JPH0480262A - Pps-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in impact resistance, hot shape stability and mechanical properties by melt-kneading a polyphenylene sulfide resinw with a specified elastomer and a polycarbodiimide compound in a specified ratio. CONSTITUTION:A polyphenylene sulfide resin (A) is melt-kneaded with at least one elastomer (B) selected from an ethylene copolymer comprising 50-90wt.% ethylene, 5-49wt.% alkyl alpha,beta-unsaturated carboxylate and 0.5-10wt.% maleic anhydride, an epoxy-containing olefin copolymer and an ionomer resin (e.g. Hondyne AX 8390: an ethylene copolymer of Sumitomo CTF Chemical Co.) and a polycarbodiimide compound (C) [e.g. poly(4,4'-diphenylmethane- carbodiimide)] in an A/B weight ratio of 50/50-98/2 and a C/(A + B) weight ratio of 0.2/100-20/100.

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.

As a resin composition consisting of a polyphenylene sulfide resin (hereinafter referred to as PPS) and an elastomer, known polymer alloy type resin compositions (for example, JP-A-58-1547
No. 57, Japanese Unexamined Patent Publication No. 62151460, etc.), and was developed against the background of the above-mentioned demands.

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. is improving. 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-mentioned circumstances, an object of the present invention is to provide a resin composition with improved impact resistance while maintaining the excellent properties of a resin composition composed of PPS and an elastomer. It's about getting.

(Means for Solving Problem 1) As a result of extensive research for this purpose, the present inventors found that: (1) polyphenylene sulfide resin (A), 50 to 90% by weight of ethylene, α, β-unsaturated carboxylic acid; Alkyl ester 5-49% by weight, maleic anhydride 0.5-10
At least one elastomer (B) selected from ethylene copolymers, epoxy group-containing olefin copolymers, and ionomer resins consisting of % by weight, and a polycarboimide compound (C), (A)/(B)
}=50150~98/2(C)/+(A)+
(B)) A resin composition obtained by melt-kneading at a weight ratio of -0.2/100 to 20/100, and It has been found that a resin composition containing an inorganic filler (E) in a weight ratio of (D)/(E}=98/2 to 40/600 achieves the above object, and the present invention has been made. It has been reached.

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 production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by JP Publication No. 52-12240. There are relatively high-molecular polymers, etc., and the polymers obtained by the method described in Japanese Patent Publication No. 45-3368 can be cured by heating in an oxygen atmosphere after polymerization, or by crosslinking with peroxide, etc. It is also possible to use PPS after highly polymerizing it by adding an agent and heating it, and 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.

M3 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, but 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 voids.

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% of α,β-unsaturated carboxylic acid alkyl ester, and malein f110. At least one type of elastomer (B) selected from 5 to 10% by weight of ethylene copolymer, epoxy group-containing olefin copolymer, and ionomer resin, (A)/(B}=5 015 0 to 98/ 2 Preferably, it is 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, , is not preferable because the effect of improving impact resistance becomes small.

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. 5-10
% by weight, preferably 1-8% 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, monobutyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl 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°C,
The melt index value 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
-500, more preferably 1-100.

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 with a polyolefin and an olefin copolymer.

α used here. The glycidyl ester of β-unsaturated carboxylic acid has the formula -a.

(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 monomers having functional groups with a composition of 0.0
1-20% by weight, preferably 0. (in the range of 5 to 5% by weight. These epoxy-containing olefin copolymers are
It is commercially available from Susumu Kagaku Kogyo ■ under the name "Pond 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 that can be ionized into the copolymer. be done.

The base copolymer contains an α-olefin represented by the 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/styrene/guacrylic 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'', Ko, Li''
. ing.

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

Ionomer #! The molecular weight of jFi is 10,000 to 1
．． 000.000. Preferably 20,000~soo,
ooo, more preferably 30,000 to 500,000
is within the range of

The ionomer resin used in the present invention is sold by Mikata-Shupon Polychemical ■ under the trade name ``Himilan''.

