JPH06234888A - Composition for blow molding - Google Patents

Abstract

PURPOSE:To provide a composition good in heat resistance, mechanical strength and antifreezing liquid resistance, little in drawdown, excellent in blow moldability, and used for blow molding. CONSTITUTION:A composition comprises (a) 45-95wt.% polyamide resin produced from a dicarboxylic acid and a diamine, (b) 2-52wt.% polyolefin and (c) 3-53wt.% modified polyolefin produced by grafting 0.5-10wt.% of a monomer having a carboxyl group or epoxy group to a polyolefin, the ratio of the mole number of the terminal amino groups of the polyamide resin to the mole number of the functional groups of the modifying monomer for the modified polyolefin being 0.1-5, and the dispersion phase in which the component (b) and the component (c) are homogeneously dispersed in the polyamide resin matrix and which has an average particle diameter of 0.5-5mum being formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blow molding composition containing a polyamide resin and a polyolefin, which has particularly good heat resistance, mechanical strength and antifreeze resistance, and has little drawdown and blow moldability. It relates to excellent blow molding compositions.

[0002]

BACKGROUND OF THE INVENTION Polyamide resins are excellent in gasoline barrier properties, mechanical strength, heat resistance, etc., and are therefore suitable for plastic parts that substitute various metals. For example, in order to reduce the weight of automobiles, radiator tanks, heater pipes and the like are manufactured by blow molding a polyamide resin. For such parts, it is common to use nylon 6 or nylon 66, which is particularly excellent in strength and heat resistance, to which a reinforcing material such as glass fiber is added.

However, the polyamide resin has a problem that it is inferior in water resistance, moldability, chemical resistance and antifreeze resistance. The above-mentioned insufficient properties are generally possessed by polyolefins. Therefore, it is possible to mix a polyamide resin and a polyolefin,
Since the polyamide resin and the polyolefin have poor compatibility with each other, various compositions have been proposed in which they are compatible with each other.

JP-B-61-26939 discloses (a) a polyamide resin, (b) a modified polymer obtained by graft-copolymerizing an ethylenically unsaturated carboxylic acid or an anhydride thereof with a polyolefin resin, and (c) a fibrous form. Includes reinforcements and (a) ingredients
(b) The components are (a) :( b) = 70: 30 to 95: 5 by weight, and
Disclosed is a composition containing the component (c) in a proportion of 40 to 200 parts by weight based on 100 parts by weight of the total of the components (a) and (b).

JP-A-60-170664 discloses that the number average molecular weight is 2
20 to 92 parts by weight of a polyamide resin (A) of 000 or more, 50 to 3 parts by weight of modified polyolefin (B), and an average diameter of 3 to 20 μ
m, and glass fiber (C) 5-50 with an average length of 50-600 μm
Part by weight is mixed (however, (A) + (B) + (C) above
Of 100 parts by weight) is disclosed.

Further, JP-A-62-241940 discloses that [A] olefin polymer: 30 to 95% by weight, [B] polyamide: 5 to
70% by weight, and [C] glass fiber using an acrylic resin as a sizing agent: 5-200 parts by weight ([A] + [B]
= 100 parts by weight), a plastic composition for forming a radiator tank of an automobile is disclosed.

However, although the conventional composition has improved compatibility between the polyamide resin and the polyolefin, it has a low melt viscosity, so drawdown easily occurs in blow molding, and thus the meat of the blow molded product obtained is obtained. There is a problem that the thickness tends to be uneven.

Therefore, an object of the present invention is to provide a blow molding composition which has good heat resistance, mechanical strength and antifreeze resistance, and has little drawdown and excellent blow moldability.

[0009]

As a result of earnest research in view of the above object, the present inventors have found that a polyamide in a composition containing a specific polyamide resin, a polyolefin, and a modified polyolefin having a high graft ratio of a modified monomer. The molar ratio of the terminal amino group of the resin to the functional group of the modified monomer of the modified polyolefin is within the range of 0.1 to 5, and the polyolefin resin is uniformly dispersed in the polyamide resin matrix, and the dispersed phase having an average diameter of 0.5 to 5 μm. It was found that the formation of the above-mentioned composition significantly increases the melt viscosity of the resulting composition and makes it difficult for drawdown to occur, and has conceived the present invention.

