JP3471125B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Engineering plastic industrial material with excellent appearance
Fees, eg connectors, ignition manifold
Useful for providing gears, gears, bumpers, coil sealants, etc.
The present invention relates to a thermoplastic resin composition. 2. Description of the Related Art Polyphenylene sulfide is known for its fluidity and resistance.
High melting point resistance with excellent organic solvent properties, electrical properties, flame retardancy, etc.
It is a thermocrystalline resin. However, for sliding members, for optical disks
Low degree of polymerization when used as a molding material for carriages, etc.
Disadvantages of poor extrusion molding stability and injection molding stability.
You. The glass transition temperature is not so high at about 90 ℃
Therefore, the rigidity of the molded article in use at a high temperature is greatly reduced.
Therefore, glass fiber, carbon fiber, talc, silica, etc.
Rigidity has been improved by compounding with inorganic fillers
(USP 4,737,539, USP 4,009,04
3) However, in this case, the appearance of the molded product is deteriorated,
However, there is a problem that warpage tends to occur. On the other hand, polyphenylene ether has excellent resistance to
Has heat, dimensional stability, non-hygroscopicity, electrical properties, etc.
Engineering plastics, but melt fluidity
Poor, difficult to mold, and oil and impact resistant
There is a disadvantage that it is inferior. So without losing the strengths of both
Various compositions for the purpose of providing molding materials with complementary disadvantages
Has been proposed. [0004] For example, polyphenylene ether
Polyphenylene sulfide blends
Technology to improve moldability of phenylene ether is disclosed
(JP-B-56-34032). This one
Indicates that polyphenylene
Polyethers and polyphenylene sulfide are inherently compatible
Is poor, and in such a simple blend system,
Poor compatibility due to poor affinity
Phase separation occurs during molding. Therefore, the resistance of the obtained molded body
Impact properties are not enough and the balance of mechanical properties is excellent
I can't say that. [0005] Therefore, a technique capable of improving the compatibility between the two.
JP-A-2-36261 discloses a polyphenylene
Lens sulfide and polyphenylene ether have molecular structures
Double or triple carbon-carbon bond and carboxylic acid
Hydrate, acid amide, imide, carboxylic acid ester, amide
Compounds containing amino, epoxy or hydroxyl groups, eg
For example, adding maleic anhydride to improve the compatibility of both resins
Is disclosed. But by this method
Also, polyphenylene ether and polyphenylene sulfite
The improvement of the compatibility of the alloy is not sufficient,
Fruit is small. SUMMARY OF THE INVENTION The present invention relates to a polyphenylene
Extreme compatibility between lensulphide and polyphenylene ether
Excellent, appearance of molded product, balance of mechanical properties, melting resistance
Provides thermoplastic resin composition that gives molded products with excellent agent properties
The purpose is to do. Means for Solving the Problems The present inventors have made intensive studies.
Results in polyphenylene sulfide and polyphenylene sulfide.
Specific ether phenol compound and alkali gold
The compatibility of both resins is significantly improved by the addition of a metal salt.
That a good resin composition with excellent mechanical strength can be obtained.
And completed the present invention. That is, the present invention
Polyphenylene containing the components (a), (b), (c) and (d)
It is a sulfide-based resin composition. (a) 10 to 90 parts by weight of polyphenylene sulfide (b) 90 to 10 parts by weight of polyphenylene ether (c) A phenol compound represented by the general formula (I) (Where R ¹ , R ^Two , R ^Three And R ^Four Is a hydrogen atom
Or a hydrocarbon group having 1 to 18 carbon atoms,
May be different. Z is a monovalent to tetravalent carbon
Represents a hydrogen residue, and n represents an integer of 1 to 4. ) The ingredients
0.01 to 10 weights based on 100 parts by weight in total of (a) and (b)
Parts (d) 100 parts by weight of alkali metal salt in total of components (a) and (b)
The present invention will be described in detail below 0.01 to 10 parts by weight based on parts. Component (a) polyphenylene sulfide The polyphenylene sulfide used in the present invention has the general formula (I
I) [0010] The repeating unit represented by
Crystalline resin. In the present invention, the above general formula
Consisting of repeating units represented by (II), or
As a main component, preferably at least 80 mol%, more preferably
Or more than 90 mol%, the point of physical properties such as heat resistance
Is preferred. Of the constituents of polyphenylene sulfide
Is substantially all the repeating unit represented by the above general formula (II)
If the composition does not consist of
The following are copolymerizable, for example, the following general formulas (II) to (IX)
To be satisfied with the component consisting of the repeating unit represented by
Can be. Embedded image Wherein Y is an alkyl group, a phenyl group,
This polyphenylene sulfide has a substantially linear structure.
Some are preferred from the viewpoint of the physical properties of the molded product. This
Within a range that does not substantially reduce the physical properties of
Use an effective amount of cross-linking agent (for example, trihalobenzene)
Polymerized cross-linked product or polyphenylene sulfite
Heat-crosslinked product in the presence of oxygen
Can also be used. Polyphenylene sulfide can be obtained at 300 ° C.
Has a melt viscosity of 100 to 100,000 poise, preferably
Is from 500 to 50,000 poise, more preferably
Those having a range of 500 to 20,000 poise are preferred.
If the melt viscosity is less than 100 poise, the fluidity is too high and the
Difficult to shape. In addition, the melt viscosity is 100,000 poi
On the contrary, even if the flow rate is excessive, the fluidity is too low, and molding becomes difficult. Polyphenylene sulfide is, for example,
Relatively molecular weight as disclosed in JP-B-45-3368
The production method of small polymer, Japanese Patent Publication No. 52-12240
Preparation of linear, relatively high molecular weight polymers as disclosed
Method or heating a low molecular weight polymer in the presence of oxygen to form a crosslinked product
According to the method of obtaining
And can be manufactured. Component (b) polyphenylene ether The polyphenylene ether used in the present invention has the general formula (X): (Where Q ¹ Is a halogen atom, primary
Or a secondary alkyl group, aryl group, aminoalkyl
Group, halohydrocarbon group, hydrocarbonoxy group or halocarbon
Q represents a hydrogen oxy group; ^Two Are hydrogen and halogen
, Primary or secondary alkyl group, halohydrocarbon group
Or a halohydrocarbon oxy group. )
And a homopolymer or a copolymer containing the same unit. Q ¹ And Q ^Two Suitable for the primary alkyl group of
Examples are methyl, ethyl, n-propyl, n-butyl, n
-Amyl, isoamyl, 2-methylbutyl, 2,3-di
Methylbutyl, 2-, 3- or 4-methylpentyl
Or heptyl. An example of a secondary alkyl group is isopro
Pill, sec-butyl or 1-ethylpropyl.
Often Q ¹ Is an alkyl or phenyl group, in particular,
An alkyl group having 1 to 4 carbon atoms, ^Two Is a hydrogen atom
is there. Specifically, poly (2,6-dimethyl-
1,4-phenylene ether), poly (2,6-diethyl)
1,4-phenylene ether), poly (2,6-di
Propyl-1,4-phenylene ether), poly (2-
Methyl-6-ethyl-1,4-phenylene ether),
Poly (2-methyl-6-propyl-1,4-phenylene)
Ether), poly (2-ethyl-6-propyl-1,4)
-Phenylene ether), 2,6-dimethylphenol
/ 2,3,6-trimethylphenol copolymer, 2,6
-Dimethylphenol / 2,3,6-triethylpheno
Copolymer, 2,6-diethylphenol / 2,3,2
6-trimethylphenol copolymer, 2,6-dipropyl
Lephenol / 2,3,6-trimethylphenol
Merging, poly (2,6-dimethyl-1,4-phenylene)
Graft copolymerization of styrene with styrene
Body, 2,6-dimethylphenol / 2,3,6-trime
Graft polymerization of styrene onto tylphenol copolymer
Examples include a graft copolymer. Preferred Polymerization of Polyphenylene Ether
As a body, for example, poly (2,6-dimethyl-1,4
-Phenylene ether). As a suitable copolymer
Is 2,6-dimethyl-1,4-phenylene ether
2,3,6-trimethyl-1,4-phenylene ether
And a random copolymer of Polyfe used in the present invention
Nylene ether is usually measured in chloroform at 30 ° C.
