JP2001011305A - Polyamide resin composition for blow molding and blow molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for blow molding, composed of a polyamide and a liquid crystal resin, having improved gas barrierness, chemical resistance and mechanical properties and giving a blow-molded article having improved uniformity of the wall thickness. SOLUTION: This polyamide resin composition for blow-molding is a composition produced by compounding (a) a polyamide resin with (b) a liquid crystal resin and satisfying the formula (Tm+10 deg.C)<=T deg.C<=(Tm+70 deg.C) wherein T is a temperature satisfying the formulas (i) and (ii) lnμa10>=10.5-0.04(T-Tm) (i), μa10/μa1000>=3.0 (ii), Tm is the melting point ( deg.C) of the polyamide, μa10 is melt viscosity (poise) of the polyamide resin composition at T deg.C and a shearing rate of 10 sec-1 and μa1000 is melt viscosity (poise) of the polyamide resin composition at T deg.C and a shearing rate of 1,000 sec-1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition for blow molding comprising a polyamide and a liquid crystalline resin, which has improved gas permeation resistance, chemical resistance, mechanical properties and wall thickness uniformity during blow molding. And blow-molded articles.

[0002]

2. Description of the Related Art Polyamide resin has excellent mechanical properties,
Since it has heat resistance and chemical resistance, it is used as various molded products as engineering plastics. Among them, utilization as a blow molded product is also being studied. However, the desired melt viscosity property for blow molding is that the melt viscosity is low at high shear rates during plasticization and the melt viscosity is high at low shear rates during parison formation, whereas polyamide is Since the change in melt viscosity is small, it is difficult to obtain a large blow molded product as it is. As an attempt to improve the melt viscosity characteristics of such a polyamide resin, Japanese Patent Publication No. 55-41659 discloses blending a polyamide resin with a polyolefin resin, and Japanese Patent Application Laid-Open No. 60-171133 discloses a polyamide resin. It is disclosed to incorporate glass fibers.

[0003] However, these methods have some effects in improving the melt viscosity characteristics, but they cannot be said to be sufficient. Particularly, when a large-sized molded product is blow-molded with a polyolefin-based resin, the resin cannot be used. In order to increase the overall melt viscosity of the composition, uneven thickness occurs, and when glass fiber is blended, the surface appearance is poor and the shapeability is reduced, and gas leakage occurs during blow molding. Good blow molded products cannot be obtained. In addition, it was found that when the molded article obtained by either method was used as a container, resistance to permeation of, for example, alcohol or the like was insufficient.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems, that is, blow molding having excellent blow moldability and excellent mechanical properties such as gas permeation resistance, chemical resistance, and impact strength. An object of the present invention is to obtain a polyamide resin composition for use and a blow molded product.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, melt-kneading a polyamide resin and a liquid crystal resin to obtain a melt viscosity suitable for blow moldability. A material exhibiting characteristics was obtained, and it was found that the problem could be solved, leading to the present invention.

That is, the present invention provides: A polyamide resin composition comprising (a) a polyamide resin and (b) a liquid crystalline resin, wherein the polyamide resin composition has the following formula (i)
And the temperature T (° C.) satisfying (ii) is (Tm + 10
C) or more and (Tm + 70 ° C) or less.

Inμa10 ≧ 10.5-0.04 (T−Tm) (i) μa10 / μa1000 ≧ 3.0 (ii) (wherein, Tm is the melting point of polyamide (° C.) μa10 : Melt viscosity (poise) of the polyamide resin composition at a temperature T (° C) and a shear rate of 10 (sec-1) μa1000: Melt viscosity of the polyamide resin composition at a temperature T (° C) and a shear rate of 1000 (sec-1) (Poise).) 2. 2. The blow molding polyamide resin composition according to the above 1, wherein the compounding amount of the liquid crystal resin is 0.1 to 200 parts by weight based on 100 parts by weight of the polyamide resin. The filler is further added in an amount of 0.5 to 200 with respect to 100 parts by weight of the total amount of the (a) polyamide resin and the (b) liquid crystal resin.
3. The blow molding polyamide resin composition according to the above 1 or 2, wherein the polyamide resin composition comprises parts by weight. Further, (c) an olefin compound having a carboxylic acid anhydride group in the molecule or a polymer of the olefin compound is used in an amount of from 0.05 to 100 parts by weight of the polyamide resin (a).
4. The polyamide resin composition for blow molding according to any one of the above items 1 to 3, which is contained in an amount of 10 parts by weight. (D) an ethylene ionomer resin and / or
5. The blow-molded polyamide resin composition according to any one of the above 1 to 4, wherein the carboxy-modified elastomer is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polyamide resin. 6. A blow molded product obtained by blow molding the polyamide resin composition for blow molding according to any one of the above 1 to 5. 6. The blow-molded article according to 6 above, which comprises a layer comprising the blow-molded polyamide resin composition according to any one of 1 to 5 above.
7. a blow-molded article composed of at least one resin layer; A polyamide resin composition comprising (a) a polyamide resin and (b) a liquid crystalline resin, wherein the polyamide resin composition has the following formula (i)
And the temperature T (° C.) satisfying (ii) is (Tm + 10
C) or more and (Tm + 70 ° C) or less, wherein the polyamide resin composition for blow molding is blow-molded at a temperature T (° C).

