JPH04239562A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition having improved antistatic properties without damage to mechanical strength such as impact resistance and without requirement of complicated operations such as post-treatment by blending a specified polyetheramide with a polyphenylene sulfide resin. CONSTITUTION:With (A) 100 pts.wt. polyphenylene sulfide resin, (B) 1-20 pts.wt. polyetheramide composed of (B1); 90-15 pts.wt. polyamide segment derived from a salt (Caprolactam, hexamethylenediamine-adipic acid salt, etc., are suitable) between <=10C aminocarboxylic acid or lactam or <=10C diamine and <=10C dicarboxylic acid and (B2); 85-10 pts.wt. polyoxyalkylene segment (Polyoxytetramethylene or polyoxyethylene is preferable) having 200-6000 number-average molecular weight and (C) a fibrous and/or non-fibrous filler preferably pre-treated with a coupling agent in an amount of 0-300 pts.wt., preferably 30-250 pts.wt. based on 100 pts.wt. (A)+(B) are blended, thus obtaining the objective resin composition.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition which has improved antistatic properties without substantially impairing mechanical strength such as impact resistance.

0002

[Prior art] Polyphenylene sulfide resin (hereinafter referred to as P
PS resin (abbreviated as PS resin) has properties suitable for engineering plastics, such as excellent heat resistance, flame retardance, rigidity, and chemical resistance, and is used mainly for injection molding, as well as various electrical parts, mechanical parts, and automobile parts. used in Furthermore, in addition to the excellent properties inherent to these PPS resins, if antistatic properties are added, it will be possible to expand the application to electronic and electrical parts that need to prevent damage caused by static electricity, as well as various types of equipment that require dustproof properties. Become.

[0003] Several studies have been made to improve the antistatic properties of PPS resins. For example, methods by surface treatment of molded products (US Pat. No.
02 specification), a method of blending a specific silane compound (U.S. Pat. No. 4,350,786), and a method of blending a sulfonic acid metal salt (Japanese Patent Application Laid-Open No. 101368/1999). There is.

On the other hand, Japanese Unexamined Patent Application Publication No. 113055/1983 discloses that P.
Compositions of PS resin, thermoplastic elastomer and inorganic and/or organic fillers are described.

[0005]

[Problems to be Solved by the Invention] However, the method described in U.S. Pat. No. 3,468,702 involves treating the molded article with a dialkanolamide after molding, which makes the process complicated. It has its drawbacks. Furthermore, the method described in US Pat. No. 4,350,786 significantly reduces mechanical strength. Method of blending sulfonic acid metal salt (JP-A-1-101368)
Although these have a large antistatic effect and little decrease in mechanical strength, they have problems in terms of moldability, such as deterioration of molded appearance and reduction in crystallization rate.

[0006] Furthermore, the polyamide elastomer, which is one of the preferred thermoplastic elastomers used in JP-A-59-113055, includes hard segments of nylon 11 and 12 and a polyether component or a polyester component. Block copolymer elastomers with soft segments are mentioned, but nylon 11 and 12 have relatively low water absorption properties because the methylene chains between the amide groups are too long, so they are used as hard segment elastomers. Even if it is used as an antistatic agent, a sufficient improvement effect cannot be obtained in terms of antistatic properties.

[0007] Therefore, the present invention has been devised to improve antistatic properties without going through complicated processes such as post-treatment of molded products, and without substantially impairing the excellent properties originally possessed by PPS resin such as high mechanical strength. The objective is to obtain a PPS resin composition with

[0008]

[Means for Solving the Problems] That is, the present invention provides (A
) 100 parts by weight of polyphenylene sulfide resin, (B)
(a) 90 to 15 parts by weight of a polyamide segment derived from an aminocarboxylic acid or lactam having up to 10 carbon atoms, or a salt of a diamine having up to 10 carbon atoms and a dicarboxylic acid having up to 10 carbon atoms, and (b) the number (A) 1 to 20 parts by weight of a polyether amide basically composed of 85 to 10 parts by weight of polyoxyalkylene segments having an average molecular weight of 200 to 6,000, and (C) a fibrous and/or non-fibrous filler; +(B)100
This is a polyphenylene sulfide resin composition containing 0 to 300 parts by weight.

[0009] In the present invention, a polyether amide basically consisting of a specific polyamide segment and a specific polyoxyalkylene segment is blended with the PPS resin, and if necessary, fibrous and/or non-fibrous By combining fillers, the above problems could be solved.

The polyphenylene sulfide resin (A) used in the present invention is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by structural formula (1),

[0011]

[Chemical formula 1]

[0012] If the repeating unit is less than 70 mol%,
This is not preferred because heat resistance is impaired. Furthermore, less than 30 mol% of the repeating units in the PPS resin can be composed of repeating units having the following structural formula.

