JP3123101B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having improved toughness of polyphenylene sulfide.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter PPS)
) Has attracted attention as a member of electric and electronic equipment and a member of automobile equipment by utilizing its excellent heat resistance and chemical resistance. Further, it can be molded into various molded parts, films, sheets, fibers and the like by injection molding, extrusion molding and the like, and is widely used in fields requiring heat resistance and chemical resistance. However, PPS has the significant drawback of poor ductility and fragility.

[0003] Conventionally, fillers such as glass fibers have been blended in order to improve the impact resistance of PPS, but the improvement is not yet sufficient for applications requiring flexibility.

On the other hand, a polymer blend with a polyolefin modified with a glycidyl group or an acid anhydride group has been attempted,
For example, Japanese Patent Application Laid-Open Nos.
It is disclosed in, for example, JP-A-151460. However, although the impact strength is improved by these methods, a good PPS molded product has not yet been obtained, such as a decrease in tensile strength, an increase in melt viscosity and a decrease in moldability.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional processing method and technical problems, and a PPS resin composition having improved toughness without impairing the characteristics of PPS is provided. To provide.

[0006]

That is, the present invention provides (a) a polyphenylene sulfide resin of 50 to 99.5% by weight,
(B) acrylic acid ester (however, ethyl acrylate is
Excluding) a resin composition comprising 50 to 94 mol%, and 50 to 0.5 mol% of an acrylate copolymer obtained by copolymerizing 50 to 6 mol% of a compound represented by the following general formula (I) and / or (II). The present invention relates to a polyphenylene sulfide resin composition obtained by blending (c) a fibrous reinforcing material and / or a granular reinforcing material in an amount of 0 to 200 parts by weight with respect to 100 parts by weight of a product.

[0007]

Embedded image (Wherein R is C ₂ -C ₁₈ having an ethylenically unsaturated bond)
Represents a hydrocarbon group. )

[0008]

Embedded image (Where R is the same as above, X is

[0009]

Embedded image Or -O-. ) The PPS used in the present invention is

[0010]

Embedded image Is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the formula, and a copolymer containing a repeating unit having the following structure in a range of less than 30 mol% of the repeating unit. It may be.

[0011]

Embedded image Examples of the method for producing PPS include a method of polymerizing a halogen-substituted aromatic compound, for example, p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide, sodium hydrogen sulfide and sodium hydroxide in a polar solvent. ,
Or a method of polymerizing p-dichlorobenzene with hydrogen sulfide and sodium hydroxide, preferably in the presence of sodium aminoalkanoate or an alkali metal salt of an organic carboxylic acid as a polymerization aid, p-chlorothiopheno-
A method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as dimethylsulfoxide or sulfolane. Particularly preferred.

These production methods are already known and are disclosed in US Pat. No. 2,513,188, JP-B-44-27671, JP-B-45-3368, and JP-B-52-122.
No. 40, JP-A-61-222517, U.S. Pat. No. 3,274,165, JP-B-46-27255 and Bergi-Japanese Patent 29437.

The PPS may be linear or branched, or may be a mixture of these structures.

These melt viscosities are measured at 300 ° C. using a Koka type flow tester (die: inner diameter 0.5 mm, length 2.0 mm; load: 10 kg).
oise to 100000 poise, preferably 50p
oise to 50,000 poise.

In order to further enhance the reactivity with the acrylate copolymer of the present invention, a highly reactive PPS, for example, a PPS containing a hydroxyl group or a sodium alcoholate which has already been filed by the present applicant (Japanese Patent Application Laid-Open No. Sho 64-64). No. 48828, JP-A-64-48829), PPS containing a carboxyl group or a sodium carboxylate, and PPS containing an amino group (Japanese Patent Application Nos. 1-107369 and 1-107).
It is preferable to use PPS containing terminal thiol or sodium thiolate.

The acrylate copolymer used in the present invention comprises 50 to 94 mol% of an acrylate, a compound 5 represented by the general formula (I) and / or (II).
It is a resin obtained by copolymerizing 0 to 6 mol%.

Examples of the acrylate include methyl acrylate , propyl acrylate, n-butyl acrylate, i-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate and the like. Can be listed.

Formulas (I) and / or (II) include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, butenecarboxylic esters, allyl glycidyl ether, vinyl glycidyl ether -Ter, methallyl glycidyl ether, 2-methylallyl glycidyl ether,
Styrene-p-glycidyl ether and the like can be listed.

As a method for producing the acrylate copolymer used in the present invention, for example, a solution polymerization method can be used. It can be produced by reacting the acrylate with the general formula (I) and / or (II) in an organic solvent in the presence of a radical initiator at 0 to 150 ° C. for 30 minutes to 30 hours.

The total concentration of the raw materials is generally between 50 and 500
A range of g / l solvent is selected. The initiator concentration is generally selected from the range of 0.001 to 0.1 g / g of all raw materials.

As the organic solvent, various solvents can be used, for example, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene, 1,4-dioxane, p-ethylphenol, p-ethylphenol,
-Chlorophenol and the like.

The radical initiator is not particularly limited as long as it is used as a usual radical polymerization initiator. For example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl Hydroperoxide and the like can be mentioned.

As still another production method, it can be produced by suspension polymerization or emulsion polymerization in water in the presence of an initiator, in the presence of a suspending agent or emulsifier.

As the fibrous reinforcing material and / or the granular reinforcing material used in the present invention, for example, glass fiber, carbon fiber,
Reinforcing fillers such as ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, calcium carbonate, mica,
Talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, Compounding inorganic fillers such as zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, and organic and inorganic pigments Can also.

As the glass fiber, for example, a fiber length of 1.
Examples include chopped strands having a diameter of 5 to 12 mm and a fiber diameter of 3 to 24 μm, milled fibers having a fiber diameter of 3 to 8 μm, and glass flakes and powders having a size of 325 mesh or less.

In the present invention, the content of PPS is from 50 to
It is 99.5% by weight, preferably 70 to 98% by weight.
When the content of PPS is less than 50% by weight, the solvent resistance and heat resistance of PPS decrease, and when the content of PPS exceeds 99.5% by weight, the toughness of PPS is not improved.

In the acrylate copolymer, the acrylate content is 50 to 94 mol%, preferably 70 to 93 mol%. The content of the acrylic acid ester is less than 50 mole%, reduced moldability at elevated melt viscosity by kneading, decreases the reactivity of the acrylic San'e scan telco polymer exceeds 94 mol%.

[0028]

Also, plasticizers and release agents such as aromatic hydroxy derivatives, silane and titanate coupling agents, lubricants, heat stabilizers, weather resistance stabilizers, crystal nucleating agents, foaming agents, rust prevention An agent, an ion trapping agent, a flame retardant, a flame retardant auxiliary, etc. may be added as necessary.

The method for obtaining the PPS resin composition of the present invention is as follows: 1) A method in which the components are mixed by a mixer or the like, then melt-kneaded using an extruder, and then pelletized. A method of adding another component to the pellets obtained, melt-kneading and pelletizing again 3) A method of dissolving each component in a solvent and stirring with heating.

In each of the above methods, known devices such as Banbury, kneaders and autoclaves can be used alone or in combination.

The PPS resin molded product of the present invention can be obtained by injection molding,
It can be processed into various molded products by sheet molding, vacuum molding, heterogeneous molding, foam molding and the like and used.

[0033]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these Examples.

Further, the melt viscosity of PPS is determined by the Koka type flow.
Tester (die: inner diameter 0.5 mm, length 2.0 mm;
The load was measured at 300 ° C.

Reference Example 1 An autoclave equipped with a stirrer and having a capacity of 15 l
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 50
00g and sodium sulfide (Na ₂ S · 2.9H
₂ O) _1898g of (14.8 mol) was added, the temperature was raised to 205 ° C., was distilled NMP of water and 5g of 420 g. Subsequently, p-dichlorobenzene (14.35 mol), 3,
Add 5-dichloroaniline (0.15 mol) and add 225
The reaction was carried out at a temperature of 250C for 3 hours and then at 250C for 3 hours. At the end of the reaction, the reaction was cooled to room temperature and the polymer was isolated by centrifugation. The conversion of the monomer was 98.5%. Wash the polymer repeatedly with warm water,
C. By drying at ℃ for 24 hours, melt viscosity 500poi
The PPS of se was obtained. Further, this PPS is cured at 250 ° C. for 5 hours in air to obtain a melt viscosity of 7000.
Poise PPS was obtained. This is designated as PPS-I.

Reference Example 2 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
Instead of 2,4-dichlorobenzoic acid (0.15 mol)
The same operation as in Reference Example 1 was performed except that was used. The conversion of the monomer was 96%, and the melt viscosities before and after curing were 480 poise and 6500 poi, respectively.
was se. This is designated as PPS-II.

Reference Example 3 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
Instead of 3,5-diaminochlorobenzene (0.15
(Mole), and the same operation as in Reference Example 1 was performed. The conversion of the monomer was 95%, and the melt viscosities before and after curing were 590 poise and 7600 respectively.
Poise. This is designated as PPS-III.

Reference Example 4 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
In the same manner as in Reference Example 1, except that 3,5-dichlorophenol (0.15 mol) was used instead. The conversion of the monomer was 97%, and the melt viscosities before and after curing were 400 poise and 6700, respectively.
Poise. This is designated as PPS-IV.

Reference Example 5 An NN was placed in an autoclave equipped with a stirrer and having a capacity of 15 l.
P5000g, sodium sulfide (Na ₂ S · 2.9H ₂
O) 1898 g (14.8 mol), 1800 g of sodium benzoate and 48 g of sodium hydroxide were added, and 20
The temperature was raised to 5 ° C., and 418 g of water and 5 g of NMP were distilled off. Subsequently, 2131 g of p-dichlorobenzene (14.
5 mol), and reacted at 220 ° C. for 2 hours and then at 250 ° C. for 3 hours. At the end of the reaction, the reaction was cooled to room temperature and the polymer was isolated by centrifugation. Monomer
Was 96.0%. The polymer was repeatedly washed with warm water and dried under reduced pressure at 100 ° C. for 24 hours to obtain PPS having a melt viscosity of 3400 poise. This is designated as PPS-V.

Reference Example 6 NM was placed in an autoclave equipped with a stirrer and having a volume of 15 l.
P5000g and sodium sulfide (Na ₂ S.2.9)
H ₂ O) 1898g of (14.8 mol) was added, 205 ° C.
Then, 420 g of water and 5 g of NMP were distilled off.
Subsequently, p-dichlorobenzene (14.5 mol) was added, and the reaction was carried out at 225 ° C for 3 hours and then at 250 ° C for 3 hours. At the end of the reaction, the reaction was cooled to room temperature and the polymer was isolated by centrifugation. Conversion of monomer is 9
8.5%. The polymer was washed repeatedly with warm water and dried under reduced pressure at 100 ° C. for 24 hours to give a melt viscosity of 5
90 poise PPS was obtained. Furthermore, this PPS is 25
PPS having a melt viscosity of 8300 poise was obtained by curing at 0 ° C. in air for 5 hours. This is called PPS-V
I.

Reference Example 7 5000 equipped with a stirrer, thermometer, nitrogen inlet tube and cooler
i-butyl acrylate 513 in a 4-ml four-necked flask.
g (4 mol), 57 g of glycidyl methacrylate (0.
4 mol) and 4400 ml of 1,4-dioxane were stirred and heated to 80 ° C., and then 3.6 g (22 mmol) of azobisisobutyronitrile was added. After stirring for 6 hours, a further 3.6 g of azobisisobutyronitrile (2
(2 mmol), and the mixture was stirred for 6 hours, cooled to room temperature, and then poured into a large amount of methanol to precipitate a polymer. The supernatant was removed, repeatedly decanted with methanol, washed, and dried in vacuo at 100 ° C. for 24 hours to obtain a colorless and transparent viscous polymer. When the molecular weight and composition of the obtained polymer were measured, the weight average molecular weight was 24,000, and the molar ratio of i-butyl acrylate to glycidyl methacrylate was 90:10.
This is called iBA-co-GMA.

Reference Example 8 513 g (4 mol) of i-butyl acrylate of Reference Example 7
Instead of n-butyl acrylate 513 g (4 mol)
The same operation as in Reference Example 7 was performed except that was used. The weight average molecular weight of the polymer was 27000, and the molar ratio of n-butyl acrylate to glycidyl methacrylate was 89:11. This is designated as nBA-co-GMA.

REFERENCE EXAMPLE 9 i-butyl acrylate of Reference Example 7 (513 g, 4 mol)
736 g of 2-ethylhexyl acrylate instead
The same operation as in Reference Example 7 was performed except that (4 mol) was used. The weight average molecular weight of the polymer was 23,000, and the molar ratio of 2-ethylhexyl acrylate to glycidyl methacrylate was 88:12. This is OA
-Co-GMA.

Reference Example 10 513 g (4 mol) of i-butyl acrylate of Reference Example 7
The same operation as in Reference Example 7 was performed, except that 1296 g (4 mol) of stearyl acrylate was used instead. The weight average molecular weight of the polymer was 25,000, and the molar ratio of stearyl acrylate to glycidyl methacrylate was 89:11. This is called SA-co-GMA
And

Reference Example 11 513 g (4 mol) of i-butyl acrylate of Reference Example 7
In the same manner as in Reference Example 7, except that 400 g (4 mol) of ethyl acrylate was used instead. The weight average molecular weight of the polymer was 28,000, and the molar ratio of ethyl acrylate to glycidyl methacrylate was 91: 9.
Met. This is designated as EA-co-GMA.

Reference Example 12 Using the apparatus of Reference Example 7, glycidyl methacrylate 6
25 g of homopolymerization was performed. The weight average molecular weight of the polymer was 32,000. This is referred to as PGMA. Reference Example 13 The amount of glycidyl methacrylate of Reference Example 7 was 28.4 g.
(0.2 mol), except that the procedure was the same as in Reference Example 7. The weight average molecular weight of the polymer was 34,000, and the molar ratio of i-butyl acrylate to glycidyl methacrylate was 96: 4. This is iBA-co
-GMA2.

Reference Example 14 The amount of glycidyl methacrylate of Reference Example 7 was 284 g.
(2 mol), 513 g of i-butyl acrylate
The same operation as in Reference Example 7 was performed, except that 736 g (4 mol) of 2-ethylhexyl acrylate was used instead of (4 mol). The weight average molecular weight of the polymer is 320
The molar ratio between 2-ethylhexyl acrylate and glycidyl methacrylate was 68:32. This is designated as OA-co-GMA2.

Example 1 950 g of PPS-I obtained in Reference Example 1 was added to i obtained in Reference Example 7.
After dispersing an acetone solution in which 50 g of BA-co-GMA was dissolved and removing acetone at 100 ° C., the sample was pelletized at 300 ° C. using Labo Plast Mill (manufactured by Toyo Seiki), and then an in-line screw injection molding machine was used. (Toshiba IS-50EP) cylinder temperature 29
A molded product was obtained at 0 ° C. and a mold temperature of 140 ° C. ASTM D638 for tensile properties of molded products, AS for Izod impact test
The measurement was performed according to TM D256. The test results are shown in Table 1.

Examples 2 to 8 and Comparative Examples 1 to 4 The same operation as in Example 1 was performed with the composition ratios shown in Table 1,
A molded product was obtained. The test results are shown in Table 1.

Example 9 An acetone solution of 50 g of OA-co-GMA obtained in Reference Example 9 was dispersed in 950 g of PPS-III obtained in Reference Example 3, and acetone was removed at 100 ° C., followed by addition of 60 g of chopped strand. After dry-blending, the sample was subjected to 300 lab using Labo Plast Mill (manufactured by Toyo Seiki).
C. and pelletized using an in-line screw type injection molding machine (IS-50EP, manufactured by Toshiba).
A molded product was obtained at 0 ° C. and a mold temperature of 140 ° C. The molded product has a tensile strength of 1850 kg / cm ² , a tensile elongation of 4.8%, and an Izod impact strength (anti-notch) of 55 kg · cm / cm.
Met.

[0051]

[Table 1]

[0052]

As described in detail above, according to the present invention,
A PPS resin composition having improved toughness without lowering other physical properties of PPS can be obtained, and its industrial value is high.

Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin (a)
To 99.5% by weight, (b) acrylic acid ester (however,
Chill acrylate are excluded) 50 to 94 mol%, the compound represented by the following general formula (I) and / or (II) 50
(C) 0-200 parts by weight of a fibrous reinforcing material and / or a granular reinforcing material is added to 100 parts by weight of a resin composition comprising 50-0.5% by weight of an acrylate ester copolymer obtained by copolymerizing -6% by weight. A polyphenylene sulfide resin composition that is blended. Embedded image (In the formula, R represents a C ₂ -C ₁₈ hydrocarbon group having an ethylenically unsaturated bond.) (Wherein R is the same as described above, and X is Or -O-. )