JPH10298431A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which gives a molded article excellent in resistances to heat and chemicals, toughness, and surface smoothness by compounding a polyphenylene sulfide resin, a polyamide resin and/or a satd. polyester resin, and a functional thermoplastic resin. SOLUTION: This compsn. is prepd. by melt mixing 100 pts.wt. polyphenylene sulfide resin (A) with at least a part of 1-200 pts.wt. thermoplastic resin (C) having functional groups selected from among epoxy, acid anhydride, carboxyl and its salt and ester groups and melt mixing the resultant mixture with the rest of ingredient C and 5-200 pts.wt. polyamide resin and/or satd. polyester resin (B). The compsn. is prepd. so that, when the surface of a gut obtd. by charging the compsn. into a melt indexer (315.5 deg.C, a dwell time of 5 min, a load of 5 kg, an orifice diameter of 0.0825 in, and a length of 0.315 in) is reflected with a projector, the number of projections having a height of 25 μm or higher and observed on the surface is one or less per cm of the gut.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin and a polyamide resin which are excellent in the appearance, toughness, heat resistance, hot water resistance, chemical resistance, alcohol gasoline permeability, surface smoothness and the like of a molded product and are excellent. And / or an alloy material with a saturated polyester resin,
It relates to a material particularly suitable for blow molding.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
PS resin) is suitable for engineering plastics, such as excellent heat resistance, flame retardancy, rigidity, chemical resistance, etc., and various electric parts, machine parts and automobile parts mainly for injection molding Used in
In recent years, the development of hollow molding such as tubes and blows has been promoted.

[0003] Although the PPS resin has the above-mentioned excellent properties, it has a high cost and a poor toughness as compared with general-purpose engineering plastics. For the purpose of improving such weaknesses, a number of studies have been made on composites of general-purpose engineering plastics such as polyamide resins with PPS resins and elastomers. For example, Japanese Patent Application Laid-Open No. 3-37263 discloses a PPS resin and nylon. 66, discloses a composition comprising an epoxy copolymer and an ethylene copolymer. In addition, Japanese Unexamined Patent Publication
JP-A-56561 discloses a composition comprising a PPS resin, a polyamide resin and an epoxy copolymer, and JP-A-5-202271 discloses a PPS resin, a thermoplastic resin capable of reacting with an epoxy group, and an epoxy copolymer. A composition comprising is disclosed.

[0004] By the way, as described above, PPS resins have been developed mainly for injection molding. However, PPS resins consist of PPS resins, polyamide resins and / or saturated polyester resins, and functional group-containing thermoplastic resins. Investigation was started to develop the composition into a blow molding method. Then, although not apparent in a molding method in which a mold is pressed at a high pressure like injection molding, such a composition is applied to a molding method in which a surface is not subjected to high pressure, such as a hollow molding method such as blow molding or tube molding. When applied, irregularities are likely to be generated on the surface, and sufficient surface smoothness cannot be obtained, or
Problems such as a narrow range of extrusion molding conditions and limitations on the extrusion molding model have been found, and it has been found that this method cannot be simply applied.
It was also found that the surface irregularities had an adverse effect on the strength of the molded product.

[0005]

SUMMARY OF THE INVENTION The present invention relates to the above-mentioned PP.
A study was made to improve the surface smoothness and the strength of a composition comprising an S resin, a polyamide resin and / or a saturated polyester resin, and a functional group-containing thermoplastic resin, particularly when the composition is applied to an extrusion molding method. result,
Has been achieved. That is, the present invention relates to a resin composition which is excellent in heat resistance, hot water resistance, chemical resistance, toughness, surface smoothness and the like.

[0006]

That is, the present invention relates to (A) 100 parts by weight of polyphenylene sulfide resin, (B)
Polyamide resin and / or saturated polyester resin 5
200 parts by weight, and (C) an epoxy group, an acid anhydride group,
A polyphenylene sulfide resin composition containing 1 to 200 parts by weight of a thermoplastic resin containing at least one functional group selected from a carboxyl group, a salt thereof, and a carboxylic acid ester, wherein the composition is a melt indexer (315 (5 ° C, residence time 5 minutes, load 5 kg, orifice diameter 0.0825 inch, length 0.315 inch)
To obtain a gut, and when the gut is projected by a projector, the height observed on the gut surface is 25 μm.
The present invention provides a polyphenylene sulfide resin composition in which the number of protrusions is one or less per cm.

Further, the present invention provides the above polyphenylene sulfide resin composition, wherein (B) the polyamide resin and / or the saturated polyester resin is a polyamide resin comprising a structural unit having a carbon number per amide group in the range of 8 to 15. Things.

Further, (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester,
(C1) The present invention provides the above polyphenylene sulfide resin composition which is an olefin copolymer containing an epoxy group. .

Further, (C1) the above polyphenylene sulfide resin composition, wherein the olefin-based copolymer containing an epoxy group is an olefin-based copolymer containing an glycidyl ester of an α-olefin and an α, β-unsaturated acid as essential components. Things to offer.

