JPH04132765A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition improved in blending compatibility and impact resistance etc., suitable for various electrical and electronic parts etc., comprising a polyarylene sulfide of specified chlorine content, other thermoplastic resin(s) and an organic silane compound. CONSTITUTION:The objective composition can be obtained by incorporating a total of 100 pts.wt. of (A) 99-5 (pref. 90-10) pts.wt. of a polyarylene sulfide <=4000ppm in chlorine content and (B) 1-95 (pref. 10-90) pts.wt. of other thermoplastic resin(s) ( polyamide, thermoplastic polyester) with (C) 0.05-10 (pref. 0.1-5) pts.wt. of an organic silane compound (e.g. aminoalkoxysilane, epoxyalkoxysilane).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a highly compatible resin composition comprising polyarylene sulfide (PAS) and other thermoplastic resins. This composition is used for injection molded products, extrusion molded products, etc., and is used for various electrical/electronic parts, mechanical parts, precision mechanical parts, automobile parts, sporting goods, miscellaneous goods, etc.

<Prior art> PA represented by polyphenylene sulfide (PPS)
S stands for heat resistance, flame retardancy, high rigidity, chemical resistance, dimensional stability,
As a crystalline enserializing plastic with excellent moldability, it is used in various fields such as electrical parts, precision machinery parts, and automobile parts.

However, since this resin has poor flexibility and is very brittle, it is usually used in a reinforced form with glass fibers, and the fields in which it can be used as a material are limited. It has also been pointed out that there are problems with weather resistance and molded product properties. Furthermore, since PPS and the like have a relatively low glass transition temperature of 80 to 90°C, they have the disadvantage that their elastic modulus rapidly decreases in a temperature range exceeding the glass transition temperature.

To date, many attempts have been made to improve the shortcomings of PAS or to impart the excellent properties of PAS to other resins by blending PAS with other thermoplastic resins. It's here. However, in either case, the compatibility between PAS and the blended resin is insufficient, so the desired effects (especially mechanical properties such as impact resistance) may not be sufficiently achieved, or in some cases, On the contrary, there was a problem that the characteristics deteriorated.

For example, Japanese Patent No. 1005081 discloses a composition of PPS and polyamide, phenochira resin, thermoplastic polyester, polyethylene, etc. for the purpose of flame retardancy, but in this case, the purpose of flame retardation is not achieved. However, due to insufficient compatibility, mechanical properties such as impact resistance do not improve or even deteriorate. Furthermore, in Japanese Patent Publication No. 56-34032, in the case of PPS and polyphenylene oxide,
In U.S. Pat. No. 4,021,596, the case of PPS, polysulfone and polyphenylene oxide is disclosed in JP-A No. 6
3-304046 discloses the cases of PPS and ABS resins. However, in either case, the mechanical properties such as impact resistance and chemical resistance did not fully match the above because of insufficient compatibility. On the other hand, JP-A-59-58052, JP-A-59-155461, JP-A-59
-155462, 59-164360, 59-20
7921 and 59-213758, PPS
A method has been disclosed in which an epoxy resin is added for the purpose of improving the blend compatibility between the thermoplastic resin and various thermoplastic resins, but at present, sufficient effects have not been obtained even with this method.

<Problems to be Solved by the Invention> As described above, in all of the conventional techniques, the blend compatibility between PAS and other thermoplastic resins was insufficient.

The purpose of the present invention is to improve the blend compatibility of other thermoplastic resins blended with PAS, for example, to improve impact resistance, which in the past has not been sufficiently improved or in some cases has been significantly reduced. The object of the present invention is to provide a resin composition that mutually imparts the excellent properties of both resins to be blended, such as improved mechanical properties such as elasticity.

Means for Solving the Problems〉 The present inventors have discovered that PAS contains PA generated during the synthesis process.
Based on the idea that impurities such as oligomer components of S or unreacted components exist, and that these impurities deteriorate the original physical properties of PAS, in particular, the chlorine components present in PAS,
That is, we investigated the chlorine component, which may be included as an impurity such as NaCQ or included in the terminal group of the molecule depending on its synthesis method. As a result of using various PASs that have been sufficiently purified and have less impurities and oligomer snow, the present inventors have found that the chlorine content is 4000pp.
In addition to the presence of an organic silane compound when using a specific PAS with a molecular weight of less than m and blending it with other thermoplastic resins, the effect of adding the silane compound becomes remarkable
The present invention was achieved by discovering that the compatibility between S and other thermoplastic resins is significantly improved.

That is, in the present invention, (A) the chlorine content is 4000 ppm.
The present invention relates to a resin composition comprising the following polyarylene sulfide, (B) another thermoplastic resin, and (C) an organic silane compound.

By the way, Japanese Patent Application Laid-Open No. 63-251430. 55-295
From Publication No. 26, etc., PAS was used for the purpose of thickening PAS and improving the adhesion between PAS and glass fibers and inorganic fillers.
It is known to add organosilane compounds to AS.

It is also known that there is a description that a silane compound may be added when blending PAS and other resins.

However, even when a silane compound is actually added to a friend of resins, unlike the case where a filler like the one mentioned above is present, the effect of the addition such as improving adhesion was not observed.And of course, until now, However, no effect of significantly improving the compatibility was observed. This is probably because the PAS used so far was outside the range specified in the present invention.

It is not clear why the presence of chlorine in PAS hinders the improvement of compatibility and various physical properties, but one reason is that chlorine has low activity against organosilane compounds, so it is probably due to the increase of chlorine at the molecular terminals. It is presumed that because the reactivity decreases, the compatibility decreases and various physical properties are suppressed.