Inμa10 ≧ 10.5-0.04 (T−Tm) (i) μa10 / μa1000 ≧ 3.0 (ii) (wherein, Tm is the melting point of polyamide (° C.) μa10 : Melt viscosity (poise) of the polyamide resin composition at a temperature T (° C) and a shear rate of 10 (sec-1) μa1000: Melt viscosity of the polyamide resin composition at a temperature T (° C) and a shear rate of 1000 (sec-1) (Poise).)

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

(A) The polyamide resin is a nylon containing amino acids, lactams or diamines and dicarboxylic acids as main raw materials. As a typical example of the raw material,
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Amino acids such as aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylene Diamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane , 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and other aliphatic, alicyclic, and aromatic diamines, and adipic acid, speric acid, azelaic acid, and sebacic acid , Dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, aliphatics such as hexahydroisophthalic acid, Alicyclic and aromatic dicarboxylic acids are exemplified by the present invention. Information, it is possible to use nylon homopolymers or copolymers derived from these raw materials each alone or in the form of mixtures.

In the present invention, particularly useful polyamides are polyamides having a melting point of 190 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene adipate. Amide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 6
10), polyhexamethylene dodecamide (nylon 61
2), polynonamethylene terephthalamide (nylon 9
T), polydodecamide / polyhexamethylene terephthalamide copolymer (nylon 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene terephthalamide / polycaproamide copolymer ( Nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polycaproamide / polyhexamethylene isophthalamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6I / 6T) Polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methyl pentamethylene terephthalamide) copolymer (nylon 6T /
M5T), polyxylylene adipamide (nylon XD
6) and mixtures or copolymers thereof.

Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 9T, nylon 6/66 copolymer, nylon 66/610, nylon 6/12 copolymer, nylon 12 / 6T copolymer, nylon 6T / 6 copolymer, Nylon 66/6
Examples include T copolymers, nylon 6T / 6I copolymers, nylon 6T / M5T copolymers, and the like. Further, these nylon resins can be used in accordance with required properties such as moldability, heat resistance, toughness, surface appearance, and roundness. A small amount of a carboxylic acid such as naphthalenedicarboxylic acid or dicarboxybiphenyl is copolymerized, or
It is also practically preferable to use them as a kind or a mixture of two kinds.

The degree of polymerization of these polyamide resins is not particularly limited, and preferably has a relative viscosity in a 1% concentrated sulfuric acid solution at 25 ° C. in the range of 2.0 to 8.0,
Those having a range of 3.0 to 7.0 are more preferable, and those having a range of 4.0 to 6.5 are most preferable.

[0014] These polyamide copolymers can be obtained by a known method. For example, as a polymerization method, a method such as melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, or solid phase polymerization is used, and generally, melt polymerization is most suitable. Furthermore, a copolymer can be obtained by introducing the above-mentioned polyamide into an extruder or an injection molding machine and causing a complete or partial exchange reaction.

(B) The liquid crystalline resin is a resin capable of forming an anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester comprising an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, a structural unit selected from an alkylenedioxy unit, and forming an anisotropic molten phase; Alternatively, a liquid crystalline polyesteramide comprising the above structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit and the like, and forming an anisotropic molten phase.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid and 6-hydroxy-2-
Examples of the structural unit and aromatic dioxy unit generated from naphthoic acid and the like include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t -Structural units formed from -butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, and aromatics And / or aliphatic dicarbonyl units include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′
-Diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'diphenyletherdicarboxylic acid acid,
Adipic acid, a structural unit formed from sebacic acid, etc., as an alkylenedioxy unit ethylene glycol,
Structural units formed from 1,3-propylene glycol, 1,4-butanediol and the like (preferably structural units formed from ethylene glycol are preferable), and aromatic iminooxy units are formed from, for example, 4-aminophenol. Structural units.

Specific examples of the liquid crystalline polyester include p
Liquid crystalline polyester comprising a structural unit formed from -hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit formed from p-hydroxybenzoic acid, 6
A structural unit formed from -hydroxy-2-naphthoic acid,
A liquid crystalline polyester comprising a structural unit formed from an aromatic dihydroxy compound and / or an aliphatic dicarboxylic acid, a structural unit formed from p-hydroxybenzoic acid,
Liquid crystalline polyester comprising a structural unit formed from 4,4′-dihydroxybiphenyl, a structural unit formed from terephthalic acid and / or adipic acid, a structural unit formed from p-hydroxybenzoic acid, a structural unit formed from ethylene glycol, Liquid crystalline polyester comprising a structural unit derived from terephthalic acid, structural unit derived from p-hydroxybenzoic acid, structural unit derived from ethylene glycol, liquid crystalline polyester comprising a structural unit derived from terephthalic acid and isophthalic acid, p- A liquid crystalline polyester comprising a structural unit derived from hydroxybenzoic acid, a structural unit derived from ethylene glycol, a structural unit derived from 4,4′-dihydroxybiphenyl, a structural unit derived from terephthalic acid and / or sebacic acid, p A structural unit derived from hydroxybenzoic acid, a structural unit derived from ethylene glycol,
Examples include a liquid crystalline polyester comprising a structural unit generated from an aromatic dihydroxy compound and a structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid.

