JPH0481465A - Resin composition containing pps - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic resin composition having excellent heat resistance, mechanical properties, and moldability. The present invention relates to molded products useful in the automobile, electrical, electronic, and mechanical fields, etc., obtained by molding means such as extrusion molding.

(Prior Art) The field of application of engineering plastics has been expanding more and more in recent years, and in particular, their use in the automobile, electrical, and electronic fields has increased significantly. Along with this, demands from users for plastic materials have become more versatile and highly functional, and meeting these demands has become a technical challenge.

However, these demands for increased versatility and higher functionality cannot be fully met with a single material alone, and for this reason, polymer alloys have been increasingly used to meet these demands.

A resin composition consisting of three components: polyphenylene sulfide resin (hereinafter referred to as PPS), an elastomer, and a polyamide resin is a known polymer alloy, and was developed with the above requirements in mind.

In other words, PPS is known as a resin with excellent flame retardancy, heat resistance, and chemical resistance, but its impact strength is not necessarily satisfactory, and for this reason, alloying of elastomer and polyamide resin Improved impact resistance.

However, although the impact resistance of such resin compositions is significantly improved compared to single PPS or compositions in which single PPS is blended with a filler such as glass fiber, it is difficult to obtain impact resistance by injection molding or extrusion molding. However, it was not sufficient as a molded product useful in the automobile, electrical, electronic, and mechanical fields.

(Problem to be solved by the invention a) In view of the above situation, an object of the present invention is to improve the impact resistance while maintaining the excellent properties of a resin composition composed of PPS, an elastomer, and a polyamide resin. The object of the present invention is to obtain a resin composition with a high temperature.

(Means for Solving the Problems) As a result of extensive research for this purpose, the present inventors have found that: Alkyl ester 5-49% by weight maleic anhydride 0. 5-1
At least one type of elastomer (B) selected from 0% by weight ethylene copolymer, epoxy group-containing olefin copolymer, and ionomer resin, and polyamide resin (C), (A) / (B) ~ 50150~98/2(C)/(
(A) + (B)] = 2/98 to 98/2 weight ratio, and further monocarbodiimide compound (D)
A resin composition obtained by melt-kneading 0.2 to 20 parts by weight per 100 parts by weight of the above composition ((A) + (B) + (C)), and further comprising (1) the above resin composition. A resin composition comprising an organic and/or inorganic filler (F) mixed with a substance at a weight ratio of (E)/(F) -98/2 to 40/6 ocv achieves the above object. This is what led to the discovery of the present invention.

There are polymers with relatively small molecular weight obtained by the production method typified by , and essentially linear and relatively high molecular weight polymers obtained by the production method typified by Japanese Patent Publication No. 52-12240. In the polymer obtained by the method described in Japanese Patent Publication No. 45-3368, high polymerization can be achieved by heating in an oxygen atmosphere after polymerization or by adding a crosslinking agent such as peroxide and heating. In the present invention, it is possible to use PPS obtained by any method.

In addition, PPS can have less than 30 mol% of its repeating units composed of repeating units having the following structural formula, etc.

It is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by the following. If the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable.

PPS is generally disclosed in Japanese Patent Publication No. 45-3368 CH3 The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain a molded product, but in terms of the toughness of PPS itself, it should be 100 voids or more. In terms of moldability, those having 10,000 voids or less are more preferably used. Particularly preferred is a range of 1.000 to 5,000 poise.

Furthermore, for the purpose of controlling the degree of crosslinking of PPS, common peroxide crosslinking agents and crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-59-131650,
or JP-A-58-204045, JP-A-58-
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 204046 and the like.

In the present invention, in order to improve the impact resistance of PPS, polyphenylene sulfide resin (A) contains 50 to 90% by weight of ethylene, 5 to 49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride. 0.
At least one elastomer (B) selected from 5 to 10% by weight of ethylene copolymer, epoxy group-containing olefin copolymer, and ionomer resin, (A)/(B}=50150 to 98/2, preferably are blended at a weight ratio of (A)/(B}=70/30 to 96/4. If the elastomer component exceeds this range, the inherent heat resistance of PPS will be lost, and if it decreases, the impact resistance will decrease. This is not preferable because the effect of improvement will be reduced.