That is, the blow molding composition of the present invention comprises:
(a) 45 to 95% by weight of polyamide resin produced from dicarboxylic acid and diamine, (b) 2 to 52% by weight of polyolefin, and (c) 0.5 to 10% by weight of a monomer having a carboxyl group or an epoxy group. The modified polyolefin containing 3 to 53% by weight, wherein the ratio of the number of moles of terminal amino groups of the polyamide resin to the number of moles of functional groups of the modified monomer of the modified polyolefin is 0.
1 to 5 and 0.5 to 5 μm in which the component (b) and the component (c) are uniformly dispersed in the polyamide resin matrix phase.
It is characterized in that a dispersed phase having an average diameter of m is formed.

The present invention is described in detail below. [A] Composition Component First, each constituent component of the blow molding composition of the present invention will be described.

(A) Polyamide Resin As the (a) polyamide resin used in the present invention,
Hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4, -trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p -Aminocyclohexylmethane), aliphatic, alicyclic or aromatic diamines such as m- or p-xylylenediamine and adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid A polyamide produced from an aliphatic, alicyclic or aromatic dicarboxylic acid, and a copolyamide comprising these components,
Alternatively, a mixture of these polyamides can be used. Specific examples include nylon 66, nylon 610, nylon 46, and amorphous nylon. Of these, nylon 66 is preferable because of its good rigidity and heat resistance.

The molecular weight of the above polyamide resin is not particularly limited, but those having a relative viscosity η _r (measured in JIS K6810, 98% sulfuric acid) of 0.5 or more are generally used, and those having a relative viscosity of 2.0 or more are excellent in mechanical strength. It is preferable in terms. The amount of terminal amino groups in the above polyamide resin (Korshak-Zamyationa
Method (Inverse titration method) (Chem.Abs. 40 , 4665, '46, ibid. 42 , 615
2, '48)) is 0.005 meq / g or more, especially 0.01
It is preferably 0.1 m equivalent / g. When the amount of the terminal amino group is less than 0.005 meq / g, it is difficult to obtain a composition having a sufficient melt viscosity, which is not preferable. However, as described later, the amount of terminal amino groups of the polyamide resin in the composition must be within the range of 0.1 to 5 with respect to the number of moles of the functional group of the modified monomer of the modified polyolefin.

(B) Polyolefin In the present invention, a crystalline polyolefin and an olefin elastomer can be used as the polyolefin.

As the crystalline polyolefin, ethylene, propylene, butene-1, pentene-1, hexene-1,
Homopolymer of α-olefin such as 4-methylpentene-1
Examples thereof include a copolymer of ethylene and propylene or another α-olefin, or a copolymer of two or more kinds of these α-olefins. Of these, polypropylene is particularly preferable. Polypropylene is not limited to homopolymers, and the propylene component is 50 mol% or more, preferably 80
Random or block copolymers with other α-olefins containing more than mol% can also be used. As the comonomer copolymerized with propylene, there are ethylene and other α-olefins, and ethylene is particularly preferable.

Melt flow rate of the above polypropylene
The (MFR, 230 ° C., 2.16 kg load) is preferably 0.01 to 50 g / 10 min, and particularly preferably 0.1 to 5 g / 10 min.

Further, as the olefin elastomer, 2 of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1 and the like are used.
Examples thereof include one or three or more copolymer rubbers, or a copolymer rubber of an α-olefin and another monomer. Above α
-The copolymer rubber of two or more kinds of olefins is typically an ethylene-propylene copolymer rubber (EP
R), ethylene-butene copolymer rubber (EBR), and ethylene-propylene-diene copolymer rubber (EPDM). Ethylene-propylene-diene copolymer rubber (EP
The diene in (DM) includes dicyclopentadiene and 1,4-
Non-conjugated dienes such as hexadiene, cyclooctadiene and methylene norbornene or conjugated dienes such as butadiene and isoprene can be used. Further, vinyl acetate, acrylic acid ester and the like can be used as the other monomer copolymerized with the α-olefin. A typical example of the copolymer of α-olefin and another monomer is ethylene-vinyl acetate copolymer (EVA).