The PAS used in the present invention has the structural formula (-ArS-)n(
A polymer represented by Ar: arylene group) with a chlorine content of 4000 ppm or less. Here, Ar of the arylene group is a divalent aromatic residue such as P-phenylene, m-phenylene, 0-phenylene, 2,6-naphthalene, 4,4'-biphenylene, or two carbon atoms having 6 carbon atoms. It is a divalent aromatic residue containing an aromatic ring, and each aromatic ring further contains F, CQ, and Br.

Substituents such as C1, etc. may be introduced. This may be a homopolymer, a random copolymer, or a block copolymer, and linear, branched, or crosslinked types and mixtures thereof are used.

These PAS must have a chlorine content of 4000 ppm or less.

The chlorine content present in PAS can be measured using known analytical methods, but it is also possible to thermally decompose the PAS polymer in acid or oxygen and measure the generated chlorine ion concentration using ion chromatography or silver titration. The method of determining is preferable.

Chlorine contained in the PAS may be contained as an impurity or oligomer, or as a terminal group of a polymer. A common method for removing impurities containing chloro and oligomers is washing with a solvent that dissolves them. A known washing method can be used, and the solvent may be
Hot water, ether-based FA solvents such as tetrahydrafuran and trioxane, ketone-based organic solvents such as N-methylpyrrolidone, dimethylbormamide, dimethylsulfone, and acetone, aromatic organic solvents such as toluene and xylene,
Ester organic solvents such as ethyl acetate and butyl acetate, 1
, 2-dichloroethane or tetrachloroethane 9: p”l-+
) Chloroethylene natonohalosaponified hydrocarbons, etc. are used. Furthermore, some PASs do not contain chlorine components, such as cyclic oligomers, but it is preferable to remove these as much as possible.

Preferred PAS for use in the present invention are polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPSS), polyphenylene sulfide ketone (
PPSK), a copolymer consisting of a PPS part and a ppss part, and a PPS part and a PPSK part, each of which has a chlorine content of 4000 ppm or less.

It is a polymer containing 70 mol %, particularly preferably 90 mol % or more. The other constituent parts contained in PPS are mainly the above-mentioned arylene group.

PPS can be polymerized using known methods such as polymerization of p-dichlorobenzene in the presence of sulfur and sodium carbonate, polymerization of sodium sulfide or sodium hydrosulfide with sodium hydroxide or There is a method of polymerization in the presence of hydrogen sulfide and sodium hydroxide, and a method of self-condensation of p-chlorothiophenol.
- The most common method is to react sodium sulfide and p-dichlorobenzene in an amide solvent such as methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane.

Considering the method of synthesis, the terminal group of the PPS molecule is -8
It is thought that H, -5Na, -CQ, -H, etc. are present, but in order to reduce the content of terminal chlorine, it is necessary to adjust the synthesis conditions, the monomers used, and the monomer ratio. For example, when sodium sulfide and p-dichlorobenzene are used, sodium sulfide is added after the synthesis is completed to further promote the reaction with the terminal chlorine of the polymer, or p-dichlorobenzene and sulfur There is a method to appropriately adjust the sodium charge ratio.

It is a polymer with repeating units. Examples of the polymerization method for ppss include a method in which a dihaloaromatic sulfone such as 4,4'-dichlorodiphenyl sulfone is reacted with an alkali metal sulfide such as sodium sulfide in an organic amide solvent. A method similar to that for PPS can be used to adjust the content of terminal chlorine.

It is a polymer with repeating units. Examples of the polymerization method for PP5K include a method in which 4,4'-dichlorobenzophenone and an alkali metal sulfide are reacted in an organic amide solvent. As a method to adjust the amount of terminal chloride, PP
A method similar to that for S is possible.

PPS part and PP5S part, and PPS part and PP
In the case of a copolymer consisting of a 5K portion, a block copolymer is preferred from the viewpoint of physical properties.

A typical method for obtaining a block copolymer is to synthesize in advance a poly-177 polymer having a chlorphenyl group as a reactive end group and a polymer having a sodium sulfide group, and then react the two in a solvent. A method similar to that for PPS can be used to adjust the content of terminal chlorine.

PA with the above chlorine content of 40001)I)m or less
The melt viscosity of S is the dynamic viscosity [η
10 to 101 voices, preferably 50 to 5ooo
o poise, but non-quality ones have a dynamic viscosity of 50 to 10' poise at 10 rad/see in a temperature range of glass transition temperature plus 100°C, preferably 100 to 100.
A glass having 5×10” voids is used. The glass transition temperature is the peak value in the temperature dispersion of the loss modulus [E'] at IHz.

As the thermoplastic resin other than PAS used in the present invention, any of the various thermoplastic resins described in known literature regarding PAS can be used, but thermoplastic polyester, polyamide, ABS resin, polysulfone, polyphenylene oxide, Particularly preferred are polyetherketone, polyetherimide, fluororesin, phenolic resin, α-olefin polymer, and styrene polymer. These thermoplastic resins may be used alone, or two or more types may be mixed,
You may also use it as

Thermoplastic polyesters include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, 4. 4
'-diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, α, β-bis (4-carbo-cow diphenoxy)
Dicarboxylic acids such as ethane, adipic acid, cepatic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohedoxanedicarboxylic acid, and dimer acid, or their ester-forming derivatives, and ethylene glyfur, propylene glycol, butanediol, and bentane. Diol, neopentyl glycol, hegyosandiol, octanediol, decanediol, cyclohesandimetatool, hytorquinone, bisphenol A, 2.
It refers to polyesters obtained from glyfurs such as 2-bis(4-hydroxyethoxyphenyl)furopane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends.

In addition, as a comonomer component, hydroxycarboxylic acids such as glyfuric acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, and naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, and caprolactone, or thermoplastic To the extent possible, polyfunctional ester-forming components such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid may be included.