The monomer components of the ethylene copolymer used in the present invention are ethylene, α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, and the ethylene content is 50 to 90% by weight, preferably 60 to 85% by weight. %, α, β-unsaturated carboxylic acid alkyl ester from 5 to 49% by weight, preferably from 7 to 45% by weight, and maleic anhydride from 0.5% to 49% by weight, preferably from 7 to 45% by weight. It is 5 to 10% by weight, preferably 1 to 8% by weight.

α,β-Unsaturated carboxylic acid alkyl ester is an alkyl ester of unsaturated carboxylic acid having 3 to 8 carbon atoms, such as acrylic acid, methacrylic acid, etc. Specific examples include methyl acrylate, acrylic acid Ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
Examples include n-butyl methacrylate, 1-butyl methacrylate, and isobutyl methacrylate. Among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferred.

As a guideline for the molecular weight of these copolymers, 190°C, 2
．． Melt index values under a load of 16 kg can be used. The melt index value of the copolymer used is from 0.1 to 1,000, preferably from 0.2 to 5.
00, more preferably from 1 to 100.

These copolymers are commercially available under the name ``Bondine'' from Jumei CPF Chemical Industry ■.

The epoxy group-containing olefin copolymer is produced by a known method such as direct copolymerization of a glycidyl ester of an α,β unsaturated carboxylic acid and an olefin, or graft copolymerization of a polyolefin and an olefin copolymer.

The glycidyl ester of α,β-unsaturated carboxylic acid used here has the general formula: % formula % (wherein R is a hydrogen atom or a lower alkyl group).
Examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. Among them, glycidyl methacrylate is preferably used.

Further, examples of the olefin to be copolymerized or graft copolymerized with the glycidyl ester of α,β-unsaturated carboxylic acid include ethylene, propylene, butene, pentene, etc., and ethylene is preferably used.

Such epoxy group-containing olefin copolymers usually contain 0.0
It ranges from 1 to 20% by weight, preferably from 0.05 to 5% by weight. These epoxy group-containing olefin copolymers are
It is commercially available from Sumiya Kagaku Kogyo■ under the name ``Bond First''.

The method for producing the ionomer resin used in the present invention is already well known (Japanese Patent Publication No. 39-6810), and is produced by reacting a base copolymer with a metal compound capable of ionizing the copolymer. .

The base copolymer is composed of an α-olefin represented by the general formula: % formula % (where R is selected from the group consisting of hydrogen and an alkyl group having 1 to 8 carbon atoms) and α,β-ethylenically unsaturated Although it is mainly composed of a carboxylic acid having 1 to 2 carboxyl groups, an α-olefin-monocarboxylic acid copolymer is particularly suitable.

Further, as other monomers that may be copolymerized, any olefinic compound can be advantageously used, such as fj4 vinyl chloride, styrene, vinyl acetate, vinyl alcohol,
Acrylonitrile and the like can be mentioned.

Further, examples of the α-olefin include fluorinated olefins such as ethylene, propylene, butene, and chlorotrifluoroethylene, and ethylene and propylene are particularly preferably used.

Examples of base copolymers that can be suitably used include ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/itaconic acid copolymers, ethylene/maleic acid copolymers, and ethylene/acrylic acid/acrylic acid copolymers. Methyl methacrylate copolymer, ethylene/methacrylic acid/vinyl acetate copolymer, ethylene/acrylic acid/vinyl alcohol copolymer, ethylene/propylene/acrylic acid copolymer, ethylene/prolene/acrylic acid copolymer, ethylene /methacrylic acid/acrylonitrile copolymer, ethylene/vinyl chloride/acrylic acid copolymer, ethylene/chlorotrifluoroethylene/methacrylic acid copolymer, polyethylene/acrylic acid graft copolymer, polypropylene/acrylic acid graft copolymer etc. can be mentioned.

In addition, when the base copolymer is an α-olefin-monocarboxylic acid copolymer, metal ions having a valence of 1 to 3 (for example, Na', K4, Li''
, Cu", Be", Mg, "Zn", AI", etc.), and in the case of α-olefin-dicarboxylic acid copolymer, Na", K", Li", etc.) are suitable. .