Among the examples of the liquid crystalline polyester forming the anisotropic molten phase, the following (I), (II) and (III)
And a liquid crystalline polyester comprising the structural units of (IV),
Alternatively, a liquid crystalline polyester composed of the structural units (I), (III) and (IV) is preferable.

Particularly preferred are liquid crystalline polyesters comprising the structural units (I), (II), (III) and (IV).

[0020]

Embedded image

(Where R ₁ in the formula is

[0022]

Embedded image

R ₂ represents one or more groups selected from

[0024]

Embedded image

And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-
4,4′-dihydroxybiphenyl, hydroquinone,
t-butylhydroquinone, phenylhydroquinone,
Methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-
A structural unit formed from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether,
The structural unit (III) is a structural unit generated from ethylene glycol, and the structural unit (IV) is terephthalic acid, isophthalic acid,
4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,
The structural units generated from one or more aromatic dicarboxylic acids selected from 4′-diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

[0026]

Embedded image

And R ₂ is

[0028]

Embedded image

Is particularly preferred.

The liquid crystalline polyester which can be preferably used in the present invention includes a copolymer comprising the above structural units (I), (III) and (IV) and the above structural units (I), (II), (III),
One or more selected from copolymers consisting of (IV),
The copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (I)
II), in the case of a copolymer consisting of (IV), the structural unit (I)
And the sum of (II) is the sum of the structural units (I), (II) and (III)
Is preferably from 30 to 95 mol%, and more preferably from 40 to 8
5 mol% is more preferred. The structural unit (III) is 70 to 1 with respect to the total of the structural units (I), (II) and (III).
0 mol% is preferable, and 60 to 15 mol% is more preferable. The molar ratio [(I) / (II)] between the structural units (I) and (II) is preferably from 75/25 to 95/5, more preferably from 78/22 to 93/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

On the other hand, when the above-mentioned structural unit (II) is not contained, the structural unit (I) should be 40 to 90 mol% with respect to the total of the structural units (I) and (III) from the viewpoint of fluidity. Is preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

The term "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar.

Further, as the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, Liquid crystalline properties of aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid are not impaired. Can be further copolymerized in the range described above.

The method for producing the liquid crystalline resin (b) used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystalline polyester, the following production method is preferably mentioned. (1) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 4,4'-diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction therefrom. (2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. The phenolic hydroxyl group is acylated, and then a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid For producing liquid crystalline polyesters from polyphenols by a dephenol removal polycondensation reaction. (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystalline polyester is produced by a phenol-elimination polycondensation reaction. (5) In the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (1) or (2). A method for producing a conductive polyester.

The melt viscosity of (b) the liquid crystalline resin is not particularly limited, but in order to further exhibit the effects of the present invention,
The value measured at the melting point of the polyamide (a) to be blended + 25 ° C. is preferably 100 Pa · s or less,
It is more preferably 0.1 to 50 Pa · s, most preferably 0.5 to 30 Pa · s. Here, the melt viscosity is determined by the nozzle diameter under the condition of a shear rate of 1,000 (1 / second).
It is a value measured by a Koka type flow tester using a nozzle having a diameter of 0.5 mm and a nozzle length of 10 mm.

Here, in the differential calorimetry, the endothermic peak temperature (Tm1) observed when the polymerized polymer is measured from room temperature under a heating condition of 20 ° C./min, and then Tm1 + 20 ° C. After holding at the temperature of 5 minutes, 2
Once cooled to room temperature at 0 ° C./min,
The melting point is the endothermic peak temperature (Tm2) observed when the measurement is performed under the temperature rising condition of 0 ° C./min.

(B) The compounding amount of the liquid crystalline resin to the polyamide resin (a) does not impair the inherent properties of the polyamide, and further improves gas permeation resistance, chemical resistance, mechanical properties, and blow molding. 0.1 to 100 parts by weight of polyamide resin from the viewpoint of imparting properties such as thickness uniformity of
200 parts by weight are preferable, and more preferably 0.5 to 10 parts by weight.
0 parts by weight, particularly preferably 0.5 to 50 parts by weight.

In the present invention, it is possible to use a filler for imparting mechanical strength and other properties to the polyamide resin composition for blowing, and the filler is not particularly limited. Fillers in the form of particles, granules and the like can be used. Specifically, for example, glass fiber, PA
N-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, oxidation Titanium fiber, silicon carbide fiber, rock wool,
Fibrous such as potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flake, glass micro balloon, clay, Molybdenum disulfide, wollastenite, titanium oxide,
A powdery, granular or plate-like filler such as zinc oxide, calcium polyphosphate, graphite and the like can be used. In the above fillers, if glass fibers and conductivity are required, PA
N-based carbon fibers are preferably used. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. Further, two or more of the above fillers can be used in combination. The filler used in the present invention has a surface with a known coupling agent (for example,
(A silane-based coupling agent, a titanate-based coupling agent, etc.) and other surface treatment agents.

The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The amount of the filler is 100 parts by weight of the total of the polyamide resin (A) and the liquid crystal resin (B).
Usually, it is 0.5 to 200 parts by weight, preferably 5 to 1 part by weight.
It is 50 parts by weight, more preferably 10 to 110 parts by weight.

