JPH05162190A - Blow molded piece made of resin composition - Google Patents

Abstract

PURPOSE:To compound respective components with a good compatibility to obtain a molded piece superior in appearance and durability by a method wherein a blow molded piece is molded out of a resin composition obtained by compounding specific three kinds of compositions in a specific weight ratio, and a filler is componded in the resin composition in a specific weight ratio. CONSTITUTION:A blow molded piece is made of a resin composition (D) obtained by compounding the following three kinds of compositions (A), (B), (C) respectively in a specific weight ratio: (A) is a polyarylene sulfide resin; (B) is a polymer selected out of an ethylene copolymer containing 50-90wt.% ethylene, 5-49wt.%, alpha, beta-unsatd. carboxylic alkylester, and 0.5-10wt.% maleic anhydride, an epoxy-containing olefin copolymer, and an ionomer resin; and (C) is an unblocked multifunctional isocyanate compound. Weight ratios are determined as follows: (A)/(B)=50/50-98/2 and (C)/[(A)+(B)]=0.1/100-20/100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blow hollow molded article, and more particularly to a blow hollow molded article made of a polyarylene sulfide resin composition which is excellent in heat resistance, chemical resistance and impact resistance.

[0002]

2. Description of the Related Art In recent years, the fields of application of engineering plastics have expanded more and more, and the applications to the automobile, electric, electronic and mechanical fields have been remarkably increasing. Along with this, users' demands for plastics have been diversified and made more functional, and more excellent ones such as heat resistance, flame retardancy, chemical resistance and mechanical properties have been demanded. Polyarylene sulfide resin (hereinafter referred to as PAS) typified by polyphenylene sulfide resin (hereinafter referred to as PPS) is a known engineering plastic, which has been developed in view of the above requirements and has been used in many conventional applications. ing. That is, PAS has been evaluated for its excellent heat resistance, flame retardancy, chemical resistance, mechanical properties, and the balance thereof, and has been used in many fields.

An attempt has been made to obtain a blow hollow molded article of this PAS and further utilize its excellent characteristics, as disclosed in JP-A-61-255832 and JP-A-3-23.
It is made in Japanese Patent No. 6931.

[0004]

However, the former Japanese Patent Application Laid-Open No. 61-255832 uses a special injection stretch blow molding method, and cannot be said to establish a general-purpose blow molding technique. In addition, although the blow hollow molded article can be obtained by either of the former and the latter methods, its impact strength is not always satisfactory, and it is insufficient for use as a bottle, a tank, etc. There was a point. And, as a result of the additional test by the inventors,
It has been found that this problem of impact resistance becomes remarkable especially in a thin blow blow molded product.

[0005]

The present invention comprises a polyarylene sulfide resin (A), ethylene of 50 to 90% by weight, and α, β-unsaturated carboxylic acid alkyl ester of 5 to 4.
9% by weight, 0.5-10% by weight of maleic anhydride, at least one polymer (B) selected from an ethylene copolymer, an epoxy group-containing olefin copolymer and an ionomer resin, and a non-blocking polyfunctional With a reactive isocyanate compound (C) (A) / (B) = 50/50 to 98/2 (C) / {(A) + (B)} = 0.1 / 100 to 20/100 A blown hollow molded article composed of the resin composition (D) blended therein, and a filler (E) for a resin represented by glass fiber in the composition (D) (D) / (E) = 98/2 to 40/60, and a blow hollow molded article made of a resin composition.

P which is preferably used as PAS in the present invention
PS is the structural formula

[0007]

[Chemical 1]

It is a polymer containing 70 mol% or more, more preferably 80 mol% or more of the repeating unit represented by: If the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. Further, less than 30 mol% can be composed of a repeating unit having the following structural formula.

[0009]

[Chemical 2]

[0010]

[Chemical 3]

PAS is generally a polymer having a relatively small molecular weight obtained by the production method typified by JP-B-45-3368 and an essential polymer obtained by the production method typified by JP-B-52-12240. There is a linear and relatively high molecular weight polymer, etc., and the polymer obtained by the method described in Japanese Patent Publication No. 3368/1985 is heated by heating in an oxygen atmosphere after the polymerization, or by peroxidation. It is also possible to use it after highly polymerizing it by adding a crosslinking agent such as a substance and heating it, and in the present invention, PAS obtained by any method can be used.