[0010] Further, as the functional group-containing thermoplastic resin (C), at least two kinds of functional groups of (C1) an olefin copolymer containing an epoxy group and (C2) an olefin copolymer containing an acid anhydride group. A polyphenylene sulfide resin composition containing an olefin-based copolymer as an essential component, wherein the weight percentage of (C1) and (C2) is (C
1): The present invention provides the above polyphenylene sulfide resin composition wherein (C2) = 1 to 99:99 to 1 (total 100% by weight).

Further, (D) a polyphenylene sulfide resin composition containing an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group, wherein (A) 100 parts by weight of the polyphenylene sulfide resin (D) 1 to 200 parts by weight of an elastomer containing no epoxy group, acid anhydride group, carboxyl group and salt thereof, and no carboxylic acid ester group,
And the total of (C) a functional group-containing thermoplastic resin and (D) an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group are (A)
2 parts per 100 parts by weight of polyphenylene sulfide resin
The polyphenylene sulfide resin composition is provided in an amount of not more than 00 parts by weight.

Further, (E) an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group is mixed with (A) a polyphenylene sulfide resin in an amount of 100% by weight. The present invention provides the above polyphenylene sulfide resin composition in which 0.05 to 5 parts by weight is added to parts.

Further, (A) a polyphenylene sulfide resin and (C) at least one selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylate esters.
After melt-kneading a part or the whole of the thermoplastic resin containing various kinds of functional groups, the obtained composition is mixed with (B) a polyamide resin and / or a saturated polyester resin, or (B) and the rest of (C). To provide a method for producing a polyphenylene sulfide resin composition obtained by melt-kneading a resin.

Further, part of (A) a polyphenylene sulfide resin and (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and salts thereof, and a carboxylic acid ester. And (B) a polyamide resin and / or a composition obtained by melt-kneading
Alternatively, there is provided a method for producing a polyphenylene sulfide resin composition obtained by separately preparing a composition obtained by melt-kneading a saturated polyester resin and the remainder of the above (C), and then melt-kneading both compositions again. Is what you do.

Further, (A) a polyphenylene sulfide resin; and (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester; D) After melt-kneading a part or all of an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group, the obtained composition is mixed with (B) a polyamide resin and / or a saturated polyester. An object of the present invention is to provide a method for producing a polyphenylene sulfide resin composition obtained by melt-kneading a resin, or (B) and (C) and the remainder of (D).

Further, a resin composition for hollow molding comprising the above polyphenylene sulfide resin composition and a resin composition obtained by the method for producing the above polyphenylene sulfide resin composition, and a hollow molded article produced using the above polyphenylene sulfide resin composition Is provided.

Furthermore, a resin composition for a multilayer hollow molded article comprising the above-mentioned polyphenylene sulfide resin composition and a resin composition obtained by the method for producing the above-mentioned polyphenylene sulfide resin composition, and a coextrusion molding method using the above-mentioned polyphenylene sulfide resin composition. It is intended to provide a manufactured multilayer hollow molded article.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene sulfide resin used in the present invention refers to a repeating unit represented by the following structural formula.

Embedded image It is a polymer containing 70 mol% or more, more preferably 90 mol% or more. When the repeating unit is less than 70 mol%, heat resistance is unfavorably deteriorated. Also PPS
Less than 30 mol% of the repeating unit of the resin can be composed of a repeating unit having the following structural formula.

[0019]

Embedded image The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible, but is usually 50 to 20,000.
00 poise (320 ° C, shear rate 1,000 sec-1)
Is used, and the range of 100 to 5000 poise is more preferable.

Such a PPS resin can be prepared by a generally known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution, or the like. Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional group-containing disulfide compound.

As a specific method for crosslinking / polymerizing the PPS resin by heating, a specific method is as follows: under an oxidizing gas atmosphere such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 ° C is selected, preferably 200-27 ° C.
The temperature is 0 ° C., and the time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of them, a target viscosity level can be obtained. The heating device may be an ordinary hot air dryer or a heating device with a rotary or stirring blade, but for efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C., heating time is 0.5 to 100 hours, preferably 2 hours
A method of performing heat treatment for up to 50 hours can be exemplified. The heating device may be an ordinary hot air dryer or a rotary or heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary or stirring blade is used. Is more preferred.

The PPS resin used in the present invention is preferably a deionized PPS resin. Specific examples of such a deionization treatment include an acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more kinds of methods.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethylsulfoxide, dimethyl Sulfoxide and sulfone solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen-based solvents such as trichloroethylene, dichlorinated ethylene, dichloroethane, tetrachloroethane, and chlorobenzene; alcohol-phenol-based solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. These organic solvents are used alone or in combination of two or more.
As a method of washing with an organic solvent, PP in an organic solvent is used.
There are methods such as immersing the S resin, and if necessary, stirring or heating can be performed. P in organic solvent
There is no particular limitation on the washing temperature for washing the PS resin, and any temperature from room temperature to about 300 ° C. can be selected.
Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C. Further, the PPS resin subjected to the organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method when the PPS resin is treated with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable effect of chemical modification of the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of PPS resin to water is preferably as high as possible, but a bath ratio of 200 g or less of PPS resin to 1 liter of water is usually selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like. If necessary, stirring or heating can be performed. The acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and may be an aliphatic saturated monocarboxylic acid such as formic acid, acetic acid, propionic acid or butyric acid, or a halo-substituted aliphatic saturated acid such as chloroacetic acid or dichloroacetic acid. Carboxylic acid, acrylic acid, aliphatic unsaturated monocarboxylic acid such as crotonic acid, benzoic acid, aromatic carboxylic acid such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acid such as fumaric acid, sulfuric acid, Examples include inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Among them, acetic acid and hydrochloric acid are more preferably used. The PPS resin subjected to the acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

