JPH0674376B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a resin composition having excellent impact properties.

<Prior Art> It is known that a composition comprising 1 to 99% by weight of a polyarylene ester and 99 to 1% by weight of a polycarbonate is an excellent composition that combines impact resistance and heat distortion resistance. (Japanese Patent Publication No. 50-27061) However, the composition exhibits a very good impact resistance under certain specific conditions, but has a drawback that the value is considerably low under other conditions. That is, when the tip diameter of the notch (notch) provided in the molded product is large, the impact strength is high, but when the tip diameter of the notch is small, the impact strength is significantly low. There is a strong demand for a composition having improved notch dependence of impact strength and having high impact strength even when a sharp notch is formed.

<Problems to be Solved by the Invention> It is an object of the present invention to provide a composition in which notch dependence of impact strength is improved without lowering the heat distortion resistance of the composition comprising a polyarylene ester and a polycarbonate. It is what

<Means for Solving Problems> As a result of intensive studies in view of the above situation, the present inventor has found that ethylene, α, β-unsaturated carboxylic acid alkyl ester can be added to a composition comprising the polyarylene ester and polycarbonate. By blending an ethylene copolymer of maleic anhydride and maleic anhydride, it is found that a composition having excellent impact properties can be obtained while maintaining the features of the composition composed of the polyarylene ester and the polycarbonate. Reached

That is, the present invention relates to (A) polyarylene ester 1 to
60 to 99% by weight of a composition comprising 99% by weight and 99 to 1% by weight of polycarbonate, and (B) 50 to 90% by weight of ethylene,
The present invention relates to a resin composition comprising 40 to 1% by weight of an ethylene copolymer comprising 5 to 49% by weight of an α, β-unsaturated carboxylic acid alkyl ester and 0.5 to 10% by weight of maleic anhydride.

The polyarylene ester used in the present invention is a polyester synthesized from a dihydric phenol or its derivative and an aromatic dibasic acid or its derivative.

Specifically, the dihydric phenol is represented by the following general formula.

In the above, Ar represents an aromatic nucleus such as a phenylene nucleus, a biphenylene nucleus or a naphthylene nucleus, and R is a hydrogen atom, an alkyl group (for example, a methyl group and an ethyl group), a halogenated alkyl group, an aryl group (for example, a phenyl group and a naphthyl group). ,
Halogenated aryl group, aralkyl group (for example, benzyl group and phenylethyl group), halogenated aralkyl group,
An alkyl-substituted aryl group, a halogenated alkyl-substituted aryl group, an alicyclic group or a halogenated substituent, X is a methylene group, an ethylene group, a propylene group, an ethylidene group,
Alkylene group such as propylidene group and isopropylidene group or alkylidene group: aromatic group, tertiary amino group (-N (alk)-) ether group (-O-), carbonyl group (-CO-), or sulfur-containing group group, for example, sulfide (-S-), sulfoxide (SO-) or sulfonyl - showing two interconnected by a group or more alkylene or alkylidene group (-SO _2).
X may also be an alicyclic group or a sulfur-containing group such as a sulfide, sulfoxide or sulfonyl group, an ether group, a carbonyl group or a tertiary amino group. Y is a halogen atom, a nitro group or a group represented by R'or OR '(wherein R'is as defined above for R), m
Is an integer from 0 to the number of replaceable hydrogen atoms on X, n
Is an integer from 0 to the number of replaceable hydrogen atoms on the aromatic nucleus Ar, p is an integer of at least 1, q is an integer of 0 to 1,
f is an integer (provided that r is 0 when q is 0)
Indicates.

In the diphenol represented by the above formula, when there are one or more substituents Y, the same substituents may be the same or different. The same is true for R and R '. The substituent Y of the aromatic nucleus and the hydroxyl group may be in the ortho, meta or para position.

Alternatively, a mixture of these may be used.

Examples of diphenols represented by the above general formula and suitable for carrying out the method of the present invention are as follows.

Bis (4-hydroxyphenyl) -methane, bis (4-
Hydroxy-8-methylphenyl) -methane, bis (4
-Hydroxy-3,5-dichlorophenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl) -methane, bis (4-hydroxy-3,5-difluorophenyl) -methane, bis (4-hydroxyphenyl) ) -Ketone, bis (4-hydroxyphenyl) -sulfide,
Bis (4-hydroxyphenyl) -sulfone, 4,4-
Dihydroxydiphenyl ether, 1,1-bis (4-hydroxyphenyl) -ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (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-hydroxynaphthyl) -propane, 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) -cyclohexasilmethane , 4,4-dihydroxydiphenyl, 2,2-dihydroxydiphenyl, dihydroxynaphthalene such as 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, 2,6-dihydroxytoluene, 2,6-dihydroxychlorobenzene, 3,6-dihydroxy toluene.

The dihydric phenol derivative is specifically a diester such as alkyl or phenyl of the dihydric phenol. Moreover, you may use these mixtures.

Aromatic dihydrochloric acid is represented by the following general formula.

HOOC-Ar'-COOH In the above formula, Ar 'is an o-phenylene group, m-phenylene group,
It represents an arylene group such as a p-phenylene group and a naphthylene group, and these arylene groups may be substituted with an alkyl group or a halogen atom.

Moreover, you may use these mixtures.

The aromatic dihydrochloride group derivative is a dichloride or an alkyl or phenyl diester of the aromatic dibasic acid. Moreover, you may use these mixtures.