Specific examples of the olefin compound having a carboxylic acid anhydride group in the molecule and the polymer of these olefin compounds used as component (c), which are blended as required in the present invention, include maleic anhydride, Examples include itaconic acid, glutaconic anhydride, citraconic anhydride, aconitic anhydride, and polymers of these substituted olefin compounds. In the olefin compound polymer, olefins other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, are copolymerized within a range that does not impair the effects of the present invention. Although it does not matter, it is preferable that the polymer is substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule. The polymerization degree of the polymer of the olefin compound is preferably 2 to 100,
2-50 are more preferable, and 2-20 are most preferable. Among them, maleic anhydride and polymaleic anhydride are most preferably used. Examples of polymaleic anhydride include, for example, J. Macromol. Sci.-Revs. Macromol. Che
m., C13 (2), 235 (1975) and the like.

The addition amount of the olefin compound having a carboxylic anhydride group in the molecule or the polymer of the olefin compound is preferably 0.05 to 10 parts by weight per 100 parts by weight of the polyamide resin to improve the impact strength. It is preferable from the viewpoint of the effect and the fluidity of the composition, more preferably in the range of 0.1 to 5 parts by weight, more preferably 0.1
３3 parts by weight.

The olefin compound having a carboxylic anhydride group in the molecule or a polymer of these olefin compounds used herein may have an anhydride structure when substantially melt-kneaded with a polyamide resin. The compound or the polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof. It may be kneaded.

The ethylene ionomer used as the component (d), if necessary, in the present invention is a copolymer of an α-olefin containing ethylene and an α, β-unsaturated carboxylic acid having a valency. It is an ionic polymer to which 1-3 metal ions have been added. Here, specific examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid, and specific examples of the metal ion having a valence of 1 to 3 include a sodium ion, a potassium ion, and a calcium ion. Zinc ions, aluminum ions and the like can be mentioned.

Specific examples of preferred ethylene ionomers include ethylene / methacrylic acid / sodium methacrylate copolymer and ethylene / methacrylic acid / zinc methacrylate copolymer.

The carboxy-modified elastomer used as component (d) in the present invention is ethylene, propylene, butene-1, butadiene, isoprene, 1,3-pentadiene, pentene-1,4-methyl. Pentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornene, 5
At least one selected from homopolymers or copolymers such as -ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1'-propenyl) -2-norbornene, styrene, α-methylstyrene, and vinyltoluene; It is a modified polyolefin obtained by introducing an α, β-unsaturated carboxylic acid into a kind of polyolefin. Specific examples of the α, β-unsaturated carboxylic acid used here include:
Maleic acid, fumaric acid, itaconic acid, acrylic acid, crotonic acid, cis-4-cyclohexane-1,2-dicarboxylic acid and their anhydrides, derivatives and maleimide derivatives thereof. There is no particular limitation on the method of introducing the α, β-unsaturated carboxylic acid, and the main component olefins and the α, β-unsaturated carboxylic acid may be mixed and copolymerized, or a polyolefin may be used with a radical initiator. α,
A method such as grafting and introducing a β-unsaturated carboxylic acid can be used. The amount of the α, β-unsaturated carboxylic acid to be introduced is preferably in the range of 0.01 to 40% by weight, preferably 0.1 to 20% by weight, based on the elastomer.

Preferred carboxy-modified elastomers include a maleic anhydride graft copolymer of ethylene / propylene copolymer, a maleic anhydride copolymer of ethylene / 1-butene copolymer, and a styrene / butadiene / styrene block copolymer. A copolymer obtained by grafting maleic anhydride after hydrogenation may be used.

For example, when it is necessary to further improve the gas permeation resistance of a blow-molded article made of the blow-molded polyamide resin composition, an acid anhydride or a polyepoxy compound can be added. Examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, trimellitic anhydride, , 8-Naphthalic acid, phthalic anhydride, maleic anhydride and the like. Among them, succinic anhydride, 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride and the like are preferable. The polyvalent epoxy compound is a compound having two or more epoxy groups in a molecule. Preferably, the polyepoxy compound has an epoxy equivalent of 10
It is selected from 0 to 1000 polyfunctional epoxy compounds. Examples of such a polyvalent epoxy compound include a novolak type epoxy compound obtained by reacting a novolak resin (phenol novolak, cresol novolak, etc.) with epichlorohydrin. Alternatively, a compound obtained by reacting a compound having two or more active hydrogens in one molecule with epichlorohydrin or 2-methylepichlorohydrin is exemplified. Examples of the compound having two or more active hydrogens in one molecule include polyhydric phenols (bisphenol A, bishydroxydiphenylmethane, resorcin, bishydroxydiphenyl ether,
Tetrabromobisphenol A, etc.), polyhydric alcohols (ethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, bisphenol A-ethylene oxide adduct, trishydroxyethyl isocyanurate, etc.), amino compounds (Eg, ethylenediamine, aniline, etc.) and polyvalent carboxy compounds (eg, adipic acid, phthalic acid, isophthalic acid, etc.). Examples of such polyepoxy compounds include terephthalic acid diglycidyl ester, triglycidyl cyanurate, hydroquinone diglycidyl ether, N, N'-diglycidylaniline, and the like. Other examples include linear aliphatic epoxy compounds such as butadiene dimer epoxide and epoxidized soybean oil, and alicyclic epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene diepoxide. These may be used alone or in combination of two or more.