In the present invention, in order to improve the compatibility between PPS and the elastomer, 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 maleic anhydride are used. At least one type of elastomer (B) selected from 0.5 to 10% by weight of ethylene copolymer, epoxy group-containing olefin copolymer, and ionomer resin,
Add polycarbodiimide compound (C) to a composition having a weight ratio of (A)/(B}=50150 to 98/2, (C)/((A)+(B))=0.2/10
0 to 20/100 Preferably, the monocarbodiimide compound (
If C) is less than this range, the effect of improving compatibility will be small, and if it is more than this range, 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, and is synthesized, for example, by polycondensation by decarboxylation of the corresponding diisocyanate.

Specific examples of polycarbodiimide compounds include poly(4
, 4'-diphenylmethanecarbodiimide), poly(
3,3°-dimethyl-44′-biphenylmethanecarbodiimide), poly(tolylcarbodiimide), poly(P
-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3'-dimethyl-4,4
-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(1,6-hexamethylenecarbodiimide), poly(1,4-tetramethylenecarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1, 4 cyclohexylenecarbodiimide), poly(135-triethylphenylenecarbodiimide), poly(44"-methylenebiscyclohexylcarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(l-methyl 35
-diisopropylphenylenecarbodiimide), poly(
isopropylphenylenecarbodiimide) and the like.

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 mixing 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 mixing is possible within the commonly used range of 280 to 340°C.

Further, it is preferable that PPS be pre-dried as a pretreatment and kneading be performed in an inert gas atmosphere.

The polycarbodiimide compound can be used as a crosslinking side for crosslinking PPS and elastomers, or as a crosslinker for crosslinking PPS and elastomers.
It is thought that it functions effectively as a chemical bond between PS and elastomer, and this is thought to be the reason for the improved impact resistance.

Further, in the resin composition of the present invention, if necessary, an inorganic and/or organic filler is added to the resin composition component (D), (D)/(E}=98/2 to 40/60, preferably can be added at a weight ratio of (D)/(E}=9515 to 50150 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 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, atalpulgite, uwolastonite, PMF, ferrite, silicic acid Reinforcing fillers such as calcium, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum oxide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, etc. I can list them.

The resin composition of the present invention may also contain a plasticizer such as an aromatic hydroxy derivative such as 2-ethylhexyl-p-hydroxyhenzoate, a sulfonic acid amide such as benzenesulfonamide, or a small amount of a mold release agent. , a coupling agent, a coloring agent, a lubricant, a heat stabilizer, a weather 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 a Henschel mixer, and then fed into a -screw or twin-screw extruder for melt-kneading and then prepared as pellets.

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.

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, thermal deterioration or gelation of the elastomer may occur. Caution is required.

In the present invention, the Izont 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 (Tovren T-4) at 140"C for 3 hours, the temperature was lowered to 50°C, and PPS, elastomer, and poly(4,4-diphenylmethanecarbodiimide) were simultaneously blended, After mixing with a Henschel mixer in nitrogen 111 atmosphere for 5 minutes,
BT-40” twin screw extruder, cylinder temperature = 290°
Pelletized at ~300°C.

Further, when blending glass fiber, side feeding was performed from the middle of the extruder. The obtained pellets were heated to a cylinder temperature of 240"C1 in the center, 290"C in the center, and 300"C in the tip! Here, the mold temperature was set at 40° 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.

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, PPS and elastomer were mixed in a Henschel mixer in a nitrogen atmosphere for 5 minutes, and then Plastinok Pelletization was performed using a "BT-40" twin-screw extruder manufactured by Kogaku Kenkyusho ■ at a cylinder temperature of 290°C to 300°C.

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 for one part of the hopper, 290°C for the center part, and 30°C for the tip part.
The mold temperature was set at 0°C and the mold temperature was set at 140°C, 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. Engineering plastic is a highly practical molding material with excellent physical properties.

(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 a polycarbodiimide compound (C), (A)/(B) =50/50 to 98/2 (C)/{(A)+(B)}=0.2/100 to 20/100 in a weight ratio of a resin composition, characterized in that it is formed by melt-kneading. . (2) Adding an organic and/or inorganic filler (E) to the composition according to claim (1) [hereinafter referred to as (D)], (D)/(E
)=98/2 to 40/60 in a weight ratio.