Furthermore, for the purpose of controlling the degree of crosslinking of PAS,
Ordinary peroxide-based cross-linking agent and JP-A-59-13165
0, a crosslinking accelerator such as a thiophosphinic acid metal salt, or JP-A-58-204045.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate or aminotriazole described in JP-A-58-204046.

The melt viscosity of PAS used in the present invention is
There is no particular limitation as long as a molded product can be obtained, but from the viewpoint of moldability, one having a poise of 1,000 poise or more at 300 ° C. and a shear rate of 10 sec ⁻¹ is more preferably used. Particularly preferably, it is 10,000 poise or more. In the present invention, in order to improve the impact resistance of the blow hollow molded article, the polyarylene sulfide resin (A) contains 50 to 90% by weight of ethylene, 5 to 49% by weight of an α, β-unsaturated carboxylic acid alkyl ester, Maleic anhydride 0.5
10% by weight of at least one polymer (B) selected from ethylene copolymer, epoxy group-containing olefin copolymer and ionomer resin (A) /
(B) = 50/50 to 98/2, preferably (A) /
(B) = 70/30 to 96/4 are mixed in a weight ratio,
If the amount of the component (B) exceeds the range, the heat resistance inherent to PAS is lost, and if it is less than the range, the effect of improving the impact resistance decreases, which is not preferable.

The ethylene copolymer used in the present invention comprises ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride as the monomer components, and the ethylene content is 50 to 90% by weight, preferably 60. ~ 85 wt%, α,
The β-unsaturated carboxylic acid alkyl ester is 5 to 49% by weight, preferably 7 to 45% by weight, and the maleic anhydride is 0.10% by weight.
It is 5 to 10% by weight, preferably 1 to 8% by weight.

Examples of the α, β-unsaturated carboxylic acid alkyl ester include unsaturated carboxylic acids having 3 to 8 carbon atoms, for example, alkyl esters such as acrylic acid and methacrylic acid. Specific examples thereof include acrylic acid. Methyl acid, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate
Butyl, isobutyl acrylate, methyl methacrylate,
Examples thereof include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate. Of these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferable.

As a measure of the molecular weight of these copolymers,
The melt index value under the load of 190 ° C. and 2.16 kg can be used. The melt index value of the copolymer used is in the range of 0.1 to 1,000, preferably 0.2 to 500, more preferably 1 to 100. These copolymers are commercially available from Sumitomo CDF Chemical Co., Ltd. under the name "Bondayne", for example.

The epoxy group-containing olefin copolymer may be prepared by a known method such as direct copolymerization of glycidyl ester of α, β-unsaturated carboxylic acid and olefin, or graft copolymerization to polyolefin and polyolefin copolymer. What is manufactured is used. The α, β-unsaturated carboxylic acid glycidyl ester used herein is a mixture of one or more represented by the following general formula, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, and the like, Of these, glycidyl methacrylate is preferably used.

[0018]

[Chemical 4]

(In the formula, R is a hydrogen atom or a lower alkyl group.) Such an epoxy group-containing olefin copolymer is usually 0.01 to 2 with an epoxy group-containing monomer as a constituent component.
It contains 0% by weight, preferably 0.05 to 5% by weight. These epoxy group-containing olefin copolymers are named, for example, "Bond First" by Sumitomo Chemical Co., Ltd.
More commercially available.

The ionomer resin used in the present invention is produced by, for example, the method described in JP-B-39-6810, and comprises a base copolymer and a metal compound capable of ionizing the copolymer. It is obtained by reacting. The base copolymer has the general formula R
CH = CH ₃ (wherein, R is chosen from the group consisting of hydrogen and alkyl groups having 1 to 8 carbon atoms) and α- olefin represented by, alpha, a has and carboxyl group β- ethylenically unsaturated group Although it is composed of 1 to 2 carboxylic acids, an α-olefin-monocarboxylic acid copolymer is particularly suitable.