Ethylene-propylene copolymer rubber (EPR)
Preferably has an ethylene content of 40 to 90 mol% and a propylene content of 10 to 60 mol%. A more preferable range is 50 to 90 mol% of ethylene and 10 to 10 of propylene.
It is 50 mol%. EPR melt index (190 ℃,
2.16 kg load) is preferably in the range of 0.5 to 15 g / 10 minutes, more preferably 3 to 9 g / 10 minutes.

The ethylene-butene copolymer rubber (EBR) is
The ethylene content is preferably 60 to 97 mol%, and the butene-1 content is preferably 3 to 40 mol%. A more preferred range is 80 to 95 mol% for ethylene and 5 to 20 mol% for butene-1. EBR melt index (190 ° C, 2.16
(kg load) is preferably in the range of 0.5 to 15 g / 10 minutes, more preferably 3 to 9 g / 10 minutes.

The ethylene-propylene-diene copolymer (EPDM) has an ethylene content of 40 to 89 mol%, a propylene content of 10 to 59 mol%, and a diene content of 1 to 10 mol%. % Is preferable. The Mooney viscosity ML _{1 + 8} (100 ° C.) of EPDM is preferably in the range of 40 to 100, more preferably 60 to 80.

Ethylene-propylene copolymer rubber (EP
R), ethylene-butene copolymer rubber (EBR) and ethylene-propylene-diene copolymer rubber (EPDM) are, for example, 4-methylpentene-1 within a range not impairing the characteristics of these copolymers. Other α-olefins may be contained up to a proportion of 10 mol% or less.

The crystalline polyolefin as described above and the olefin elastomer may be used alone or in combination.

(C) Modified Polyolefin In the modified polyolefin, the above-mentioned crystalline polyolefin and olefin elastomer can be used as the polyolefin to be modified.

A monomer containing a carboxyl group or an epoxy group is used as the polyolefin-modifying monomer.

The carboxy group-containing monomer is preferably an unsaturated carboxylic acid or an anhydride thereof, for example, a monocarboxylic acid such as acrylic acid or methacrylic acid, maleic acid,
Dicarboxylic acids such as fumaric acid and itaconic acid, maleic anhydride, itaconic anhydride, endo-bicyclo- [2,2,1] -5
Examples thereof include dicarboxylic acid anhydrides such as -heptene-2,3-dicarboxylic acid anhydride (hymic acid anhydride), and dicarboxylic acid and its anhydride are particularly preferable.

Examples of the epoxy group-containing monomer include glycidyl methacrylate and glycidyl acrylate.

Further, the following general formula (1):

[Chemical 1] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n represents an integer of 1 to 4), and a glycidyl compound having an acrylamide group and an epoxy group It can also be used as a modifying monomer.

Preferred glycidyl compounds include those represented by the following general formula (2).

[Chemical 2] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms)

Such a glycidyl compound can be produced, for example, by the method disclosed in JP-A-60-130580.

The modified polyolefin with the modifying monomer may be a block copolymer, a graft copolymer, a random copolymer or an alternating copolymer.

Regarding the melt viscosity of the modified polyolefin as described above, the modified polypropylene preferably has a melt flow rate (MFR, 190 ° C., 1.05 kg load) of 0.1 to 500 g / 10 min. , Melt flow rate (MFR, 190 ℃, 1.05kg load) is 0.1-50
It is preferably 0 g / 10 minutes.

In the case of the modified ethylene-propylene copolymer rubber, the melt flow rate (MFR, 230 ° C., 2.16
(kg load) is preferably 0.1 to 500 g / 10 min. In the case of modified ethylene-butene copolymer rubber, the melt flow rate (MFR, 230 ℃, 2.16 kg load) is 0.1 to 500 g / 1
It is preferably 0 minutes.

The above modified crystalline polyolefin and the modified olefin elastomer may be used alone or in combination.

The content (grafting ratio) of the modified monomer in the modified polyolefin is 0.5 to 10% by weight (based on the olefin monomer), preferably 1 to 8% by weight, particularly preferably 2 to 6% by weight. If the graft ratio is less than 0.5% by weight, it becomes difficult to make the composition highly viscous, while if it exceeds 10% by weight, the heat resistance of the composition decreases. Specifically, it is preferably 0.5 to 10% by weight, particularly 1 to 8% by weight in the case of maleic anhydride, and 0.8 to 10% by weight, particularly preferably 1.6 to 8% by weight in the case of hymic acid anhydride. . However, as described later, the molar ratio of the terminal amino group in the polyamide resin in the composition to the functional group of the modified monomer of the modified polyolefin needs to be within the range of 0.1 to 5.

