JPH0481464A - Resin composition containing pps - Google Patents

Abstract

PURPOSE:To provide the composition having excellent heat resistance, mechanical properties and moldability by compounding a polycarbodiimide compound and a filler with a composition comprising a polyphenylene sulfide resin, an elastomer and a polyamide resin. CONSTITUTION: (A) A Polyphenylene sulfide resin, (B) an elastomer selected from an ethylenic copolymer comprising 50-90wt.% of ethylene units, 5-49wt.% of an alpha, beta-unsaturated carboxylic acid alkyl ester and 0.5-10wt.% of maleic anhydride, an epoxy groupcontaining olefinic copolymer and an ionomer resin and (C) a polyamide resin are compounded with each other in an A/B ratio of 50/50 to 98/2 and in a C/(A+B) ratio of 2/98 to 98/2. The composition is melt-kneaded with (D) a polycarbodiimide compound in an amount of 0.2-20 pts.wt. per 100 pts.wt. of A+B+C, and further compounded with (E) an organic and/or inorganic filler in an (A+B+C+D)/E of 98/2 to 40/60.

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 against the background of the above requirements.

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.

(Problems to be Solved by the Invention) In view of the above circumstances, an object of the present invention is to maintain the excellent properties of a resin composition composed of PPS, an elastomer, and a polyamide resin, while improving impact resistance. 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 repeated research for this purpose, the present inventors found that: (1) polyphenylene sulfide H1m(A), 50 to 90% by weight of ethylene, α,β-unsaturated carboxylic acid; 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, evoquino group-containing olefin copolymer, and ionomer resin, and polyamide resin (C), (A)/(B}= 50150~98/2(C)/(
(A) + (B)l = 2/98 to 98/2 weight ratio, and further polycarbodiimide compound (D)
A resin composition obtained by melt-kneading 0.2 to 20 parts by weight of the above composition [(A) + (B) 10 (C)] in an amount of 0.2 to 20 parts by weight, and further comprising (1) the above resin composition. A resin composition comprising a material and/or an inorganic filler (F) in a weight ratio of (E)/(F}=98/2 to 40/600 achieves the above object. This is what led to the discovery of the present invention.

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 a polymer with a relatively small molecular weight obtained by the manufacturing method typified by Japanese Patent Publication No. 45-3368, and a polymer with a relatively low molecular weight obtained by the manufacturing method typified by Japanese Patent Publication No. 52-12240. There are linear polymers with relatively high molecular weight, and in the case of the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, it is possible to obtain the polymer by heating in an oxygen atmosphere after polymerization or by adding a peroxide or the like. PPS can be highly polymerized by adding a crosslinking agent and heating, and in the present invention, PPS obtained by any method can be used.

Furthermore, less than 30 mol% of the repeating units in PPS can be composed of repeating units having the following structural formula.

It is also possible to do so.

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 is 100 poise or more, and in terms of moldability, it is 10, 000 poise or less is 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-
In the present invention, in order to improve the impact resistance of PPS, ethylene 50 is added to the polyphenylene sulfide resin (A) in order to improve the impact resistance of PPS. ~90% by weight, α,β-unsaturated carboxylic acid alkyl ester 5-49% by weight, maleic anhydride 0.
At least one elastomer (B) selected from ethylene copolymers, epoxy group-containing olefin copolymers, and ionomer resins consisting of 5 to 10% by weight, (A)/(B}=50150 to 98/2, preferably (A) / (B} = 70/30 to 96/4 by weight. 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 ethylene copolymer used in the present invention has an intermediate component consisting of ethylene, α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, and contains 50 to 90% by weight of ethylene, 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, thi-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isopropyl methacrylate,
Examples include n-butyl methacrylate, butyl methacrylate, and isobutyl methacrylate, and among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferred.

As a guideline for the molecular weight of these copolymers, 190°C1
Melt index values under a load of 2,16 kg can be used. The melt index value of the copolymer used is 0.1 to 1,000, preferably 0.2 to 1,000.
500, more preferably in the range of 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 onto a polyolefin and an olefin copolymer.

The glycidyl ester of α,β-unsaturated carboxylic acid used here is -aX.

(In the formula, 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 Susumu Kagaku Kogyo Co., Ltd. under the name "Bond First".

The MITi method for the ionomer resin used in the present invention is already well known (Japanese Patent Publication No. 39-6810),
It is produced by reacting a base copolymer with a metal compound that can ionize 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.

As other monomers that may be further copolymerized, any olefinic compound can be advantageously used, such as vinyl chloride, styrene, vinyl acetate, vinyl alcohol, acrylonitrile, and the like.

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/nuccrylic 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', K', Li'
, Cu", Be", M g 2 "Zn", AI", etc.), and in the case of α-olefin-dicarboxylic acid copolymer, Na', K", Li", etc.) are suitable. There is.

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 800,000
, 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, sheric acid, sehanic 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, 6/6 nylon (a copolymer of a salt of caprolactam, terephthalic acid, and hexamethylene diamine), etc., and more preferred ones include is 66 nylon, 46 nylon, or 66 nylon, and 66 nylon is 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
, 5-49% by weight of β-unsaturated carboxylic acid alkyl ester, ethylene copolymer consisting of 0.5-10% by weight of maleic anhydride, epoxy group-containing olefin copolymer, and at least one type of ionomer resin. Elastomer (B) and polyamide resin (C) (A)/
(B) -50150~98/2 (C) / + (
A) + (B) l −2/98 to 98/2 weight ratio and polycarbodiimide compound (D
) to the above composition [(A) + (B) + (C)] 100
0.2 to 20 parts by weight, preferably 1 to 1 parts by weight
0 parts by weight, but polycarbodiimide compound (C
) is less than 0.2 parts by weight, the effect of improving compatibility will be small, and if it is more than 20 parts by weight, the melt viscosity of the resin will become too high, which is not preferable.

The polycarbodiimide 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 two or more carbodiimide groups. I can do it.

The above-mentioned polycarbodiimide compound (C) can be easily produced by a method known per se, for example, by polycondensation by decarboxylation of the corresponding diisocyanate.

Specific examples of polycarbodiimide compounds include poly(4
, 4”-diphenylmethanecarbodiimide), poly(
3,3'-dimethyl-4,4"-biphenylmethanecarbodiimide), poly(tricarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3-dimethyl-4,
4-diphenylmethanecarbodiimide), poly(naflethylenecarbodiimide), poly(1,6-hexamethylenecarbodiimide), poly(1,4-tetramethylenecarbodiimide), poly(1,3-cyclohexylenecarbodiimide), , 4-isochlorohexylenecarbodiimide), poly(13,5-triethylphenylenecarbodiimide), poly(44'-methylenebiscyclohexylcarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(1-methyl3. 5-diisopropylphenylenecarbodiimide),
Examples include poly(isopropylphenylenecarbodiimide).

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 polycarbodiimide compound is thought to function effectively as a crosslinking agent for crosslinking PPS, elastomers, and polyamide resins, or as a chemical bonding agent for PPS, elastomers, and polyamide resins. This is thought to be the reason for the improved impact resistance.

In addition, the resin composition of the present invention may include an inorganic and/or organic filler in the resin composition component (E) if necessary, (E), / (F} = 98/2 to 40/60, Preferably, it can be added at a weight ratio of (E)/(F}=9515 to 50150 to improve rigidity, etc., but if the amount of filler exceeds this range, the surface of the molded product will deteriorate. This is not preferable because it becomes rough and physically 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, atalbulgite, uwolastonite, PMF, ferrite, silicic acid Reinforcing fillers such as calcium, 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, etc. I can do it.

The resin composition of the present invention may also contain a plasticizer such as an aromatic hydroxy derivative, such as 2-ethylhexyl-P-hydroquinhenshade, a sulfonic acid amide, such as Hensensulfonamide, or a small amount of mold release agent. Agents, coupling agents, coloring agents, lubricants, heat stabilizers, weather stabilizers, foaming agents, rust preventives, flame retardants, 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 pelletized.

The filler can also be mixed at the same time, but when using an extruder, it is preferable to side-feed from the middle of the extruder in order to prevent the filler from being destroyed.

In addition, the melt-kneading temperature is preferably 280 to 320''C; if it is less than 280°C, the melting of PPS may be insufficient, and if it exceeds 320°C, thermal deterioration or gelation of the elastomer will occur. Caution is required.

In the present invention, the Izot impact test, bending test, and heat distortion temperature are conducted 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 (1-1 Blen T-4) at 140°C for 3 hours, the temperature was lowered to 50°C, and PPS and poly(
44-diphenylmethanecarbodiimide), and
After mixing in a Henschel mixer in a nitrogen atmosphere for a minute,
Pelletization was performed using a "BT-40" twin-screw extruder manufactured by Plastinok 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. The mixture was melted and kneaded to obtain pellets using a conventional method.

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

The obtained pellets were heated to a cylinder temperature of 240'C, a center part of 290'C, a tip part of 300'C, and a mold temperature of 14'C.
The temperature was set at 0'C, and test pieces were 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 (Toprene T-4) at 140°C for 3 hours, the temperature was lowered to 50°C, and PPS, elastomer, and polyamide were mixed in a blender. Partially 240°C1 central part 300°C
The mixture was melt-kneaded using the same extruder with the C1 tip 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 pellet was heated to a cylinder temperature of 240°C, a center part of 290°C, a tip part of 300°C, and a mold temperature of 140°C.
°C, test pieces were 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 idiot)

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 polycarbodiimide 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.