide resin such as polyamide 12 depending on the usage form. Therefore, the resin composition of the present invention may be required to have adhesiveness with an aliphatic polyamide resin. From the viewpoint of adhesiveness with an aliphatic polyamide resin, the resin composition of the present invention is preferably an embodiment of the blend.
In addition, as an embodiment of the molded article of the present invention, it includes a core material and a coating layer (first coating layer) of the core material, and the first coating layer is formed from the resin composition of the present invention, And a molded article having a second coating layer mainly composed of an aliphatic polyamide resin (preferably at least one of polyamide 11 and polyamide 12, more preferably polyamide 12) in contact with the first coating layer. . The first coating layer is formed from the resin composition of the present invention. In particular, 70% by mole or more of the structural unit derived from dicarboxylic acid is contained in 10 to 90 parts by weight of the polyamide resin in which the polyamide resin contained in the resin composition is derived from 10 to 90 parts by weight of the structural unit derived from adipic acid. It is preferable to contain 90 to 10 parts by weight of a polyamide resin derived from sebacic acid.
Here, “having an aliphatic polyamide resin as a main component” means that the resin component having the largest content among the components contained in the second coating layer is an aliphatic polyamide resin. It is preferable that 80% by weight or more of the resin component contained is an aliphatic polyamide resin.
The second coating layer may be an outer layer of the first coating layer or 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 having excellent sulfuric acid resistance can be 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 also as an inner layer of a 1st coating layer.
In the second coating layer, a polyamide resin other than the aliphatic polyamide resin, a modified polyolefin, other thermoplastic resins, various additives, and reinforcing agents such as glass fibers may be blended. Details of these can be referred to the description in paragraphs 0018 to 0025 of the pamphlet of International Publication No. WO2015 / 022818, the contents of which are incorporated herein. In addition, with regard to the layer structure of the first coating layer and the second coating layer and the molding method, the description in paragraphs 0051 to 0054 of International Publication WO2015 / 022818 can be referred to, and the contents thereof are incorporated herein. .

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate 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)>
After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 8.9 kg of adipic acid and heating and melting at 170 ° C. at 0.1 MPaA in a reaction can, the contents were stirred. Then, 8.3 kg of metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) was gradually added dropwise over 2 hours to raise the temperature to 250 ° C. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg pellets. The obtained pellets were charged into a tumbler (rotary vacuum tank) having a heating medium heating mantle, and heated at 200 ° C. for 1 hour in a reduced pressure state (0.5 to 10 Torr), thereby solidifying the obtained pellets. Phase polymerization was performed to obtain a polyamide resin (MXD6). The melting point of MXD6 obtained was 237 ° C.

<Synthesis of polyamide resin (MP6)>
After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 8.9 kg of adipic acid and heating and melting at 170 ° C. at 0.1 MPaA in a reaction can, the contents were stirred. However, 8.3 kg of xylylenediamine (mixed diamine having a molar ratio of paraxylylenediamine to metaxylylenediamine of 3: 7, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was gradually added dropwise over 2 hours, and the temperature was increased to 270 ° C. Raised. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg pellets. The obtained pellets were charged into a tumbler (rotary vacuum tank) having a heating medium heating mantle, and heated at 200 ° C. for 1 hour in a reduced pressure state (0.5 to 10 Torr), thereby solidifying the obtained pellets. Phase polymerization was performed to obtain a polyamide resin (MP6). The resulting MP6 had a melting point of 254 ° C.

<Synthesis of polyamide resin (MXD10)>
To 10.00 kg of sebacic acid were added 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate, and the mixture was heated and melted at 170 ° C. at 0.1 MPaA in a reaction vessel. However, 6.69 kg of metaxylylenediamine was gradually added dropwise over 2 hours to raise the temperature to 250 ° C. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg of polyamide resin (MXD10) pellets. The melting point of MXD10 obtained was 190 ° C.