In addition, aromatic compounds such as dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A1 and ethylene oxide adduct of tetrabromobisphenol A Also included are thermoplastic polyester resins which have a halogen compound such as chlorine or bromine as a substituent and are copolymerized with a halogen compound having an ester-forming group.

Particularly preferred thermoplastic polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly(ethylene/butylene terephthalate), poly(cyclohexane dimethylene terephthalate), poly(butylene/tetramethylene terephthalate), 2. Examples include 2-bis(β-hydroxyethoxytetrabromophenyl)propane copolymerized polybutylene terephthalate.

Examples of the polyamide include various well-known polyamides. For example, oxalic acid, adipic acid, speric acid, sebacic acid,
Dicarboxylic acids such as terephthalic acid, isophthalic acid, 1°4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, mexamethylenediamine,
Polyamides obtained by polycondensing diamines such as decamethylene diamine, 1,4-cyclohexyldiamine, and m-xylene diamine; Polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurin lactam; or cyclic Examples include polyamides obtained by copolymerizing lactams, dicarboxylic acids, and diamine salts. Among these polyamides, preferably 6
Nylon, 66 nylon, 46 nylon, MXD6 nylon (copolymer of m-xylene diamine and adipic acid), 6.10 nylon, 66/6.10 nylon, 6/
66t iron, 12 nylon, 11 nylon, 6/6T
Examples include nylon (a copolymer of caprolactam, terephthalic acid, and hexamethylene diamine salts), and two or more types of these polyamides may be used in combination. Particularly preferred are nylon 6, nylon 66, nylon 46, and MXD6 nylon.

Polyphenylene oxide (ppo
) is also referred to as polyphenylene ether (PPE), and can be obtained by polycondensing one or more types of monocyclic phenols represented by the following formula [1].

(However, R1 is a lower alkyl group having 1 to 3 carbon atoms, R2 and R3 are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, and a lower alkyl substituent is always present at the ortho position of at least one of the hydroxyl groups. ) The above PPO may be a homopolymer or a copolymer.

[1] Examples of the monocyclic phenol represented by the formula include 2,6-dimethylphenol, 2゜6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2- Methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-
Cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2
-Methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3- Ethylphenol, 2. 3. 6-trimethylphenol, 2
．． 3. 6-triethylphenol, 2. 3. 6
-tribrobylphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-propylphenol, and the like.

The PPO obtained from this is, for example, poly(2,
6-dimethyl-1,4-)unicine) ether, poly(
2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly( 2-methyl-6-broby-1,
4-) unicine) ether, poly(2-ethyl-6-brobyl-1,4-)unicine) ether, 2,6 dimethylfunol/2. 3. 6-1-dimethylphenol copolymer, 2,6-dimethylphenol/2. 3.
6-) Ethylphenol copolymer, 2.6-dimethylphenol/2. 3. 6-4 trimethylphenol copolymer, 2. 6-C7' Rohilphenol/2.
3. 6-)limethylphenol copolymer, poly(2,6-dimethyl-1゜4-)unicine) ether, 2,6-dimethylphenol/2. 3. 6. Examples include copolymers obtained by graft-polymerizing styrene onto -trimethylphenol copolymers.

In particular, preferred PPO for use in the present invention is poly(2,
6-dimethyl-1,4-phenylene)ether, 2,6
-Simethylphenol/2. It is a 3°6-trimethylphenol copolymer.

Polysulfone (P S F) is defined as a polyarylene compound in which arylene units are located in a disordered or ordered manner with ether and sulfone linkages,
For example, those consisting of the following structural formulas from ■ to @ (in the formula, -φ- represents a p-phenylene group, -Ph represents a phenyl group, and n represents an integer of 10 or more) may be mentioned, but preferably is■
Or one having the structure of ■ is desirable. These may be a single substance or a block copolymer. Examples of block copolymers include block copolymers of (1) and (2), block copolymers of (1) and polycarbonate, and block copolymers of (1) and arylate.

■ (-φ-0-φ-3O*-)- ■ (−φ−φ−SO, −).

■ (-3O, -φ-0-φ-8Os-φ-CH, -φ
-)SO(-φ-C(CH,),-φ-0-φ-SO,
−φ−−0−).

CH.

■ (-0-φ-C-φ-0-φ-SO, -φ-).

Ph ■ (−0−φ−CH, −φ−0−φ−SO, −φ−)
.

■ (-0-φ-0-φ-SO,-φ-)3@l (
-0-φ-Co-φ-0-φ-Sow-φ-)-Ph (11) (-o-φ-c-φ-o-φ-9ow-φ
-).

Ph 0 (-〇-φ-0-φ-〇-φ-8O3-φ-)So
<-0-φ-3O2-φ-0-φ-CF 2-φ-
) −@ (−O−SO, −φ−φ−SO, −φ−0
-φ-〇--φ-C(CHI)! -φ-0-)1■
(−φ−SO, −φ−0−φ−So!−φ−0−φ−
-C(CHI)! -φ-0-).

@ (-φ-SO, -φ-〇-φ-802-φ-).

O(−φ−φ−0−φ−SO, −φ−0−).

@l (-φ-O-φ-SO, -φ-φ-SO, -).

The polyetherketone contains two repeating units and/or three repeating units of the following formula, alone or together with other repeating units, and has an intrinsic viscosity (1, V,
) is 0.7 or more, and is a tough crystalline thermoplastic aromatic polyetherketone.

Other repeating units other than the above formula [2] and/or formula [3] include formula [4] [wherein A is a direct bond, oxygen, sulfur, -5Oz-1-〇〇- or divalent is a hydrocarbon group. and the formula [5]. Furthermore, as a copolymer unit, the formula
[at the ortho position or rose position with respect to the 6-group Y or Y',
Y and Y' are the same or different, -CO- or -S
O2-, Ar is a divalent aromatic group, and n is 0.1.2 or 3. ) is included.