Next, of the polyamide resin (B) and / or the saturated polyester resin used in the present invention, the polyamide resin is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid;
lactams such as ε-aminocaprolactam and ω-laurolactam, tetramethylenediamine, hexamerenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnona Methylenediamine, metaxylenediamine, paraxylylenediamine, 1,3
-Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,
Bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine,
Aliphatic, alicyclic and aromatic diamines such as 2-methylpentamethylenediamine, and adipic acid, spearic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, Aliphatic, alicyclic, such as -methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid;
An aromatic dicarboxylic acid is mentioned, and in the present invention,
The polyamide homopolymer or copolymer derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, useful polyamide resins include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamethylene sebacamide. (Nylon 610), polyhexamethylene dodecamide (nylon 612), polydodecaneamide (nylon 12), polyundecaneamide (nylon 1
1), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6)
And mixtures or copolymers thereof.

In particular, the number of carbon atoms per amide group is from 8 to
A polyamide resin having a structural unit in the range of 15 is preferable from the viewpoint of obtaining more excellent toughness, and a polyamide resin containing an aminocarboxylic acid or a derivative thereof as a monomer is particularly preferable. Examples of such polyamides include polydodecaneamide (nylon 12) and polyundecaneamide (nylon 11).

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution (1 g of polymer, 100 ml of concentrated sulfuric acid) is 1.5 to 1.5%.
7.0, especially 2.0-6.5, and more preferably 2.5-
The relative viscosity measured at 25 ° C. in metacresol (polymer concentration 0.5% by weight) at 25 ° C. is 1.0 to 7.0, particularly 1.5 to 5 .
A polyamide resin in the range of 0 can be exemplified. Examples of the preferred saturated polyester resin used in the present invention,
Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, and the like, among which polybutylene terephthalate or polyethylene terephthalate having appropriate mechanical strength are preferably used .

The degree of polymerization of the saturated thermoplastic polyester resin is not particularly limited. For example, in the case of polybutylene terephthalate (hereinafter abbreviated as PBT resin) and copolyester, which are preferably used, the degree of polymerization is preferably 0. The relative viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.5 to 2.5, in particular 0.8.
Those having a range of from 2.0 to 2.0 are preferable. In the case of polyethylene terephthalate, the intrinsic viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is 0.54 to 1.5.
, Particularly preferably in the range of 0.6 to 1.2.

The amount of the (B) polyamide resin and / or saturated polyester resin to be blended is 5 to 200 parts by weight of the (B) polyamide resin and / or saturated polyester resin per 100 parts by weight of the (A) polyphenylene sulfide resin. In order to obtain better chemical resistance and hot water resistance, the compounding amount of (B) the polyamide resin and / or the saturated polyester resin is 5 to 60 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin composition (A). The range is particularly preferred, and the range of 10 to 55 parts by weight is particularly preferred.

In the present invention, blending of (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester is excellent in toughness. , In order to obtain extrudability. Examples of the thermoplastic resin containing such a functional group include an olefin polymer and a fluorine polymer containing at least one selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. it can.

Examples of the epoxy group-containing polyolefin polymer include an olefin copolymer having a glycidyl ester, glycidyl ether, glycidyl diamine, or the like in a side chain, and a double bond portion of an olefin copolymer having a double bond. Olefin-based copolymers obtained by copolymerizing a monomer having an epoxy group are preferred. Particularly, glycidyl esters of α-olefins and α, β-unsaturated acids are main components. Is preferably used.

Specific examples of such α-olefin include:
Examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene-1, and octene-1, and among them, ethylene is preferably used. Also, two or more of these can be used simultaneously.

On the other hand, glycidyl esters of α, β-unsaturated acids are represented by the general formula

Embedded image (Where R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is preferably used. .

The olefin copolymer containing the α-olefin and the glycidyl ester of an α, β-unsaturated acid as a main component can be obtained by randomizing the above-mentioned α-olefin and the glycidyl ester of an α, β-unsaturated acid. Any of block and graft copolymers may be used.

The copolymerization amount of the glycidyl ester of an α, β-unsaturated acid in an olefin-based copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated acid as a main constituent component may have a desired effect. From the viewpoint of the effect on the polymer, gelation, heat resistance, flowability, and strength
0.5 to 40% by weight, especially 3 to 30% by weight is preferred.
In the present invention, as the epoxy group-containing olefin copolymer, in addition to the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2), a monomer (3) represented by the following general formula is further used. An epoxy group-containing olefin copolymer as an essential component is also suitably used.

[0039]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Represents a group selected from a —COOR ² group, a —CN group or an aromatic group, and R ² represents an alkyl group having 1 to 10 carbon atoms. The details of the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2) used in such an olefin copolymer are the same as (B) the olefin copolymer.