<Synthesis of polyamide resin (MP10)>
To 10.00 kg of sebacic acid were added 7.7 g of sodium hypophosphite monohydrate and 4.0 g of sodium acetate, and the mixture was heated and melted at 170 ° C. at 0.1 MPaA in a reaction vessel. However, 6.68 kg of xylylenediamine (mixed diamine having a molar ratio of paraxylylenediamine to metaxylylenediamine of 3: 7, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was gradually added dropwise over 2 hours, and the temperature was increased to 250 ° C. Raised. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg of polyamide resin (MP10) pellets. The resulting MP10 had a melting point of 215 ° C.

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

<Acid-modified polyolefin>
Tuffmer MH5020: maleic anhydride modification rate 1.0 wt%, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin carbon number 4
Tafmer MH5010: maleic anhydride modification rate 0.5 wt%, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin carbon number 4
Tafmer MH5040: maleic anhydride modification rate 2.0% by weight, manufactured by Mitsubishi Chemical Co., Ltd., α-olefin carbon number 4
TAFMER DF610: Acid-unmodified polyolefin, manufactured by Mitsubishi Chemical Corporation, α-olefin having 4 carbon atoms
ZeMacE60: maleic anhydride modification rate: 50% by weight, manufactured by Vertellus, α-olefin having 0 carbon atoms

<Measurement of acid modification rate>
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 dissolution of the sample, 2 mL of ethanol and an indicator (phenolphthalein solution) were added, and neutralization titration was performed using a 0.1 N methanol solution of potassium hydroxide as a titrant. The same titration without adding a sample was used as a blank, and the modification rate by the acid derivative was calculated from the following formula.
Modification rate by acid derivative (% by weight) = (A−B) × f × 100 / C / 2/1000000 × D × 100
(A: titer (mL), B: blank titer (mL), f: factor of titrant, C: sample amount (g), D: molecular weight of acid derivative unit).
The factor f of the titrant used above is 1.005.

<Compound represented by the general formula (1)>
HD-PB: Hexyldecyl p-hydroxybenzoate, manufactured by Kao Corporation, Exepearl HD-PB
EH-PB: ethyl hexyl p-hydroxybenzoate, obtained from Tokyo Chemical Industry Co., Ltd. EH-OB: ethyl hexyl o-hydroxybenzoate, obtained from Tokyo Chemical Industry Co., Ltd.

Example 1
The polyamide resin, acid-modified polyolefin and the compound represented by the general formula (1) shown in Table 1 are weighed so as to have the amount (parts by weight) shown in Table 1, blended with a tumbler, and a twin-screw extruder (TOSHIBA) A TEM37BS (manufactured by Kikai Co., Ltd.) was introduced from the base, melted and extruded, and the strand was air-cooled with a net belt and pelletized to prepare polyamide resin composition pellets. The extrusion temperature of the extruder was set to the melting point of the polyamide resin + 20 ° C.

<Preparation of covering>
For the core material formed from PMMA having a diameter of 5 mm, a melt of the polyamide resin composition pellets obtained above is used for the PMMA core material in a resin coating apparatus equipped with one extruder and a crosshead. And 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, the average diameter of the obtained covering was 6 mm, and the length was 1 m.

<Oxygen barrier property evaluation>
Both ends of the coated body obtained above were sealed with Swagelok and left 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 5 mm long pellet, and the YI value was measured in accordance with JIS K 7373. The difference between the YI values before and after the test (ΔYI) was 5 or less, and the case where it exceeded 5 was rated as x. As the oxygen barrier property is higher, oxygen does not permeate to the core material, and a lower YI value can be maintained.
For the measurement of the YI value, a color difference measuring apparatus (“Z-Σ80 Color Measuring System” manufactured by Nippon Denshoku Industries Co., Ltd.) was used.

<Impact resistance evaluation>
Using the injection molding machine (model “SE130DU-HP” manufactured by Sumitomo Heavy Industries, Ltd.), the cylinder temperature of the polyamide resin composition pellets obtained above was set to the melting point of the polyamide resin + 20 ° C., and the mold temperature Injection molding was performed under the conditions of 130 ° C. and a molding cycle of 55 seconds to form an ISO multipurpose test piece (thickness: 4 mm). The Charpy impact value of the obtained ISO multipurpose test piece was measured according to ISO 179 1eA.

<Coverability evaluation>
A sample having a length of 10 cm was cut out from the covering (1 m in length) obtained above. About the sample of length 10cm, the thickness of the coating layer was measured in the circumferential direction in the cross section of a core material using the digital microscope and the product made by Anneo Electronics. Evaluation was performed as follows.
A: A portion where the thickness of the coating layer is 400 μm or less was not recognized.
X: The location where the thickness of a coating layer became 400 micrometers or less was recognized.

<Examples 2 to 12 and Comparative Examples 2 to 7>
In Example 1, as shown in Tables 1 to 3, the amounts and types of the polyamide resin, the acid-modified polyolefin, and the compound represented by the general formula (1) were changed, and the others were performed in the same manner.
In addition, about impact resistance evaluation, when it did not destroy, it showed as NB.
In Comparative Example 5, thickening was remarkable and extrusion molding could not be performed.

<Comparative Example 1>
Evaluation was performed in the same manner as in Example 1 except that PA12 was used as the polyamide resin.

<Examples 13 to 15>
The polyamide resin composition pellets obtained in each example were dry blended so that the weight ratio shown in Table 4 was obtained. Molding was performed in the same manner as in Example 1, and the oxygen barrier property, Charpy impact value, and covering property were evaluated. Moreover, the adhesiveness with polyamide 12 (PA12) was evaluated with the following method. Example 2 was also evaluated for adhesion to PA12 and shown in Table 4 together with Examples 13-15.

<Adhesive evaluation with PA12>
The polyamide resin composition pellets are made into an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model “SE130DU-HP”), the cylinder temperature is set to the melting point of the polyamide resin + 20 ° C., the mold temperature is 130 ° C., and the molding cycle is 120 A test piece having a width of 55 mm, a length of 110 mm, and a thickness of 3 mm (shown as 1 in FIG. 1 to be described later) was formed by injection molding under the conditions of seconds. Similarly, for polyamide 12 pellets (manufacturer: Arkema, product number: AZM30 T6LD), the cylinder temperature was (240) ° C., the mold temperature (80) ° C., and the molding cycle (120) seconds were injection molded. A test piece having a width of 55 mm, a length of 110 mm, and a thickness of 3 mm (shown as 2 in FIG. 1 described later) was molded.
The obtained two test pieces were arranged in parallel so that the length direction (longitudinal direction) was in contact as shown in FIG. 1 (a), and a vibration welding tester (VWMAC-103, manufactured by BRANSON) was used. Vibration welding was performed at a frequency of 240 Hz for 2 seconds while applying a vibration width of 1.5 mm and a pressure of 1 MPa to obtain a welding test piece having a thickness of 3 mm. In FIG. 1, an arrow 3 indicates a vibration direction. An arrow 4 indicates the welding pressure direction of vibration welding.
As shown in FIG. 1 (b), a specimen having a width of 20 mm is cut out from the obtained welded test piece, and a three-point bending test with a distance between supporting points of 64 mm is performed with the joint surface as the center. The adhesion with polyamide 12 was evaluated from the load. Specifically, the case where the load when the fracture occurred on the joint surface was less than 50N, and the case where the load exceeded 50N was rated as ◯.