Suitable base copolymers that can be preferably used include, for example, ethylene / acrylic acid copolymers and ethylene / acrylic acid copolymers.
Methacrylic acid copolymer, ethylene / itaconic acid copolymer, ethylene / maleic acid copolymer, ethylene / acrylic acid / methyl methacrylate copolymer, ethylene / methacrylic acid / vinyl acetate copolymer, ethylene / acrylic acid /
Vinyl alcohol copolymer, ethylene / propylene / acrylic acid copolymer, ethylene / styrene / acrylic acid copolymer, ethylene / methacrylic acid / acrylonitrile copolymer, ethylene / vinyl chloride / acrylic acid copolymer,
Examples thereof include ethylene / chlorotrifluoroethylene / methacrylic acid copolymer, polyethylene / acrylic acid graft copolymer polypropylene / acrylic acid graft copolymer, and the like.

The metal ion having a valence of 1 to 3 when the base copolymer is an α-olefin-monocarboxylic acid copolymer (for example, Na ⁺ , K
⁺ , Li ⁺ , Cu ²⁺ , Be ²⁺ , Mg ²⁺ , Zn ²⁺ , Al ³⁺
Etc.) are suitable, and those having a monovalent valence in the case of α-olefin-dicarboxylic acid copolymer (for example,
Na ⁺ , K ⁺ , Li ⁺ etc.) are suitable.

An example of the ionomer resin used is a combination of an ethylene-acrylic acid copolymer and Na ⁺ and Zn ²⁺ as metal ions. The ionomer resin having a molecular weight of 10,000 to 1,000,000, preferably 20,000 to 800,000, more preferably 30,000 to 500,000 is used.

The ionomer resin used in the present invention is sold, for example, by Mitsui DuPont Polychemical Co., Ltd. under the trade name of "HIMIRAN". In the present invention, P
In order to improve the compatibility between AS and the elastomer, polyarylene sulfide resin (A) and ethylene 50 to 9 are used.
0% by weight, α-β-unsaturated carboxylic acid alkyl ester 5 to 49% by weight, maleic anhydride 0.5 to 10% by weight selected from ethylene copolymers, epoxy group-containing olefin copolymers and ionomer resins. At least one type of elastomer (B) is (A) / (B) = 5
The composition having a weight ratio of 0/50 to 98/2 contains the non-blocking polyfunctional isocyanate compound (C) (C) /
{(A) + (B)} = 0.1 / 100 to 20/100,
Preferably (C) / {(A) + (B)} = 1 / 100-
It is blended in a weight ratio of 10/100, but if the amount of the non-blocking polyfunctional isocyanate compound is less than this range, the effect of improving the compatibility is small, and if it is more than this range, the melt viscosity of the resin becomes too high, which is not preferable.

As the non-blocking polyfunctional isocyanate compound used in the present invention, there is an isocyanate compound having two or more non-blocking isocyanates in one molecule, and it has the general formula R- (N = C = O) _n. , Or R-
(N = C = S) _n (In the formula, R is an organic group composed of elements such as carbon, hydrogen, sulfur, phosphorus, nitrogen, and oxygen, and n
Is an integer of 2 or more. ) Are unblocked polyfunctional isocyanates or isothiocyanate compounds.

The general types are roughly classified into an aliphatic type and an aromatic type, and a modified type is a dimer type,
There are trimer type (isocyanurate type), multimer type, carbodiimide modified type and the like, but any isocyanate compound can be used in the present invention. However, blocked isocyanates (also known as masked isocyanates), namely acidic sodium sulfite, phenol,
A block type isocyanate compound which is obtained by reacting cresol, lactam, heterocyclic compound, hydrocyanic acid, sulfite and the like with isocyanate in advance and regenerating at high temperature is hardly included for this purpose.