Examples of ionomer resins used include ethylene-
Acrylic acid copolymer and metal ions such as Na” and Zn”
An example is a combination of

The molecular weight of the ionomer resin is 10.000 to 1.00.
0,000, preferably 20,000 to soo, ooo
, more preferably in the range of 30,000 to 500,000.

The ionomer resin used in the present invention is sold under the trade name "Himilan" by Mitsui Shubon Polychemicals.

Various well-known polyamide resins can be mentioned as the polyamide resin used in the present invention. For example, dicarboxylic acids such as oxalic acid, adipic acid, superric acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid, and ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, Polyamide obtained by polycondensation with diamines such as decamethylene diamine, 1,4-cyclohexyl diamine, and m-xylene diamine: caprolactam,
Examples include polyamides obtained by polymerizing cyclic lactams such as laurinlactam; or polyamides obtained by copolymerizing salts of cyclic lactams, dicarboxylic acids, and diamines.

Among these polyamides, preferably nylon 6,
46 nylon, 66 nylon, 6/10 nylon, 66
/6/10 nylon, 6/66 nylon, 12 nylon, 11 nylon, 6/6T nylon (a copolymer of salts of caprolactam, terephthalic acid, and hexamethylene diamine), and more preferred ones include , 6 nylon, 46 nylon, and 66 nylon, with 66 nylon being particularly preferred.

In the present invention, in order to improve the compatibility of PPS, elastomer, and polyamide resin, polyphenylene sulfide resin (A), 50 to 90% by weight of ethylene, α
, an ethylene copolymer consisting of 5 to 49% by weight of β-unsaturated carponthialkyl ester and 0.5 to 10% by weight of maleic anhydride, an olefin copolymer containing an epoxy group, and an ionomer resin. Elastomer (B) and polyamide resin (C) (A)/
(B}=50150~98/2(C)/((A)+
(B)] −2/98 to 98/2, and a monocarbodiimide compound (D
) to the above composition C(A) + (B) + (C)]1
0.00 parts by weight. It is blended in an amount of 2 to 20 parts by weight, preferably 1 to 10 parts by weight, but if the monocarbodiimide compound (C) is less than 0.2 parts by weight, the effect of improving compatibility is small, and if it is more than 20 parts by weight, the resin It is not preferable because the melt viscosity of is too high.

The monocarbodiimide compound (C) used in the present invention is a compound having a carbodiimide group (-N=C=N-) in the molecule, and any compound can be used as long as it has one carbodiimide group. .

Specific examples of monocarbodiimide compounds include dicyclohexylcarbodiimide, diphenylcarbodiimide,
Ditolylcarbodiimide, di(triisopropylphenyl)carbodiimide, dinaphthylcarbodiimide, di(
Examples include triisopropyl) carbodiimide.

In addition, in the present invention, two or three types of these compounds are used.
More than one type can be used together.

The melt-kneading in the present invention can be carried out using a known device, such as a kneader roll mill or an extruder, which is commonly used for kneading resin melts. Types of extruders include single-screw, twin-screw, co-kneader, etc. Although the composition of the present invention can be obtained using any of these extruders, a twin-screw extruder is preferred.

The kneading temperature is higher than the melting point of PPS, and sufficient kneading is possible within the commonly used range of 280 to 340°C.

Furthermore, it is preferable that the PPS and polyamide resin be pre-dried as a pre-treatment, and that the kneading be carried out in an inert gas atmosphere.

The monocarbodiimide compound is thought to function effectively as a crosslinking agent for crosslinking PPS and elastomer and polyamide resin, or as a chemical bond between PPS, elastomer, and polyamide resin. This is thought to be the reason for the improved impact resistance.

Furthermore, in the resin composition of the present invention, an inorganic and/or organic filler is added to the resin composition component (E) as necessary, (E)/(F}=98/2 to 40/60, preferably , (E) / (F} = 9515 to 50150, by weight ratio, it can be added to improve rigidity, etc. However, if the amount of filler exceeds this range, the surface of the molded product will become rough and the physical properties will deteriorate. This is not preferable because it becomes brittle.

Suitable fillers include glass fiber, carbon fiber, aramid fiber, potassium titanate, asbestos, silicon carbide,
Ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, atalpulgite, uwolastonite, PMF, ferrite, silicon Calcium oxide, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, and other reinforcing fillers. I can list them.

