CA1269778A - Impact-resistant polyamide resin composition and process for producing the same - Google Patents
Impact-resistant polyamide resin composition and process for producing the sameInfo
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- CA1269778A CA1269778A CA000532316A CA532316A CA1269778A CA 1269778 A CA1269778 A CA 1269778A CA 000532316 A CA000532316 A CA 000532316A CA 532316 A CA532316 A CA 532316A CA 1269778 A CA1269778 A CA 1269778A
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Abstract
ABSTRACT OF THE DISCLOSURE
An impact-resistant polyamide resin composition which comprises (a) a polyamide resin (hereinafter abbreviated as PA), (b) a polyphenylene ether type resin (hereinafter abbre-viated as PPE), and (c) a hydrogenated block copolymer type elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 µm or less, and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20% by weight or more relative to the total amount of PPE and TPE present in the composition, and a process for producing the same.
An impact-resistant polyamide resin composition which comprises (a) a polyamide resin (hereinafter abbreviated as PA), (b) a polyphenylene ether type resin (hereinafter abbre-viated as PPE), and (c) a hydrogenated block copolymer type elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 µm or less, and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20% by weight or more relative to the total amount of PPE and TPE present in the composition, and a process for producing the same.
Description
7~3 FIELD OF THE INVENTION AND RELATES ART ST~TEMENT
This invention relates to a polyamide resin co~position with an excellent impact resistarlce, particularly that at low temperature, and thermal 5 resistance as well as a low level of anisotropy of mechanical properties. More particularly, it relates to a polyamide resin composition which comprises (a) a polyamide resin, (b) a polyphenylene ether type resin and (c) a hydrogenated block copolymer type elastomer which is a copolymer comprising a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20~.
The composition can be used in a wide field including the field of materials for automative, electric, electronic, and mechanical industry.
Although polyamide resins have excellent mechanical properties, chemical resistance, abrasion resistance etc., they are poor in impact resistance, particularly that at low temperature. Accordingly, they are restricted as to their field of applications.
Various compositions have been proposed to obviate the above-mentioned drawback. Compositions incorporated with elastomers have been disclosed (Japanese Patent Application Kokoku (Post-Exam. Publn.) No.
11,941/85, published March 29, 1985, Japanese Patent Application Kokai (Laid-Open) Nos. 7,443/83 and 56,451/84, published January 17, 1983 and March 31, 1~8~, respectively), but they have a drawback of being poor in impact strength at low temperatures. Further, they have another drawback of decreased thermal resistance owiny to the-incorporation of elastomars.
Japanese Patent Application KGkai (Laid-Open) No. 49~753/81, published May 6, 1981 discloses a composition which comprises 100 parts by weight of a resin (I) consisting of 5 to 95~ by weight of polyphenylene oxide and 95 to 5% by weight of polyamide, 5 to 100 parts by weight of a rubber-like substance (II), and 0.01 to 50 parts by weight of a compound having in the molecule simultaneously (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) a carboxylic acid group, acid anhydride group, acid amide group, imido group, carboxylic ester group, epoxy group, amino group or hydroxyl group and which undergoes no phase separation in molding and is excellent in solvent resistance and impact strength and is hence of high practical value. However, the composition is unsatisfactory in low temperature impact resistance.
U.S. Patent No. 4,315,086 discloses a composition excellent in solvent resistance and impact resistance which comprises 100 parts by weight of a resin (I) consisting of 5 to 95% by weight of polyphenylene oxide and 95 to 5% by weight of polyamide, and 0.01 to 30 parts by weight of at least one substance selected from (A) liquid diene polymers, (B) epoxy compounds, and (C) compounds having simultaneously (a) an ethylenic carbon-~ ~9~
1 carbon double bond or a carbon-carbon tripple hond and (b) a carboxylic acid ~roup, acid anhydride group, acid arnide group, imido grollp, carbo~ylic ester group, amino gro-lp or hydroxyl group, but it has an unsatisfactory low S temperature impact strength.
U.S. Patent No. 4,421,892 discloses a composi~
tion excellent in thermal resistance and impact strength which comprises 5 to 95~ by weight of an aromatic polyether type resin, 0.5 to 90% by weight of a copolymer containing as its components a styrene type compound and an ~ unsaturated dicarboxylic acid anhydride, 1 to 90%
by weight of polyamide, and 0 to 80% by weight of an impact strength reinforcing material. However, this composition is not excellent in low temperature impact strength and is also unsatisfactory in thermal resistance.
U.S. Patent No. 4,600,741 discloses a composi-tion excellent in chemical resistance and impact resist-ance which comprises a polyphenylene ether resin, a polyamide resin, and a polyphenylene ether resin modified with an acyl compound comprising (i) a structure oE the o general formulas (X-C-t, wherein X denotes F, Cl, Br, I, or OH, and/or O-C-R, wherein R denotes a hydrogen atom, alkyl radical, or aryl radical, and (ii) one member selected from a carboxylic acid, acid anhydride, acid amide, carboxylic ester, amine, and hydroxyl group, said (i) and (ii) being covalent-bonded through a divalent .. ..
~, .
~ ~i9~7~
1 hydrocarbon radical. However, even when the co~position is further incorporatecl with lmpact resistance improving agents such as natural rubber, polybutadiene, butadiene/
styrene copolymer, and hydrogenated butadiene/styrene copolymer, the resulting composition is still unsatis-factory in low temperature impact resistance Among compositions comprising polyphenylene ether resin and polyamide resin, Noryl GTX ~a trade name, mfd. by General Electric Co.) is commercially availabe as a material for automobile outer panels. The features of this PPE/PA type polymer alloy is described in Plastic Age, No. 2, 160 - 163 ~1986). Noryl GTX 910 has an impact strength at -30C of about 13 kg-cm/cm and a thermal resistance, as expressed in terms of heat distortion tem-perature (4.6 kg/cm2 load), of 190C. The alloy assumesa form wherein PPE is micro-dispersed in the continuous phase of PA, and comprises an utterly incompatible microdispersions when judged from the determination of its dynamic viscoelasticity. As to the details of its phase structure, it is described in the Proceedings, p 53 - 58 (Jan. 1987), of Tokai Symposium on "Material Characteri-zation and Material Design~ sponsored by the Tokai Branch of The Soc. of Polymer Science, Japan that it assumes a state featured by, so to call it, a sea-island-lake-like structure wherein PPE is dispersed in the continuous phase of PA and further rubber is dispersed in said PPE, and the dispersed particles of PPE have mostly a particle diameter of 2 to 4 ~m.
r~2~j97~
1 ~he present inventors have previously found, as a composition of polyamide resin excellent in irnpact stren~th and rigidity, a composition characterized by comprising (A) not less than 10~, by weight and not more than 35~ by weight of at least one copolymer selected from the group consisting of styrene type hydrocarbon polymer block - conjugated diene type elastomer block copolymers and styrene type hydrocarbon polymer block - olein type elastomer block copolymers, ~B) not less than 2% by weight and not more than the percentage by weight of (A) of a maleic anhydride-modified polyphenylene ether type resin, and (C) not less than 30~ by weight and not more than 88 by weight of a polyamide resin [Japanese Patent Appli-cation Kokai (Laid-Open) No. 204,262/86]. ~owever, when the above-mentioned composition is processed by conven-tional forming methods such as injection molding, the resulting formed articles show so called anisotropy of mechanical properties, a phenomenon wherein mechanical properties differ markedly between the direction or resin flow and the direction perpendicular to the former.
Accordingly, in practical applications, the composition is restricted as to forming methods and uses.
In recent years, requirements for improving the impact resistance of polyamide resin have increased further as the resin has come to be more widely used.
Impact resistance is usually expressed in terms of Izod impact strength. When polyamide resin is use singly, its Izod impact strength is several to about 10 kg-cm~cm (with . .
. '' ~ .
~,, , ~ .
:, - . ' ;
:. . ..... -- - ...
~LX~ t~
1 notcn; determined under an absolute dry condi~ion) at 23C
and decreases down to 2 to 3 kg~cm/cm or less ~It lower temperatures. ~ccordingly, the field oE appl~cation of the resin alone is subject to limitation.
The object of this invention is to improve the impact resistance of polyamide resin. More particularly, it is to provide a polyamide resin composition which has an improved low temperature impact resistance while retaining a high level of thermal resistance and which shows a low-level of anisotropy oE mechanical properties when formed or molded.
After extensive studies conducted to obtain such an improved resin composition, the present inventors have found a novel polyamide resin composition which can answer the object of this invention.
Thus, this invention relates, in one aspect, to an impact-resistant polyamide resin composition which comprises (a) a polyamide resin (hereinafter abbreviated as PA), (b) â polyphenylene ether type resin (hereinafter abbreviated âS PPE), and (c) a hydrogenated block copolymer type elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20~, .
, ., , .. ~
', ~97~7~
l the diame~er of the dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less, and the insoluble portion of the composition remaining ~fter extraction thereof with formic acid ollowed by chloroform being 20~ by welght or more relative to the total amount of PPE and TPE present in the composition.
In another aspect, this invention relates to a process for producing an impact-resistant polyamide resin composition comprising (a) a polyamide resin, (b) a polyphenylene ether type resin, and (c) a hydrogenated block copolymer type elastomer which is a copolymer containing a vinyl aromatic compound polymer block A ar,d an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less, and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20~ by weight or more relative to the total amount of PPE.and TPE present in the composition which process comprises melt kneading a polyphenylene ether type resin obtained by reacting, in the presence of : a radical producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a polymer obtained by oxidative polymerization of at least one phenolic compound represented by the general formula ~ : .
7~3 R~ ~R5 R2 Rl R1, R2, R3, R4 and R5 are, independently, a hydrogen atom, nalogen atom, or substituted or unsubsti~
tuted hydrocarbon group, provided that at least one of them must be hydrogen, a hydrogenated block copolymer type elastomer obtained by reacting, in the presence of a radical producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a hydrogenated block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the said block B not exceeding 20%, and a polyamide resin.
BRIEF DESCRIPTION OF THE DRAWINGS
Figs. l to 3 and 5 to 13 are electron photomicrographs oE the compositions of Examples of this invention and Comparative Examples which have been stained with osmium tetroxide. Deeply stained portions are dispersed phases of PPEt whereas white, not stained portions are the dispersed pnase of TPE. Portions with scattered micro dots are PA phases.
Fig.4 is an electron photomicrograph of the ~ .
.. , ~
~ 7~
1 composi`tion of Comparative Example 4 which has been stained with osmium tetroxide lightly and then Wittl ruthenium tetroxide. Deeply stained portions are dispersed phase o 'rPE; white, not stained portions are S the dispersed phases of PPE; and lightly stained portions are PA phases.
- DESCRIPTION OF THE PREFERRED EM~ODIMENT
The polyamide resins which can be used in this invention include polycondensation products o a dicarboxylic acid with a diamine, polycondensation products of an ~-aminocarboxylic acid, and ring opening polymerization products of a cyclic lactam. As specific examples thereof, there may be mentioned aliphatic polyamides such as nylon 6, nylon 4,6, nylon 6,6, nylon 6,10, nylon 11, and nylon 12; aliphatic-aromatic poly-amides such as poly(hexamethylene terephthalamide), poly(hexamethylene isophthalamide), and poly(tetramethyl-ene isophthalamide); and the copolymers and mixture thereof.
The polyphenylene ether type resin used in this invention is a polymer obtained by the oxidative polymeri-zation of at least one phenolic compound represented by the general formula .. ,., -:. :
~.. :.- :.. :........... ..
, .., ", ......
37~
R ~ l~5
This invention relates to a polyamide resin co~position with an excellent impact resistarlce, particularly that at low temperature, and thermal 5 resistance as well as a low level of anisotropy of mechanical properties. More particularly, it relates to a polyamide resin composition which comprises (a) a polyamide resin, (b) a polyphenylene ether type resin and (c) a hydrogenated block copolymer type elastomer which is a copolymer comprising a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20~.
The composition can be used in a wide field including the field of materials for automative, electric, electronic, and mechanical industry.
Although polyamide resins have excellent mechanical properties, chemical resistance, abrasion resistance etc., they are poor in impact resistance, particularly that at low temperature. Accordingly, they are restricted as to their field of applications.
Various compositions have been proposed to obviate the above-mentioned drawback. Compositions incorporated with elastomers have been disclosed (Japanese Patent Application Kokoku (Post-Exam. Publn.) No.
11,941/85, published March 29, 1985, Japanese Patent Application Kokai (Laid-Open) Nos. 7,443/83 and 56,451/84, published January 17, 1983 and March 31, 1~8~, respectively), but they have a drawback of being poor in impact strength at low temperatures. Further, they have another drawback of decreased thermal resistance owiny to the-incorporation of elastomars.
Japanese Patent Application KGkai (Laid-Open) No. 49~753/81, published May 6, 1981 discloses a composition which comprises 100 parts by weight of a resin (I) consisting of 5 to 95~ by weight of polyphenylene oxide and 95 to 5% by weight of polyamide, 5 to 100 parts by weight of a rubber-like substance (II), and 0.01 to 50 parts by weight of a compound having in the molecule simultaneously (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) a carboxylic acid group, acid anhydride group, acid amide group, imido group, carboxylic ester group, epoxy group, amino group or hydroxyl group and which undergoes no phase separation in molding and is excellent in solvent resistance and impact strength and is hence of high practical value. However, the composition is unsatisfactory in low temperature impact resistance.
U.S. Patent No. 4,315,086 discloses a composition excellent in solvent resistance and impact resistance which comprises 100 parts by weight of a resin (I) consisting of 5 to 95% by weight of polyphenylene oxide and 95 to 5% by weight of polyamide, and 0.01 to 30 parts by weight of at least one substance selected from (A) liquid diene polymers, (B) epoxy compounds, and (C) compounds having simultaneously (a) an ethylenic carbon-~ ~9~
1 carbon double bond or a carbon-carbon tripple hond and (b) a carboxylic acid ~roup, acid anhydride group, acid arnide group, imido grollp, carbo~ylic ester group, amino gro-lp or hydroxyl group, but it has an unsatisfactory low S temperature impact strength.
U.S. Patent No. 4,421,892 discloses a composi~
tion excellent in thermal resistance and impact strength which comprises 5 to 95~ by weight of an aromatic polyether type resin, 0.5 to 90% by weight of a copolymer containing as its components a styrene type compound and an ~ unsaturated dicarboxylic acid anhydride, 1 to 90%
by weight of polyamide, and 0 to 80% by weight of an impact strength reinforcing material. However, this composition is not excellent in low temperature impact strength and is also unsatisfactory in thermal resistance.
U.S. Patent No. 4,600,741 discloses a composi-tion excellent in chemical resistance and impact resist-ance which comprises a polyphenylene ether resin, a polyamide resin, and a polyphenylene ether resin modified with an acyl compound comprising (i) a structure oE the o general formulas (X-C-t, wherein X denotes F, Cl, Br, I, or OH, and/or O-C-R, wherein R denotes a hydrogen atom, alkyl radical, or aryl radical, and (ii) one member selected from a carboxylic acid, acid anhydride, acid amide, carboxylic ester, amine, and hydroxyl group, said (i) and (ii) being covalent-bonded through a divalent .. ..
~, .
~ ~i9~7~
1 hydrocarbon radical. However, even when the co~position is further incorporatecl with lmpact resistance improving agents such as natural rubber, polybutadiene, butadiene/
styrene copolymer, and hydrogenated butadiene/styrene copolymer, the resulting composition is still unsatis-factory in low temperature impact resistance Among compositions comprising polyphenylene ether resin and polyamide resin, Noryl GTX ~a trade name, mfd. by General Electric Co.) is commercially availabe as a material for automobile outer panels. The features of this PPE/PA type polymer alloy is described in Plastic Age, No. 2, 160 - 163 ~1986). Noryl GTX 910 has an impact strength at -30C of about 13 kg-cm/cm and a thermal resistance, as expressed in terms of heat distortion tem-perature (4.6 kg/cm2 load), of 190C. The alloy assumesa form wherein PPE is micro-dispersed in the continuous phase of PA, and comprises an utterly incompatible microdispersions when judged from the determination of its dynamic viscoelasticity. As to the details of its phase structure, it is described in the Proceedings, p 53 - 58 (Jan. 1987), of Tokai Symposium on "Material Characteri-zation and Material Design~ sponsored by the Tokai Branch of The Soc. of Polymer Science, Japan that it assumes a state featured by, so to call it, a sea-island-lake-like structure wherein PPE is dispersed in the continuous phase of PA and further rubber is dispersed in said PPE, and the dispersed particles of PPE have mostly a particle diameter of 2 to 4 ~m.
r~2~j97~
1 ~he present inventors have previously found, as a composition of polyamide resin excellent in irnpact stren~th and rigidity, a composition characterized by comprising (A) not less than 10~, by weight and not more than 35~ by weight of at least one copolymer selected from the group consisting of styrene type hydrocarbon polymer block - conjugated diene type elastomer block copolymers and styrene type hydrocarbon polymer block - olein type elastomer block copolymers, ~B) not less than 2% by weight and not more than the percentage by weight of (A) of a maleic anhydride-modified polyphenylene ether type resin, and (C) not less than 30~ by weight and not more than 88 by weight of a polyamide resin [Japanese Patent Appli-cation Kokai (Laid-Open) No. 204,262/86]. ~owever, when the above-mentioned composition is processed by conven-tional forming methods such as injection molding, the resulting formed articles show so called anisotropy of mechanical properties, a phenomenon wherein mechanical properties differ markedly between the direction or resin flow and the direction perpendicular to the former.
Accordingly, in practical applications, the composition is restricted as to forming methods and uses.
In recent years, requirements for improving the impact resistance of polyamide resin have increased further as the resin has come to be more widely used.
Impact resistance is usually expressed in terms of Izod impact strength. When polyamide resin is use singly, its Izod impact strength is several to about 10 kg-cm~cm (with . .
. '' ~ .
~,, , ~ .
:, - . ' ;
:. . ..... -- - ...
~LX~ t~
1 notcn; determined under an absolute dry condi~ion) at 23C
and decreases down to 2 to 3 kg~cm/cm or less ~It lower temperatures. ~ccordingly, the field oE appl~cation of the resin alone is subject to limitation.
The object of this invention is to improve the impact resistance of polyamide resin. More particularly, it is to provide a polyamide resin composition which has an improved low temperature impact resistance while retaining a high level of thermal resistance and which shows a low-level of anisotropy oE mechanical properties when formed or molded.
After extensive studies conducted to obtain such an improved resin composition, the present inventors have found a novel polyamide resin composition which can answer the object of this invention.
Thus, this invention relates, in one aspect, to an impact-resistant polyamide resin composition which comprises (a) a polyamide resin (hereinafter abbreviated as PA), (b) â polyphenylene ether type resin (hereinafter abbreviated âS PPE), and (c) a hydrogenated block copolymer type elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20~, .
, ., , .. ~
', ~97~7~
l the diame~er of the dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less, and the insoluble portion of the composition remaining ~fter extraction thereof with formic acid ollowed by chloroform being 20~ by welght or more relative to the total amount of PPE and TPE present in the composition.
In another aspect, this invention relates to a process for producing an impact-resistant polyamide resin composition comprising (a) a polyamide resin, (b) a polyphenylene ether type resin, and (c) a hydrogenated block copolymer type elastomer which is a copolymer containing a vinyl aromatic compound polymer block A ar,d an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less, and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20~ by weight or more relative to the total amount of PPE.and TPE present in the composition which process comprises melt kneading a polyphenylene ether type resin obtained by reacting, in the presence of : a radical producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a polymer obtained by oxidative polymerization of at least one phenolic compound represented by the general formula ~ : .