Polyetherimide (PEI) has the following formula.

and formula [7 [8] In the above formula, -0-Q and -0- are 3 or 4 and 3
' or 4' position, Q, is 8 (Q''
・−゛“9” or (Q′)・−・> independently 01 to C6 alkyl,
Aryl or halogen. Q, is -o--s-
-co--so, -1-SO-cycloalkylene having 1 to 6 carbon atoms, alkylidene having 1 to 6 carbon atoms, or 4 carbon atoms
~8 cycloalkylidene, Q is 6~2
Aromatic hydrocarbon radicals with 0 carbon atoms and their halogenated derivatives (wherein the alkyl group contains 1 to 6 carbon atoms), alkylene and cycloalkylene with 2 to 20 carbon atoms and a polydiorganosiloxane having a C3-C8 alkylene terminal group or the above formula [11].

Phenoxy resin is a combination of dihydric phenol, bisphenol such as bisphenol A1, bisphenol F1, and tetrachlorobisphenol, diphenolic acid, diol compound such as bisphenol and p-xylene dichloride condensate, and epoxy compound such as epichlorohydrin, butadiene oxide, and glycidyl compound. It is a thermoplastic polyether resin that does not have epoxy groups at both ends and is synthesized by the reaction of Among them, those synthesized using bisphenol A and shrimp chlorohydrin as main raw materials are preferred.

Preferred phenoxy resins for use in the present invention have a solution viscosity of 40% non-volatile content in methyl ethyl ketone (MEK) solution in the range of 5 x 10'' to 106 epS%, preferably 108 to 5 x 10' cps.

Commercially available products include UCAR phenoxy (grades PKHH, PKHJ) manufactured by Union Carbide.

PKHC, etc.).

ABS resin is obtained by polymerizing two or more compounds selected from vinyl cyanide monomers, aromatic vinyl monomers, and acrylic monomers in the presence of conjugated diene rubber. It is a graft copolymer. Also, if necessary,
It can contain a copolymer obtained by polymerizing two or more compounds selected from vinyl cyanide monomers, aromatic vinyl monomers, and acrylic monomers. Conjugated diene rubbers in the graft copolymer include polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, etc.; vinyl cyanide monomers include acrylonitrile, methacrylate trile, etc.; As the monomer, styrene,
Vinyltoluene, dimethylstyrene, chlorostyrene, etc., and particularly preferred is α-methylstyrene. In addition, acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Examples include hydroxyethyl acrylate.

The fluororesin used in the present invention is a general term for synthetic polymers containing fluorine atoms in the repeating units of the polymer and their co-fi polymers, such as polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene/hexafluoroethylene. So-called fluororesins such as propylene copolymer, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene/ethylene copolymer, and vinylidene fluoride/hexafluoropropylene copolymer The main one is fluororubber, which is mainly made by combining.

Examples of the α-olefin of the α-olefin polymer include ethylene, propylene, butene-1, isobutyne, pentene-1,4-methylpentene-1, hexene-1, and the like. These are used as one or more (co)polymers.

Furthermore, other monomers copolymerizable with these α-olefins, such as vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, acrylonitrile,
It is also possible to copolymerize styrene, vinyl ether, acrylic acid, methacrylic acid, and unsaturated dicarboxylic acids such as maleic acid. In addition, an ionomer containing metal ions such as Na+ or Zn''+ may be used as a copolymer having a carboxylic acid. Among the above α-olefin (co)polymers, especially ethylene (co) Polymers are preferably used.

Styrene polymers include styrene homopolymers and copolymers of styrene monomers with other copolymerizable monomers, such as styrene derivative monomers such as α-methylstyrene, dimethylstyrene, and chlorstyrene, and acrylic acid. , unsaturated carboxylic acids such as methacrylic acid, maleic acid, and maleic anhydride; acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate; or vinyl such as vinyl acetate and vinyl ether. It is a copolymer of one or more monomers.

The mixing ratio of PAS and these thermoplastic resins varies depending on the purpose of use and the type of resin used, so it cannot be generally specified, but it is usually 99 to 5 parts by weight of PAS and other thermoplastic resins. 1 to 95 parts by weight of the plastic resin, preferably 90 to 10 parts by weight of PAS, and 10 to 90 parts by weight of other thermoplastic resins (however, the total is 100 parts by weight). If the amount of PAS is less than 5 parts by weight or the amount of other thermoplastic resin is less than 1 part by weight, the improvement effect will be small.

The organic silane compound used in the present invention is generally called a silane coupling agent, and is a compound represented by the formula [12] or a polymer thereof.

CcHs>s-嘗Y-R4-3i-x, [12] However,
n is an integer of 1 to 3, R4 is a direct bond or carbon number 1 to 3
represents a straight chain alkylene group, Y is a carbon chain with or without a functional group such as a vinyl group, acrylate group, amino group, norogen group, epoxy group, or mercapto group;
represents a chloro group or an alkoxy group.

Among these, preferred are aminoalkoxysilanes, epoxyalkoxysilanes, and mercaptoalkoxysilanes in which Y is an amino group, an epoxy group, or a mercapto group, and X is an alkoxy group. Specifically, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, γamitsubu g
These include pyrutriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

The amount of the organic silane compound to be added varies depending on the purpose of use and the type of resin used, so it cannot be generally specified, but it is 0.05 to 10 parts by weight per 100 parts by weight of PAS and other thermoplastic resins in total. parts, preferably 0.1 to 5 parts by weight. If it is less than 0.05 parts by weight, the desired effect of the present invention will not be achieved, and if it exceeds 10 parts by weight, the influence of decomposition of the organic silane will become significant, which is not preferable.

