JPH0692527B2 - Impact resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel resin composition having excellent impact strength and excellent chemical and thermal properties, more specifically, polyarylate. The present invention relates to a resin composition obtained by adding an impact strength imparting material composed of a mixture of an epoxy group-containing ethylene-based copolymer and an acid anhydride-containing ethylene-based copolymer to a matrix of a polyamide and a polyamide.

(Prior Art) A resin composition comprising polyarylate and polyamide, or polyarylate, polyamide and polyester is known. For example, Japanese Examined Patent Publication (Kokoku) No. 58-50260 discloses the characteristics of a ternary resin composition of polyarylate, polyamide, polyester or polyester ether. Further, JP-A-52-100552 and 52-100553 disclose the manufacturing method thereof. JP-A-53-943
Japanese Patent No. 66 discloses the flame retardant method.

A resin composition composed of polyarylate and polyamide (optionally containing polyester or polyester ether) has excellent chemical properties and has extremely high heat resistance. Moldability is also good.

For example, polyarylate 30 obtained from bisphenol A and a mixed phthalic acid of terephthalic acid and isophthalic acid 30
The resin composition consisting of 50% by weight, 50% by weight of polycaprolactam and 20% by weight of polyethylene terephthalate exhibits excellent resistance to organic solvents and has a high heat distortion temperature of 160 ° C. The flow length of spiral molding is about 10 times longer than that of polyarylate alone.

As described above, such a resin composition has excellent chemical properties, heat resistance, and moldability, and has already been put to practical use as a well-balanced molding material.

However, the impact strength of the resin composition is not always a satisfactory value. For example, in the case of a resin composition consisting of 50% by weight of polyarylate and 50% by weight of polycaprolactam, the Izod impact strength is 7 kg · cm / cm. When used as exterior parts for automobiles, an Izod impact strength of at least 20 kg · cm / cm is required. Since the resin composition has outstanding features such as excellent chemical properties, heat resistance, and moldability, it is expected from various fields that its application can be increased by dramatically improving its impact strength. It had been.

Although various means have been proposed as a method for improving the impact strength of the thermoplastic molding material, a method of adding a copolymer having an active group is typical. In particular, it is said to be particularly effective when it has a carboxyl group or an amino group like the matrix forming the resin composition.

However, when a copolymer having an epoxy group as an active group is added to the resin composition in order to obtain a satisfactory impact strength, it is necessary to add a large amount of the resulting resin composition gel. It is not practical because it becomes colored, colored, and decomposed. In addition, in the case of a copolymer containing an acid anhydride, when a large amount is blended, phase separation occurs, and not only the gloss of the molded product is lowered, but also when a large amount is added, the initial desired impact strength cannot be obtained. As described above, all attempts to improve impact strength while maintaining other excellent properties of the resin composition have been unsuccessful.

(Problems to be Solved by the Invention) In view of such circumstances, an object of the present invention is to significantly improve impact strength without impairing excellent chemical properties, heat resistance and moldability of a resin composition comprising polyarylate and polyamide. Can be improved. Another object of the present invention is to provide a molding material which is excellent in chemical properties, heat resistance, moldability and impact resistance and gives a molded article having good gloss.

(Means for Solving the Problems) As a result of intensive studies conducted by the present inventors for such a purpose, the matrix composed of polyarylate and polyamide was used as an impact strength-imparting material in which an epoxy group-containing ethylene copolymer and an acid were used. It has been found that all the objects of the invention can be achieved by adding a mixture with an anhydride-containing ethylene-based copolymer. Satisfactory impact strength cannot be obtained when the epoxy group-containing ethylene copolymer and the acid anhydride-containing ethylene copolymer are used alone, but rather gelation, coloring, decomposition or phase separation occurs, and molded products Despite various defects such as poor surface gloss, it is surprising that when used together, these problems do not occur and the impact strength is improved more than when used alone. That is.

That is, the present invention relates to a matrix composed of 10 to 70% by weight of polyarylate and 90 to 30% by weight of polyamide, and (A) ethylene and at least one unsaturated glycidyl monomer as an impact resistance-imparting material; Epoxy group-containing ethylenic copolymer obtained by copolymerizing at least one other ethylenically unsaturated monomer, (B) ethylene and at least one α, β-unsaturated dicarboxylic anhydride Relates to a resin composition obtained by adding 3 to 30% by weight of a mixture with an acid anhydride ethylene-based copolymer obtained by copolymerizing an α, β-unsaturated carboxylic acid ester.