Examples of the compound (C) include 4,4^'−
Diphenylethane diisocyanate, 4,4^'-Jiffe
Nylpropane diisocyanate, carbodiimide modified di
Phenylethane diisocyanate, naphthylene-1,5
-Diisocyanate, toluene diisocyanate, dimer
Toluene diisocyanate, hexamethylene diisocyanate
Anate, trimerized hexamethylene diisocyanate, 5
Quantified hexamethylene diisocyanate, heptameric hexamer
Tolylene diisocyanate, polymethylene polyphenylpo
Reisocyanate, phenylene diisocyanate, 3,
Three^'-Dimethyldiphenylmethane-4,4^'-Diiso
Anate, 3,3^'-Dimethyl-4,4 ^'-Diphenyle
Diisocyanate, 3,3^'-Bitluene-4,4^'
-Diisocyanate, xylene diisocyanate, iso
Holon diisocyanate, triphenylmethane triiso
Cyanate, lysine diisocyanate, dicyclohexyl
Didimethylmethane diisocyanate, diethyl fumaray
Todiisocyanate, triisocyanate benzene,
Lisocyanate naphthalene, bis (4-isocyanate)
Tophenyl) ether, bis (4-isocyanate)
Nyl) thioether, bis (4-isocyanate phenyl)
Le) sulfone, tris (4-isocyanatephenyl)
Phosphite, tris (4-isocyanatophenyl)
Phosphates and their corresponding isothiocyanates
Of the above compound, and the above-mentioned aromatic isocyanate added with water
Non-blocking polyfunctional isocyanates such as salt compounds
Compounds.

The isocyanate compound (C) is PA
It is considered that they function effectively as a cross-linking agent for cross-linking S with each other or polymers (B), or as a chemical bond between PAS and polymer (B), particularly PAS and polymer ( It is considered that B) functions more effectively as a chemical bond, and thus the impact resistance is significantly improved.

In addition, the resin composition (D) comprising (A), (B) and (C) may optionally contain an inorganic and / or organic filler (E) (D) / (E) = 98 / 2-40
/ 60, preferably (D) / (E) = 95/5 to 50 /
It is possible to improve the rigidity and the like by adding it in a weight ratio of 50, but if the amount of the filler exceeds this range, the surface of the molded product becomes rough and the physical properties become brittle, which is not preferable.

Suitable fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, potassium titanate, asbestos, silicon carbide, ceramics, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, Bentonite, sericite, zeolite,
Mica, mica, nepheline sinite, talc, attarpulgite, wollastonite, PMF, ferrite,
Reinforcing filler such as calcium silicate, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, etc. These may be hollow. Further, two or more kinds of these reinforcing fillers can be used in combination, and if necessary, they can be pretreated with a coupling agent such as a silane type or titanium type and used.

The resin composition used in the present invention also contains an aromatic hydroxy derivative such as 2-ethylhexyl-p.
-Hydroxybenzoate, sulphonic acid amide, plasticizer such as benzene sulphonamide, or a small amount of release agent, coupling agent, colorant, lubricant, heat resistance stabilizer, weather resistance stabilizer, foaming agent, rust inhibitor You may add additives, such as. The resin composition used in the present invention can be adjusted by various known methods. For example, after the raw materials are uniformly mixed with a mixer such as a tumbler or a Henschel mixer in advance, they are melt-kneaded by being supplied to a known device usually used for kneading a resin melt such as a kneader, a roll mill, and an extruder. There is a method to prepare it as pellets. A single-screw, twin-screw, co-kneader or the like is used as the extruder at this time. The composition can be obtained by any extruder, but the preferred extruder is a twin-screw extruder. When an extruder is used, it is preferable to carry out side feed from the middle of the extruder in order to prevent breakage of the filler.

The kneading temperature is not lower than the melting point of PAS and can be sufficiently kneaded within the range of 280 to 340 ° C. which is usually used, but more preferably 280 to 320 ° C.,
If the temperature is lower than 280 ° C, the PAS may be insufficiently melted, and if the temperature exceeds 320 ° C, the polymer (B) may be thermally deteriorated or gelled, or the additive may be decomposed. It costs.