7~3 R~ ~R5 R2 Rl R1, R2, R3, R4 and R5 are, independently, a hydrogen atom, nalogen atom, or substituted or unsubsti~
tuted hydrocarbon group, provided that at least one of them must be hydrogen, a hydrogenated block copolymer type elastomer obtained by reacting, in the presence of a radical producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a hydrogenated block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the said block B not exceeding 20%, and a polyamide resin.
BRIEF DESCRIPTION OF THE DRAWINGS
Figs. l to 3 and 5 to 13 are electron photomicrographs oE the compositions of Examples of this invention and Comparative Examples which have been stained with osmium tetroxide. Deeply stained portions are dispersed phases of PPEt whereas white, not stained portions are the dispersed pnase of TPE. Portions with scattered micro dots are PA phases.
Fig.4 is an electron photomicrograph of the ~ .
.. , ~
~ 7~
1 composi`tion of Comparative Example 4 which has been stained with osmium tetroxide lightly and then Wittl ruthenium tetroxide. Deeply stained portions are dispersed phase o 'rPE; white, not stained portions are S the dispersed phases of PPE; and lightly stained portions are PA phases.
- DESCRIPTION OF THE PREFERRED EM~ODIMENT
The polyamide resins which can be used in this invention include polycondensation products o a dicarboxylic acid with a diamine, polycondensation products of an ~-aminocarboxylic acid, and ring opening polymerization products of a cyclic lactam. As specific examples thereof, there may be mentioned aliphatic polyamides such as nylon 6, nylon 4,6, nylon 6,6, nylon 6,10, nylon 11, and nylon 12; aliphatic-aromatic poly-amides such as poly(hexamethylene terephthalamide), poly(hexamethylene isophthalamide), and poly(tetramethyl-ene isophthalamide); and the copolymers and mixture thereof.
The polyphenylene ether type resin used in this invention is a polymer obtained by the oxidative polymeri-zation of at least one phenolic compound represented by the general formula .. ,., -:. :
~.. :.- :.. :........... ..
, .., ", ......
37~
R ~ l~5
2 Rl n Rl, R2, R3, R4 and R5 are, independently, a hydrogen atom, halogen atom, or substituted or unsubsti-tuted hydrocarbon group, provided that at least one of them must be hydrogen. That is, said polymer may include any of the products obtainable by oxidative polymeri ation of phenolic compounds.
SpecifiC examples of Rl, R2, R3, R4 and R5 in the above general formula include hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxy-methyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, ; phenyl, chlorophenyl, methylphenyl, dimethylphenyl, and ethylphenyl.
Specific examples of the compound represented by the above general formula include phenol, o-, m- or p-cresol, 2,6-, 2,5-, 2,4- and 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethyl-phenol, 2-methyl-6-ethylphenol, and 2,3,5-, 2,3,6- and 2,4,6~trimethylphenol. These phenolic compounds may also be used in combinations of two or more kinds thereof.
The phenolic compounds of the above general formula may also be copolymerized with phenolic compounds other than those of the said formula, such as bisphenol A, ~, , - ~ :
~ '7~
l tetrabromobisphenol A, resorcinol, and hydroquinone.
It is well known that polymers oE phenolic compound can be obtained by oxi~atively polymerizing the compound by means of oxygen or an oxygen-containing gas using an oxidative coupling catalyst. For example, polymers can be obtained by reacting phenolic compounds with oxygen in the presence of a copper or manganese complex.
Further~ there can also be used a graft copolymer obtained by grafting a styrene type compound to the above-mentioned phenolic compound polymer. Examples of the styrene type compound include styrene, ~-methyl-styrene, methylstyrene, vinyltoluene, and chlorostyrene.
Further, to improve processability, styrene type polymers may be added within a range not detrimental to the mechanical properties of the product. As specific examples of such styrene type polymers, there may be mentioned styrene homopolymer; rubber-modified polystyrene resins using various kinds of rubbers, for example, polystyrene modified with butadiene type rubber (of various content of microstructures), polystyrene modified with acrylic rubber, polystyrene modified with ethylene-propylene copolymer, polystyrene modified with ethylene-propylene-diene copolymer rubber, and polystyrene modified with butadiene-styrene rubber; styrene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile copolymer (so-called ABS resin), butadiene-styrene-methyl methacry-late copolymer, and styrene-ethylene copolymer.
..~' .
,~
7~
1 The hydrogenated block copolymer type e:lastolner used in this invention is a hydroyenated block A copol~mer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%.
The hydrogenated block copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, used in this invention, is obtained by selective hydrogenation of t'ne conjugated diene portions of a block copolymer containing a vinyl aromatic compound polymer block and a conjugated diene type compound polymer block.
Among the above-mentioned block copolymer ; containing a vinyl aromatic compound polymer block and a conjugated diene type compound polymer block, there may be mentioned a linear ~lock copolymer represented by the formulas (X~Y)n, (X-Y-X')n, X-~ Y-X-Y-t-nX, or X-t-Y-x tnY
(n is an integer from 1 to 10) which is a copolymer consisting of a vinyl aromatic compound polymer blocks (X) and (X') and a conjugated diene type compound polymer block (Y) (X and X' may be the same or di~ferent), and a radial block copolymer represented by the general formulas [(Y-~) ] ~2Z' [(X~Y)n ~ 2Z' [(Y~X)n~Y ]m+2Z
[(X-Y)n-X ~ z (wherein X, Y and n are as defined above;
m is an integer from 1 to 4 and Z is the residue of a coupling agent such as silicon tetrachloride and tin tetrachloride or that of an initiator such as a polyfunc-tional organolithium compound).
~ ' . ' ' , .
.. ~
., . ~'............... .....
7~
1Typical examples of vinyl aromatic compounds used herein include styrene, ~-methylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and the mixtures thereof. These of conjugated d.iene type compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-diethylbutadiene, and the mixtures thereof.
The terminal blocks of these block copolymers may be the same or different from each other.
The number average molecular weight of these block copolymers is 10,000 to 800,000, preferably 20,000 to 500,000.
The content of the vinyl aromatic compound in these block copolymers is preferably 10 to 70% by weight, more preferably 10 to 55% by weight.
15The hydrogenated block copolymer used in this invention is obtained by selective hydrogenation of the conjugated diene portion of the above-mentioned block ; copolymer. For example, a hydrogenated block copolymer wherein not more than 20~ of the aromatic double bonds in the vinyl aromatic compound polymer block and at least 80%
of the aliphatic double bonds in the conjugated diene compound polymer block have been hydrogenated can be obtained by hydrogenating the above-mentioned block ccpolymer according to the method described in Japanese Patent Application Rokoku (Post-Exam. Publn.) No; 8704/67, published September 10, 1986.
The ~degree of unsaturation of block B~ referred to in this invention means the proportion of carbon-carbon double bonds contained in the block B, and is usually in a . ~ ~
: . , . ' ' ' ,:
, :: .. ,: . : .. :
, .: , ...
': .' ' .
1 range not e~ceeding 20Q~. It can be deter~ined by instru-mental analysis such as nuclear magnetic resonance method and infrared absorption spectroscopy, and chemcial analysis such as idodometric titration.
These hydrogenated block copolymers can be used each alone or as a mixture of two or more thereof.
In the resin composition of this invention, the compounding ratio is not specifically limited so long as it is a composition comprising polyamide, PPE anD TPE, the diameter of dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less and the insoluble portion of the composition after extraction thereof with formic acid followed by chloroform being 20~ by weight or more.
More preferably, the content of polyamide resin is in the range of 45 to 75% by weight. A content of less than 40% by weight is unfavorable because sometimes it leads to a low thermal resistance. A content exceeding 75% by weight is unfavorable because sometimes it results in the decrease of low temperature impact strength.
The content of PPE is more preferably in the range of 5 to 40~ by weight. A content of less than 5~ by weight is unfavorable because it results in the decrease of low temperature impact strength. A content exceeding 40% by weight is unfaovrable because it leads to the decrease of thermal stability in molding.
The content of TPE is more preferably in the range of 10 to 30~ by weight. A content of less than 10%
by weight is unfavorable because it results in the : : .
, . ::. , : .
. . .~ ~ - :., .. ..
~ ~ 9~
1 decrease of low temperature impact strength. A content e~ceeding 30~ by weight is unfavorable becau.se lt results in a low thermal resistance.
The morphology of the composition of this invention can be examined by observing with a transmission electron microscope an ultrathin slice of the composition stained and fixed by means of osmium tetroxide and/or ruthenium tetroxide. In the morphology of the composition of this invention, PA forms a continuous pnase, whereas PPE and TPE form dispersed phases. More particularly, for example in case of nylon 6,6, the main structure of dispersed phases involve such phase structures as a TPE
dispersed phase enveloping PPE, a TPE dispersed phase enveloping PPE and PA, and a TPE dispersed phase envelop-lS ing PA; and in case of nylon 6 they invo~ve a TPE
dispersed phase enveloping PPE and PA, and a dispersed phase of PPE alone. The PPE dispersed phases range in their size from a very finely dispersed phase to a dispersed phase reaching several ~m in diameter.
As to the diameter of the PPE dispersed phase of the composition according to this invention, it is preferable that most of the PPE dispersed phases have a diameter of 0.6 ~m or less. A diameter of less than 0.01 ~m, namely so fine a dispersion is to make observation with an electron microscope virtually impossible even at amagnification of 10,000, is unfavorable because it leads to the decrease of low temperature impact strength. On the other hand, when the number of particles larger than '. ' ~ ' ." . ' .
~. . .
.~ , .. . .. .
l 0.6 ~m is large, it leads to the decrease o~ low temperature impact strength and is hence unfavorable.