Further, those having an intrinsic viscosity of 0.2 to 0.8 dl / g are preferable. The polyphenylene ether is generally used in the above-mentioned mode.
Produced by oxidative coupling of nomers. Polyfe
For oxidative coupling polymerization of nylene ethers,
Many catalyst systems are known. Regarding catalyst selection,
There is no limitation, and any of known catalysts can be used.
You. For example, heavy metal compounds such as copper, manganese, and cobalt
At least one of which is usually combined with various other substances
Etc. Component (c) phenolic compound The phenol compound used in the present invention is represented by the following general formula (I): Where R ¹ , R ^Two , R ^Three And R ^Four Is a hydrogen atom
Or a hydrocarbon group having 1 to 18 carbon atoms,
May be different. Z is a monovalent to tetravalent carbon
Represents a hydrogen residue, and n represents an integer of 1 to 4. )
Compound. As a specific example, n-octadecy
Ru-3- (3,5-di-tert-butyl-4-hydro
Xyphenyl) propionate, 1,6-hexanedioxide
Yl-bis {3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate｝, triethylene
Glycol-bis {3- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propione
｝, 2,2-thiodiethylene-bis {3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) pro
Pionate}, 1,3,5-tris-2- {3- (3
5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxydiethyl isocyanurate, tetra
Quismethylene-3- (3,5-di-tert-butyl)
-4-hydroxyphenyl) propionate @ methane,
3,9-bis [2- {3- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy
1,2-dimethylethyl] -2,4,8,10-te
Traoxaspiro [5,5] undecane is a typical example
No. Particularly preferably, n-octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphene
Nyl) propionate, tetrakis methylene-3-
(3,5-di-tert-butyl-4-hydroxyphene
Nyl) propionate @ methane, 3,9-bis [2-
{3- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy {-2,4,8,
10-tetraoxaspiro [5,5] undecane is an example
Can be [0024] Component (d) alkali metal salt The alkali metal salt used in the present invention is an alkali metal (Li,
Na, K, Rb, Cs, Fr)
It is a compound consisting of a conjugate base of a basic acid. Alkali metal
Is preferably Li, Na, K, Cs, and more preferably N
a, K, Cs. Hydroxyl ion as a conjugate base of monobasic acid
Ion, carbonate ion, acetate ion and alkoxyl ion
preferable. As the alkali metal salt, specifically, sodium hydroxide
Hydroxidation of alkali metals such as thorium and potassium hydroxide
Products, sodium carbonate, potassium carbonate, cesium carbonate, etc.
Alkali metal carbonate, sodium methoxide, nato
Lium ethoxide, sodium n-butoxide, potassium
Alcohol of alkali metal such as um-tert-butoxide
, Sodium acetate, potassium acetate, cesium acetate
And basic compounds such as acetates of alkali metals such as
You. Among these, specifically, sodium methoxide,
Sodium ethoxide, sodium hydroxide, potassium carbonate
And cesium acetate are preferred. These alkali metal salts
May be added alone or in combination of two or more.
May be added. [0025] Additional ingredients In the resin composition according to the present invention, the above components (a), (b),
If necessary other than (c) and (d), the resin composition of the present invention
Add other additional components to the extent that the properties are not impaired.
Can be. As an additional component used in the present invention, for example,
For example, impact modifiers, fillers, flame retardants, crystallization accelerators (
Nucleating agent), silane coupling agent, antioxidant, heat stable
Agent, UV absorber, hindered amine light stabilizer, coloring
The reaction of the components, catalysts, crosslinking accelerators, crosslinking inhibitors and each component
A catalyst or the like for accelerating can be added. Addition of additional components
The amount is 100 parts by weight each of the components (a) and (b).