[0013]

[Chemical 2]

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but it is usually 5.
0 to 20000 poise (320℃, shear rate 10sec
-1) is used.

The polyamide segment (a), which is a constituent component of the polyetheramide (B) used in the present invention, is composed of an aminocarboxylic acid or lactam having up to 10 carbon atoms, or a diamine having up to 10 carbon atoms, and a diamine having up to 10 carbon atoms. Examples of compounds used as raw materials include 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid,
Aminocarboxylic acids such as 9-aminononanoic acid and 10-aminodecanoic acid, lactams such as caprolactam, enantholactam and capryllactam, and ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylene diamine,
Nonamethylene diamine, decamethylene diamine, 2,2
, 4-/2,4,4-trimethylhexamethylene diamine, 1,3-/1,4-bis(aminomethyl)cyclohexane, metaxylylene diamine, paraxylylene diamine, etc. , aromatic diamine and adipic acid, suberic acid, sebacic acid, 1,3-/1
, 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, etc., and salts consisting of aliphatic, alicyclic, and aromatic dicarboxylic acids, which may be used alone or in the form of a mixture of two or more. Can be used. Among these, caprolactam, hexamethylenediamine-adipate, and hexamethylenediamine-sebacate are particularly preferably used.

[0016] In the present invention, it is important that the methylene chains between the amide groups of the polyamide segment are not too long as described above, thereby imparting excellent antistatic properties to the PPS resin. it is conceivable that.

Examples of the polyoxyalkylene segment (b) which is a constituent component of the polyetheramide (B) include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxypentamethylene, polyoxyhexamethylene, and polyoxyalkylene segment. Examples include oxyethylene/propylene and polyoxyethylene/tetramethylene. Among these, polyoxyethylene, polyoxypropylene, and polyoxytetramethylene are preferred;
In particular, polyoxyethylene and polyoxytetramethylene are particularly preferably used.

[0018] There are no particular restrictions on the method for producing polyether amide having such polyamide segments and polyoxyalkylene segments as basic constituent units, and polyoxyalkylene having an amino group or carboxyl group at the terminal and the above polyoxyalkylene terminal and a salt are used. A method of melt polymerizing a polyamide-forming monomer containing an amount of dicarboxylic acid or diamine (for example, Japanese Patent Publication No. 59-2686
Alternatively, using polyalkylene glycol, a polyamide-forming monomer, and a small amount of dicarboxylic acid as raw materials, first, the polyamide-forming monomer and dicarboxylic acid are reacted to form a polyamide prepolymer with carboxylated at both ends. A method in which polyalkylene glycol is melt-reacted with the polyalkylene glycol under vacuum (e.g., JP-A-54-47798
(Japanese Patent Laid-Open No. 53-1), a method in which the three raw materials are simultaneously charged into a reaction tank and mixed, and then subjected to melt polymerization under vacuum (for example, Japanese Patent Application Laid-Open No. 53-1
A conventionally known polymerization method such as Japanese Patent No. 19997) can be appropriately employed.

Examples of dicarboxylic acids used as necessary in the production of these polyetheramides include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4' - Alicyclic dicarboxylic acids such as dicarboxylic acids and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid and Examples include aliphatic dicarboxylic acids such as eicosandioic acid, and in particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, decanedic acid, and dodecanedic acid are preferably used.

It is also possible to use a polymerization catalyst in the polymerization of the polyether amide used in the present invention, such as antimony-based catalysts such as antimony trioxide, tin-based catalysts such as monobutyltin oxide, and tetrabutyl titanate. One or more types selected from titanium-based catalysts such as titanium catalysts, zirconate-based catalysts such as tetrabutyl zirconate, etc. can be used.

The number average molecular weight of the polyoxyalkylene segment is selected to be in the range of 200 to 6,000, particularly 25
A range of 0 to 4000 is more preferably selected. If the number average molecular weight is less than 200, the mechanical properties of the resulting polyetheramide will be significantly inferior, and if the number average molecular weight exceeds 6,000, the antistatic properties will be significantly impaired, which is not preferred.

The polyoxyalkylene segment is a structural unit of polyetheramide and is used in an amount of 85 to 10 parts by weight, more preferably 75 to 40 parts by weight, still more preferably 70 to 50 parts by weight. If the polyoxyalkylene segment exceeds 95 parts by weight, the mechanical strength of the polyetheramide will be markedly poor, and if it is less than 10 parts by weight, the antistatic properties of the resin will be markedly poor, which is not preferred.

In the present invention, the blending ratio of (B) polyether amide to 100 parts by weight of (A) PPS resin is 1
~20 parts by weight, more preferably 3 to 15 parts by weight are selected. If the amount is less than 1 part by weight, a sufficient antistatic effect cannot be obtained, and if the amount exceeds 20 parts by weight, the mechanical properties will be significantly impaired, which is not preferable.

The fibrous and/or non-fibrous filler (C) in the present invention is not an essential component, but may be added in an amount of 300 parts by weight based on 100 parts by weight of (A) PPS resin + (B) polyetheramide. In order to obtain higher mechanical properties, dimensional stability, etc., (A) PPS resin + (B) polyetheramide (C) fibrous It is preferable to blend 30 to 250 parts by weight of and/or non-fibrous filler.

[0025] In the present invention, (
C) Fibrous and/or non-fibrous fillers include glass fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, etc. Fibrous fillers, silicates such as wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide,
Metal compounds such as magnesium oxide, zirconium oxide, titanium oxide, iron oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, Examples include non-fibrous fillers such as silicon carbide and silica, which may be hollow, and it is also possible to use two or more of these fillers in combination. Further, it is more preferable to use these fibrous and/or non-fibrous fillers after being pretreated with a coupling agent such as a silane type or a titanate type from the viewpoint of mechanical strength.

The PPS resin composition of the present invention may contain antioxidants, heat stabilizers,
Conventional additives such as lubricants, plasticizers, nucleating agents, UV inhibitors, colorants, flame retardants, etc. can be added. Also,
The PPS resin composition of the present invention may contain polyamide, PPO, polysulfone, polytetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyether, etc., within a range that does not impair the effects of the present invention. It may also contain resins such as terketone, polyetheretherketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, and polyester.

The PPS resin composition of the present invention contains γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. for the purpose of improving mechanical strength and moldability such as burrs within a range that does not impair the effects of the present invention. Glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ- ureidopropyltrimethoxysilane and γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ
-isocyanatopropylmethyldimethoxysilane, γ-
Organic silane compounds such as isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane can be added.

The method for preparing the composition of the present invention is not particularly limited, but the raw material mixture may be melted using a commonly known melting method such as a single- or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Examples include a method in which the mixture is supplied to a mixer and kneaded at a temperature of 280 to 380°C. Furthermore, there is no particular restriction on the mixing order of the raw materials, and there is a method in which PPS resin, polyether amide, and fibrous and/or non-fibrous filler are dry blended and then melt-kneaded by the method described above, or PPS A typical method is to dry blend two of the resin, polyetheramide, and fibrous and/or non-fibrous filler, melt-knead them, and then melt-knead this and the remaining one.

The present invention will be explained in more detail with reference to Examples below.

[0030]

EXAMPLES The tensile strength, bending strength, Izod impact strength, volume resistivity, and surface resistivity described in the Examples and Comparative Examples were each evaluated and measured according to the following methods.

Tensile strength: ASTM-D638 Bending strength:
ASTM-D790 Izod impact strength: ASTM-D256 Volume resistivity and surface resistivity: Measured using a square plate with a thickness of 2 mm and a side of 30 mm at room temperature and a humidity of 50% RH. For measurement, we used a super insulation resistance meter S manufactured by Toa Denpa Kogyo Co., Ltd.
M-10 type was used.

Reference Example 1 (Polymerization of PPS) PPS-1: In an autoclave, 3.26 kg of sodium sulfide (25 mol, containing 40% crystal water), 4 g of sodium hydroxide, and 1.20 kg of sodium acetate trihydrate (approx. 8.8 mol) and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, and the temperature was gradually raised to 205°C while stirring, and about 1.8 mol of distilled water containing 1.36 kg of water was added. 5 liters were removed. 1,4-dichlorobenzene 3.7% in the residual mixture
Add 5Kg (25.5mol) and 2Kg of NMP,
Heated at 65°C for 3 hours. The reaction product was washed 5 times with hot water at 70°C and dried under reduced pressure at 80°C for 24 hours to give a melt viscosity of about 600 poise (310°C, shear rate 1,000 s-1).
) About 2 kg of powdered polyarylene sulfide (PPS-1) was obtained.

PPS-2: 3.26 kg of sodium sulfide (25 mol, containing 40% crystal water) in an autoclave,
Sodium hydroxide 4g, sodium acetate trihydrate 1.2
9 kg (approximately 9.5 mol) and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, and the temperature was gradually raised to 205°C while stirring, and 1.36 kg of water was added.
Approximately 1.5 liters of distillate containing water were removed. 1 to the residual mixture
3.75 kg (25.5 mol) of 4-dichlorobenzene and 2 kg of NMP were added, and the mixture was heated at 265° C. for 3.5 hours. The reaction product was washed 5 times with hot water at 70°C and dried under reduced pressure at 80°C for 24 hours to give a melt viscosity of about 900 poise (31
About 2 kg of powdered polyarylene sulfide (PPS-2) was obtained at 0°C and a shear rate of 1,000 sec-1).

PPS-3: As polyarylene sulfide, M21 manufactured by Toray-Philips Petroleum Co., Ltd.
00 was used.

Reference Example 2 (Preparation of polyetheramide) A
-1: 50 parts of caprolactam, number average molecular weight is 1000
44.2 parts of polyethylene glycol and 7.6 parts of terephthalic acid were charged together with 0.1 part of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated and stirred at 260°C for 60 minutes. After making a transparent homogeneous solution, polymerization was carried out for 4 hours at 260° C. and 0.5 mmHg or less to obtain a viscous and transparent polymer.

[0036] By discharging the polymer in a gut shape onto a cooling belt and pelletizing it, pelletized polyester is produced.
Tellamide (A-1) was prepared.

A-2: Exactly the same method as (A-1) except that 60 parts of nylon 6.6 salt, 33.8 parts of polyethylene glycol with a number average molecular weight of 600 and 8.6 parts of adipic acid were used. Polyetheramide (A-2) was prepared.

A-3: 30 parts of caprolactam, 65 parts of polytettremethylene glycol having a number average molecular weight of 2000.
(A-
Polyetheramide (A-3) was prepared in exactly the same manner as in 1).

Examples 1 to 9 PPS resin, polyetheramide and filler are shown in Table 1.
After dry blending at the ratio shown in 280-320℃
The mixture was melt-kneaded and pelletized using a screw extruder set at a temperature of . Using the obtained pellets, test pieces for evaluating mechanical properties, volume resistivity, and surface resistivity were molded.

Table 3 shows the tensile strength, bending strength, Izod impact strength, surface resistivity, and volume resistivity measured for the obtained test piece.

Comparative Examples 1 to 5 Examples 1 to 2 except that polyetheramide was not used.
, 5, 8 to 9, dry blending, melt kneading and pelletizing were carried out at the ratios shown in Table 2. Using the obtained pellets, test pieces for evaluating mechanical properties, volume resistivity, and surface resistivity were molded.

Table 4 shows the tensile strength, bending strength, Izod impact strength, surface resistivity and volume resistivity measured for the obtained test piece.

Comparative Example 6 Dry blending, melt kneading and pelletizing were carried out in the same manner as in Example 4 except that 30 parts by weight of polyether amide was added to PPS at the proportions shown in Table 2. Using the obtained pellets, test pieces for evaluating mechanical properties, volume resistivity, and surface resistivity were molded.

Table 4 shows the tensile strength, bending strength, Izod impact strength, surface resistivity, and volume resistivity measured for the obtained test piece.

Comparative Examples 7 to 9 Instead of polyetheramide, octadecyltrimethoxysilane (Comparative Example 7), PEBAX, which is a polyetheramide basically composed of nylon 12 segments and polytetramethylene glycol segments, was used. "45
33. Stearic acid monoglyceride “Excel” 20
In the same manner as in Example 4 except that 0 (Comparative Example 9) was used,
Dry blending, melt kneading and pelletizing were carried out in the proportions shown in Table 2. Using the obtained pellets, test pieces for evaluating mechanical properties, volume resistivity, and surface resistivity were molded.

Table 4 shows the tensile strength, bending strength, Izod impact strength, surface resistivity, and volume resistivity measured for the obtained test piece.

Octadecyltrimethoxysilane exhibits a decrease in surface resistivity and volume resistivity, but also a large decrease in strength. In addition, "PEBAX" 4533, a polyetheramide basically composed of nylon 12 segments and polytetramethylene glycol segments, and "EXCEL" 200, a stearic acid monoglyceride, a common antistatic agent, have surface-specific properties. Sufficient reduction in resistance and volume resistivity does not occur.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

Effects of the Invention The polyphenylene sulfide resin composition of the present invention is a resin composition that has improved antistatic properties without substantially impairing mechanical strength such as impact resistance, and is useful for electronic and electrical applications where it is desired to prevent damage caused by static electricity. Suitable for parts and various devices that require dustproof properties.

Claims (1)

[Claims] Claim 1: (A) 100 parts by weight of polyphenylene sulfide resin, (B) (a) an aminocarboxylic acid or lactam having 10 or less carbon atoms, or 10 carbon atoms or less;
Basically, from 90 to 15 parts by weight of a polyamide segment derived from the following diamine and a salt of a dicarboxylic acid having 10 or less carbon atoms, and (b) 85 to 10 parts by weight of a polyoxyalkylene segment having a number average molecular weight of 200 to 6,000. A polyphenylene comprising 1 to 20 parts by weight of polyether amide and (C) fibrous and/or non-fibrous filler in an amount of 0 to 300 parts by weight based on 100 parts by weight of (A) + (B). Sulfide resin composition.