The amount of the acid anhydride or polyepoxy compound used in the present invention is preferably 0.01 to 5 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the polyamide in view of the effect of improving gas permeability resistance. 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight. By using the acid anhydride, the particle size distribution width of the liquid crystalline resin dispersed in the polyamide resin is narrowed, and as a result, the gas permeation resistance due to the addition of the liquid crystalline resin is more improved. But,
If the amount of the acid anhydride is too large, gas is generated at the time of compounding and blow molding, and poor gelation, gas burning of the molded product and bursting of the molded product at the time of blowing and gas leakage occur, or gelation due to excessive reaction occurs, In the worst case, molding is impossible. Further, for example, even if a molded product is obtained, the obtained molded product also tends to have reduced mechanical properties as well as surface appearance.

The presence state of the acid anhydride used in the present invention in the polyamide resin composition is not particularly limited, and any state of the acid anhydride, water or polyamide, a liquid crystal resin and a reaction product thereof with a monomer / oligomer can be used. It may be present at.

Further, a copper compound is preferably used in the blowing polyamide resin composition of the present invention in order to improve long-term heat resistance. Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds, are preferred, and cuprous acetate and iodide iodide are preferred.
Copper etc. can be illustrated as a particularly suitable copper compound. The addition amount of the copper compound is usually preferably 0.01 to 2 parts by weight, more preferably 0.015 to 1 part by weight, based on 100 parts by weight of the polyamide resin. If the addition amount is too large, metal copper is released during melt molding,
Coloring will reduce the value of the product. In the present invention, it is also possible to add an alkali halide in a form used in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide, and potassium iodide, iodine Sodium chloride is particularly preferred.

Addition of an alkoxysilane, preferably an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureide group, to the resin composition of the present invention. Is effective for improving mechanical strength, toughness and the like. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl A) ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2- Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-
Hydroxy group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane and the like.

In the composition of the present invention, other components such as an antioxidant and a heat stabilizer (a hindered phenol type, a hydroquinone type, a phosphite type and substituted products thereof) are provided as long as the effects of the present invention are not impaired. ), Weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides) , Bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate) , N-butylbenzenesulfonamide, etc.) Antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), difficult Combustion agents (for example, hydroxides such as red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc., ammonium polyphosphate, brominated polystyrene, brominated PPO, brominated PC, brominated epoxy resin, or brominated epoxy resins thereof) Combination of flame retardant and antimony trioxide, etc., other polymers (polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyether sulfone, ABS resin, SAN resin, polystyrene, acrylic resin, polyethylene, polypropylene, SBS, SEBS ) Can be added.

The polyamide resin composition for blow molding of the present invention is prepared so that the temperature T (° C.) satisfying the following formulas (i) and (ii) is in the range from (Tm + 10 ° C.) to (Tm + 70 ° C.). It is necessary.

Inμa10 ≧ 10.5-0.04 (T−Tm) (i) μa10 / μa1000 ≧ 3.0 (ii) (wherein, Tm is the melting point of polyamide (° C.) μa10 : Melt viscosity (poise) of the polyamide resin composition at a temperature T (° C) and a shear rate of 10 (sec-1) μa1000: Melt viscosity of the polyamide resin composition at a temperature T (° C) and a shear rate of 1000 (sec-1) (Poise) is shown.) Formula (i) is a formula that specifies the melt viscosity of a certain level or more necessary for blow molding, and when formula (i) is not satisfied, the viscosity is low and blow molding is performed well. Can not.

In general, the melt viscosity of a polymer is expressed as a function of the measurement temperature and the shear rate. Since the measurement temperature is determined by the melting point of the polymer, when discussing a specific value of the melt viscosity, the measurement temperature and the melting point are used. , Ie, (T−T
It is appropriate to display m) as a parameter. The method for measuring the melt viscosity conforms to the method specified in ASTM D-1238. The measurement temperature is selected from the temperature range of 10 to 70C higher than the melting point of the polyamide, which is the same temperature as the blow molding temperature, preferably 15 to 60C higher, more preferably 20 to 40C higher. In addition,
The melting point of the polyamide is determined by measuring the endothermic peak temperature (Tm1) observed when the polymerized polymer is measured from room temperature under a heating condition of 20 ° C./min. After holding for 5 minutes, 20 ° C
/ Minute cooling once to room temperature, then again at 20 ° C
The melting point is the endothermic peak temperature (Tm2) observed when the measurement is performed under the heating condition of / min.

Equation (ii) is an equation representing the magnitude of the shear rate dependence of the melt viscosity, and is the ratio of the melt viscosity in the low shear rate region to the melt viscosity in the high shear region. If the melt viscosity characteristic does not satisfy the formula (ii), it is not preferable because blow molding cannot be performed well. Melt viscosity at a shear rate of 10 sec-1 and a shear rate of 1000 s expressed by equation (ii)
The melt viscosity ratio (μa10 / μa1000) at ec-1 is 3.
It is essential that it is 0 or more, but it is preferably 3.3 or more, more preferably 3.5 or more. Although the upper limit of the ratio of the melt viscosity is not particularly limited, a value of about 20 is generally the upper limit in view of the performance of the molding machine.