The diameter of the PPE dispersed phase is measured with an electron photomicrograph taken at a magnification of lO,000. ~hen the phase is elliptic, the length of its major axis (~) and that of the minor axis (~) (defined herein as the distance between the points at which a perpendicular line drawn through the center of the major axis intersects the ellipsoid) were determined, and a value D calculated from the equation D ~ (~ + ~)/2 is taken as the diameter of the dispersed phase.
The insoluble portion of the composition of this invention remaining after extraction thereof with formic acid followed by chloroform is preferably 20% by weight or more relative to the total amount of PPE and TPE in the composition. Further, from the viewpoint of practical molding processability, it is not more than 150% by weight. An insoluble proportion of less than 20% by weight is unfavorable ~ecause it leads to the decrease of low temperature impact strength and/or to anisotropy of mechanical properties of formed articles.
The insoluble portion is determined in the following manner. A formed article is pulverized mechani-cally to give powders having a particle diameter of about 0.5 mm or less. After l g of the powdery composition is weighed accurately, and mixed with 50 ml of 39~ formic acid. The mixture is stirred at room temperature (20 to 25C) for 5 hours, filtered through a glass filter to ;, '. ~ . .
.. - . .. ~ - .
~ 7~7~
1 separate insoluble matter, which is then washed with formic acid, water and acetone, and then dried. The insoluble matter is then mixed with 50 ml o~ chloroform, and the mixture is stirred at room temperature (20 to 25C) for 17 hours, and then filtered throu~h a glass filter to separate insoluble matter, which is washed with chloroform and methylene chloride, dried and then weighed The amount of PPE and TPE in the composition can be determined by first calculating the amount of polyamide from the amount of nitrogen in the composition obtained by elemental analysis and then by substraction. If addi-tives are contained in the composition they are removed before the calculation of the polyamide amount.
The characteristics of the present composition lS lies in the state of the dispersion of each said component (a), (b) and (c) and the insoluble portion of the composi-tion remaining after the extraction while a polyamide resin, a polyphenylene ether resin and an elastomer of a hydrogenated block copolymer are employed. The above-mentioned characteristics are attained firstly byemploying the present process mentioned hereinafter which is entirely different from that of the conventional one.
Although the detailed physico-chemical mechanism showing the excellent effect in the present invention is not clear, it is believed that it can be attained by the process of the present invention that the dispersed state of the present composition is not a mere mixture of PA, ,~
. .-- ~ -.
.... .
~ - ',. ~; '.
~9t7,~,~
1 PPE alld rrpE~ but the :Eormation of a stable dispersioll of PPE and TPE in the PA phase which may have been clerived rom a strong interactlon between them which has never been known, whereby a smaller particle size of PPE ~pecified as in this invention can be formed therein; and that a higher content of said insoluble portion can be attained as a result of employing the present process.
The resin composition of this invention may be incorporated, at optional steps of its production and molding, with other ingredients including pigments, dyes, reinforcing materials, fillers, thermal stabilizers, antioxidants, weather proofing agents, nucleating agents, lubricant, plasticizers, antistatic agents, and other polymers within a range not detrimental to its moldability and mechanical properties.
A preferred process for producing the resin composition of this invention comprises melt-kneading a polyphenylene ether type resin obtained by reacting, in the presence of a radical producing agent, a 1,2-substi-tuted olefinic compound having an acid anhydride structurewith a polyrner obtained by oxidative polymerization of at least one phenolic cornpound represented by the general formula .
"
' 7~7~
R~ R 5 R2 Rl 1 wherein Rl, R2, R3, R4 and R5 arer independentlyr a hydrogen atom, halogen atom, or substituted or unsubsti-tuted hydrocarbon group, provided that at least one of them must be hydrogen; a hydrogenated block copolymer type elastomer obtained by reacting, in the presence o a radi-cal producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a hydrogenated block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the said block B not exceeding 20%; and a polyamide resin. Another process may also be used which comprises melt-kneading optional two components preliminarily and then melt-kneading the remaining component therewith.
As specific examples o 1,2-substituted olefinic compounds having a carboxylic acid group, acid anhydride group, or epoxy group, there may be mentioned maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, methylnadic anhydride, dichloromaleic anhydride, acrylic acid, methacrylic acid, and glycidyl methacrylate.
The radical producing agents usuable in this invention include organic peroxides and diazo compounds known to the art. As speciic examples thereof, mention : -- 19 --' : -.; ~ , .-:
: , ~;
.. ,. , 1 may be made o~ ben~oyl peroxide, dicumyl peroxide, t-buty:L
hydropero~ide, cumene hydroperoxide, and aæobisisobutyro-nitrile. These radical producing agents may also be used in a combination of two or more kinds thereof.
In executing the present invention, the poly-phenylene ether type resin to be used is not specifically limited as to the method of its production. For example, the following methods can be used.
(1) a method which comprises adding a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group to a solution containing the polymer of a phenolic compound in the presence of a radical producing agent and stirring the resulting mixture at 50 to 200C for several ten minutes to several hours.
(2) a method which comprises making the reaction compo-nents contact with one another by melt-kneading them in a system containing substantially no solvent or a small amount of solvent.
Method (1) is favorably adopted if the necessary reaction apparatus and purification apparatus are already in hand. Method (2) has advantages in that the rnodifi-cation of the polymer can be performed with inexpensive equipment such as a general purpose twin screw extruder and in a short time without the need of steps of solvent removal and polymer purification.
More preferably, a method is adapted which comprises reacting 0.05 to 15 parts by weight, preferably 0.1 to 7 parts by weight, of a 1,2-substituted olefinic ,' :
. , }~
1 compound having an acid anhydri.de steucture with 100 parts by weight of the polymer of a phenolic compound in ~he presence of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, o a eadical producing a~ent in the tem-perature range o 200 to 350C, preferably 220 to 330C.
As specific examples of a 1~2-substituted olefinic compound having a carboxylic acid group or acid anhydride geoup used in the reaction with the hydrogenated block copolymer, there may be mentioned maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, methylnadic anhydride, dichloromaleic anhydride, acrylic acid, and methacrylic acid.
As to the radical producing agent employed for the reaction o~ the above-mentioned block copolymer with the above-mentioned 1,2-substituted olefinic compound, there may be used benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisiso-butyronitrile, and the like. These radical producing agents may also be used in a combination of two or more thereof.
Although no particular limitation is placed as to the method of preparing the hydrogenated block copolymer type elastomer used in this invention, those methods are not preferable in which the resulting elastomer has a markedly increased melt viscosity and hence a poor processability. A preferred method comprises reacting a hydrogenated block copolymer with an unsatu-rated carboxylic acid anhydride or with an unsaturated . .:
' ' .
~2 ~
1 carboxylic acid in the presence oE a radical lnitiator in an e~truder.
The amount of the 1,2-substituted olefinic compound having a carboxylic acid group or an acid anhydride group added to the hydrogenated block copolymer is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the hydrogenated block copolymer. When the added amount is less than 0.05~ by weight, the resulting polymer is poor in the effect expected for modified hydrogenated block copolymer, and cannot give a satisfactory impact resistance when compounded into a final composition. At an added amount exceeding 10% by weight, further increase in the effect of modification is scarecely observed as compared with products of smaller added amount.
As typical examples of melt-kneading apparatus which can be used in this invention, mention may be made of extruders, mixing rolls, Banbury mixture, and kneaders. Particularly preferable in this invention is the method of kneading using a twin screw extruder. The kneading temperature, though depending also on the melting temperature of component resins, is preferably 220 to 350C for kneading a mixture wherein no polyamide resin is contained, and is a temperature ranging from the melting point of polyamide resin to a temperature of 100C higher than its melting point for kneading a mixture wherein polyamide resin is contained.
The composition of this invention can be .-.~
... ... ..
:: :
~ 7~
1 processed by known methods of Eorming yenerally used eor thermoplastic resins, for example injection molding, extrusion, flo~ molding and vacuum forming.
EFFECT OF THE INVENTION
Products obtained by simply mixing by mechanical means such polymers incompatible with one another as PA
resin, a phenolic compound polymer, and a block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block 3, ; lO the degree of unsaturation of the block B not exceeding 20%, do not form a dispersed phase, or even when they form a dispersed phase, they give rise to macroscopic phase separation in moldins; or even when such phenomena do not occur, they are very brittle.
Since the polyphenylene ether type resin used in this invention is a product obtained by reacting a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group with a phenolic compound polymer, it can form, in the final resin composition, dispersed phases wherein amount all of the particles are present as fine particles of 0.6 ~m or less.
Also, since the block copolymer type elastomer : used in this invention is a product obtained by reacting a 1,2-substituted olefinic compound having a carboxylic acid group or acid anhydride group with the above-mentioned block copolymer, it can form dispersed phases in the composition.
:~2S;~7~
1 Further, in the polyphenylene ether ~ype resin and the block copolymer type el~stomer, which are polymecs to which a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group has been reacted, it is considered that the double bond moiety of the olefinic compound has undergone grafting to leave a polar group, namely carboxylic acid group, acid anhydride group or epoxy group, bonded to the main chain of PPE and TPE. It is estimated that the above-mentioned polar group reacts with the terminal amino group or carboxylic acid group of PA and the amido group present in its main chain, whereby the PP2 dispersed phase and TPE dispersed phase are stabilized. Further, it is estimated that said reaction results in the increase of insoluble portion remaining after extraction with formic acid, a solvent for PA, and with chloroform, a solvent for PPE and TPE, thereby to give a composition which has an insoluble portion of 20~ by weight or more and is of excellent mechanical properties and low anisotropy thereof.
Example This invention will be further described below with reference to Examples in order to be more clearly understood. However, the scope of this invention is not limited to these Examples. In the Examples, all ~parts~
are part by weight.