For example, thermoplastic elastomers as impact modifiers
5-40 parts by weight of tomer, 5-40 parts by weight of filler, difficult
2 to 20 parts by weight of flame retardant, crystallization accelerator (nucleating agent), mel
Captosilane, vinylsilane, aminosilane, epoxy
Silane coupling agent such as silane, antioxidant, heat resistance
Stabilizer, ultraviolet absorber, hindered amine light stabilizer and
0.1-5 parts by weight of a coloring agent, polyphenylene sulfide
Thiophosphine as a crosslinking accelerator to control the degree of crosslinking of
Dialkyltin dicarboxylate
0.1-5 parts by weight of xylate, aminotriazole, etc.
Can be added. Promotes the reaction of each component
Less than 10 parts by weight, more preferably 5 parts by weight
Less than parts can be added. Catalyst that promotes the reaction
However, if the amount is more than 10 parts by weight, gas is generated during molding,
Deteriorating the appearance of the product or causing deterioration of physical properties
It is not preferable because there is also. As the filler used in the present invention, metal oxide
Products (silicon oxide, titanium oxide, zinc oxide, iron oxide, oxide
Magnesium, alumina, etc.), silicates (kaolin,
Leh, Mica, Pentonite, Silica, Talc, Huaraz
Tenite, montmorillonite, etc.), iron hydroxide, hydro
Talcite, calcium carbonate, magnesium carbonate, sulfuric acid
Barium, calcium sulfate, boron nitride, silicon carbide,
Glass beads, glass fiber, alumina fiber, silica
Lumina fiber, zirconia fiber, silicon nitride fiber,
Iodine fiber, asbestos fiber, silicon carbide fiber, calcium silicate
Lucium fiber, gypsum fiber, polyamide fiber, phenol
Fiber, silicon carbide whisker, potassium titanate whisker
Mosquito and carbon fibers can be used. A catalyst for accelerating the reaction of each component used in the present invention.
As the medium, tri-n-butylamine, triethylamido
, Triphenylamine, benzyldimethylamine,
Lis (dimethylamino) methylphenol, 4- (N,
Tertiary amines such as N-dimethyl) pyridine;
Ammonium dichloride, tetramethylammonium
Um chloride, trioctylmethyl ammonium chloride
Quaternary ammonium salts such as
Umbromide, tetraphenylphosphonium bromide
Quaternary phosphonium salts such as
Midazole, 2-methylimidazole, 1-cyanoethyl
Imidazole compounds such as ru-2-methylimidazole,
Metal acetates such as zinc acetate and cobalt acetate, anti-trioxide
Promotion of transesterification of mon, tetraoctyl titanate, etc.
Agent, basic compound such as pyridine can be added
You. The polyphenylene sulfide resin of the present invention
Thermoplastic resins used as impact modifiers added to compositions
As the lastmer, for example, polyolefin-based elastomer
Tomer, diene elastomer, polystyrene elastomer
Tomer, polyamide-based elastomer, polyester-based
Lastmer, polyurethane elastomer, fluorine-based elastomer
Known products such as lastomer or silicone elastomer
But preferably, polyolefin-based elastomer
Tomer, diene elastomer, or polystyrene elastomer
Lastmer. Added to the resin composition of the present invention
JIS K 720 as thermoplastic elastomers
The three-point flexural modulus measured in accordance with No. 3 is 1000 kg /
cm ^Two Polymerization with a glass transition temperature of -10 ° C or less
Is preferred, and the thermoplastic elastomer is
By adding to the phenylene sulfide resin composition
Improve the impact resistance of the resin composition. The polyolefin elastomer used in the present invention
Examples of the mer include polyisobutylene and ethylene-
Propylene copolymer, ethylene-propylene-non-conjugated di
Ene copolymer, ethylene-butene-1 copolymer, ethylene
-Propylene-butene-1 copolymer, ethylene-hexene
Sen-1 copolymer, ethylene-vinyl acetate copolymer, d
Tylene-acrylic acid, ethylene-methacrylic acid copolymer
, Ethylene-glycidyl acrylate copolymer, ethyl
Len-glycidyl methacrylate copolymer, ethylene-
Vinyl acetate-glycidyl methacrylate copolymer, ethyl
Len-maleic acid copolymer or ethylene-maleic anhydride
Acid copolymer and the like. The diene elastomer used in the present invention is
For example, polybutadiene and its hydride, polybutadiene
Liisoprene and its hydride, butadiene-styrene
Random copolymers and hydrides thereof
You. As a polystyrene elastomer used in the present invention
Is a block of a vinyl aromatic compound and a conjugated diene compound
Copolymer or hydrogenated product of this block copolymer (hereinafter referred to as
Below, abbreviated as hydrogenated block copolymer).
Physically, it is mainly composed of at least one vinyl aromatic compound.
Polymer block and at least one conjugated diene
Block consisting of a polymer block mainly composed of a compound
The polymer and the block copolymer are hydrogenated and the
Aliphatic based on conjugated diene compounds in block copolymers
Water obtained by hydrogenating at least 80% of double bonds
It is an addition block copolymer. The polystyrene-based elastomer used in the present invention
Vinyl aromatic compounds that constitute the block copolymer
Examples of the product include styrene, α-methylstyrene,
Vinyl toluene, p-tert-butylstyrene, 1,
One or more of 1-diphenylethylene and the like
And styrene is preferred. Also conjugate die
For example, butadiene, isoprene,
1,3-pentadiene, 2,3-dimethyl-1,3-bu
One or two or more are selected from Tadiene etc.
Butadiene, isoprene and their combinations
preferable. Then, polymerization mainly using a conjugated diene compound
The body block has an arbitrary microstructure in that block.
For example, in polybutadiene block
And the 1,2-vinyl bond structure is 5 to 65%, preferably
Or 10 to 50%. Molecular structure of block copolymer
Is linear, branched, radial or any combination of these
Any combination may be used. The method for producing these block copolymers is as follows.
For example, as described in Japanese Patent Publication No. 40-23798.
In an inert solvent using a lithium catalyst
Nyl aromatic compound-conjugated diene compound block copolymer
Can be synthesized. In addition, the police used in the present invention
Hydrogenated block copolymer which is a Tylene elastomer
Is the above vinyl aromatic compound-conjugated diene compound
Obtained by hydrogenating a block copolymer
And a method for producing the hydrogenated block copolymer and
For example, Japanese Patent Publication No. 42-8704,
Also, it can be obtained by the method described in JP-A-43-6636.
Wear. In particular, the heat resistance of the obtained hydrogenated block copolymer,
Titanium-based hydrogenation catalyst that demonstrates excellent performance in heat deterioration resistance
Block copolymers synthesized using
For example, JP-A-59-133203,
Inactive by the method described in JP-A-60-79005
In the presence of a titanium-based hydrogenation catalyst in a neutral solvent,
Can be obtained by hydrogenating a block copolymer having
Wear. At that time, vinyl aromatic compound-conjugated diene compound
Aliphatic diblock based conjugated diene compounds
Heavy bonds hydrogenate at least 80% of the
Morphology of polymer blocks mainly composed of
It is necessary to convert the compound into a polymer having an intrinsic compound. The non-hydrogenated block copolymer contains
The amount of hydrogenated aliphatic double bonds was determined by Fourier transform infrared spectroscopy.
It can be easily known with a densitometer, nuclear magnetic resonance equipment, etc.
You. Further, as the thermoplastic elastomer used in the present invention,
Are polyolefin elastomers, diene elastomers
100 parts by weight of tomer or styrene elastomer
On the other hand, there are α, β-unsaturated carboxylic acids and derivatives thereof.
Or one or two of acrylamide and its derivatives
At least 0.01 to 10 parts by weight of a radical initiator
Denatured product (denatured polyolefin)
Elastomer, modified diene elastomer or
Modified styrene-based elastomer)
You. Specific examples of α, β-unsaturated carboxylic acids and derivatives thereof
Examples include maleic acid, maleic anhydride, fumaric acid,
Itaconic acid, acrylic acid, glycidyl acrylate, 2
-Hydroxyethyl acrylate, methacrylic acid,
Sidyl methacrylate, 2-hydroxyethyl methacrylate
Rate, crotonic acid, cis-4-cyclohexene-1,
2-dicarboxylic acid and its anhydride, endo-cis-
Bicyclo [2.2.1] -5-heptene-2,3-dica
Rubonic acid and its anhydride, maleimide compound, etc.
Is mentioned. Acrylamide and its derivatives
Specific examples of acrylamide, methacrylamide
, N- [4- (2,3-epoxypropoxy) -3,
5-dimethylphenylmethyl] acrylamide, N-meth
Tyrol acrylamide and the like. The thermoplastic elastomer used in the present invention
A radical initiator used as necessary in the modification of
Therefore, there is no limitation as long as it is publicly known.
For example, dicumyl peroxide, di-tert-butyl
Chil peroxide, tert-butyl cumyl peroxy
Side, 2,5-dimethyl-2,5-di (tert-butyl
(Tilperoxy) hexane, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexyne-3, n
-Butyl-4,4-bis (tert-butylperoxy
B) Valerate, 1,1-bis (tert-butyl par)
Oxy) 3,3,5-trimethylcyclohexane, te
rt-butyl peroxytriphenylsilane and te
rt-butylperoxytrimethylsilane and the like.
One or more of these can be selected
You. Also, as another radical initiator of the organic peroxide,
2,3-dimethyl-2,3-diphenylbutane, 2,3
-Diethyl-2,3-diphenylbutane, 2,3-dimethyl
Tyl-2,3-di (p-methylphenyl) butane, 2,
3-dimethyl-2,3-di (bromophenyl) butane, etc.
The denaturation reaction may be carried out using the compound of formula (I). Radiation used for modifying thermoplastic elastomer
The amount of cal initiator used depends on the polyolefin-based elastomer.
-, Diene elastomer or polystyrene elastomer
Usually 0.01 to 10 parts by weight based on 100 parts by weight of stoma
Parts, preferably 0.05 to 5 parts by weight. In addition, denaturation
Polyolefin elastomer, modified diene elastomer
For producing polymer or modified styrenic elastomer
Can be carried out by melt-kneading denaturation or solution mixing denaturation.
Wear. The polyphenylene sulfide resin of the present invention
Suitable for use as a thermoplastic elastomer to be added to the composition.
Specific examples of the olefin-based elastomer, for example,
Ethylene-acrylic acid copolymer, ethylene-methacryl
Acid copolymer, ethylene-glycidyl acrylate copolymer
, Ethylene-glycidyl methacrylate copolymer,
Tylene-vinyl acetate copolymer, ethylene-maleic anhydride
Acid and modified ethylene-propylene-5-
Ethylidene-2-norbornene copolymer, ethylene-p
Propylene-dicyclopentadiene copolymer, ethylene-
Propylene copolymer and ethylene-butene-1 copolymer
Modified maleic anhydride, glycidyl methacrylate
And N- [4- (2,3-epoxypropoxy)-
2,5-dimethylphenylmethyl] acrylamide modification
Objects and the like. The polyphenylene sulfide resin of the present invention
Diene suitable as a thermoplastic elastomer to be added to the composition
Specific examples of ene elastomers include carboxyl groups
Or polybutadiene or polybutadiene containing an epoxy group
Anhydrous ene hydride and polyisoprene hydride
Maleic acid modified, glycidyl methacrylate modified
And N- [4- (2,3-epoxypropoxy) -2,
5-dimethylphenylmethyl] acrylamide modified product, etc.
Is mentioned. The polyphenylene sulfide resin of the present invention
Suitable for use as a thermoplastic elastomer to be added to the composition.
A specific example of the styrene-based elastomer is styrene-
Butadiene block copolymer and its hydrogenated block copolymer
Polymer, styrene-isoprene block copolymer and
As the hydrogenated block copolymer, and the modified product,
Tylene-butadiene hydrogenated block copolymer and styrene
Maleic anhydride modification of isoprene hydrogenated block copolymer
Glycidyl methacrylate and N- [4-
(2,3-epoxypropoxy) -2,5-dimethylphenyl
[Enylmethyl] acrylamide modified product.
Added to the polyphenylene sulfide resin composition of the present invention
Thermoplastic elastomers, not only one, but two or more
You may use together. [0040] Composition ratio of constituent components The composition ratio of the components (a), (b), (c) and (d) of the present invention is
For the total of 100 parts by weight of (a) and (b),
You. Component (a) is 10 to 90 parts by weight, preferably
20 to 80 parts by weight, more preferably 30 to 70 parts by weight,
Particularly preferred is 50 to 70 parts by weight. Component (a) is 1
If the amount is less than 0 parts by weight, the solvent resistance is inferior and is not preferable.
Exceeding the weight part is not preferable because the heat resistance rigidity is insufficient. Component (b) is 90 to 10 parts by weight, preferably
Preferably 80 to 20 parts by weight, more preferably 70 to 30 parts by weight.
Parts by weight, particularly preferably 50 to 30 parts by weight. component
If (b) is more than 90 parts by weight, the solvent resistance is inferior and is not preferable.
Less than 10 parts by weight is not preferable because the heat resistance is insufficient.
Absent. The amount of the component (c) phenolic compound added depends on the amount of the component (a) and the component (a).
And 10 to 10 parts by weight based on a total of 100 parts by weight of
Parts by weight, preferably 0.1 to 5 parts by weight. 0.01 weight
If the amount is less than the above, the compatibility of both resins is sufficiently improved.
If added over 10 parts by weight, physical properties such as impact strength
Is undesirably reduced. The amount of the alkali metal salt of component (d) is
For a total of 100 parts by weight of the minutes (a) and (b), 0.01 to
It is 10 parts by weight, preferably 0.1 to 5 parts by weight. 0.
If the amount is less than 01 parts by weight, physical properties such as impact strength of the molded product are deteriorated.
10 parts by weight
If added in excess, gas will be generated during molding and impact strength etc.
Is not preferred because the physical properties of [0043] Production and molding method of thermoplastic resin composition The method for producing the resin composition of the present invention is not limited to a particular method.
However, it is preferably by melt kneading. Melt kneading
The method is generally used for thermoplastic resins.
The known kneading method can be applied. For example, powdery, granular or
Describes each component in liquid form, if necessary, in the section on additional components.
Henschel mixer, ribbon shaker with additives
After mixing evenly with a blender, V-type blender, etc.
Shaft or multi-screw kneading extruder, roll, Banbury mixer
And the like. Including the additional components mentioned above
Therefore, even if each component is fed at once during kneading,
May be loaded. In addition, a mixture of two or more components in advance
May be used. The melting and kneading temperature is 150 to 370.
° C, preferably 250-350 ° C. Tree of the present invention
The molding method of the fat composition is not particularly limited.
In addition, molding methods commonly used for thermoplastic resins,
That is, injection molding, hollow molding, extrusion molding, sheet molding,
Molding methods such as thermoforming and compression molding can be applied. EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
As will be described, the present invention is not limited to these embodiments.
Absent. The components used are as follows. Component (a) polyphenylene sulfide Topren's polyphenylene sulfide resin (product
Name: Toprene T-7) was used. (In the table, PPS
You. ) Component (b) polyphenylene ether Poly (2,6-dimethyl-1,4) manufactured by Japan Polyether Company
-Phenylene ether) in chloroform at 30 ° C.
(Intrinsic viscosity of 0.4 dl / g) measured in the above. (In the table, P
Expressed by PE. ) Component (c) phenolic compound n-octadecyl-3- (3,5-di-tert-butyl)
Ru-4-hydroxyphenyl) propionate (product
Name: Irganox 1076, Ciba Geigy
Manufactured), tetrakis methylene-3- (3,5-di-te)
rt-butyl-4-hydroxyphenyl) propione
Tomethane (trade name: Irganox 1010, Ciba
・ Geigy), 3,9-bis [2- {3- (3-t)
tert-butyl-4-hydroxy-5-methylphenyi
L) propionyloxy {-1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5,5] un
Decane (trade name: Sumilizer GA-80, Sumitomo Chemical)
Was used. [0046] Component (d) alkali metal salt Sodium ethoxide (represented by NaOEt in the table) and water
Sodium oxide (represented by NaOH in the table) was used. Other phenolic compounds 2,6-di-tert-butyl-4-methylphenol
(Product name: BHT, manufactured by Yoshitomi Pharmaceutical Co., Ltd.), 1,3,5-tri
Methyl-2,4,6-tris (3,5-di-tert-
Butyl-4-hydroxybenzyl) benzene (trade name:
Irganox 1330, Ciba-Geigy), bird
(3,5-di-tert-butyl-4-hydroxybe)
Nzil) Isocyanurate (Product name: Good Light 3)
114, manufactured by Goodrich Co., Ltd.). [0047] Additional ingredients Hydrogenated styrene-butadiene-styrene block copolymer
(Product name: Clayton G1651, manufactured by Shell Chemical Company)
(Represented by SEBS in the table). <Example 1> 70 parts by weight of polyphenylene sulfide,
30 parts by weight of polyphenylene ether and 0.3 parts by weight of
Irganox 1010 and 1.0 parts by weight of sodium
After dry-blending muethoxide, a laminator made by Toyo Seiki
Using a Boplast mill, temperature 310 ° C, rotor speed
The mixture was kneaded at 180 rpm for 5 minutes. After kneading, use a crusher
It was crushed into granules. Granulated sample is compressed by Toyo Seiki Co., Ltd.
Using a shaper, at a temperature of 310 ° C, a 2 mm thick shell
The sheet was molded. This sheet is placed in a hot air drier for 120
Heat at 4 ℃ for 4 hours to crystallize polyphenylene sulfide
Went well. From this sheet, a test piece for evaluating physical properties
It was cut. The test piece for evaluating physical properties is placed in a desiccator for 2 days.
And then evaluated. Flexural rigidity is JIS-K-71
It measured at 23 degreeC according to 06. The impact strength is J
According to IS-K-7110, three 2mm thick test pieces
Then, it was measured with an Izod impact tester. Distributed form
Cuts a part of the sheet and scans it with Hitachi
Using a scanning microscope S-2400 at magnifications of 1000 and 5
Observed at 000x. From the observed morphological photos, Nippon Avio
Shunpei using Nix's SPICCAII image analyzer
The uniform dispersion particle size Dn was determined by the following equation. Dn = Σnidi / Σnidi is the measured value of the dispersed particle size ni is the number of the dispersed particles having the dispersed particle size di.
△ indicates that the surface is rough and X indicates that there is a problem in practice.
Was. The results are shown in Table 1. <Examples 2 to 9, Comparative Examples 1 to 6> Shown in Table 1 or Table 2
A test piece was obtained in the same manner as in Example 1 with the compounding. these
Are shown in Table 1 or Table 2. [Table 1] [Table 2] The polyphenylene sulfide tree of the present invention
The fat composition comprises polyphenylene sulfide, polyphenylene
Ethers, certain phenolic compounds and alkali gold
By using the genus salt, polyphenylene sulfide and
The compatibility of polyphenylene ether is significantly improved,
Thermoplasticity that gives molded products excellent in heat resistance, impact strength and appearance
It is a resin composition.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-179432 (JP, A) JP-A-7-278427 (JP, A) JP-A-4-142365 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 71/12 C08K 3/10-3/14 C08K 5/134 C08L 81/02

Claims (1)

(57) [Claims] (1) A polyphenylene sulfide resin composition containing the following components (a), (b), (c) and (d). (a) 10 to 90 parts by weight of polyphenylene sulfide (b) 90 to 10 parts by weight of polyphenylene ether (c) A phenol compound represented by the general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms or carbon atoms 1
To 18 hydrocarbon groups, which may be the same or different. Z represents a monovalent to tetravalent hydrocarbon residue, and n represents an integer of 1 to 4. ) Is 0.01 to 10 parts by weight based on 100 parts by weight of the total of components (a) and (b). (D) The alkali metal salt is added in an amount of 0.1 to 100 parts by weight of the total of components (a) and (b). 01 to 10 parts by weight