On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, Α, β-unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate, acrylonitrile, styrene, Examples thereof include α-methylstyrene, styrene in which an aromatic ring is substituted with an alkyl group, and acrylonitrile-styrene copolymer, and two or more of these can be used simultaneously.

The olefin copolymer is a random or / and block or / and graft copolymer of α-olefin (1), glycidyl ester of α, β-unsaturated acid (2) and monomer (3). Or any copolymerization mode, for example, α-olefin (1) and α,
Even if the copolymer is a combination of two or more copolymerization modes, such as a monomer (3) graft-copolymerized with a random copolymer of glycidyl ester of β-unsaturated acid (2). good.

The copolymerization ratio of the olefin-based copolymer depends on the α-olefin (1) / α-olefin (1) / α-olefin copolymer in view of the effects on the intended effects, the effects on polymerizability, gelation, heat resistance, fluidity, and strength. Glycidyl esters of α, β-unsaturated acids (2)
= 60-99% by weight / 40-1% by weight is preferably selected. The copolymerization ratio of the monomer (3) is based on the total amount of the α-olefin (1) and the glycidyl ester of the α, β-unsaturated acid (2) being 95 to 40% by weight, and A range of 5 to 60% by weight is preferably selected.

Examples of the polyolefin polymer containing a carboxyl group and a salt thereof, a carboxylic acid ester group and an acid anhydride group preferably used in the present invention include polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer and ethylene-propylene copolymer. -Butene copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, and styrene-ethylene / butylene-styrene block copolymer (S
EBS), polystyrene resins such as styrene-ethylene-propylene-styrene block copolymer (SEPS), and maleic anhydride, succinic anhydride, fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate and its N
a, salts of Zn, K, Ca, Mg, etc., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, etc. were copolymerized. Olefin-based copolymers and the like, more specifically, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-isopropyl acrylate copolymer Polymer, ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer Coalescence, ethylene-n-propyl methacrylate copolymer, ethylene-meth Isopropyl copolymer acrylic acid, ethylene - methacrylic acid n- butyl copolymer, ethylene -
Olefin- (meth) acrylate copolymers such as t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, (Meth) acrylate-acrylonitrile copolymers such as propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer Coal, ethylene- (meth) acrylic acid copolymer and its metal salts such as Na, Zn, K, Ca, Mg, ethylene-maleic anhydride copolymer, ethylene-
Butene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, or maleic anhydride-modified SB
Examples thereof include S, SIS, SEBS, SEPS, and ethylene-ethyl acrylate copolymer.

The mode of copolymerization of the olefin-based copolymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer, and a block copolymer may be used.

The amount of the olefin copolymer (C) containing at least one functional group selected from the group consisting of an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is as follows. From the viewpoint of smoothness, extrusion moldability, etc., 1 to 100 parts by weight of the (A) PPS resin
A range of 200 parts by weight is selected, preferably 1-100
Parts by weight, more preferably in the range of 3 to 60 parts by weight, are selected.

The above (C) epoxy group, acid anhydride group,
Two or more olefin copolymers containing at least one functional group selected from a carboxyl group, a salt thereof, and a carboxylic acid ester group may be used in combination. Especially,
The combined use of an olefin copolymer containing an epoxy group and an olefin copolymer containing an acid anhydride group,
It is particularly preferable in that excellent toughness is obtained.

Further, (D) the use of an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group does not improve the toughness, especially the low-temperature toughness and the extrusion moldability. It is valid.

(D) epoxy group, acid anhydride group,
Examples of the elastomer not containing a carboxyl group and a salt thereof, and a carboxylic acid ester group include, for example, polyolefin-based elastomer, diene-based elastomer, silicone rubber,
Examples thereof include fluorine rubber, urethane rubber, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, and polyamide thermoplastic elastomer. Specific examples of the polyolefin-based elastomer include an ethylene-propylene copolymer, an ethylene-butene copolymer, a polybutene, and an ethylene-propylene-diene copolymer. Specific examples of diene elastomers include:
Styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene,
Butene-isoprene copolymer, and SBS, SIS,
SEBS, SEPS, and the like.

Among them, ethylene-propylene copolymer, ethylene-butene copolymer and ethylene-propylene-diene copolymer are particularly preferred.

The elastomer (D) containing no epoxy group, acid anhydride group or carboxyl group may be used in combination of two or more.

(D) When an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is used, the preferred amount thereof is determined in view of toughness, extrusion molding and surface smoothness. , (A) The range of 1 to 200 parts by weight is selected with respect to 100 parts by weight of the PPS resin, 5 to 100 parts by weight is more preferable, and 10 to 80 parts by weight is more preferable. However, from the viewpoint of the balance between the heat resistance, chemical resistance and toughness of the PPS resin, (B) an olefin copolymer containing a functional group and (C) an epoxy group,
The sum of the elastomers containing no acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid ester groups is (A) PP
It is preferably at most 200 parts by weight, more preferably at most 120 parts by weight, based on 100 parts by weight of the S resin.