~ 7 l Example l (l) Preparation of maleic anhydride mocli~ied polyphen~-l~ne ether type resin Poly(2,6-dimethylphenylene-1,4-ether) with a number average polymeeization degree of 140, di-t-butyl peroxide, and maleic anhydride were dry-blended in a weight ratio of 100/l/5 at room temperature. ~y means of a twin screw extruder with vent of reverse rotation type, a screw diameter of 30 mm and L/D of 30, the blend was melted under conditions of a cylinder temperature of 300C
and a screw rotating speed of 75 rpm, then extruded at a residence time of l minute, passed through a cooling bath, and then pelletized. A 0.05 g portion of the pellet was formed into film of about 15 ~m thickness by the use of chloroform. The film was then heated with ethanol under reflux in a Soxhlet's extractor for 10 hours. It was then dried and used as the sample for infrared spectrophoto-metry. The presence of the -CO2- structure in the sample originating from the reaction with maleic anhydride was confirmed from the analysis of the absorption peak of 1700 ~ l~00 cm l in the infrared absorption spectrum.
(2) Preparation of maleic anhydride-modified hydrogenated block copolymer A uniform mixture of 100 parts by weight of a hydrogenated block copolymer (Kraton G1652, mfd. by Shell Chemical Co.; styrene content; 29~; SEBS-typer S denoting styrene and EB denoting ethylene butylene), 1.2 parts by weight of maleic anhydride, and 0.3 part by weight of '' ' .
,' . :
: -, -1 ~ ~9~7~
1 Perhexa (a trade name oE a peroxide, mfd. b~ Nippo~l Oil &Fat Co., Ltd.) was fed to a twin screw extruder (screw diameter 45 mm; L/D: 33; with vent) and subjected to maleic acid addition reaction at a cylinder temperature oE
260C while unreacted rnaleic anhydride was being removed by suction through the vent hole. The resulting modified hydrogenated block copolymer was dried by heating it under reduced pressure and analyzed to show an addition amount of maleic anhydride of 0.6% by weight. The addition amount of maleic anhydride was determined by titration with sodium methylate.
SpecifiC examples of Rl, R2, R3, R4 and R5 in the above general formula include hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxy-methyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, ; phenyl, chlorophenyl, methylphenyl, dimethylphenyl, and ethylphenyl.
Specific examples of the compound represented by the above general formula include phenol, o-, m- or p-cresol, 2,6-, 2,5-, 2,4- and 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethyl-phenol, 2-methyl-6-ethylphenol, and 2,3,5-, 2,3,6- and 2,4,6~trimethylphenol. These phenolic compounds may also be used in combinations of two or more kinds thereof.
The phenolic compounds of the above general formula may also be copolymerized with phenolic compounds other than those of the said formula, such as bisphenol A, ~, , - ~ :
~ '7~
l tetrabromobisphenol A, resorcinol, and hydroquinone.
It is well known that polymers oE phenolic compound can be obtained by oxi~atively polymerizing the compound by means of oxygen or an oxygen-containing gas using an oxidative coupling catalyst. For example, polymers can be obtained by reacting phenolic compounds with oxygen in the presence of a copper or manganese complex.
Further~ there can also be used a graft copolymer obtained by grafting a styrene type compound to the above-mentioned phenolic compound polymer. Examples of the styrene type compound include styrene, ~-methyl-styrene, methylstyrene, vinyltoluene, and chlorostyrene.
Further, to improve processability, styrene type polymers may be added within a range not detrimental to the mechanical properties of the product. As specific examples of such styrene type polymers, there may be mentioned styrene homopolymer; rubber-modified polystyrene resins using various kinds of rubbers, for example, polystyrene modified with butadiene type rubber (of various content of microstructures), polystyrene modified with acrylic rubber, polystyrene modified with ethylene-propylene copolymer, polystyrene modified with ethylene-propylene-diene copolymer rubber, and polystyrene modified with butadiene-styrene rubber; styrene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile copolymer (so-called ABS resin), butadiene-styrene-methyl methacry-late copolymer, and styrene-ethylene copolymer.
..~' .
,~
7~
1 The hydrogenated block copolymer type e:lastolner used in this invention is a hydroyenated block A copol~mer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the block B not exceeding 20%.
The hydrogenated block copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, used in this invention, is obtained by selective hydrogenation of t'ne conjugated diene portions of a block copolymer containing a vinyl aromatic compound polymer block and a conjugated diene type compound polymer block.
Among the above-mentioned block copolymer ; containing a vinyl aromatic compound polymer block and a conjugated diene type compound polymer block, there may be mentioned a linear ~lock copolymer represented by the formulas (X~Y)n, (X-Y-X')n, X-~ Y-X-Y-t-nX, or X-t-Y-x tnY
(n is an integer from 1 to 10) which is a copolymer consisting of a vinyl aromatic compound polymer blocks (X) and (X') and a conjugated diene type compound polymer block (Y) (X and X' may be the same or di~ferent), and a radial block copolymer represented by the general formulas [(Y-~) ] ~2Z' [(X~Y)n ~ 2Z' [(Y~X)n~Y ]m+2Z
[(X-Y)n-X ~ z (wherein X, Y and n are as defined above;
m is an integer from 1 to 4 and Z is the residue of a coupling agent such as silicon tetrachloride and tin tetrachloride or that of an initiator such as a polyfunc-tional organolithium compound).
~ ' . ' ' , .
.. ~
., . ~'............... .....
7~
1Typical examples of vinyl aromatic compounds used herein include styrene, ~-methylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and the mixtures thereof. These of conjugated d.iene type compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-diethylbutadiene, and the mixtures thereof.
The terminal blocks of these block copolymers may be the same or different from each other.
The number average molecular weight of these block copolymers is 10,000 to 800,000, preferably 20,000 to 500,000.
The content of the vinyl aromatic compound in these block copolymers is preferably 10 to 70% by weight, more preferably 10 to 55% by weight.
15The hydrogenated block copolymer used in this invention is obtained by selective hydrogenation of the conjugated diene portion of the above-mentioned block ; copolymer. For example, a hydrogenated block copolymer wherein not more than 20~ of the aromatic double bonds in the vinyl aromatic compound polymer block and at least 80%
of the aliphatic double bonds in the conjugated diene compound polymer block have been hydrogenated can be obtained by hydrogenating the above-mentioned block ccpolymer according to the method described in Japanese Patent Application Rokoku (Post-Exam. Publn.) No; 8704/67, published September 10, 1986.
The ~degree of unsaturation of block B~ referred to in this invention means the proportion of carbon-carbon double bonds contained in the block B, and is usually in a . ~ ~
: . , . ' ' ' ,:
, :: .. ,: . : .. :
, .: , ...
': .' ' .
1 range not e~ceeding 20Q~. It can be deter~ined by instru-mental analysis such as nuclear magnetic resonance method and infrared absorption spectroscopy, and chemcial analysis such as idodometric titration.
These hydrogenated block copolymers can be used each alone or as a mixture of two or more thereof.
In the resin composition of this invention, the compounding ratio is not specifically limited so long as it is a composition comprising polyamide, PPE anD TPE, the diameter of dispersed phase of PPE dispersed in the said composition being 0.6 ~m or less and the insoluble portion of the composition after extraction thereof with formic acid followed by chloroform being 20~ by weight or more.
More preferably, the content of polyamide resin is in the range of 45 to 75% by weight. A content of less than 40% by weight is unfavorable because sometimes it leads to a low thermal resistance. A content exceeding 75% by weight is unfavorable because sometimes it results in the decrease of low temperature impact strength.
The content of PPE is more preferably in the range of 5 to 40~ by weight. A content of less than 5~ by weight is unfavorable because it results in the decrease of low temperature impact strength. A content exceeding 40% by weight is unfaovrable because it leads to the decrease of thermal stability in molding.
The content of TPE is more preferably in the range of 10 to 30~ by weight. A content of less than 10%
by weight is unfavorable because it results in the : : .
, . ::. , : .
. . .~ ~ - :., .. ..
~ ~ 9~
1 decrease of low temperature impact strength. A content e~ceeding 30~ by weight is unfavorable becau.se lt results in a low thermal resistance.
The morphology of the composition of this invention can be examined by observing with a transmission electron microscope an ultrathin slice of the composition stained and fixed by means of osmium tetroxide and/or ruthenium tetroxide. In the morphology of the composition of this invention, PA forms a continuous pnase, whereas PPE and TPE form dispersed phases. More particularly, for example in case of nylon 6,6, the main structure of dispersed phases involve such phase structures as a TPE
dispersed phase enveloping PPE, a TPE dispersed phase enveloping PPE and PA, and a TPE dispersed phase envelop-lS ing PA; and in case of nylon 6 they invo~ve a TPE
dispersed phase enveloping PPE and PA, and a dispersed phase of PPE alone. The PPE dispersed phases range in their size from a very finely dispersed phase to a dispersed phase reaching several ~m in diameter.
As to the diameter of the PPE dispersed phase of the composition according to this invention, it is preferable that most of the PPE dispersed phases have a diameter of 0.6 ~m or less. A diameter of less than 0.01 ~m, namely so fine a dispersion is to make observation with an electron microscope virtually impossible even at amagnification of 10,000, is unfavorable because it leads to the decrease of low temperature impact strength. On the other hand, when the number of particles larger than '. ' ~ ' ." . ' .
~. . .
.~ , .. . .. .
l 0.6 ~m is large, it leads to the decrease o~ low temperature impact strength and is hence unfavorable.
The diameter of the PPE dispersed phase is measured with an electron photomicrograph taken at a magnification of lO,000. ~hen the phase is elliptic, the length of its major axis (~) and that of the minor axis (~) (defined herein as the distance between the points at which a perpendicular line drawn through the center of the major axis intersects the ellipsoid) were determined, and a value D calculated from the equation D ~ (~ + ~)/2 is taken as the diameter of the dispersed phase.
The insoluble portion of the composition of this invention remaining after extraction thereof with formic acid followed by chloroform is preferably 20% by weight or more relative to the total amount of PPE and TPE in the composition. Further, from the viewpoint of practical molding processability, it is not more than 150% by weight. An insoluble proportion of less than 20% by weight is unfavorable ~ecause it leads to the decrease of low temperature impact strength and/or to anisotropy of mechanical properties of formed articles.
The insoluble portion is determined in the following manner. A formed article is pulverized mechani-cally to give powders having a particle diameter of about 0.5 mm or less. After l g of the powdery composition is weighed accurately, and mixed with 50 ml of 39~ formic acid. The mixture is stirred at room temperature (20 to 25C) for 5 hours, filtered through a glass filter to ;, '. ~ . .
.. - . .. ~ - .
~ 7~7~
1 separate insoluble matter, which is then washed with formic acid, water and acetone, and then dried. The insoluble matter is then mixed with 50 ml o~ chloroform, and the mixture is stirred at room temperature (20 to 25C) for 17 hours, and then filtered throu~h a glass filter to separate insoluble matter, which is washed with chloroform and methylene chloride, dried and then weighed The amount of PPE and TPE in the composition can be determined by first calculating the amount of polyamide from the amount of nitrogen in the composition obtained by elemental analysis and then by substraction. If addi-tives are contained in the composition they are removed before the calculation of the polyamide amount.
The characteristics of the present composition lS lies in the state of the dispersion of each said component (a), (b) and (c) and the insoluble portion of the composi-tion remaining after the extraction while a polyamide resin, a polyphenylene ether resin and an elastomer of a hydrogenated block copolymer are employed. The above-mentioned characteristics are attained firstly byemploying the present process mentioned hereinafter which is entirely different from that of the conventional one.
Although the detailed physico-chemical mechanism showing the excellent effect in the present invention is not clear, it is believed that it can be attained by the process of the present invention that the dispersed state of the present composition is not a mere mixture of PA, ,~
. .-- ~ -.
.... .
~ - ',. ~; '.
~9t7,~,~
1 PPE alld rrpE~ but the :Eormation of a stable dispersioll of PPE and TPE in the PA phase which may have been clerived rom a strong interactlon between them which has never been known, whereby a smaller particle size of PPE ~pecified as in this invention can be formed therein; and that a higher content of said insoluble portion can be attained as a result of employing the present process.
The resin composition of this invention may be incorporated, at optional steps of its production and molding, with other ingredients including pigments, dyes, reinforcing materials, fillers, thermal stabilizers, antioxidants, weather proofing agents, nucleating agents, lubricant, plasticizers, antistatic agents, and other polymers within a range not detrimental to its moldability and mechanical properties.
A preferred process for producing the resin composition of this invention comprises melt-kneading a polyphenylene ether type resin obtained by reacting, in the presence of a radical producing agent, a 1,2-substi-tuted olefinic compound having an acid anhydride structurewith a polyrner obtained by oxidative polymerization of at least one phenolic cornpound represented by the general formula .
"
' 7~7~
R~ R 5 R2 Rl 1 wherein Rl, R2, R3, R4 and R5 arer independentlyr a hydrogen atom, halogen atom, or substituted or unsubsti-tuted hydrocarbon group, provided that at least one of them must be hydrogen; a hydrogenated block copolymer type elastomer obtained by reacting, in the presence o a radi-cal producing agent, a 1,2-substituted olefinic compound having an acid anhydride structure with a hydrogenated block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block B, the degree of unsaturation of the said block B not exceeding 20%; and a polyamide resin. Another process may also be used which comprises melt-kneading optional two components preliminarily and then melt-kneading the remaining component therewith.
As specific examples o 1,2-substituted olefinic compounds having a carboxylic acid group, acid anhydride group, or epoxy group, there may be mentioned maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, methylnadic anhydride, dichloromaleic anhydride, acrylic acid, methacrylic acid, and glycidyl methacrylate.
The radical producing agents usuable in this invention include organic peroxides and diazo compounds known to the art. As speciic examples thereof, mention : -- 19 --' : -.; ~ , .-:
: , ~;
.. ,. , 1 may be made o~ ben~oyl peroxide, dicumyl peroxide, t-buty:L
hydropero~ide, cumene hydroperoxide, and aæobisisobutyro-nitrile. These radical producing agents may also be used in a combination of two or more kinds thereof.
In executing the present invention, the poly-phenylene ether type resin to be used is not specifically limited as to the method of its production. For example, the following methods can be used.
(1) a method which comprises adding a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group to a solution containing the polymer of a phenolic compound in the presence of a radical producing agent and stirring the resulting mixture at 50 to 200C for several ten minutes to several hours.
(2) a method which comprises making the reaction compo-nents contact with one another by melt-kneading them in a system containing substantially no solvent or a small amount of solvent.
Method (1) is favorably adopted if the necessary reaction apparatus and purification apparatus are already in hand. Method (2) has advantages in that the rnodifi-cation of the polymer can be performed with inexpensive equipment such as a general purpose twin screw extruder and in a short time without the need of steps of solvent removal and polymer purification.
More preferably, a method is adapted which comprises reacting 0.05 to 15 parts by weight, preferably 0.1 to 7 parts by weight, of a 1,2-substituted olefinic ,' :
. , }~
1 compound having an acid anhydri.de steucture with 100 parts by weight of the polymer of a phenolic compound in ~he presence of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, o a eadical producing a~ent in the tem-perature range o 200 to 350C, preferably 220 to 330C.
As specific examples of a 1~2-substituted olefinic compound having a carboxylic acid group or acid anhydride geoup used in the reaction with the hydrogenated block copolymer, there may be mentioned maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, methylnadic anhydride, dichloromaleic anhydride, acrylic acid, and methacrylic acid.
As to the radical producing agent employed for the reaction o~ the above-mentioned block copolymer with the above-mentioned 1,2-substituted olefinic compound, there may be used benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisiso-butyronitrile, and the like. These radical producing agents may also be used in a combination of two or more thereof.
Although no particular limitation is placed as to the method of preparing the hydrogenated block copolymer type elastomer used in this invention, those methods are not preferable in which the resulting elastomer has a markedly increased melt viscosity and hence a poor processability. A preferred method comprises reacting a hydrogenated block copolymer with an unsatu-rated carboxylic acid anhydride or with an unsaturated . .:
' ' .
~2 ~
1 carboxylic acid in the presence oE a radical lnitiator in an e~truder.
The amount of the 1,2-substituted olefinic compound having a carboxylic acid group or an acid anhydride group added to the hydrogenated block copolymer is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the hydrogenated block copolymer. When the added amount is less than 0.05~ by weight, the resulting polymer is poor in the effect expected for modified hydrogenated block copolymer, and cannot give a satisfactory impact resistance when compounded into a final composition. At an added amount exceeding 10% by weight, further increase in the effect of modification is scarecely observed as compared with products of smaller added amount.
As typical examples of melt-kneading apparatus which can be used in this invention, mention may be made of extruders, mixing rolls, Banbury mixture, and kneaders. Particularly preferable in this invention is the method of kneading using a twin screw extruder. The kneading temperature, though depending also on the melting temperature of component resins, is preferably 220 to 350C for kneading a mixture wherein no polyamide resin is contained, and is a temperature ranging from the melting point of polyamide resin to a temperature of 100C higher than its melting point for kneading a mixture wherein polyamide resin is contained.
The composition of this invention can be .-.~
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1 processed by known methods of Eorming yenerally used eor thermoplastic resins, for example injection molding, extrusion, flo~ molding and vacuum forming.
EFFECT OF THE INVENTION
Products obtained by simply mixing by mechanical means such polymers incompatible with one another as PA
resin, a phenolic compound polymer, and a block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A and an olefinic compound polymer block 3, ; lO the degree of unsaturation of the block B not exceeding 20%, do not form a dispersed phase, or even when they form a dispersed phase, they give rise to macroscopic phase separation in moldins; or even when such phenomena do not occur, they are very brittle.
Since the polyphenylene ether type resin used in this invention is a product obtained by reacting a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group with a phenolic compound polymer, it can form, in the final resin composition, dispersed phases wherein amount all of the particles are present as fine particles of 0.6 ~m or less.
Also, since the block copolymer type elastomer : used in this invention is a product obtained by reacting a 1,2-substituted olefinic compound having a carboxylic acid group or acid anhydride group with the above-mentioned block copolymer, it can form dispersed phases in the composition.
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1 Further, in the polyphenylene ether ~ype resin and the block copolymer type el~stomer, which are polymecs to which a 1,2-substituted olefinic compound having a carboxylic acid group, acid anhydride group, or epoxy group has been reacted, it is considered that the double bond moiety of the olefinic compound has undergone grafting to leave a polar group, namely carboxylic acid group, acid anhydride group or epoxy group, bonded to the main chain of PPE and TPE. It is estimated that the above-mentioned polar group reacts with the terminal amino group or carboxylic acid group of PA and the amido group present in its main chain, whereby the PP2 dispersed phase and TPE dispersed phase are stabilized. Further, it is estimated that said reaction results in the increase of insoluble portion remaining after extraction with formic acid, a solvent for PA, and with chloroform, a solvent for PPE and TPE, thereby to give a composition which has an insoluble portion of 20~ by weight or more and is of excellent mechanical properties and low anisotropy thereof.
Example This invention will be further described below with reference to Examples in order to be more clearly understood. However, the scope of this invention is not limited to these Examples. In the Examples, all ~parts~
are part by weight.
~ 7 l Example l (l) Preparation of maleic anhydride mocli~ied polyphen~-l~ne ether type resin Poly(2,6-dimethylphenylene-1,4-ether) with a number average polymeeization degree of 140, di-t-butyl peroxide, and maleic anhydride were dry-blended in a weight ratio of 100/l/5 at room temperature. ~y means of a twin screw extruder with vent of reverse rotation type, a screw diameter of 30 mm and L/D of 30, the blend was melted under conditions of a cylinder temperature of 300C
and a screw rotating speed of 75 rpm, then extruded at a residence time of l minute, passed through a cooling bath, and then pelletized. A 0.05 g portion of the pellet was formed into film of about 15 ~m thickness by the use of chloroform. The film was then heated with ethanol under reflux in a Soxhlet's extractor for 10 hours. It was then dried and used as the sample for infrared spectrophoto-metry. The presence of the -CO2- structure in the sample originating from the reaction with maleic anhydride was confirmed from the analysis of the absorption peak of 1700 ~ l~00 cm l in the infrared absorption spectrum.