A fibrous or granular filler can be added to the resin composition of the present invention, if necessary, and is usually added in an amount of 3 to 200 parts by weight based on the resin composition. Strength, rigidity, heat resistance, and dimensional stability can be further improved.

Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, boron fiber, whisker potassium titanate, asbestos, silicon carbide, aramid fiber, ceramic fiber, and metal fiber. Further, examples of the granular filler include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica. Two or more of these may be used in combination, and these fillers can also be treated with a silane-based or titanium-based coupling agent that is usually used as a processing agent for fillers.

In addition, the composition of the present invention may contain small amounts of a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a blowing agent, a flame retardant, a flame retardant aid, and a rust preventive agent within a range that does not depart from the purpose of the present invention. It can be made to contain.

The composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are mixed in advance in a mixer such as a dumbler or Henschel mixer, then supplied to a single or twin screw extruder, melted and kneaded at 230 to 400°C, and then prepared as pellets. .

The composition of the present invention has significantly improved blend compatibility, and has significantly improved mechanical properties such as impact resistance and mechanical properties such as chemical resistance. Therefore, the resin composition of the present invention can be used, for example, in electrical/electronic parts such as connectors, printed X-boards, and encapsulation molded products, automotive parts such as lamp reflectors and various electrical equipment parts, various buildings, aircraft, and automobiles. interior materials, leisure and sports equipment such as tennis rackets, skis, golf clubs, and fishing rods, acoustic materials such as enclosures for speakers, back decks for stringed instruments, etc., and precision parts such as OA equipment parts, camera parts, and clock parts. It is used as a molding material with excellent mechanical properties such as heat resistance and impact resistance in various molding fields such as injection molding and compression molding, and extrusion molding and pultrusion molding of composites, sheets, and vibrators.

<Examples> The present invention will be specifically explained below using Examples, but the present invention is not limited only to these Examples.

Reference Example 1> Sodium bisulfide (NaSH・2H
tO) 9.55Kg, sodium hydroxide 4.05K
A dehydration operation was performed on 50.0 kg of n-methylpyrrolidone at 190° C. for 1 hour while stirring and flowing nitrogen gas. The autoclave was then sealed and heated for 20
14.7 kg of p-dichlorobenzene and 1 kg of N-methylpyrrolidone were added to the system obtained by the dehydration operation heated to 0°C.
The solution with 0 kg was compressed for about 40 minutes, and the solution was compressed for 24 hours under pressure.
After raising the temperature to 0°C and carrying out the reaction for 4 hours, the polymer was separated, washed with warm water and acetone, and dried to produce PP.
I got 5-1. PP5-1 was further heat-treated at 2600C for about 2 hours to obtain PP5-2.

PP5-1 and PP5-2 are differential scanning calorimeters (DSC).
) The melting point Tm measured at 305°C, 1
The dynamic viscosity [η-] at 0 rad/sec was 500 poise and 2000 poise, respectively.

In addition, the chlorine content measured with a chlorine sulfur analyzer (TSX-10 type, manufactured by Mitsubishi Chemical Corporation) was 1500 pp.
m and 1400 ppm.

Reference Example 2 PPS was synthesized in the same manner as Reference Example 1 except that the amount of p-dichlorobenzene added was 15.1 kg.
P5-3 was obtained. PP5-3 was heat treated at 260°C for about 3 hours to obtain PP5-4.

The melting point of the obtained PP5-3 and PP5-4 measured by DSC was 285°C, and the melting point was 285°C at 305°C and 10 rad/see.
The dynamic viscosity of these materials was 400 voids and 2500 voids, respectively. Moreover, the chlorine content measured with a chlorine-sulfur analyzer (TSX-10 type, manufactured by Mitsubishi Kasei Corporation) was 5000 ppm and 4500 ppm, respectively.

Example 1.2.3/Comparative Example 1.2.3 PP5-1 obtained in Reference Example 1, PPO, and aminosilane were mixed in the formulation shown in Table 1, and heated at 330° using an extruder.
After melt-kneading and pelletizing with C, sample pieces were created using an injection molding machine. An isot impact test (no notch) and a bending test were conducted. The moldability was good. Furthermore, as a comparative example, a similar study was conducted in the case where aminosilane was not used. The results are shown in Table 1. It can be seen that the addition of the silane compound significantly improves the Izot impact value, bending deflection, etc.

Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using a scanning electron microscope (SEM), it was found that the fine particles were uniformly about 1 micron in Example 1 and 1 to 4 microns in Example 2.3. On the other hand, Comparative Examples 1~
In No. 3, spherical coarse particles of about 10 to 8 microns were observed to be non-uniformly dispersed. In addition, in the example, the dispersed particles and the matrix polymer were destroyed as one, and the adhesion between them was good, but in the comparative example, the dispersed particles were spherical and appeared to have completely fallen through, and the adhesion between them was good. It lacked sex.

Note that poly(2,6-dimethyl-1,4-phenylene) ether was used as the PPO, and γ-aminopropyltrimethoxysilane was used as the organic silane compound, NUC Sili: I-7A-1100 manufactured by Nippon Unicar Co., Ltd.

In addition, the sample piece has a cross-sectional area of 3.2X in the Izotsu impact test.
3.2 cm", the thickness was 2 mm in the bending test.
A piece with a width of 10 mm and a span length of 30 mm was used.