The modified polyolefin can be produced by either a solution method or a melt-kneading method. In the case of the solution method, the polyolefin, the modified monomer and the catalyst are dissolved in an organic solvent such as xylene and the stirring is carried out at a temperature of 80 to 140 ° C. In the case of the melt-kneading method, the above-mentioned starting materials are put into an extruder, a twin-screw kneader, or the like, heated to a temperature of 150 to 250 ° C, and kneaded while melting. In any case, a usual radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxides such as peroxybenzoic acid, peroxyacetic acid and tertiary butyl peroxypivalate, and diazo compounds such as azobisisobutyronitrile are preferable. The amount of the catalyst added is about 1 to 100 parts by weight per 100 parts by weight of the unsaturated carboxylic acid for modification or its anhydride.

[B] Blending Ratio The blending ratio of the above resin components (polyamide resin + polyolefin + modified polyolefin) is 45 to 95% by weight of polyamide resin and 2 to 2% of polyolefin, with the total of each being 100% by weight. 52% by weight and modified polyolefin 3 to 53% by weight. 45% by weight of polyamide resin
If it is less than 1, heat resistance and mechanical strength are insufficient, while
If it exceeds 95% by weight, moldability and antifreeze resistance will be insufficient and the cost will increase. 2% by weight of polyolefin
If the amount is less than this, the antifreeze resistance becomes insufficient, while if it exceeds 52% by weight, the amount of the polyamide resin and / or the modified polyolefin becomes too small. Further, if the modified polyolefin is less than 3% by weight, it becomes difficult to increase the viscosity of the composition,
Blow moldability deteriorates, while when it exceeds 53% by weight, heat resistance and mechanical strength become insufficient. The preferred blending ratio is 50 to 90% by weight of polyamide resin and 5 to 5 of polyolefin.
47% by weight, modified polyolefin is 3 to 45% by weight.

[C] A terminal amino group of the polyamide resin is changed.
Molar ratio of the functional polyolefin to the functional group of the modified monomer The polyamide resin and the modified polyolefin are blended in the above-described blending ratio, but in the present invention, the terminal amino group in the composition / the mole of the functional group of the modified monomer is mixed. The ratio is 0.
It must be within the range of 1-5.

This is because of the following reasons. That is, when the modified polyolefin and the polyamide resin are melt-kneaded, the modified monomer in the modified polyolefin reacts with the terminal amino group of the polyamide resin to form a modified polyolefin-polyamide graft copolymer. The larger the number, the larger the melt viscosity. If the molar ratio of terminal amino group / functional group of modified monomer is 5 or more, the viscosity of the composition required as a resin for blow molding cannot be obtained. If the molar ratio of terminal amino group / functional group of modified monomer is less than 0.1, the ratio of the modified polyolefin in the entire composition becomes too large (the ratio of the polyamide resin decreases), which is a characteristic of the polyamide resin. And physical properties such as heat resistance are deteriorated. The preferred molar ratio of terminal amino group / functional group of modified monomer is 0.
It is within the range of 3 to 3.

[D] Polyamide of Polyolefin Resin
Polyolefin resin in the composition in an average diameter present invention the dispersed phase in the resin matrix phase ((b)
The average diameter of the dispersed phase in the polyamide resin matrix phase of polyolefin + (c) modified polyolefin) is 0.
It is within the range of 5 to 5 μm. The average diameter of this dispersed phase is 0.5
When it is less than μm, the compatibilization of the polyolefin proceeds excessively, so that the properties of the polyamide resin and the polyolefin resin are averaged, and the heat resistance decreases. Further, when the average diameter of the dispersed phase of the polyolefin resin exceeds 5 μm, the impact resistance, particularly the impact resistance at low temperature water absorption is deteriorated.

[E] Other Components Inorganic Filler To the blow molding composition of the present invention, an inorganic filler such as glass fiber, talc, calcium carbonate, mica, or whisker may be added for the purpose of reinforcing the composition. it can. Of these, glass fiber is particularly preferable.