As is clear from the above results, the resin composition of the present invention can significantly improve impact resistance while maintaining excellent oxygen barrier properties (Examples 1 to 12). Further, those having excellent covering properties were obtained (Examples 1 to 12).
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.
Moreover, when not mix | blending the compound represented by General formula (1) (comparative example 2), although oxygen barrier property was excellent, impact resistance was remarkably inferior. In Comparative Example 2, although the acid-modified polyolefin, which is known as an impact resistance improver, was blended in the same ratio as in Examples 2 and 3, etc., the impact resistance was remarkably inferior. Therefore, it turns out that the effect of this invention is an unexpected effect.
On the other hand, when there are too many compounding quantities of the compound represented by General formula (1) (Comparative Example 3), although it was excellent in impact resistance, oxygen barrier property was inferior.
Moreover, when polyolefin which is not acid-modified is used (Comparative Example 4), the oxygen barrier property is excellent, but the impact resistance is inferior. Furthermore, the coverage was also poor.
Furthermore, when a polyolefin having a high acid modification rate was used (Comparative Example 5), thickening was remarkable and extrusion molding could not be performed.
Further, when no acid-modified polyolefin was blended (Comparative Example 6), the oxygen barrier property was excellent, but the impact resistance was poor.
Furthermore, when there are too many compounding quantities of acid-modified polyolefin (comparative example 7), although it was excellent in impact resistance, oxygen barrier property was inferior. Furthermore, the coverage was also poor.

In addition, when a polycarboxylic acid-derived structural unit derived from dicarboxylic acid is blended with adipic acid and a structural unit derived from dicarboxylic acid is sebacic acid, excellent oxygen barrier properties, impact resistance and covering properties are maintained. However, a polyamide resin composition having excellent adhesion to the polyamide 12 was obtained (comparison between Example 2 and Examples 13 to 15).

Since the resin composition of the present invention can achieve high impact resistance while maintaining oxygen barrier properties, it can be preferably used for various molded products.
Furthermore, the resin composition of the present invention is also excellent in coverage. Conventionally, polyamide 11 (PA11) and polyamide 12 (PA12) have been used as coating materials for optical waveguides and the like because of their excellent impact resistance and covering properties. However, when the optical waveguide is used in a high temperature atmosphere, the oxygen barrier property may be insufficient. The resin composition of the present invention is preferably used as a coating material used in a high-temperature atmosphere because it has excellent oxygen barrier properties and impact resistance, and also has excellent coating properties.

DESCRIPTION OF SYMBOLS 1 Test piece shape | molded from polyamide resin composition pellet of this invention 2 Test piece shape | molded from polyamide 12 pellet 3 Arrow which shows the vibration direction of a vibration welding test machine 4 Arrow which shows the welding pressure direction of vibration welding

Claims

It is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, 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 to 4 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 with respect to 100 parts by weight of a polyamide resin derived from 20 α, ω-linear aliphatic dicarboxylic acid, and A resin composition comprising 1 to 15 parts by weight of the compound represented by the general formula (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.
The resin composition according to claim 1, wherein the xylylenediamine contains at least one of metaxylylenediamine and paraxylylenediamine.
The resin composition according to claim 1 or 2, wherein the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms includes at least one of sebacic acid and adipic acid.
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 3:10 to 16:10. 2. The resin composition according to item 1.
The resin composition according to any one of claims 1 to 4, wherein the acid-modified polyolefin contains at least one of maleic acid-modified polyolefin and maleic anhydride-modified polyolefin.
The polyamide resin is a polyamide in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid and 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 is derived from sebacic acid. The resin composition according to any one of claims 1 to 5, comprising a resin in a proportion of 90 to 10 parts by weight.
The resin composition according to any one of claims 1 to 6, which is a coating material for the core material.
A molded article obtained by molding the resin composition according to any one of claims 1 to 7.
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 claims 1 to 5.
Furthermore, the molded article of Claim 9 which has a 2nd coating layer which has an aliphatic polyamide resin as a main component in contact with the said coating layer.
The molded article according to claim 10, wherein the aliphatic polyamide resin is polyamide 12.
The polyamide resin constituting the coating layer is composed of 10 to 90 parts by weight of a polyamide resin in which 70 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid, and 70 mol% or more of the structural unit derived from dicarboxylic acid is sebacic acid. The molded article according to claim 10 or 11, which contains 90 to 10 parts by weight of a polyamide resin derived from the above.
The molded article according to any one of claims 9 to 12, wherein the core material is an optical waveguide or a continuous hollow body.
A method for producing a molded article, comprising coating a core material with the resin composition according to any one of claims 1 to 7.