The addition of (E) an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureide group can improve mechanical strength and toughness. It is effective for

Specific examples of such compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ
Ureido group-containing alkoxysilane compounds such as-(2-ureidoethyl) aminopropyltrimethoxysilane;
γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanato Isocyanato group-containing alkoxysilane compounds such as propylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Amino group-containing alkoxysilane compounds such as γ-aminopropyltrimethoxysilane, hydroxyl group-containing alkoxy such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane And the like. Among them, an epoxy group-containing alkoxy such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane A silane compound, γ-ureidopropyltriethoxysilane,
γ-ureidopropyltrimethoxysilane, γ- (2
-Ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-
Amino group-containing alkoxysilane compounds such as (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ- Isocyanato group-containing alkoxysilane compounds such as isocyanatopropyltrichlorosilane are particularly preferred.

The preferred addition amount of the (E) alkoxysilane compound is selected from the range of 0.05 to 5 parts by weight, based on 100 parts by weight of the (A) PPS resin, and is preferably 0.1 to 3 parts by weight.
A range of parts by weight is more preferably selected.

Further, the thermoplastic resin composition of the present invention comprises
Depending on the purpose and application, within the scope not impairing the scope of the present invention,
Fibrous and / or non-fibrous fillers may be included. Specific examples of such a fibrous and / or non-fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, and ceramic. Fibrous fillers such as fiber, asbestos fiber, masonry fiber, metal fiber, walasteinite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc,
Metal compounds such as silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; Magnesium hydroxide,
Non-fibrous fillers such as calcium hydroxide, hydroxides such as aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, carbon black, metal powders and silica, even if they are hollow It is also possible to use two or more of these fillers in combination. In addition, these fibrous and / or non-fibrous fillers are used as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds,
Pretreatment with a coupling agent such as an epoxy compound before use is preferred from the viewpoint of obtaining more excellent mechanical strength.

Further, the thermoplastic resin composition of the present invention includes:
Plasticizers such as polyalkylene oxide oligomeric compounds, thioether compounds, ester compounds, and organic phosphorus compounds; crystal nucleating agents such as talc, kaolin, organic phosphorus compounds, and polyetheretherketone; and coloring prevention such as hypophosphite Conventional additives such as agents, antioxidants, heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants, and foaming agents can be added.

Further, the thermoplastic resin of the present invention may be a polysulfone resin, a polytetrafluoroethylene resin, a polyetherimide resin, a polyamideimide resin, a polyimide resin, a polyethersulfone resin, a polyethersulfone resin as long as the effects of the present invention are not impaired. Other resins such as ketone resin, polythioether ketone resin, polyether ether ketone resin, thermoplastic polyurethane resin, ABS resin, polyamide elastomer, polyester elastomer, epoxy resin, and phenol resin may be added and blended.

The main object of the present invention is to provide P having excellent surface smoothness.
It is to obtain a composition comprising a PS resin, a polyamide resin and / or a saturated polyester resin, and a functional group-containing thermoplastic resin. Specifically, the gut obtained by throwing into a melt indexer (315.5 ° C., residence time 5 minutes, load 5 kg, orifice diameter 0.0825 inch, length 0.315 inch) was projected by a projector. In this case, the polyphenylene sulfide resin composition is such that the number of protrusions having a height of 25 μm or more observed on the gut surface is 1 or less per cm.

We first melt-kneaded a mixture consisting of a PPS resin, a polyamide resin and a functional group-containing thermoplastic resin using a single-screw extruder (screw: dalmage). Observation of the melt indexer gut of such a composition revealed many protrusions. Next, when the protruding portion was observed with a transmission electron microscope, it was found that the polyamide resin and the functional group-containing thermoplastic resin were abnormally reacted to form a gel, which was the cause of a decrease in surface properties.

The method for preparing the resin composition of the present invention is not particularly limited as long as the above-mentioned excellent surface properties can be obtained. For example, a mixture of the raw materials may be mixed with a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. As a typical example, a method of kneading the mixture at a temperature of 280 to 340 ° C. by supplying it to a generally known melt mixer can be mentioned.

However, as a method for suppressing the abnormal reaction and improving the surface smoothness, a method selected from (A) a polyphenylene sulfide resin and (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. After melt kneading all or a part of the thermoplastic resin containing at least one functional group, (B) a polyamide resin and / or a saturated polyester resin, and (C) an epoxy group, an acid anhydride group, a carboxyl group and A method of melt-kneading the remainder of the thermoplastic resin containing at least one functional group selected from salts and carboxylic acid esters, or (A) a polyphenylene sulfide resin and (C) an epoxy group, an acid anhydride group, A part of a thermoplastic resin containing at least one functional group selected from a group, a salt thereof, and a carboxylic acid ester. A composition obtained by kneading, (B)
The polyamide resin and / or the saturated polyester resin and (C) the remainder of the thermoplastic resin containing at least one functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid esters are melt-kneaded. It is very effective to separately knead the resulting compositions and then melt-knead the two compositions again.

Further, (A) a polyphenylene sulfide resin, (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester; D) After melt-kneading a part or all of an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group, the obtained composition is mixed with (B) a polyamide resin and / or a saturated polyester. A method of melt-kneading the resin, or (B) and the remainder of (C) and (D) is also effective.

When such multi-stage kneading is carried out, (A) a polyphenylene sulfide resin, (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a heat containing at least one functional group selected from carboxylic acid esters. For the compounds other than the plastic resin, the (B) polyamide resin and / or the saturated polyester resin, the kneading order is not particularly limited.