The resin composition of the present invention also contains a plasticizer such as an aromatic hydroxy derivative such as 2-ethylhexyl-p-hydroxybenzoate, a sulfonic acid amide such as benzenesulfonamide, and a small amount of a mold release agent. A coupling agent, a coloring agent, a heat stabilizer, a weathering stabilizer, a foaming agent, a rust preventive, a flame retardant, etc. may be added.

The resin composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance in a mixer such as a tumbler or Henschel mixer, then fed into a -screw or twin-screw extruder, melted and kneaded, and then prepared as pellets. However, when using an extruder, it is preferable to side-feed from the middle of the extruder in order to prevent destruction of the filler.

Note that the melt-kneading temperature is preferably 280 to 320°C; if it is less than 280°C, the melting of PPS may become insufficient, and if it exceeds 320°C, the elastomer may undergo thermal deterioration or gelation, so be careful. It takes.

In the present invention, the aided impact test, bending test, and heat distortion temperature are in accordance with ASTM D-256 and D-790, respectively.
, D-648.

(Example) The present invention will be explained in more detail with reference to Examples below.
This does not limit the invention.

Examples 1 to 6 After drying PPS powder (Tovren T-4) at 140 °C for 3 hours, the temperature was lowered to 50 °C, PPS and dicyclohexylcarbodiimide were blended, and Henschel powder was dried in a nitrogen atmosphere for 5 minutes. After mixing with a mixer, the mixture was pelletized using a BT-40 twin-screw extruder manufactured by Plastisoku Engineering Research Institute ■ at a cylinder temperature of 290"C to 300"C.

The modified PPS obtained in the above process was mixed with elastomer and polyamide in a blender, and these were mixed using the same extruder with the cylinder temperature set at 240°C for the hopper, 300°C for the center, and 300°C for the tip. Melt and knead,
Pellets were obtained using a conventional method.

In addition, when blending the filler, side feeding was performed from the middle of the extruder.

The obtained pellet is heated to the cylinder temperature at the honbar section 240.
°C1 center part 290°C1 tip part 300'C4: The mold temperature was set at 140°C, a test piece was obtained by a normal injection molding method, and various physical properties were measured.

The results obtained are shown in the table.

Comparative Examples 1 to 6 After drying PPS powder (Tope l/7T-4) at 140'C for 3 hours, the temperature was lowered to 50°C, PPS, elastomer, and polyamide were mixed in a blender, and these were mixed at Norinder temperature. The hopper part is 240°C, the center part is 30°C
Melt kneading was performed using the same extruder with the tip of 0° C. set at 300° C., and pellets were obtained in a conventional manner.

In addition, when blending the filler, side feeding was performed from the middle of the extruder.

The obtained pellets are transferred to the hopper section 240 at a cylinder temperature.
The temperature of the mold was set at 140°C at 290°C at the center and 300°C at the tip, and a test piece was obtained by a normal injection molding method, and various physical properties were measured.

The results obtained are shown in the table.

(Effects of the Invention) The resin composition of the present invention is a resin composition in which each component is blended with good compatibility, has good impact resistance, and is also excellent in thermal shape stability and mechanical properties. It is a highly practical molding material with excellent physical properties as an engineering plastic.

(1 other person)

Claims (2)

[Claims] (1) Polyphenylene sulfide resin (A), 50 to 90% by weight of ethylene, 5 to 49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and 0.5 to 1% of maleic anhydride
At least one type of elastomer (B) selected from 0% by weight ethylene copolymer, epoxy group-containing olefin copolymer, and ionomer resin, and polyamide resin (C), (A)/(B)= The weight ratio is 50/50 to 98/2 (C)/{(A)+(B)}=2/98 to 98/2, and further monocarbodiimide compound (D)
A resin composition obtained by melt-kneading 0.2 to 20 parts by weight of the above composition [(A)+(B)+(C)] in an amount of 0.2 to 20 parts by weight. (2) Organic and/or inorganic filler (F) is added to the composition according to claim (1) [hereinafter referred to as (E)].
)=98/2 to 40/60 in a weight ratio.