The polyamide resin composition for blow molding of the present invention has a temperature T (° C.) at which the melt viscosity satisfies both of the above formulas (i) and (ii) is (Tm + 10 ° C.) or more (Tm + 70).
° C) It is necessary to be in the following range, and even if only one of the conditions is satisfied, a good blow molded product cannot be obtained. For example, if the viscosity of the polyamide resin is simply increased to improve the blow moldability, the formula (i) is satisfied, but the formula (ii) cannot be satisfied. And good molded products cannot be obtained. Also, if a large amount of liquid crystalline resin is added simply to satisfy the formula (ii), the shear rate dependency is certainly improved, but the parison during blow molding draws down to blow gas into the molded product. It is because it does not reach.

The blow molding resin composition of the present invention comprises:
In the entire range from (Tm + 10 ° C.) to (Tm + 70 ° C.), both of the above formulas (i) and (ii) may be satisfied, but it is not always necessary. At least one part of the above formula (i) It is only necessary to satisfy both (ii) and (ii). This is because, in the present invention, the temperature of the blow molding is usually selected from the temperature range of 10 to 70 ° C. higher than the melting point of the polyamide as described above, but is further blown around a temperature satisfying the above formulas (i) and (ii). By molding, a temperature T (° C.) that preferably satisfies both the above formulas (i) and (ii)
(However, T is a temperature range that is 10 to 70 ° C. higher than the melting point of the polyamide.) By performing blow molding, an extremely good blow molded product can be produced.

The method for obtaining the polyamide resin composition for blow molding of the present invention is not limited as long as a polyamide resin composition satisfying the requirements of the present invention is obtained, but the method for improving the interaction between the polyamide and the liquid crystal resin is improved. In order to exhibit the effects of the present invention (especially gas barrier properties), insert a kneading disk or the like and perform melt-kneading with a screw pattern that applies a high shearing force, or when there is no screw pattern that can obtain a high shearing force Use a method such as kneading twice. The extrusion temperature may be a normal extrusion temperature (the melting point of the polyamide + 25 ° C.). However, if it is necessary to further improve the interaction between the polyamide resin and the liquid crystal resin, the extrusion temperature may be 10 to less than the normal extrusion temperature.
It is better to set the temperature higher in the range of 80 ° C. When the filler and other additives are added, they may be added at any stage in the preferred kneading method of (a) the polyamide resin and (b) the liquid crystalline resin. Specifically, polyamide resin and acid anhydride or polyepoxy compound,
(C) An olefin compound having a carboxylic anhydride group in the molecule or a polymer of the olefin compound, (d) an ethylene ionomer resin and / or a carboxy-modified elastomer are melt-kneaded, and then kneaded with a liquid crystal resin and a filler. Method, kneading all components at once, once polyamide resin and acid anhydride or polyepoxy compound,
A method of kneading a filler and other additives after kneading a liquid crystal resin, once kneading a polyamide resin and an acid anhydride or a polyvalent epoxy compound, a liquid crystal resin to obtain a resin composition (A), For example, a high-concentration composition (master) (B) of a filler is prepared using the obtained resin composition (A), and any method may be used.

The polyamide resin composition for blow molding of the present invention can be produced by a master batch method.
In this case, (a) a part of the polyamide resin, (b) a liquid crystal resin, and, if necessary, (c) an olefin compound having a carboxylic anhydride group in the molecule or a polymer of these olefin compounds or (d) ) A master obtained by melt-kneading an ethylene ionomer resin and / or a carboxy-modified elastomer and other additives is mixed with (a) a polyamide resin or (a) a polyamide resin and the rest of an acid anhydride or a polyepoxy compound. And can be directly subjected to melt molding.

The method for blow-molding the polyamide resin composition for blow-molding of the present invention is not limited, and any known method can be used. Blow molding is usually performed in a temperature range of 10 to 70 ° C. higher than the melting point of the polyamide, preferably in a temperature range of 15 to 60 ° C. higher than the melting point, and particularly preferably in a temperature range of 2 to 60 ° C.
The temperature T is selected from a temperature range higher by 0 to 40 ° C., and further within the range and satisfying the above formulas (i) and (ii).
(° C.), it is preferable to perform blow molding.
(° C.).

In general, after forming a parison using an ordinary blow molding machine, blow molding may be performed at an appropriate temperature. The form of blow molding may be either a single-layer blow molded article or a multilayer blow molded article.

Next, the method 1 for producing the blow molded article of the present invention is described.
An example of a multilayer blow molded article will be described as an example, but is not limited to the following. That is, the molten resin extruded from the extruder of the number of layers or the number of materials is introduced into one multilayer blowing die, and is adhered to the inside of the die or immediately after leaving the die, thereby producing a multilayer blow molded product. can do. Alternatively, a method may be used in which a single-layer blow-molded article is once manufactured, and another layer is laminated on the inside or outside thereof to manufacture a multilayer blow-molded article.

When manufacturing a multilayer blow-molded article having a multilayer structure of three or more layers, extruders are appropriately added, each extruder is connected to a co-extrusion die, and a multilayer parison is pressed. It is obtained by putting out.