The multi-stage kneading method also includes a method in which the first-stage compound is supplied from a main hopper and the second-stage compound is supplied from a side feeder.

Further, when a small amount of an additive component is used,
After kneading other components by the above method and pelletizing,
Of course, it is also possible to add it before the forming process and to provide it for forming.

The composition of the present invention is particularly suitable for producing hollow molded articles such as tube molded articles and blow molded articles.
When applied to the production of a multilayer hollow molded article by co-extrusion with another resin, particularly a polyamide resin or a saturated polyester resin, not only is it possible to obtain excellent surface smoothness, but it is also effective for improving interlayer adhesion.

The hollow molded article of the present invention thus obtained is excellent in heat resistance, hot water resistance, chemical resistance, toughness and appearance of a molded article. From such characteristics, blow molded articles such as bottles, tanks and ducts can be used. As an extruded product such as pipes, tubes, and fuel tubes, it is effective for automotive parts, especially for internal combustion engines, electric / electronic parts, and chemicals.
Not only the hollow molding method but also other molding methods such as a round bar, other extrusion molding methods, injection molding methods, transfer molding methods, etc., can be applied to electric and electronic parts such as connectors and coils. Especially suitable for the application,
Sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards,
Transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, F
Other electronic components such as DD carriage, FDD chassis, motor brush holder, parabolic antenna, computer-related components, etc .; generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power supplies Contacts, switches, circuit breakers, knife switches,
Applications of electrical equipment parts such as other pole rods, electrical parts cabinets, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting Home and office electrical product parts represented by parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, Motor parts, lighters,
Machine-related parts such as typewriters: optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery-related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, exhaust Various valves such as gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature Sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner , Heating and hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, Automobiles / vehicles such as fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. It can be applied to various uses such as related parts.

[0068]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The surface smoothness in the following examples,
The notched impact strength and tube toughness were measured by the following methods.

[Surface Smoothness] A pellet was melted with a melt indexer (Type C-5059D2-, manufactured by Toyo Seiki Co., Ltd.).
1. Orifice diameter 0.0825 inch, length 0.31
5 inches), stayed at 315.5 ° C. for 5 minutes, and extruded gut with a load of 5 kg. Perform this operation 10 times and 1
0 guts were obtained. Such a gut is connected to a projector (Nikon Corporation, profile projector, V-1).
The projection was performed in 2), and the number of protrusions having a height of 25 μm or more on the gut surface was observed. Observation, 10 gut each 5cm,
The measurement was performed for a total of 50 cm, and the number was counted as the number of protrusions observed per cm.

[Notched Impact Strength] The pellets were subjected to injection molding under the conditions of a resin temperature of 320 ° C. and a mold temperature of 150 ° C. to form a measurement sample. Using this sample, A
Notch Izod impact strength was measured according to the STMD256 method.

[Evaluation of low-temperature toughness of tube] Ten tubes each having a length of 30 cm were prepared, and were left in a cooling device at -40 ° C for 4 hours. Remove the tube from the cooling device,
A 0.454 kg weight was dropped onto the tube from a height of 304.8 mm, and the presence or absence of breakage of the tube was observed.

Reference Example 1 (Polymerization of PPS resin) Sodium sulfide nonahydrate 6.005 in an autoclave equipped with a stirrer.
kg (25 mol), sodium acetate 0.205 kg
(2.5 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and N
3.7 kg of MP was added, the mixture was sealed under nitrogen, heated to 270 ° C., and reacted at 270 ° C. for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain 2.45 kg of PPS-1.

The polymerization was carried out in the same manner as described above, and the reaction product was washed five times with warm water.
After stirring for about 1 hour, the mixture was filtered and washed with hot water several times. This was poured into 25 liters of an aqueous acetic acid solution of pH 4 heated to 90 ° C.
After stirring was continued for an hour, the mixture was filtered, washed with ion-exchanged water at about 90 ° C. until the pH of the filtrate reached 7, and then dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-2. The number average molecular weight of this PPS was 9,200, and the total ash content was 0.07% by weight.

[Blending Materials Used in Examples and Comparative Examples] (B) Polyamide resin B-1: Nylon 11 (“Rilsan” BES manufactured by Toray Industries, Inc.)
NOTL) B-2: Nylon 12 (“Rilsan” AES by Toray Industries, Inc.)
NOTL) B-3: Nylon 6 (Amilan CM10 of Toray Industries, Inc.)
46X04) B-4: Polybutylene terephthalate (Toray Industries, Inc. PB
T 1400S)

(C) Thermoplastic resin having a functional group C-1: an olefin copolymer containing glycidyl ester of α-olefin and α, β-unsaturated acid as a main component ethylene / glycidyl methacrylate = 88/12 (wt%) copolymer C-2: ethylene / glycidyl methacrylate (E / G
MA) having a main skeleton of 85/15 (% by weight) and graft copolymerization of acrylonitrile / styrene (AS) = 30/70 (% by weight), wherein (E / GMA) /
(AS) = 70/30 (wt%) copolymer C-3: maleic anhydride (0.5 wt%) modified ethylene propylene rubber