The aromatic polyester copolymer used in the present invention is a mixture of terephthalic acid and isophthalic acid or a functional derivative thereof (where the molar ratio of terephthalic acid group to isophthalic acid group is 1: 9 to 9: 1) and the general formula Bisphenols (where -X- is -0
Selected from the group consisting of —, —S—, —SO ₂ —, —CO—, alkylene group or alkylidene group, R ₁ , R ₂ , R ₃ ,
R ₄ , R ′ ₁ , R ′ ₂ , R ′ ₃ and R ′ ₄ are selected from the group consisting of hydrogen atom, halogen atom and hydrocarbon).

Examples of such bisphenols represented by the above general formula include 4,4′-dihydroxy-diphenyl ether, bis (4-hydroxy-2-methylphenyl) -ether,
Bis (4-hydroxy-3-chlorophenyl) -ether, bis (4-hydroxyphenyl) -sulfide,
Bis (4-hydroxyphenyl) -sulfone, bis (4
-Hydroxyphenyl) -ketone, bis (4-hydroxyphenyl) -methane, bis (4-hydroxy-3-methylphenyl) -methane, bis (4-hydroxy-3,5
-Dichlorophenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl) -methane, bis (4-hydroxy-3,5-difluorophenyl) -methane, 1,1-bis (4-hydroxyphenyl)- Ethane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2- Bis (4-hydroxy-3,5-dibromophenyl) -propane, 1,1-bis (4-hydroxyphenyl) n-butane, bis (4-hydroxyphenyl) -phenylmethane, bis (4-hydroxyphenyl)- Diphenylmethane, bis (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis (4-hydroxyphenyl) -2,2,2, -trichloroethane, bis (4-hydroxyphenyl)-(4'- Chlorophenyl) -methane, 1,1-bis (4-hydroxyphenyl)-
Cyclohexane, bis (4-hydroxyphenyl) -cyclohexylmethane, 2,2-bis (4-hydroxynaphthyl) -propane and the like can be mentioned, but the most commonly produced and representative one is 2,2-bis (4- Hydroxyphenyl)
What is called propane or bisphenol A. If necessary, a mixture of said bisphenols or a small amount of other divalent compounds with bisphenols, for example dihydroxynaphthalene such as 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, hydroquinone, nozorcinol, 2,6- Mixtures of dihydroxychlorobenzene, 2,6-dihydroxytoluene, 3,6-dihydroxytoluene and the like can be used.

Functional derivatives of terephthalic acid or isophthalic acid are dichlorides or diesters of alkyl, aryl and the like of these acids.

The phenylene group of terephthalic acid or isophthalic acid or a functional derivative thereof used in the present invention may be substituted with a halogen atom or an alkyl group.

The aromatic polyester copolymer used in the present invention is synthesized by any method such as an interfacial polymerization method, a solution polymerization method and a solution polymerization method.

In order to obtain a resin composition having preferable physical properties, it is preferable to use an aromatic polyester copolymer having an average molecular weight of 5,000 to 100,000.

The polyamide used as one component of the resin composition of the present invention has the general formula It is represented by. Here, R ₅ , R ₆ and R ₇ represent a phenylene group or an alkylene group. The polyamide used in the present invention includes a polymer formed by condensation reaction of diamine and dibasic acid, self-condensation of amino acid and polymerization reaction of lactam.

The polyamide used in the present invention may be any polyamide as long as it is represented by the above general formula. Preferred polyamides are polytetramethylene adipamide, polyhexamethylene adipamide, polycaprolactam, polyhexamethylene sebacamide. , Polydecamethylene adipamide and the like.

It may also be a ternary or higher copolymer,
For example, a copolymer of terephthalic acid and 2,2,4-trimethylhexamethylenediamine and / or 2,4,4-trimethylhexamethylenediamine, or isophthalic acid and bis (4
It may be a copolymer of -amino, 3-methylcyclohexyl) methane with caprolactam and / or lauryllactam. The polyamide used as one component of the present invention may be one kind or a mixture of two or more kinds.

The unsaturated glycidyl monomer which is a copolymerization component of the epoxy group-containing ethylene copolymer used in the present invention is 1
It is a monomer having one unsaturated bond capable of copolymerizing with ethylene-based monomers in the molecule and having one or more epoxy groups.