Example 4.5.6 Regarding the case where epoxysilane was used instead of aminosilane (Example 4), the addition rate of aminosilane was 0.5 parts by weight (Example 5) and 2 parts by weight (Example 6). Regarding this case, the same study as in Example 2 was conducted. The results are shown in Table 1. Further, SEM observation of the fracture surface of the test piece showed that fine particles of 1 to 5 microns were uniformly dispersed in all cases. The appearance of the fractured surface was the same as in Example 1.

The epoxy silane is γ-glycidoxypropyltrimethoxysilane, NUC silicone A- manufactured by Nippon Unicar Co., Ltd.
187 was used.

Example 7.8.9/Comparative Example 4.5 When PP5-2 is used instead of PPS-1 (Example 7.8/Comparative Example 4) and PP5-1 and PP5-4 are 1:1
When using PPS mixed with (Example 9/Comparative Example 5)
Example 1
A similar study was conducted. The results are shown in Table 1. Furthermore, when SEM observation of the sample fracture surface was performed, uniform fine particles of 1 to 8 microns were observed in the Examples, similar to those in Example 1, whereas in the Comparative Examples, uniform fine particles of 1 to 8 microns were observed, similar to those in Comparative Example 1.
Non-uniform spherical coarse particles of ~100 microns were observed.

Comparative Example 6.7 P with a chlorine content of 4500 ppm instead of PPS-1
Regarding the case of using P5-4, the same study as in Example 2 and Comparative Example 2 was conducted. The results are shown in Table 1. Even when a silane compound was added, no improvement in properties was observed. In all cases, spherical coarse particles of 20 to 100 microns, similar to those in Comparative Example 1, were dispersed non-uniformly in the cross-sectional observation of the sample pieces in the Izod test.

Examples 10 to 18/Comparative Examples 8 to 12 PPS, polysulfone (PSF), and epoxy silane were blended as shown in Table 2, sample pieces were prepared under the same conditions as in Example 1, and the same studies were conducted. The results are shown in Table 2. It can be seen that when PPS containing chlorine of 14,000 ppm or less is used, the properties are significantly improved by adding a silane compound. In Example 12, the sample did not break in both the bending and isot tests. On the other hand, when PPS with a chlorine content of 4500 ppm is used, it can be seen that the properties do not improve even if a silane compound is added. SEM observation of the fracture surfaces of Example 10 and Comparative Examples 8 and 11 revealed that Example 10 had 1 to 1 similar to Example 1.
Fine particles of 5 microns or 5 to 50 in Comparative Example 8.11
Coarse particles of micron size were observed. In addition, in the comparative example,
The adhesion between the resins forming the sea/island structure was poor, and on the fractured surface, the resin on the islands appeared to have completely fallen out like whiskers.

PSF is UDEL P-3703 manufactured by Amoco, and epoxysilane and aminosilane are NUC silicone.
A-187 and A-1100 were used.

Example 19.20/Comparative Example 13 The same study as in Example 10 was conducted using the formulations shown in Table 3 in the case where polyethersulfone (PES) was used as PSF. In Example 12, both the molding processability and the appearance of the molded product were good, but in the comparative example, the appearance of the molded product was poor. I did this. In Example 19, fine particles of approximately 1 to 8 microns were uniformly dispersed, and in Comparative Example, fine particles of approximately 1 to 8 microns were uniformly dispersed.
It was observed that spherical coarse particles of about 60 microns were dispersed non-uniformly.

The appearance of the fractured surface was similar to that of Example 1 and Comparative Example 1, respectively.

In addition, PES is VICTREX manufactured by I.C.I.
PES-3600 was used, and NUC silicone A-187 and A-1100 were used as epoxy silane and amino silane. (PEI), a silane compound, each mixed,
After melt-kneading and pelletizing at 340°C using an extruder, sample pieces were prepared using an injection molding machine. An isot impact test (no notch) and a bending test were conducted. The results are shown in Table 3. It can be seen that in the examples in which the silane compound was added, the characteristic values were significantly improved. When the fracture surfaces of Example 21 and Comparative Example 14 were observed using SEM, it was found that fine particles of about 1 to 5 microns were uniformly dispersed in Example 1, and in Comparative Example 1, fine particles of about 1 to 5 microns were uniformly dispersed. It was observed that spherical coarse particles of about 5 to 80 microns were dispersed non-uniformly.

In addition, in Comparative Examples 16 and 17, the chlor content was 4500
A study was conducted on the case where ppm of PP5-4 was used, but it was found that the characteristic values did not improve even if a silane compound was added. We performed SEM observation of the fractured surface of the sample, but
The fracture surface seems to be the same as Comparative Example 1, and both have 5 to 40
It was observed that spherical coarse particles of micron size were non-uniformly dispersed.

Incidentally, as PEI, Ultem 1000 manufactured by General Electric Company was used.

Examples 27-33/Comparative Examples 18-22 PPS, polyethylene terephthalate (PET
), polybutylene terephthalate (PBT), and a silane compound as shown in Table 4, and each mixture was melt-kneaded at 300 °C using an extruder to pelletize it, and then a sample was created using an injection molding machine. did. and,
The same study as in Example 1 was conducted. The results are shown in Table 4. SE of the fractured surfaces of the samples for Example 27 and Comparative Example 18
Observed with M.

In Example 27, no dispersed particles were observed.

On the other hand, in Comparative Example 18, spherical particles of about 5 to 10 microns were observed to be completely dispersed. It can be seen that when PPS with a chlorine content of 4 ooo ppm or less is used, the properties are significantly improved by the addition of a silane compound. On the other hand, PP5 with a chlorine content of 5000 ppm
In Comparative Examples 20.22 using -3, the characteristic values are extremely low. Regarding the case where no silane compound was added, the same study as Comparative Example 20.22 was conducted, but the respective characteristic values were almost unchanged from Comparative Example 20.22. SEM observation was performed for Comparative Example 20, and it was observed that the fracture surface was the same as Comparative Example 1, and spherical particles of 5 to 50 microns were observed to be non-uniformly dispersed.

The PET is Mitsui PET J-12 manufactured by Mitsui BET Co., Ltd.
5, PBT is Planac B manufactured by Dainippon Ink Chemical Co., Ltd.
T-128 was used.

Examples 34-41/Comparative Examples 23-26 PPS, nylon 66, nylon 6, and a silane compound were blended as shown in Table 5, and each mixture was melt-kneaded at 300°C using an extruder to form pellets. After that, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are shown in Table 5. Chlor content is 40
It can be seen that when PPS of 00 ppm or less is used, the characteristic values are improved by adding a silane compound. On the other hand, in PPS with a chlor content of 4000 ppm or more, the effect of adding a silane compound is not apparent.

The fracture surfaces of Example 34 and Comparative Examples 23 and 25 were observed by SEM. In the examples, fine particles of 2 microns or less were uniformly dispersed, and in the comparative examples, spherical particles of 5 to 10 microns were observed to be completely dispersed.

The nylon 66 is Vydyne manufactured by Monsanto.
22H, and nylon 6 is Kanebo's nylon 6MC.
112L, NUC Silicone A-189 manufactured by Nippon Unicar Co., Ltd., which is γ-mercaptopropyltrimethoxysilane, was used as the mercaptosilane.

Examples 42 to 46/Comparative Examples 26 to 29 PPS, nylon 46, and silane compounds were blended as shown in Table 6, and each was melt-kneaded at 320°C using an extruder to form pellets, and then molded using an injection molding machine. A sample piece was created. The same study as in Example 1 was conducted, and the results are shown in Table 6.
Shown below. PPS with chlorine content of 4000 ppm or less
In this case, it can be seen that the properties are improved by adding a silane compound. On the other hand, the chlor content is 4 soopppm
In the case of Comparative Example 29 using PPS, only poor characteristics were obtained even if a silane compound was added. Regarding the case in which no silane compound was added, the same study as in Comparative Example 29 was conducted, and the characteristic values were almost the same.

The nylon 46 is JSR nylon 46 manufactured by DSM.

Examples 47 to 53/Comparative Examples 30 to 33 PPS, ABS resin, and organic silane compound were blended as shown in Table 7 and examined. Melt kneading temperature is 300°
It was set as C. The results are shown in Table 7. In the examples, the properties are significantly improved by adding silane. On the other hand, in Comparative Example 33, a study was conducted on the case where PPS with a chlorine content of 4500 ppm (7) was used, but the characteristics did not improve even when a silane compound was added. Example 47 and Comparative Example 30
When the fractured surface of the sample was observed by SEM, in Example 47 the particles were approximately 1 micron or less, and in Comparative Example 30, spherical coarse particles of 5 to 30 microns were observed.

The ABS is Kane Ace MUHM-3 manufactured by Kanebuchi Chemical Co., Ltd.
It is 000.

Examples 54-61/Comparative Examples 34-38 PPS, polyethylene, ionomer, and aminosilane were blended as shown in Table 8 and examined. The melting crosstalk temperature was 300°C. The results are shown in Table 8. In the previous examples, the properties were significantly improved by adding the silane compound, and the samples did not break in any case during the bending test. Further, when 30 parts by weight of polyethylene was blended, no sample breakage occurred even in the Izot test. Regarding the case of 30 parts by weight of ionomer,
Although only the Izot test was investigated, the samples were not destroyed with any of the ionomers.

Example 54.58.59, Comparative Example 34.36.37.3
Regarding No. 8, the fracture surface was observed using SEM. In the examples, dispersed particles were not observed, but in Comparative Example 34, particles were 5 to 50 microns, and in Comparative Examples 36, 37, and 38, particles were 3 to 50 microns.
It was observed that spherical dispersed particles of about 20 microns were completely dispersed.

In addition, PE is Showa Denko's Shorex F-501.
The ionomer used was Himilan-1855 (ionomer-1, ion type Zn++) and 1856 (ionomer-2, ion type Na'') manufactured by DuPont Mitsui Polychemicals.

Examples 62 to 67/Comparative Example 39.4°PPS, phenoxy resin, and organic silane were blended in the proportions shown in Table 9 and examined. The melting crosstalk temperature was 310°C. The results are shown in Table 9. Chlor content 4o
It can be seen that when PPS of ooppm or less is used, the properties are significantly improved by the addition of a silane compound. In particular, the sample pieces did not break during the bending test.

The phenoxy resin is UCA manufactured by Union Carbide.
R phenoxy PKHH.

Examples 68-71/Comparative Examples 41-43 PPS, polyetheretherketone (PEEK) and aminosilane were mixed in the proportions shown in Table 10, and samples were prepared in the same manner as in Example 1. We conducted a thorough study. Note that the melt-kneading temperature was 360°C.

The results are shown in Table 10.

In the examples, it can be seen that the properties are significantly improved by adding a silane compound.

The PEEK used is VICT manufactured by I.C.I.
It is REX PEEK380.

Examples 72-75/Comparative Example 44.45 Polyvinylidene fluoride (
Daiel Thermoplastic T-5 manufactured by Daikin Industries, Ltd. is a copolymer of PVdF), fluororubber, and fluororesin.
Using No. 30, PPS, the above fluororesin and organic silane compound were mixed as shown in Table 11, samples were prepared in the same manner as in Example 1, and the same studies were conducted. In addition,
The melting crosstalk temperature was 300°C. The results are shown in Table 11.

It can be seen that in the case of PPS with a chlorine content of 4000 ppm or less, the properties are improved by adding a silane compound.

Note that PVdF is Neof 07 manufactured by Daikin Industries, Ltd.
VDF VP-810 was used.