The arrangement of each layer in the multilayer blow-molded article of the present invention is not particularly limited, and all layers may be composed of the polyamide resin composition for blow-molding of the present invention, or at least one layer of the blow-molded polyamide resin of the present invention. The polyamide resin composition for molding may be used, and another layer may be formed using another thermoplastic resin. The layer made of the polyamide resin composition of the present invention is preferably the innermost layer in the case of two layers and the innermost layer or the intermediate layer in the case of three or more layers, in order to sufficiently exhibit the gas permeation resistance effect. .

The thermoplastic resin used herein other than the blow molding polyamide resin composition of the present invention includes saturated polyester resin, polysulfone resin, polyethylene tetrafluoride resin, polyetherimide resin, polyamideimide resin, polyamide resin, Polyphenylene ether resin,
Polyimide resins, polyether sulfone resins, polyether ketone resins, polythioether ketone resins, polyether ether ketone resins, thermoplastic polyurethane resins, polyolefin resins, ABS resins, polyamide elastomers, polyester elastomers, etc. It is of course possible to use one or more kinds of thermoplastic resins in combination, or to add various additives to them to impart desired physical properties.

Since the polyamide resin composition for blow molding of the present invention has excellent melt viscosity characteristics, it is suitable for three-dimensional blow molding requiring a long parison length. The obtained blow molded articles are, for example, Freon-11, Freon-12, Freon-21, Freon-22, Freon-113, Freon-113.
114, Freon-115, Freon-134a, Freon-
32, CFC-123, CFC-124, CFC-12
5, Freon-143a, Freon-141b, Freon-1
42b, Freon-225, Freon-C318, R-50
2,1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil based brake fluid, glycol ether brake fluid, borate brake fluid , Extreme cold brake fluid, silicone oil-based brake fluid, mineral oil-based brake fluid, power sillilling oil, window washer fluid, gasoline, methanol, nitrogen, oxygen, carbon dioxide, methane,
Low gas permeability of propane, argon, helium, xenon, pharmaceutical agents, etc., and excellent mechanical properties such as chemical resistance and impact strength, so that spoilers, air intake ducts, intake manifolds, resonators, roofs Not only can it be applied to hollow molded products such as carriers, but also fuel tanks, reservoir tanks for oil, chemical liquid storage containers such as various chemical bottles or parts thereof, and other applications where gas permeability resistance is required, such as Starting with mechanical parts such as automobile parts and power tool housings, electrical and electronic parts, home and office supplies, building material related parts,
It is effective for various uses such as furniture parts.

[0072]

The present invention will be described in more detail with reference to the following examples.

Reference Example 1 (Polyamide resin) A-1: ε-caprolactam was polymerized by a conventional method to obtain nylon 6 pellets. The relative viscosity of this polyamide was 4.20 and the melting point was 222 ° C.

A-2: Equimolar salt of hexamethylenediamine-adipic acid 20% by weight, ε-caprolactam in 80%
% By weight of a mixed aqueous solution (solid raw material concentration: 60% by weight) was charged into a pressure polymerization vessel, and the temperature was raised with stirring, and the steam pressure was 17 kg / cm.
After reacting for 1.5 hours at ² , the pressure was gradually released over about 2 hours, and further reacted for about 30 minutes under a normal pressure nitrogen stream to obtain a polyamide resin having a relative viscosity of 4.25 and a melting point of 192 ° C.

A-3: ε-caprolactam was polymerized by a conventional method to obtain nylon 6 pellets. The relative viscosity of this polyamide was measured to be 2.80, and the melting point was 222 ° C.
Met. Reference Example 2 (liquid crystalline resin) B-1: 528 parts by weight of p-hydroxybenzoic acid, 4,4
126 parts by weight of '-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 864 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 586 acetic anhydride
The weight part was charged into a reaction vessel equipped with a stirring blade and a distilling tube, and polymerization was performed. 42.5 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 50 molar equivalents of ethylenedioxy units, 5 aromatic dicarboxylic acid units
A liquid crystalline resin having a melting point of 213 ° C. consisting of 7.5 molar equivalents was obtained. The melt viscosity at each temperature is 25 Pa
s, 38 Pa · s at 217 ° C (orifice 0.5φ × 1
0 mm and a shear rate of 1,000 (1 / sec)).

Examples 1 to 6 and Comparative Examples 1 to 5 Polyamide resins (A-1, A-
2) 100 parts by weight of liquid crystal resin (B-1), filler (9 μm diameter, 3 mm long glass fiber), maleic anhydride (MAH) as component (c), and ethylene ionomer resin as component (d) (Himilan 1706: manufactured by Du Pont-Mitsui Polychemicals) was pre-blended with a tumbler mixer, and then PCM30 with a cylinder temperature set to 250 ° C.
The mixture was melt-kneaded with a twin-screw extruder (Ikegai Iron and Steel) to obtain a resin composition. The resulting composition was pelletized and then heated at 80 ° C. for 1 hour.
It was vacuum dried for 0 hour and evaluated by the following method.

(1) Blow Moldability Using a blow molding machine having an extruder having a diameter of 40 mm, 250
A parison having an outer shape of 20 mm and a thickness of 2 mm is formed at 5 ° C.
A 00 ml reagent bottle was molded and evaluated. The evaluation was ○: no sagging of the parison, ×: sagging of the parison (thickness unevenness).

(2) Melt Viscosity The melt viscosities (μa10 and μa1000) at a temperature of 250 ° C. and a shear rate of 10 sec-1 and 1000 sec-1 were measured using a flow tester prepared according to ASTM D-1238.

(3) Chemical resistance The product was supplied to a Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) and the cylinder temperature was set to 250.
℃, mold temperature 80 ℃, molded 12.7 × 127 × 3.2mm thick molded product, 50% calcium chloride on the surface of the molded product 10%
Cracks of the molded product when dropped and treated at the temperature shown in Table 1 for 30 minutes were evaluated. Evaluation: ○: no crack, ×: crack.

(4) Impact Resistance Using the same molding machine as used in the above (3), with the same cylinder temperature and mold temperature condition settings, ASTM D2
According to No. 56, 1/8 inch notched Izod impact strength was evaluated.

(5) Gas Permeability (Alcohol Gasoline Permeability) An alcohol gasoline mixture obtained by mixing a commercially available regular gasoline and methyl alcohol at a weight ratio of 85 to 15 was placed in the bottle prepared in the above (1), and sealed. afterwards,
The total weight was measured, the sealed bottle was placed in an explosion-proof oven at 40 ° C., and the change in weight was evaluated for alcohol gasoline permeability.

[0082]

[Table 1]

From the results in Table 1, when the polyamide resin composition for blow molding of the present invention is used for blow molding, the molded product obtained with good blow moldability has chemical resistance, impact resistance and gas resistance. A molded article having excellent permeability can be obtained.

[0084]

EFFECTS OF THE INVENTION The polyamide resin composition for blow molding of the present invention has good blow moldability and can provide a new molded article having excellent chemical resistance, impact resistance and gas permeability resistance. Utilizes blow molding and gas permeation resistance for electric / electronic related equipment, precision machine related equipment, office equipment, automobile / vehicle related parts, etc., and uses automobile parts such as tanks and bottles, electric / electronic parts, building materials, furniture It is suitable for blow molded articles such as daily necessities.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 23:26) F-term (reference) 4J002 BB205 BB215 BB235 BH004 BH014 BH024 CF03X CF04X CF05X CF06X CF07X CF08X CL01W CL03W CL05W CL063 DA016 DA026 DA086 DA096 DE096 DE106 DE136 DE146 DE236 DG026 DH056 DJ006 DJ016 DJ026 DJ046 DJ056 DK006 DL006 FA043 FA046 FA066 FB086 FD013 FD016 FD020 FD030 FD090 FD130 FD160 FD170 FD200

Claims (8)

[Claims] 1. A polyamide resin composition comprising (a) a polyamide resin and (b) a liquid crystalline resin, wherein a temperature T (° C.) satisfying the following formulas (i) and (ii) is ( Tm
(B + 10 ° C) or more and (Tm + 70 ° C) or less. lnμa10 ≧ 10.5-0.04 (T−Tm) (i) μa10 / μa1000 ≧ 3.0 (ii) (in the above formula, Tm: melting point of polyamide (° C.) μa10: temperature T (° C), melt viscosity (poise) of the polyamide resin composition at a shear rate of 10 (sec-1) μa1000: melt viscosity (poise) of the polyamide resin composition at a temperature T (° C) and a shear rate of 1000 (sec-1) Is shown.) 2. The blow molding polyamide resin composition according to claim 1, wherein the amount of the liquid crystal resin (b) is 0.1 to 200 parts by weight based on 100 parts by weight of the polyamide resin (a). 3. A filler of 0.5 parts per 100 parts by weight of the total of (a) polyamide resin and (b) liquid crystal resin.
The blow-molded polyamide resin composition according to claim 1 or 2, which is added in an amount of from 200 to 200 parts by weight. 4. The composition further comprises (c) an olefin compound having a carboxylic anhydride group in the molecule or a polymer of the olefin compound in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polyamide resin (a). The blow molding polyamide resin composition according to any one of claims 1 to 3, characterized in that: 5. The method according to claim 1, further comprising 1 to 100 parts by weight of (d) an ethylene ionomer resin and / or a carboxy-modified elastomer based on 100 parts by weight of the polyamide resin (a). The polyamide resin composition for blow molding according to 1. 6. A blow molded article obtained by blow molding the polyamide resin composition for blow molding according to claim 1. 7. A blow-molded article according to claim 6, wherein the blow-molded article comprises two or more resin layers including a layer comprising the polyamide resin composition for blow-molding according to claim 1. 8. A polyamide resin composition comprising (a) a polyamide resin and (b) a liquid crystalline resin, wherein the temperature T (° C.) satisfying the following formulas (i) and (ii) is ( Tm
A method for producing a blow-molded article, comprising: blowing a polyamide resin composition for blow molding having a temperature of (+ 10 ° C.) or more and (Tm + 70 ° C.) or less at a temperature T (° C.). lnμa10 ≧ 10.5-0.04 (T−Tm) (i) μa10 / μa1000 ≧ 3.0 (ii) (in the above formula, Tm: melting point of polyamide (° C.) μa10: temperature T (° C), melt viscosity (poise) of the polyamide resin composition at a shear rate of 10 (sec-1) μa1000: melt viscosity (poise) of the polyamide resin composition at a temperature T (° C) and a shear rate of 1000 (sec-1) Is shown.)