For example, the general formula (Wherein R ₈ represents a hydrocarbon group having an ethylenically unsaturated bond.) And an unsaturated glycidyl ester represented by the general formula (Wherein Y is -CH ₂ -C- or And R ₈ is the same as the description of the formula [I]. ) Unsaturated glycidyl ethers represented by (Here, R ₈ is a hydrocarbon group having an ester unsaturated bond, and R ′ ₈ is hydrogen or a methyl group.) Epoxy alkenes, etc., such as glycidyl acrylate and glycidyl Methacrylate,
Itaconic acid monoglycidyl ester, Itaconic acid diglycidyl ester, Butene tricarboxylic acid monoglycidyl ester, Butene tricarboxylic acid diglycidyl ester, Butene tricarboxylic acid triglycidyl ester, P-
Styrenecarboxylic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene P-glycidyl ether or P-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3
-Methyl-1-butene, 3,4-epoxy-1-pentene,
Mention may be made of 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene and vinylcyclohensen monoxide.

Examples of the ethylenically unsaturated monomer which is a copolymer component of the epoxy group-containing ethylenic copolymer used in the present invention include the following.

2 to 6 for olefins such as propylene, butene-1, decene-1, octacene-1, styrene, and saturated carboxylic acid components
Esters containing 1 to 8 carbon atoms such as vinyl acetate, vinyl propionate, vinyl benzoate, etc. Methyl-, ethyl-, propyl-, butyl of acrylic acid and methacrylic acid containing 1 to 8 carbon atoms in the saturated alcohol component -, 2-Ethylhexyl-, cyclohexyl-, dodecyl-, octadecyl-, etc. esters, maleic acid diesters, vinyl chlorides, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, N
-Vinyl lactams such as N-vinyl picolidone or N
-Vinylcaprolactam and acrylic acid amide compounds, secondary acid N-vinylcarboxylic acid amide, N-vinyl-N
-Alkylcarboxylic acid amides and the like.

Of the above-mentioned ethylenically unsaturated monomers, vinyl acetate and acrylic acid esters are particularly conveniently used among them.

The copolymerization ratio of the unsaturated glycidyl monomer in the epoxy group-containing ethylene copolymer used in the present invention is 0.
It is from 05 to 95 mol%, preferably from 0.1 to 50 mol%.

The α, β-unsaturated dicarboxylic acid anhydride, which is the copolymerization component of the acid anhydride-containing ethylene copolymer used in the present invention, has the following formula: (Wherein R ₉ and R ₁₀ represent hydrogen, an alkyl group or a halogen group), and examples thereof include maleic anhydride, methyl maleic anhydride, chloromaleic anhydride, citraconic anhydride, butynyl. Examples include succinic anhydride and tetrasidrophthalic anhydride.

Α, β optionally used as a copolymerization component of the acid anhydride-containing ethylene-based copolymer used in the present invention
-Specific examples of the unsaturated carboxylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid 2
-Methacrylic acid esters such as hydroxyethyl, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid esters such as 2-hydroxyethyl acrylate, and the like, or mixtures thereof. Examples of the monomer copolymerizable with ethylene, α, β-unsaturated carboxylic acid ester and α, β-unsaturated dicarboxylic acid anhydride include styrene compounds such as styrene, α-methylstyrene and vinyltoluene, and acrylonitrile. , Α, β-unsaturated nitriles such as methacrylonitrile, α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, vinyl acetate, vinyl ether, etc., and these can also be copolymerized if necessary. .

The copolymerization ratio of the α, β-unsaturated dicarboxylic acid anhydride in the acid anhydride-containing ethylene copolymer used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 50 mol%. As a method for producing such an epoxy group-containing ethylene-based copolymer or an acid anhydride-containing ethylene-based copolymer, a so-called known radical copolymerization method is used, as well as ethylene or styrene homopolymer or ethylene-based copolymer. Alternatively, a method in which a radical generator is present in a styrene-based copolymer and one or more unsaturated monomers having the above groups are subjected to a radical graft reaction in the presence or absence of a solvent or a dispersion medium can be mentioned. In particular, when grafting in a molten state, a melt kneader such as an extruder, a kneader, or a pan-par mixer can be used to obtain a desired product in a very short time with a simplified method.

The composition ratio of polyarylate and polyamide constituting the matrix of the present invention is 10 to 70% by weight of polyarylate and 90 to 30% by weight of polyamide. Most preferably, the polyarylate is 30 to 60% by weight and the polyamide is 70 to 40% by weight. The mixing ratio of the epoxy group-containing ethylene copolymer used as the impact resistance imparting agent and the acid anhydride-containing ethylene copolymer is such that the epoxy group / acid anhydride equivalent ratio is 1: 9 to 9: 1. Preferably
Most preferred is the range 3 to 7 to 7: 3.

The amount of the mixture of the epoxy group-containing ethylene copolymer and the acid anhydride-containing ethylene copolymer used as a material for imparting impact resistance to the matrix is preferably 3 to 30% by weight. If it is less than 3% by weight, the impact strength improving effect is remarkable, and if it exceeds 30% by weight, the heat resistance is largely lowered.

The resin composition of the present invention may further contain additives such as heat stabilizers, oxidation stabilizers, light stabilizers, lubricants, pigments, flame retardants and plasticizers.

Glass fiber, metal fiber, potassium titanate whisker,
Fibrous reinforcing agents such as carbon fibers, talc, calcium carbonate, mica, glass flakes, milled fibers, metal flakes, filler type reinforcing agents such as metal powders may be mixed. In particular, by mixing glass fibers in an amount of 10 to 50% by weight with respect to 50 to 90% by weight of the resin composition of the present invention, not only the mechanical strength and heat resistant temperature are significantly improved, but also the water resistance is further improved. Can be seen and is preferable in achieving the object of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1 to 8 1/1 of bisphenol A and terephthalic acid / isophthalic acid
Polyarylate obtained from the mixture (Unitika, U
Polymer, U-100), Polycaprolactam (A1030 BRL manufactured by Unitika Ltd.) as polyamide, ethylene-glycidyl methacrylate-vinyl acetate copolymer (Sumitomo Chemical, Bondfast E) as epoxy group-containing ethylene-based copolymer, acid Ethylene-maleic anhydride-acrylic acid ester copolymer (Sumitomo CDF, Bondine LX4110) was used as the anhydride-containing ethylene-based copolymer, and after mixing with the composition shown in Table 1, vacuum drying was performed overnight at 80 ° C. , 270 ℃ each
Pellets were obtained using a twin-screw extruder at. Using the pellets thus obtained, test pieces were obtained by ordinary injection molding and subjected to measurement. The results obtained are listed in Table 1.

Examples 9-15 The same polyarylate used in Examples 1-8, isophthalic acid-lauryl lactam-bis (4-amino, 3-methylcyclohexyl) methane copolymerized polyamide (EMS, TR-5).
5), and the same epoxy group-containing ethylene copolymer used in Examples 1 to 8 and ethylene-maleic anhydride-acrylic acid copolymer as an acid anhydride-containing ethylene copolymer (Sumika CDF, Bondine AX8040) was mixed with the composition shown in Table 2 to obtain a test piece in the same manner, which was then used for measurement.
The results obtained are listed in Table 2.

(Effects of the Invention) As shown in Tables 1 and 2, when the epoxy group-containing ethylene copolymer is used alone in the matrix composed of polyarylate and polyamide, gelation or coloring occurs during pelletization. ， In addition, the heat distortion temperature drops significantly. On the other hand, when the acid anhydride-containing ethylene copolymer is used alone,
The effect of improving impact strength is small, and the gloss on the surface of the molded product is lost.

In contrast, the resin composition of the present invention has no drawbacks when these impact resistance imparting materials are used alone, and surprisingly the impact strength is remarkably improved as compared with the case where they are used alone.

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Claims (4)

[Claims] 1. A matrix comprising 10 to 70% by weight of polyarylate and 90 to 30% by weight of polyamide, and (A) ethylene and at least one unsaturated glycidyl monomer as an impact resistance-imparting material, An epoxy group-containing ethylenic copolymer obtained by copolymerizing one or more other ethylenically unsaturated monomers, (B) ethylene, and one or more α, β-
3 to 30% by weight of a mixture of an unsaturated dicarboxylic acid anhydride and, if necessary, an acid anhydride-containing ethylene copolymer obtained by copolymerizing an α, β-unsaturated carboxylic acid ester
A resin composition obtained by addition. 2. The epoxy group-containing ethylene-based copolymer is an ethylene-glycidyl methacrylate-vinyl acetate copolymer, and the acid anhydride ethylene-based copolymer is an ethylene-maleic anhydride-acrylic acid ester copolymer. The resin composition according to claim 1, which is 3. The resin composition according to claim 1, wherein the equivalent ratio of the epoxy group and the acid anhydride in the impact resistance imparting material mixture is in the range of 1: 9 to 9: 1. 4. The resin composition according to claim 1, wherein the polyarylate is obtained from bisphenol A and a mixed phthalic acid of terephthalic acid and isophthalic acid.