(2) Preparation of maleic anhydride-modified hydrogenated block copolymer A uniform mixture of 100 parts by weight of a hydrogenated block copolymer (Kraton G1652, mfd. by Shell Chemical Co.; styrene content; 29~; SEBS-typer S denoting styrene and EB denoting ethylene butylene), 1.2 parts by weight of maleic anhydride, and 0.3 part by weight of '' ' .
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1 Perhexa (a trade name oE a peroxide, mfd. b~ Nippo~l Oil &Fat Co., Ltd.) was fed to a twin screw extruder (screw diameter 45 mm; L/D: 33; with vent) and subjected to maleic acid addition reaction at a cylinder temperature oE
260C while unreacted rnaleic anhydride was being removed by suction through the vent hole. The resulting modified hydrogenated block copolymer was dried by heating it under reduced pressure and analyzed to show an addition amount of maleic anhydride of 0.6% by weight. The addition amount of maleic anhydride was determined by titration with sodium methylate.
(3) Preparation of composition A mixture of 50 parts of nylon 6,~ ILeona 1300S, mfd. by Asahi Chemical Industry Co., Ltd.), 25 parts of the maleic anhydride-modified polyphenylene ether type resin obtained in (1) above, and 25 parts of the maleic anhydride-modified hydrogenated block copolymer obtained in (2) above was extruded through a twin screw extruder (screw diameter: ~5 mm, L/D: 33) set at 300C, then passed through a cooling bath, and pelletized. The pellets were dried at 80C for 8 hours under reduced pressure an~ then injection-molded under the following conditions to obtain molded pieces for determination of their properties.
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1 Injection moldin~ machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2 Injection time lS seconds Cooling time 20 seconds ~old temperature 80C
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1 Injection moldin~ machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2 Injection time lS seconds Cooling time 20 seconds ~old temperature 80C
(4) Determination of properties Thermal resistance: A 1/8" thick test piece was used to determine its heat distortion temperature at 4.6 kg/cm2 load under an absolte dry condition according to ASTM D 648.
Impact resistance: Izod impact strength was determined by using a 1/8" thick test piece with notch at room temperature (23C) and under an absolute dry condition according to AST~ D 256.
Low temperature impact resistance: Izod impact strength at -30C was determined by using a 1/8" thick test piece with notch.
Rigidity: Flexural modulus was determined by using a 1/8" thick test piece under absolute dry condition according to AS~M D790-80.
Anisotropy of mechanical properties: A test piece having a notch in the direction of resin flow cut from the gate part and a test piece having a notch in the direction perpendicular to resin flow cut from the central part were prepared from flat plates of 12 x 8 cm and 1/8"
: thickness. I~od impact strength was determined according '..' .. . .. . . . . ..... ... . . . . .. .... . .. ..... .. .. .. .. . . .. . .... . . . .
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condition. The anisotropy of mechanical propertles was defined in terms of the ratio of the impact strength at the gate part to that at the central part and calculated by the following equation.
Aniso~ropy of mechanical properties Impact strength at gate part _ x 100 (~) Impact strength at central part The results of these determinations are shown in Table 1. It can be seen that the composition has remark-ably excellent impact strength not only at room temperature but also at -30C, and has also excellent thermal resistance; further it has ve-ry well balanced mechanical properties, the anisotropy of mechanical properties being 91%.
Figs. 1 and 2 are transmission electron photomicrographs of molded articles. The photograph of Fig. 2 shows the morphology of a molded article formed after residence in an injection machine at 310C for 10 minutes. Though the dispersed phases of elastomer are in an agglomerated states, the PPE dispersed phase do not form agglomeration and most of the dispersed phases are about 0.5 ~m or less in size; the number of dispersed phases larger than 0.6 ~m was found to be only one. The impact strength at 23C of the said molded article subjected to 10 minutes of residence is 55 kg-cm/cm, a .
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comparative ~xample l s The properties of the nylon 6,6 resin used in Example l are shown in Table l.
Comparative Example 2 The procedures of Example 1 were repeated by using a hydrogenated block copolymer (Kraton Gl652, mfd.
by Shell Chemical Co.) in place of the maleic anhydride-modified hydrogenated block copolymer used in Example l.
The results, shown in Table l, reveals that the resulting composition is very poor in anisotropy of mechanical properties. Fig. 3 shows the electron photomicrograph of the composition.
Comparative Example, 3 The procedures of Example l were repeated except that unmodified polyphenylene ether was used in place of the maleic anhydride-modified polyphenylene ether used in Example l, and the results obtained are shown in Table l.
The resulting composition shows low values both in low temperature impact strength and thermal resistance. The electron photomicrograph of the composition is shown in Fig. 4.
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~ 97 1 Comparatlve Example 4 Under the same conditions as in Example 1, a mixture of 50 parts of nylon 6,6 (Leona 1300 S, mfd. by ~sahi Chemical Industry Co., Ltd.), 25 parts oE poly-(2,6-dimethylphenylene-1,4-ether) having a number average polymerization degree of 140, 25 parts of a hydrogenated block copolymer (Kraton G1652, mfd. by Shell Chemical Co.) and 1 part of maleic anhydride was melt-kneaded and injec-tion-molded to determine their properties. The results are shown in Table 1. The electron photomicrograh of the resulting composition is shown in Fig. 5.
Comparative Example 5 The procedures of Comparative Example 4 were repeated except that 0.3 part of di-t-butyl peroxide was further added to the formulation of Comparative Example 4. The results obtained are shown in Table 1. The electron photomicrograph of the resulting composition is shown in Fig. 6.
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~ 7~7 1 Examples 2 to 10 Compositlons were prepared from mixtures comprising the three components, used in Ex~mple 1, in proportions shown in Table 2, and their properties are shown in Table 2.
Compositions were obtained which were remarkably excellent in impact strength, particularly that at -30C, and also excellent in thermal resistance and of low level of anisotropy of mechanical properties.
The test pieces obtained by molding the composi-tions of Examples 4, 6 and 9 after residence of 10 minutes at 310C in an injection machine showed considerably high values of Izod impact strength at 23C of 77, 73 and 65 kg-cm/cm, respectively, revealing also their resistance stability in molding machines.
Flgs 7 to 11 show the electron photcmicro-graphs of the compositions of Examples 2, 3, 4, 7 and 9, respectively.
Comparative Examples 6 and 7 Compositions were obtained by melt-kneading, by extrusion, mixtures comprising the three components, used in Example 1, in proportions shown in Table 2. Their properties are shown in Table 2.
The compositions of Comparative Examples 6 and 7 are both excellent in thermal resistance but show low Izod impact stren~th at -30C. Further, when they are retained in an injection molding machine at 310C, increase of . ,, ; , ~
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1 Example 11 A mixture of 50 parts of nylon 6 (Amilan 1017, md. by Toray Industrials, Inc.) 25 parts of the maleic anhydride-modiEied polyphenylene ether used in Example 1, and 25 parts of the maleic anhydride-modified hydrogenated block copolymer used in Example 1 was extruded through a twin screw extruder (screw diameter: 45 mm, L/D: 33) set at 300C, then passed through a cooling bath and pelletized. The pellets thus obtained were dried at 80C
under reduced pressure and then injection-molded under the following conditions to obtain test pieces for determination of their properties.
Injection molding machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2 Injection time 15 seconds Cooling time 20 seconds Mold temperature 80C
The results thus obtained are shown in Table 3.
The electron photomicrograph of the composition is shown in Fig. 13.
Comparative Example 8 The properties of the nylon 6 resin used in Example 11 is shown in Table 3.
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l INDUSTRIAL AepLIcABILITy one feature Oe the composition of this inventionis its excellent impact resistance, particularly an excellent impact strenyth at low temperature, combined with excellent thermal resistance.
Another feature of the composition is its low level of anisotropy of mechanical properties.
Resultantly, the composition can be used in a wide field of application without being restricted as to forming techniques and uses.
A further is that the composition is stable even when retained in molding machines for a long time in molding. Resultantly, it is suitable also for forming a large-size articles which require a long residence time.
Further, since a large amount of polyphenylene ether type resin and of block copolymer type resin, which are both nonhydroscopic, can be added to polyamide resin according to the process of this invention, it also exhibits an effect of decreasing the moisture absorption of polyamide resin simultaneously with improving the dimensional stability.
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Impact resistance: Izod impact strength was determined by using a 1/8" thick test piece with notch at room temperature (23C) and under an absolute dry condition according to AST~ D 256.
Low temperature impact resistance: Izod impact strength at -30C was determined by using a 1/8" thick test piece with notch.
Rigidity: Flexural modulus was determined by using a 1/8" thick test piece under absolute dry condition according to AS~M D790-80.
Anisotropy of mechanical properties: A test piece having a notch in the direction of resin flow cut from the gate part and a test piece having a notch in the direction perpendicular to resin flow cut from the central part were prepared from flat plates of 12 x 8 cm and 1/8"
: thickness. I~od impact strength was determined according '..' .. . .. . . . . ..... ... . . . . .. .... . .. ..... .. .. .. .. . . .. . .... . . . .
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~ ~i9 7 1 to ASTM D 256 with the test pieces under an absolute dr,~
condition. The anisotropy of mechanical propertles was defined in terms of the ratio of the impact strength at the gate part to that at the central part and calculated by the following equation.
Aniso~ropy of mechanical properties Impact strength at gate part _ x 100 (~) Impact strength at central part The results of these determinations are shown in Table 1. It can be seen that the composition has remark-ably excellent impact strength not only at room temperature but also at -30C, and has also excellent thermal resistance; further it has ve-ry well balanced mechanical properties, the anisotropy of mechanical properties being 91%.