Reference Example-3> N-methylpyrolidrine 198 in a 10Q autoclave
0 g, 388 g of sodium hydrosulfide hemihydrate, 200 g of sodium hydroxide, and 1436 g of bis(p-chlorophenyl) sulfone, and placed in a nitrogen atmosphere.
The reaction was allowed to take place at °C for approximately 6 hours. Furthermore, 72 g of bis(p-chlorophenyl)sulfone and 200 g of N-methylpyrrolidone
g was added thereto and reacted at 200° C. for 1 hour to obtain a ppss reactant slurry having a terminal chlorine group.

Next, N-methylpyrrolidone 3 was added to a 10Q autoclave.
100 g, sodium hydrosulfide hemihydrate 597.5
g and 308 g of sodium hydroxide were charged, the temperature was raised while water was flowing out, dehydration was performed, the autoclave was sealed, and 1029 g of p-dichlorobenzene was added to the dehydrated system at 220 ''C. 700g of N-methylpyrrolidone was added under pressure, and the temperature was further increased to 260″C.
The reaction was carried out at a temperature of 2 hours to obtain a PPS reactant slurry having terminal sodium sulfide groups.

The above PP5S reactant slurry and PPS reactant slurry were charged into an autoclave and reacted at 220"C for 3 hours, and purified by a known method to obtain a block copolymer (PTES-1) containing approximately 50% by weight of the PP5S portion. The melting point measured by DSC was 270°C, and 290"C
The dynamic viscosity at 110 rad/sec was about 2000 poise, and the chlorine content was 2500 ppm.

Reference Example 4> When obtaining a PPS reactant slurry, the following raw materials were charged in the following amounts: 4656 g of sodium hydrosulfide monohydrate, 240 g of sodium hydroxide, and 882 g of p-dichlorobenzene.
PPS and PP5S under the same conditions as Reference Example 3 except that
A block copolymer (PTES-2) was obtained. The melting point measured by DSC was 270°C, and the melting point was 290°C, 10r.
The dynamic viscosity in ad/sec was about 1,800 voids, and the chlorine content was 4,600 ppm.

Examples 76-80/Comparative Examples 46-50 PTES-1 obtained in Reference Example 3, polyphenylene oxide (PPO), polyetherimide (PEI), ABS
Table 12 shows resins, nylon 6, nylon 46 and organic silane.
After blending as shown in Figure 1, melt-kneading and pelletizing each using an extruder, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The melt-kneading temperature is 330°C for PPO and 340°C for PEI.
, nylon 6 at 300°C, and nylon 46 at 320°C. The results are shown in Table 12. It can be seen that the characteristic values are improved by adding the silane compound.

Examples 81 to 85, Comparative Examples 51 to 55 PTES-1 obtained in Reference Example 3, polyethylene, ionomer ethylene-ethyl acrylate copolymer (EEA)
The same study as in Example 1 was conducted using a phenoxy resin and an organic silane compound mixed in the proportions shown in Table 13. The melting crosstalk temperature was 300''C in all cases.The results are shown in Table 1.
Shown in 3. It can be seen that the characteristic values are improved by adding the silane compound. In the examples, none of the samples failed in the bending test. In particular, samples of ionomer and phenoxy resin did not break even in the Izot impact test. In addition, EEA is NUC copolymer EEA DPDJ-61 manufactured by Nippon Unicar Co., Ltd.
Hymilan-1855 (ionomer-1, ion type Zn+''V) and Himilan-1856 (ionomer-2, ion type Na'') manufactured by Mitsui DuPont Po'no Chemical Co., Ltd. were used as the ionomers.

Comparative Examples 56 to 61 PTES with a chlorine content of 4 sooppm obtained in Reference Example 4
-2, PPO, PEI, polyethylene and an organic silane compound were blended as shown in Table 14,
A similar study was conducted. The results are shown in Table 14. It can be seen that the properties do not improve even if a silane compound is added.

Comparative Examples 62 to 67 PPS (Rydon PR-0 manufactured by Flimbs Petrochemical Co., Ltd.
6), PPO, PSF, polyethylene, and a silane compound were mixed as shown in Table 15, and the same study as in Example 1 was conducted. The results are shown in Table 15. It can be seen that the characteristic values do not improve even if a silane compound is added.

The melting point of PPS is 282°C, and the melting point of PPS is 302°C110°C.
The dynamic viscosity in rad/see was 1500 poise, and the chlorine content was 4800 ppm.

<Effects of the Invention> The first composition of the present invention has significantly improved blend compatibility,
Mechanical properties such as impact resistance and mechanical properties such as chemical resistance are significantly improved.

Claims (1)

[Claims] 1. A resin composition comprising (A) a polyarylene sulfide having a chlorine content of 4000 ppm or less, (B) another thermoplastic resin, and (C) an organic silane compound. thing. 2. The ratio of (A) and (B) used is in the range of (A) 99 to 5 parts by weight to (B) 1 to 95 parts by weight (however, the total is 100 parts by weight), and ( The usage rate of C) is (
(C) 0.05 to 100 parts by weight of A) + (B)
The resin composition according to claim 1, wherein the amount is in the range of 10 parts by weight. 3. (B) Other thermoplastic resins include polyamide,
Thermoplastic polyester, polyphenylene oxide, polysulfone, polyetherimide, polyether ketone, ABS resin, fluorine resin, phenoxy resin, α-
2. The resin composition according to claim 1, wherein at least one thermoplastic resin selected from olefin polymers and styrene polymers is used. 4. The resin composition according to claim 1, wherein at least one selected from aminoalkoxysilane, epoxyalkoxysilane and mercaptoalkoxysilane is used as the organic silane compound (C).