(D) Elastomer containing no epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylate group D-1: ethylene / butene-1 = 82/18 (% by weight)
Copolymer D-2: ethylene / propylene copolymer (E) alkoxysilane compound E-1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

Examples 1 to 8 and 10 The first-stage compounding materials shown in Table 1 were dry-blended at the ratios shown in Table 1 and preliminarily mixed in a tumbler for 2 minutes, and then the cylinder temperature was set at 300 to 320 ° C. The mixture was melted and kneaded by a single screw extruder (screw: Dalmage), pelletized by a strand cutter, and dried at 120 ° C. overnight. Next, after pre-mixing the pellets and the second-stage composition with a tumbler for 2 minutes, the cylinder temperature was set to 300 to 32.
Single-screw extruder set at 0 ° C (screw: Dalmage)
, And pelletized by a strand cutter, and dried at 120 ° C. overnight. Using such pellets,
A molded body for measuring impact strength was molded, and the surface smoothness was measured. Table 1 shows the results.

Comparative Examples 1 to 3 The same type and the same amount of the compounding materials as in Examples 1, 2 and 6 were dry-blended in a lump and preliminarily mixed in a tumbler for 2 minutes. The mixture was melt-kneaded with an extruder (screw: Dalmage), pelletized by a strand cutter, and dried at 120 ° C. overnight. Using the pellets, a molded article for measuring impact strength was molded, and the surface smoothness was measured. Table 2 shows the results.

As can be seen from a comparison between Comparative Examples 1 to 3 and Examples 1, 2, and 6, remarkable improvements in surface smoothness and impact strength are recognized by performing the two-stage kneading.

Comparative Example 4 The pellets obtained in Comparative Example 1 were again subjected to cylinder temperature 3
The mixture was melted and kneaded with a single screw extruder (screw: Dalmage) set at 00 to 320 ° C, pelletized by a strand cutter, and dried at 120 ° C overnight. Using the pellets, a molded article for measuring impact strength was molded, and the surface smoothness was measured. Table 2 shows the results.

As can be seen from the results of Comparative Example 4, even if the batch compound was melt-kneaded twice, the surface smoothness and the impact strength as shown in Example 1 were not remarkably improved. It turns out that the order is important.

Example 9 The first-stage and second-stage blended materials of Example 9 shown in Table 1 are shown in Table 1.
After dry-blending at the ratios shown in Table 1 and pre-mixing each with a tumbler for 2 minutes, each was melt-kneaded with a single screw extruder (screw: dalmage) set at a cylinder temperature of 300 to 320 ° C, and pelletized with a strand cutter, respectively. And dried at 120 ° C. overnight.
Next, after preliminarily mixing the obtained two kinds of pellets with a tumbler for 2 minutes, the mixture is melt-kneaded again with a single screw extruder (screw: dalmage) set at a cylinder temperature of 300 to 320 ° C., and pelletized with a strand cutter. 80
Vacuum dried at 0 ° C. overnight. Using the pellets, a molded article for measuring impact strength was molded, and the surface smoothness was measured.

As can be seen from the comparison between Examples 8 and 9, the three-stage kneading is effective in obtaining more excellent impact strength.

Comparative Example 5 The blended materials of Comparative Example 5 shown in Table 2 were dry-blended at the ratios shown in Table 2 and preliminarily mixed in a tumbler for 2 minutes.
The mixture was melt-kneaded with a single screw extruder (screw: Dalmage) set at a cylinder temperature of 300 to 320 ° C, pelletized by a strand cutter, and dried at 120 ° C overnight. Using the pellets, a molded article for measuring impact strength was molded, and the surface smoothness was measured.

(C) When the functional group-containing thermoplastic resin is not blended, although protrusions are not observed, gut breaks frequently occur during extrusion kneading, extrusion kneading is difficult, and a waving phenomenon is observed on the gut surface. No satisfactory gut was obtained. Also, the impact strength was low.

Evaluation of Tube Forming Next, nylon 11 (“Rilsan” B, manufactured by Toray Industries, Inc.) was used for the outer layer.
ESN BKP 20) Using pellets, using the pellets obtained in Example 2 or Comparative Example 2 in the inner layer, outer diameter: 8
mm, inner diameter: 6 mm, outer layer thickness: 0.8 mm, and inner layer thickness: 0.2 mm were formed into a two-layer tube. As the molding device, two single-screw extruders of 65 mm, a die for collecting the resin discharged from the two extruders by an adapter to form a tube, a sizing die for cooling and controlling the size of the tube, and a take-off Using a machine consisting of
A tube was formed at a take-up speed of 50 cm / min, and samples for evaluating the inner surface smoothness and the low-temperature toughness of the tube were collected.

When the pellets of Comparative Example 2 were used, protrusions were observed on the inner surface, resulting in poor smoothness. In the evaluation of the low-temperature toughness of the tube, cracks were observed in 5 out of 10 tubes. On the other hand, when the pellets of Example 2 were used, the smoothness of the inner surface was good.
No crack was observed in any one of the 0 pieces.