Figs. 1 and 2 are transmission electron photomicrographs of molded articles. The photograph of Fig. 2 shows the morphology of a molded article formed after residence in an injection machine at 310C for 10 minutes. Though the dispersed phases of elastomer are in an agglomerated states, the PPE dispersed phase do not form agglomeration and most of the dispersed phases are about 0.5 ~m or less in size; the number of dispersed phases larger than 0.6 ~m was found to be only one. The impact strength at 23C of the said molded article subjected to 10 minutes of residence is 55 kg-cm/cm, a .
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: , l property oE a considerably high level, reveali.ng that the composition shows remarkably excellent residence stability in molding machines.
comparative ~xample l s The properties of the nylon 6,6 resin used in Example l are shown in Table l.
Comparative Example 2 The procedures of Example 1 were repeated by using a hydrogenated block copolymer (Kraton Gl652, mfd.
by Shell Chemical Co.) in place of the maleic anhydride-modified hydrogenated block copolymer used in Example l.
The results, shown in Table l, reveals that the resulting composition is very poor in anisotropy of mechanical properties. Fig. 3 shows the electron photomicrograph of the composition.
Comparative Example, 3 The procedures of Example l were repeated except that unmodified polyphenylene ether was used in place of the maleic anhydride-modified polyphenylene ether used in Example l, and the results obtained are shown in Table l.
The resulting composition shows low values both in low temperature impact strength and thermal resistance. The electron photomicrograph of the composition is shown in Fig. 4.
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~ 97 1 Comparatlve Example 4 Under the same conditions as in Example 1, a mixture of 50 parts of nylon 6,6 (Leona 1300 S, mfd. by ~sahi Chemical Industry Co., Ltd.), 25 parts oE poly-(2,6-dimethylphenylene-1,4-ether) having a number average polymerization degree of 140, 25 parts of a hydrogenated block copolymer (Kraton G1652, mfd. by Shell Chemical Co.) and 1 part of maleic anhydride was melt-kneaded and injec-tion-molded to determine their properties. The results are shown in Table 1. The electron photomicrograh of the resulting composition is shown in Fig. 5.
Comparative Example 5 The procedures of Comparative Example 4 were repeated except that 0.3 part of di-t-butyl peroxide was further added to the formulation of Comparative Example 4. The results obtained are shown in Table 1. The electron photomicrograph of the resulting composition is shown in Fig. 6.
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~ 7~7 1 Examples 2 to 10 Compositlons were prepared from mixtures comprising the three components, used in Ex~mple 1, in proportions shown in Table 2, and their properties are shown in Table 2.
Compositions were obtained which were remarkably excellent in impact strength, particularly that at -30C, and also excellent in thermal resistance and of low level of anisotropy of mechanical properties.
The test pieces obtained by molding the composi-tions of Examples 4, 6 and 9 after residence of 10 minutes at 310C in an injection machine showed considerably high values of Izod impact strength at 23C of 77, 73 and 65 kg-cm/cm, respectively, revealing also their resistance stability in molding machines.
Flgs 7 to 11 show the electron photcmicro-graphs of the compositions of Examples 2, 3, 4, 7 and 9, respectively.
Comparative Examples 6 and 7 Compositions were obtained by melt-kneading, by extrusion, mixtures comprising the three components, used in Example 1, in proportions shown in Table 2. Their properties are shown in Table 2.
The compositions of Comparative Examples 6 and 7 are both excellent in thermal resistance but show low Izod impact stren~th at -30C. Further, when they are retained in an injection molding machine at 310C, increase of . ,, ; , ~
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Fig. 12 shows the electron photomicrograph oE
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1 Example 11 A mixture of 50 parts of nylon 6 (Amilan 1017, md. by Toray Industrials, Inc.) 25 parts of the maleic anhydride-modiEied polyphenylene ether used in Example 1, and 25 parts of the maleic anhydride-modified hydrogenated block copolymer used in Example 1 was extruded through a twin screw extruder (screw diameter: 45 mm, L/D: 33) set at 300C, then passed through a cooling bath and pelletized. The pellets thus obtained were dried at 80C
under reduced pressure and then injection-molded under the following conditions to obtain test pieces for determination of their properties.
Injection molding machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2 Injection time 15 seconds Cooling time 20 seconds Mold temperature 80C
The results thus obtained are shown in Table 3.
The electron photomicrograph of the composition is shown in Fig. 13.
Comparative Example 8 The properties of the nylon 6 resin used in Example 11 is shown in Table 3.
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l INDUSTRIAL AepLIcABILITy one feature Oe the composition of this inventionis its excellent impact resistance, particularly an excellent impact strenyth at low temperature, combined with excellent thermal resistance.
Another feature of the composition is its low level of anisotropy of mechanical properties.
Resultantly, the composition can be used in a wide field of application without being restricted as to forming techniques and uses.
A further is that the composition is stable even when retained in molding machines for a long time in molding. Resultantly, it is suitable also for forming a large-size articles which require a long residence time.
Further, since a large amount of polyphenylene ether type resin and of block copolymer type resin, which are both nonhydroscopic, can be added to polyamide resin according to the process of this invention, it also exhibits an effect of decreasing the moisture absorption of polyamide resin simultaneously with improving the dimensional stability.
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Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An impact-resistant polyamide resin composition which comprises (a) a polyamide resin (hereinafter abbreviated as PA), (b) a polyphenylene ether resin (hereinafter abbreviated as PPE), and (c) a hydrogenated block copolymer elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and a conjugated diene polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 µm or less, and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20% by weight or more relative to the total amount of PPE and TPE present in the composition.
2. An impact-resistant polyamide resin composition according to claim 1 which comprises 40 to 75% by weight of a polyamide resin, 5 to 40% by weight of a polyphenylene ether resin, and 10 to 30% by weight of a hydrogenated block copolymer elastomer which is a copolymer containing a vinyl aromatic compound polymer block A and a conjugated diene polymer block B, the degree of unsaturation of the block B not exceeding 20%.
3. An impact-resistant polyamide resin composition according to Claim 1 or 2, wherein said PPE is a product obtained by subjecting 100 parts by weight of a phenolic compound to reaction with 0.05 to 15 parts by weight of a 1,2-substituted conjugated diene compound having an acid anhydride structure in the presence of 0.05 to 5 parts by weight of a radical producing agent.
4. An impact-resistant polyamide resin composition according to claim 1, wherein the content of said vinyl aromatic compound in said block copolymer is 10 to 70 parks by weight per 100 parts by weight of said block copolymer.
5. An impact-resistant polyamide resin composition according to claim 4, wherein said content of said vinyl aromatic compound in said block copolymer is 10 to 55 parts by weight per 100 parts by weight of said block copolymer.
6. A process for producing an impact-resistant polyamide resin composition comprising (a) a polyamide resin (hereinafter abbreviated as PA), (b) a polyphenylene ether resin (hereinafter abbreviated as PPE), and (c) a hydrogenated block copolymer elastomer (hereinafter abbreviated as TPE) which is a copolymer containing a vinyl aromatic compound polymer block A and a conjugated diene compound polymer block B, the degree of unsaturation of the block B not exceeding 20%, the diameter of the dispersed phase of PPE dispersed in the said composition being 0.6 µm or less and the insoluble portion of the composition remaining after extraction thereof with formic acid followed by chloroform being 20% by weight or more relative to the total amount of PPE and TPE present in the composition, which process comprises melt-kneading a polyphenylene ether resin obtained by reacting, in the presence of a radical producing agent, a 1,2-substituted conjugated diene compound having a carboxylic acid group, acid anhydride group or epoxy group with a polymer obtained by oxidative polymerization of at least one phenolic compound represented by the general formula therein R1, R2, R3, R4 and R5 are, independently, a hydrogen atom, halogen atom, or substituted or unsubstituted hydrocarbon group, provided that at least one of them must be hydrogen, a hydrogenated block copolymer elastomer obtained by reacting, in the presence of a radical producing agent, a 1,2-substituted conjugated diene compound having an acid anhydride structure with a hydrogenated block copolymer which is a copolymer containing a vinyl aromatic compound polymer block A
and a conjugated diene compound polymer block B, the degree of unsaturation of the block B exceeding 20%, and a polyamide resin.
and a conjugated diene compound polymer block B, the degree of unsaturation of the block B exceeding 20%, and a polyamide resin.
7. A process for producing an impact-resistant polyamide resin composition according to claim 6, wherein the amount of said 1,2-substituted conjugated diene compound is 0.1 to 7 parts by weight and that of said radical producing agent is 0.1 to 3 parts by weight per 100 parts by weight of said phenolic compound.
8. A process for producing an impact-resistant polyamide resin composition according to claim 6, wherein said TPE is a product obtained by subjecting 100 parts by weight of said hydrogenated block copolymer to reaction with 0.05 to 10 parts by weight of a carboxylic acid or its anhydride.
9. A process for producing an impact-resistant polyamide resin composition according to claim 8, wherein an amount of said carboxylic acid or the anhydride thereof is 0.1 to 5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000532316A CA1269778A (en) | 1987-03-18 | 1987-03-18 | Impact-resistant polyamide resin composition and process for producing the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP87302322A EP0282664B1 (en) | 1987-03-18 | 1987-03-18 | Novel impact-resistant polyamide resin composition and process for producing the same |
| CA000532316A CA1269778A (en) | 1987-03-18 | 1987-03-18 | Impact-resistant polyamide resin composition and process for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269778A true CA1269778A (en) | 1990-05-29 |
Family
ID=4135214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000532316A Expired CA1269778A (en) | 1987-03-18 | 1987-03-18 | Impact-resistant polyamide resin composition and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1269778A (en) |
-
1987
- 1987-03-18 CA CA000532316A patent/CA1269778A/en not_active Expired
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