PAS is preferably preliminarily dried as a pretreatment, and kneading is preferably performed in an inert gas atmosphere. The blow hollow molded article of the present invention is a known blow molding method for the resin composition obtained as described above, that is, basically the resin composition is fed to an extruder and melt-extruded to form a parison. It can be obtained by subjecting it to a desired two-dimensional hollow molded body. Typical examples of generally known blow molding methods include a direct blow method, an accumulator blow method, and a multidimensional blow method, and a multilayer blow molding method and an exchange blow molding method used in combination with other materials. It is also possible to apply

Specific examples of the blow hollow molded article of the present invention thus molded include bottles, tanks and ducts, which are hollow with excellent heat resistance, chemical resistance and impact resistance. As a molded product, it is useful as a container for chemicals, an air conditioning duct, a duct and a pipe in an automobile engine room, and the like.

[0035]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. Blow molding tests in Examples and Comparative Examples were conducted as follows. After drying the resin composition pellets at 140 ° C. for 3 hours,
It is supplied to a blow molding machine equipped with a 55 mmφ extruder and the cylinder temperature is set to 240 ° C. in the hopper, 290 ° C. in the center and 300 ° C. at the tip, and after forming a parison with an outer diameter of 10 mm and a wall thickness of 3 mm, set it to 130 ° C. 5kg / c in the die
Air was blown (upward) at m ² to form a cube-shaped container having a side of 200 mm.

The impact characteristics of the molded product are that the molded product is placed on the concrete floor with the bottom surface (the surface on the side opposite to the blow mouth surface) facing upward, and an iron ball weighing 1 kg is molded from a height of 50 cm. The sample was allowed to fall to the center of one piece, and the presence or absence of breakage was visually observed. Then, the breakage rate was calculated from (breakdown rate:%) = {(number of broken molded pieces) / (number of n)} × 100.
Further, the surface gloss was evaluated by visually observing the molded product and relatively evaluating the degree of gloss.

[0037]

Examples 1 to 11 Various PPS, polymer (B) and 4,4
^' -Diphenylmethane diisocyanate (hereinafter abbreviated as MDI) was blended at a ratio shown in Table 1, mixed with a Henschel mixer in a nitrogen atmosphere for 5 minutes, and then, using a BT-40 twin screw extruder manufactured by Plastic Engineering Laboratory Co., Ltd., Pelletizing was performed at a cylinder temperature of 290 to 300 ° C. When a filler such as glass fiber was blended, side feeding was performed from the middle of the extruder. A blow molding test was performed using the obtained pellets. The results are shown in Table 1.

[0038]

[Comparative Examples 1 to 7] PPS powder and various blends were blended in the proportions shown in Table 2, and BT- manufactured by Plastic Engineering Laboratory Co., Ltd.
Pelletization was carried out on a 40-screw extruder at a cylinder temperature of 290 to 300 ° C. When a filler such as glass fiber was blended, side feeding was performed from the middle of the extruder. A blow molding test was performed using the obtained pellets.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

EFFECTS OF THE INVENTION The blow hollow molded article of the present invention is a molded article in which the respective components are blended with each other with good compatibility, and the appearance of the molded article is good and also the impact strength, heat resistance and mechanical properties are excellent. It is a highly practical molded product.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 75/04 NGJ 8620-4J 81/02 LRG 7167-4J // C08L 23/26 LDP 7107-4J B29K 81:00 B29L 22:00 4F

Claims (2)

[Claims] 1. A polyarylene sulfide resin (A)
And an ethylene copolymer comprising 50 to 90% by weight of ethylene, 5 to 49% by weight of an α, β-unsaturated carboxylic acid alkyl ester, and 0.5 to 10% by weight of maleic anhydride, an epoxy group-containing olefin copolymer, and At least one polymer (B) selected from ionomer resins and the non-blocking polyfunctional isocyanate compound (C) are (A) / (B) = 50/50 to 98/2 (C) / {( A blow hollow molded article comprising a resin composition (D) blended in a weight ratio of A) + (B)} = 0.1 / 100 to 20/100. 2. A resin composition comprising the resin composition (D) according to claim 1 and the filler (E) in a weight ratio of (D) / (E) = 98/2 to 40/60. Blow blow molded products.