[0089]

[Table 1]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08L 81/02 77:00 33:06) (C08L 81/02 67:02 33:06)

Claims (23)

[Claims] 1. A polyphenylene sulfide resin (A)
(B) 5 to 200 parts by weight of a polyamide resin and / or a saturated polyester resin, and (C) at least one kind selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester based on 0 part by weight. A polyphenylene sulfide resin composition containing 1 to 200 parts by weight of a thermoplastic resin containing a functional group, wherein the composition is melt-indexed (315.5 ° C., residence time 5
Min, load 5 kg, orifice diameter 0.0825 inch,
(Length 0.315 inch) to obtain a gut, and when the gut is projected by a projector, a projection having a height of 25 μm or more observed on the gut surface has a gut of 1 cm.
1 or less per polyphenylene sulfide resin composition. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the compounding amount of (B) the polyamide resin and / or the saturated polyester resin is 5 to 60 parts by weight based on 100 parts by weight of (A) the polyphenylene sulfide resin composition. Stuff. (B) a polyamide resin and / or a saturated polyester resin having a carbon number of 8 to 10 per amide group;
3. The polyphenylene sulfide resin composition according to claim 1, which is a polyamide resin having a structural unit having a range of 15. 4. The polyphenylene sulfide resin composition according to claim 3, wherein the polyamide resin (B) is polydodecaneamide (nylon 12) or polyundecaneamide (nylon 11). 5. A thermoplastic resin containing at least one functional group selected from the group consisting of an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester.
1) The polyphenylene sulfide resin composition according to claim 1, which is an olefin copolymer containing an epoxy group. 6. The olefin copolymer having an epoxy group-containing (C1) olefin copolymer containing glycidyl ester of an α-olefin and an α, β-unsaturated acid as essential components. Polyphenylene sulfide resin composition. 7. An epoxy group-containing olefin copolymer (C1) comprising an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer represented by the following general formula: The polyphenylene sulfide resin composition according to claim 5, which is an olefin-based copolymer containing the compound (3) as an essential component. Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Represents a group selected from a —COOR ² group, a —CN group or an aromatic group, and R ² represents an alkyl group having 1 to 10 carbon atoms. ) 8. A thermoplastic resin having a functional group (C) comprising (C)
1) An olefin copolymer containing an epoxy group and (C)
2) A polyphenylene sulfide resin composition containing, as an essential component, at least two functional group-containing olefin copolymers of an olefin copolymer containing an acid anhydride group, wherein (C1) and (C2) % By weight (C1):
The polyphenylene sulfide resin composition according to any one of claims 1 to 7, wherein (C2) is 1 to 99:99 to 1 (total 100% by weight). 9. A polyphenylene sulfide resin composition containing (D) an elastomer containing no epoxy group, acid anhydride group, carboxyl group and its salt, and no carboxylic acid ester group, wherein (A) the polyphenylene sulfide resin 100 (D) 1 to 200 parts by weight of an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group, based on parts by weight,
And the total of (C) the functional group-containing thermoplastic resin and (D) the elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group are (A)
2 parts per 100 parts by weight of polyphenylene sulfide resin
The polyphenylene sulfide resin composition according to any one of claims 1 to 8, which is not more than 00 parts by weight. 10. A polyphenylene sulfide resin comprising: (E) an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group; The polyphenylene sulfide resin composition according to any one of claims 1 to 9, which is obtained by adding 0.05 to 5 parts by weight to 100 parts by weight. 11. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin (A) has been deionized. 12. A part of a thermoplastic resin containing (A) a polyphenylene sulfide resin and (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. Or, after melt kneading all, the obtained composition and (B) a polyamide resin and / or a saturated polyester resin, or a polyphenylene sulfide resin composition obtained by melt kneading the remainder of (B) and (C) Manufacturing method. 13. A part of (A) a polyphenylene sulfide resin and (C) a thermoplastic resin containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. And a composition obtained by melt-kneading (B) a polyamide resin and / or a saturated polyester resin and the remainder of (C) are separately prepared. A method for producing a polyphenylene sulfide resin composition obtained by melt-kneading again. 14. A thermoplastic resin containing (A) a polyphenylene sulfide resin and (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. D) After melt-kneading a part or all of an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group, the obtained composition is mixed with (B) a polyamide resin and / or a saturated polyester. With resin or
A method for producing a polyphenylene sulfide resin composition obtained by melt-kneading (B), (C) and the remainder of (D). 15. The resin composition according to any one of claims 1 to 11, which is obtained by the production method according to any one of claims 12 to 14. 16. The polyphenylene sulfide resin composition for hollow molding according to any one of claims 1 to 11 and 15. 17. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is a multi-layer hollow molded article. 18. A hollow molded article produced by using the polyphenylene sulfide resin composition according to any one of claims 1 to 11 and 15. 19. A multilayer hollow molded article produced by a coextrusion molding method using the polyphenylene sulfide resin composition according to any one of claims 1 to 11 and 15. 20. A polyphenylene sulfide resin composition for hollow molding obtained by the production method according to claim 12. 21. A polyphenylene sulfide resin composition for multilayer hollow molding obtained by the production method according to claim 12. 22. A hollow molded article produced by using the polyphenylene sulfide resin composition for hollow molding according to claim 20. 23. A multilayer hollow molded article produced by using the polyphenylene sulfide resin composition for multilayer hollow molding according to claim 21.