As the glass fiber, either chopped strand or roving can be used, but it is preferable that the average fiber diameter is 6 to 20 μm and the aspect ratio is 100 to 500. In addition, it is preferable to use those which have been surface-treated with a silane coupling agent and / or a binding agent made of a polymer having a carboxyl group or an acid anhydride group. Such surface treatment improves the adhesion between the glass fiber and the polyamide resin.

The compounding amount of the above-mentioned inorganic filler is 100 parts by weight or less, especially 100 parts by weight based on 100 parts by weight of the resin components in total.
It is preferably 10 to 70 parts by weight. If the amount of the inorganic filler compounded exceeds 100 parts by weight, the moldability will decrease, making it difficult to produce a molded product, and the mechanical strength will also decrease.

For the purpose of modifying the blow molding composition of the present invention, other additives such as a heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, a plasticizer and an antistatic agent. , A release agent and a foaming agent can be added.

[F] Production Method The blow molding composition of the present invention is obtained by heating and melting the above-mentioned components at 200 to 320 ° C. using a kneading device such as an extruder such as a single-screw extruder or a twin-screw extruder. It can be obtained by kneading in the state. At that time, in order to keep the average diameter of the dispersed phase of the polyolefin resin within the range of 0.5 to 5 μm, it is preferable to use a twin-screw extruder as disclosed in JP-A 1-240561. When glass fibers are blended, the glass fibers may be added together with the polyamide resin, the polyolefin and the modified polyolefin from the beginning, or may be added halfway after the resin components are melt-kneaded to some extent.

The blow molding composition of the present invention thus obtained can be molded into a desired shape by a blow molding method. The method of blow molding is not limited to the ordinary method, and can be applied to a three-dimensional bending blow molding method (for example, IHI method or Placo method).

[0046]

In the present invention, the specific polyamide resin,
Polyolefin, in a composition containing a modified polyolefin, a modified polyolefin having a high graft ratio of the modified monomer is used, and the molar ratio of the terminal amino group of the polyamide resin and the functional group of the modified monomer of the modified polyolefin is 0.1. Since the range is from 5 to 5, the melt viscosity of the composition is significantly increased, the blow moldability is improved, and drawdown is not significantly generated.

Although the reason why such an effect is obtained is not always clear, when the modified polyolefin and the polyamide resin are melt-blended, the carboxyl group of the modified polyolefin and the terminal amino group of the polyamide resin react with each other to form the modified polyolefin. A polyamide graft copolymer is formed. When the proportion of this graft copolymer in the composition is increased, the melt viscosity of the composition can be increased, but a modified polyolefin having a high graft ratio is used, and a polyamide resin is produced from dicarboxylic acid and diamine. It is believed that the use of such a polyamide resin (or a mixture or copolymer of two or more thereof) achieves that and has a viscosity suitable as a resin for blow molding.

Further, the average diameter of the polyolefin dispersed phase is set to 0.
By adjusting the thickness to 5 to 5 μm, the compatibilization is appropriately adjusted,
A blow molded product can be obtained without impairing the heat resistance and mechanical strength of the polyamide resin.

[0049]

The present invention will be described in more detail by the following examples. The following resin components were used as raw materials. [1] Polyamide resin Nylon 66 Ny66: [T-300, manufactured by Ems Co., Ltd., relative viscosity (JIS K6810, measured in 98% sulfuric acid) [η _r ] 2.5, Kors
hak-Zamyationa method (inverse titration method) (Chem.Abs.40,466
5, '46, ibid. 42,6152, '48)
0.051 mEq / g] [2] Modified polyolefin Maleic anhydride modified polypropylene CMPP: [manufactured by Toyo Kasei Co., Ltd., high concentration modified polypropylene, graft rate of maleic anhydride 5% by weight (0.5 m
Equivalent / g), melt flow rate (190 ° C., 1050 g load) 50 g / 10 minutes] CMPP: [propylene homopolymer (manufactured by Tonen Kagaku KK, E200X) perhexin 2.5B (manufactured by NOF Corporation)] As an initiator, modified with maleic anhydride, graft rate of maleic anhydride 0.3% by weight
(0.03 meq / g), melt flow rate (190 ℃, 10
50 g load) 40 g / 10 min] [3] Polyolefin polypropylene HPP: [Tonen Kagaku KK, E-200X3] [5] Glass fiber GF: [Asahi Fiber Glass KK, 03MAFT2A, average fiber diameter 13 μm, Aspect ratio 230, surface treatment with maleic anhydride)

Examples 1 to 10 and Comparative Examples 1 to 10 Nylon 66 (Ny66), polypropylene (HPP) and polypropylene modified with maleic anhydride (CMPP) were mixed in the proportions shown in Table 1, and the twin screw extruder ( 45 mm
φ, L / D = 28) was charged from the main hopper. Further, glass fibers (GF) were added from the middle of the twin-screw extruder at a ratio shown in Table 1 with respect to 100 parts by weight of the total of the resin components and kneaded at 280 ° C and 200 rpm to obtain pellets of the composition. .

Using the obtained pellets, a test piece for a physical property test described later was prepared by injection molding, and the specific gravity, tensile strength, water absorption and refrigerant resistance (tensile strength after immersion in the refrigerant) were evaluated. The results are shown in Table 2.

Using the above pellets, a parison was extruded at a rotation speed of 30 rpm and a temperature of 280 ° C. from a circular die having an outer diameter of 32 mmφ and an inner diameter of 13 mmφ installed in a 50 mmφ extruder. At that time, the time to reach the length of 10 cm from the bottom surface of the die (t ₁₀ ) and the time to reach the length of 60 cm (t ₆₀
) And were measured, and the ratio (t ₆₀ / t ₁₀ ) was taken as the drawdown ratio. Further, a part of the fracture surface of the parison was observed by SEM, and the average diameter of the polypropylene dispersed phase was calculated. The results are shown in Table 2.

Table 1 Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Ny66 60 60 60 60 50 CMPP 3.5 12 20 10 5 HPP 36.5 28 20 30 45 GF 17.6 17.6 17.6-17.6 Terminal amino group / carboxyl group molar ratio ^* 1.7 0.5 0.3 0.6 1.0

Table 1 (continued) Composition (parts by weight) Example 6 Example 7 Example 8 Example 9 Example 10 Ny66 70 70 80 80 90 CMPP 5 10 10 15 5 HPP 25 20 10 5 5 GF 17.6 − 17.6 − 17.6Molar ratio of terminal amino group / carboxyl group ^*  1.4 0.7 0.8 0.5 1.8

Table 1 Composition (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Ny66 100 60 60 100 50 CMPP-1 --- CMPP--20-20 HPP-39 20-40 GF 17.6 17.6 17.6-17.6 Terminal amino group / carboxyl group molar ratio ^* -6.1 5.0-8.3

Table 1 (continued) Composition (parts by weight) Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Ny66 70 70 80 80 90 CMPP 2 − − − − CMPP − 10 5 10 5 HPP 28 20 15 10 5 GF 17.6 − 17.6 − 17.6Molar ratio of terminal amino group / carboxyl group ^*  3.5 11.7 26.7 13.3 30 Note) *: Terminal amino group in nylon 66 and modified poly
Molar ratio with carboxyl groups in ropylene.

[0057] The second table object properties Example 1 Example 2 Example 3 Example 4 Example 5 a specific gravity ⁽¹⁾ 1.13 1.13 1.13 1.03 1.10 Tensile strength ⁽²⁾ Ze'inuiji 1150 1150 1150 600 1100 at equilibrium water 900 900 900 500 850 After immersion in refrigerant 700 700 700 300 650 Water absorption rate ⁽³⁾ 0.3 0.3 0.3 0.4 0.2 Drawdown ratio ⁽⁴⁾ ○ ○ ○ ○ ○ Polypropylene diameter Average diameter of resin dispersed phase ⁽⁵⁾ 4.5 4.0 3.5 4.0 4.3

[0058] Table 2 (cont) product of Example 6 Example 7 Example 8 Example 9 Example 10 specific gravity ⁽¹⁾ 1.16 1.06 1.18 1.08 1.21 Tensile strength ⁽²⁾ Ze'inuiji 1200 600 1200 600 1200 equilibrium Water absorption 900 450 800 400 750 After immersion in refrigerant 600 150 500 100 450 Water absorption ⁽³⁾ 0.4 0.5 0.5 0.5 0.6 Drawdown ratio ⁽⁴⁾ ○ ○ ○ ○ ○ Polypropylene diameter Average diameter of resin dispersed phase ⁽⁵⁾ 4.3 4.0 4.0 4.0 4.5

Table 2 (continued ⁾ Physical properties Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Specific gravity ⁽¹⁾ 1.25 1.13 1.13 1.14 1.14 Tensile strength ⁽²⁾ Absolute dry 1200 900 1150 800 1100 Equilibrium Water absorption 700 800 900 500 800 After immersion in refrigerant 400 500 700 200 600 Water absorption ⁽³⁾ 0.7 0.3 0.3 1.0 0.2 Drawdown ratio ⁽⁴⁾ × △ △ × × Polypropylene diameter Average diameter of resin dispersed phase ⁽⁵⁾ − 12 1.5 − 1.5

Table 2 (continued ⁾ Physical Properties Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Specific Gravity ⁽¹⁾ 1.16 1.06 1.18 1.08 1.21 Tensile Strength ⁽²⁾ Absolute Dry 1200 600 1200 600 1200 Equilibrium Water absorption 900 450 800 400 750 After immersion in refrigerant 600 150 500 100 450 Water absorption ⁽³⁾ 0.4 0.3 0.5 0.4 0.6 Drawdown ratio ⁽⁴⁾ △ △ × × × Polypropylene diameter Average diameter of resin dispersed phase ⁽⁵⁾ 9 1.8 2.0 1.9 10

(1) Specific gravity: Measured according to ASTM D792. (2) Tensile strength: According to ASTM D638, absolutely dry condition, equilibrium water absorption condition (23 ℃, 50% RH equilibrium) and refrigerant (Long Life Co
Measured after being immersed in a 50% aqueous solution of olant (120 ° C) for 1000 hours (unit: kg / cm ² ). (3) Water absorption: Measured after being left in water (23 ° C) for 24 hours. (4) Drawdown ratio: Outer diameter 32 installed in an extruder with a diameter of 50 mm
When a parison is extruded from a circular die with a diameter of mmφ and an inner diameter of 13 mmφ at a rotation speed of 30 rpm and a temperature of 280 ° C, the time required to reach the length of 10 cm from the bottom surface of the die (t ₁₀ ) and the length of 60 cm From the ratio t ₆₀ / t ₁₀ to the time (t ₆₀ ),
The following criteria evaluated. ○: Drawdown ratio of 4.5 or more △: Drawdown ratio of 2.5 or more and less than 4.5 ×: Drawdown ratio of less than 2.5 (5) Dispersion diameter of polyolefin resin: Part of the parison obtained in (4) above was cut and freeze fractured. The post fracture surface was etched with hot xylene, observed with SEM, and image-processed for calculation (unit: μm).

As is clear from Table 2, the compositions of the respective examples had good tensile strength, water absorption and drawdown ratio, and improved blow moldability.

[0063]

As described in detail above, in the present invention, a composition containing a specific polyamide resin, a polyolefin, and a modified polyolefin, which has a high graft ratio of the modified monomer as the modified polyolefin, is used. And the molar ratio of the terminal amino groups of the polyamide resin to the functional groups of the modified monomer of the modified polyolefin.
Since it is in the range of 0.1 to 5, the melt viscosity of the composition is significantly increased, the blow moldability is improved, drawdown is less likely to occur, and the average diameter of the dispersed phase of the polyolefin resin is also reduced. Is in the range of 0.5 to 5 μm, a blow molded product can be obtained without impairing the mechanical properties of the polyamide resin.

The composition of the present invention is suitable for use in automobile parts such as radiator tanks and heat pipes, parts for household electric appliances and the like.

Claims (1)

[Claims] 1. A polyamide resin (a) comprising 45 to 95% by weight of a dicarboxylic acid and a diamine, (b) 2 to 52% by weight of a polyolefin, and (c) 0.5% of a monomer having a carboxyl group or an epoxy group. A composition containing 3 to 53% by weight of modified polyolefin obtained by grafting 10 to 10% by weight, wherein the number of moles of terminal amino groups of the polyamide resin and the number of moles of functional groups of the modified monomer of the modified polyolefin are Is 0.1 to 5, and the component (b) and the component (c) form a dispersed phase having an average diameter of 0.5 to 5 μm, which is uniformly dispersed in the polyamide resin matrix phase. Blow molding composition.