The polyarylene ester used as a component of the composition of the present invention is obtained by subjecting the above dihydric phenol or its derivative and the above aromatic dibasic acid or its derivative to an interfacial polycondensation method, a solution polycondensation method, a melt polycondensation method or the like. Is synthesized by the method.

Preferred polyarylene ester is bisphenol A
It has a structure composed of a (2,2-bis (4-hydroxyphenyl) propane) residue, a terephthalic acid residue and an isophthalic acid residue.

This is marketed by Unitika Ltd. as "U Polymer".

The polycarbonate used in the present invention is a 4,4-dioxydiallylalkane-based polycarbonate, and includes, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). Propane, bis (4-hydroxy-3,5-dichlorophenyl) methane, 2,2- (4-hydroxy-3,5
A polycarbonate obtained from 4,4-dioxydiphenylalkane such as dimethylphenyl) propane and bis (4-hydroxyphenyl) phenylmethane, and phosgene or diphenylcarbonate.

The ethylene copolymer used in the present invention has a monomer component consisting of ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, and ethylene is 50
To 90% by weight, preferably 60 to 85% by weight, α, β-unsaturated carboxylic acid alkyl ester 5 to 49% by weight, preferably 7 to 45% by weight, and maleic anhydride 0.5 to 10% by weight, preferably Is 1 to 8% by weight.

The α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, acrylic acid,
An alkyl ester such as methacrylic acid, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methacrylic acid. Methyl acid, ethyl methacrylate,
There are n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, and the like. Among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferable. preferable.

These ethylene copolymers are polyarylene ester 1 to
The composition of 99% by weight and 99 to 1% by weight of polycarbonate (hereinafter referred to as Ac composition) is added in an amount of 60 to 99% by weight based on the total amount of the Ac composition and the ethylene copolymer. %, 40 to 1% by weight of the ethylene copolymer is suitable,
When the Ac composition is more than 99% by weight and the ethylene copolymer is less than 1% by weight, the effect of improving the intended impact strength is insufficient, and the Ac composition is less than 60% by weight, ethylene When the content of the copolymer exceeds 40% by weight, the heat distortion resistance, which is a characteristic of the Ac composition, is significantly lowered, which is not preferable.

The compounding means of the composition of the present invention is not particularly limited.

It is possible to supply each to the melt mixer separately, and it is also possible to pre-mix these raw materials using a mortar, a Herschel mixer, a ball mill, a ribbon blender, etc., and then supply them to the melt mixer. .

Incidentally, with respect to the composition of the present invention, within a range that does not impair the object of the present invention, antioxidants and heat stabilizers, ultraviolet absorbers, lubricants, release agents, dyes, colorants such as pigments, flame retardants,
One or more conventional additives such as flame retardant aids and antistatic agents can be added.

In addition, a small amount of other thermoplastic resin (for example, polyethylene, polypropylene, polyamide, polysulfone, polyether sulfone, modified polyphenylene oxide, polyphenylene sulfide, etc.), thermosetting resin (for example, phenol resin, epoxy resin, etc.) or glass fiber. Reinforcing agents such as carbon fiber, boron fiber, silicon carbide fiber, asbestos fiber, metal fiber, clay, mica,
Fillers such as silica, graphite, glass beads, alumina and calcium carbonate may be added in an appropriate amount according to the purpose.

The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto.

Example 1-8 Polyarylene ester having the following structure as a main structure (manufactured by Unitika Ltd., U polymer U-100, (However, m / n = about 5/5) Polycarbonate (Mitsubishi Gas Chemical Co., Inc., Iupilon S-2000) and 67% ethylene, ethyl acrylate 80.5
Ethylene copolymer consisting of 2.5% maleic anhydride and the composition shown in Table 1 was mixed and melt-kneaded at 260-800 ° C by a twin-screw extruder (PCM-30 made by Ikegu Tekko Co., Ltd.), and then strand Was cooled with water and cut to obtain pellets.

The pellets obtained were injection-molded at 280-320 ℃ (using Sumitomo Heavy Industries-Nestal 47/28 injection molding machine), Izod impact test piece (12.7 × 64 × 6.4mm, notch) and test piece for measuring heat distortion temperature. (12.7 × 127 × 6.4 mm) was obtained. Further, notch blades having various tip diameters were used for the Izod impact test pieces, and notches were formed by cutting.

ASTM for Izod impact test and heat distortion temperature measurement
According to D-256 and D-648.

Comparative Examples 1 to 6 The polyarylene ester, the polycarbonate and the ethylene copolymer used in Examples 1 to 8 were mixed in the proportions shown in Table 1, and the same effect as in Examples 1 to 8 was applied to improve the physical properties. It was measured.

The results are summarized in Table 1. It is clear from the comparison with the comparative example that the compositions of the examples have a small notch dependency and have extremely excellent impact properties and heat distortion resistance.

<Effects of the Invention> The composition comprising the polyarylene ester of the present invention and the polycarbonate and the ethylene copolymer composed of ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride is a polyarylene ester. The notch dependence of the impact strength is remarkably improved without lowering the heat distortion resistance of the composition composed of and polycarbonate.

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Claims (1)

[Claims] 1. A composition 60 comprising (A) 1 to 99% by weight of a polyarylene ester and 99 to 1% by weight of a polycarbonate.
To 99% by weight and (B) ethylene 50 to 90% by weight, α, β-unsaturated carboxylic acid alkyl ester 5 to 49% by weight, and maleic anhydride
Ethylene copolymer consisting of 0.5-10% by weight 40-1% by weight
A resin composition comprising: