JPS62184051A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having an excellent surface appearance, low-temperature impact resistance, thermal properties and moldability, consisting of an arom. polyester, an arom. polycarbonate, a specified butadiene graft copolymer, an ethylene copolymer and an olefin copolymer. CONSTITUTION:90-5wt% at least one vinyl monomer selected from the group consisting of a methacrylic ester, an arom. monovinyl compd. and a vinyl cyanide is grafted onto 10-85wt% butadiene polymer to obtain a butadiene graft copolymer (C) having a grafting rate of 5-200%. 4-95wt% arom. polyester (A) is melt-kneaded with 4-95wt% arom. polycarbonate (B) (e.g., a 4,4'- dihydroxydiphenylalkane polycarbonate), 1-20wt% component C and 0.5-10wt% olefin copolymer (D) having a glass transition temp. of not higher than 0 deg.C, composed of an alpha-olefin and a glycidyl ester of an alpha,beta-unsaturated acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition, and more specifically, it has excellent surface appearance, moldability and mechanical properties, especially low 1! ! This invention relates to a thermoplastic resin composition with excellent impact resistance.

[Prior art] Aromatic polystyrene is a thermoplastic material that generally has various excellent properties including oxidation resistance and solvent resistance, and can be melt-molded to obtain fibers and films with good physical and mechanical properties. suitable for. However, since these polymers have a highly crystalline structure, they have poor dimensional stability when molded by injection molding or the like, and also have poor impact resistance and heat resistance.

On the other hand, aromatic polycarbonates (especially 4,4'-dihydroxydiphenylcan polycarbonates) are wJF
It is very difficult to mold because the viscosity is too high, and it also has the disadvantage of poor solvent resistance.

Therefore, attempts have been made to mix aromatic polyester and aromatic polycarbonate uniformly in a molten state to compensate for the above-mentioned defects of both polymers (see, for example, Japanese Patent Publication No. 14035/1982). By mixing aromatic polyester and aromatic polycarbonate in this way, the physical properties of aromatic polyester as a molding resin such as dimensional stability are improved, and at the same time, the melt viscosity of aromatic polycarbonate is reduced, making molding easier. However, the resin composition obtained in this way has the disadvantage that it has insufficient impact resistance, which limits its application to applications that require impact resistance. have

As a method of improving the impact resistance of aromatic polyester and aromatic polycarbonate resin compositions, a method of blending olefins or olefin copolymers has been proposed (
JP-A No. 59-89352), however, the improvement in impact resistance is not sufficient, and since such resin compositions are incompatible, the resulting molded products tend to cause delamination and a striped pattern on the surface.
A product with a good appearance cannot be obtained.

Therefore, in the present invention, in order to improve the impact resistance of such a resin composition, an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid was added, and an improvement in impact strength was observed. However, the properties at low temperatures were not sufficient, and satisfactory surface properties could not be obtained.

[Objective of the Invention 1] The object of the present invention is to provide a resin composition that has excellent surface appearance and good mechanical properties, particularly low 11ij impact properties, thermal properties, and moldability.

[Structure of the invention] The present invention (A) Aromatic polyester 4-95% by weight.

(B) Aromatic polycarbonate (B) 4-95 weight 6%.

(C) A vinyl monomer selected from the group consisting of a butadiene polymer (a), a methacrylic acid ester (b), and an aromatic monovinyl compound (/su and vinyl cyanide compound).
butadiene-based graft copolymer graft copolymerized with one or more of the following: 1-20ffi%.

(D) ethylene copolymer 1-20111%, and (
E) Olefinic copolymer consisting of α-olefin and glycidyl ester of α,β-unsaturated acid
It is a thermoplastic resin composition consisting of 0.5 to 10% by weight.

The aromatic polyester used in the present invention (A> is a polyester having an aromatic group in the main chain of the polymer, and the main components are an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. The aromatic dicarboxylic acid component is, for example, a dicarboxylic acid having a benzene nucleus such as terephthalic acid and isophthalic acid.

naphthalene-2,6-dicarboxylic acid, naphthalene-1,
5-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid M
A dicarboxylic acid having a naphthalene nucleus such as or its ester forming property l! One example is jintai.

In place of such aromatic dicarboxylic acids or their ester-forming derivatives, dicarboxylic acids other than aromatic dicarboxylic acids, such as adipine 10. It is also possible to use sebacic acid or ester-forming derivatives thereof. Examples of diol components include ethylene glycol, tetramethylene glycol, and hexamethylene glycol.

Examples include aliphatic glycols such as diethylene glycol and cyclohexane dimetatool, diols having an aromatic ring such as 1,4-bisoxyethoxybenzene and bisphenol A, and ester-forming derivatives thereof.

The aromatic polyester used in the present invention may be not only one type of aromatic polyester but also a mixture of two or more types of aromatic polyester.

The aromatic polycarbonate (B) used in the present invention is
In particular, 4,4'-dihydroxydiphenylalkane polycarbonate, more specifically 2,2-(4
, 4'-dihydroxydiphenyl)propane (hereinafter abbreviated as bisphenol A) as a dihydroxy component, and a polycarbonate obtained by a transesterification method or a phosgene method is preferred. Furthermore, bisphenol A
Part or all of may be substituted with 4,4'-dihydroxydiphenylalkane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, etc., or two or more You may use a mixture of aromatic polycarbonates.

Butadiene-based graft copolymer (C) used in the present invention
is methacrylic M on butadiene-based graft polymer (a)
(0) is a product obtained by graft copolymerizing one or more vinyl monomers selected from the group consisting of aromatic monovinyl compounds (/su and vinyl cyanide compounds). The graft copolymer ( In C), the amount of butadiene polymer (A) is 10 to 85% by weight, particularly 30 to 70% by weight.
Preferably, it is % by weight. When it is less than 10%, the impact strength of the resulting resin composition is low;
If it is more than % by weight, the moldability of the resulting resin composition will deteriorate, which is not preferable. As the butadiene polymer (a), a copolymer of a butadiene i-mer and a vinyl monomer, such as styrene, can also be used, but in terms of impact resistance, the butadiene component is It is preferably 50% by weight or more.

The vinyl monomer to be graft copolymerized to the butadiene polymer (a) is one or more of methacrylic acid ester (0), aromatic monovinyl compound (4), and vinyl cyanide compound (2); The ratio of the monomers to be used is arbitrary, and a small proportion thereof may be replaced with other vinyl monomers. In addition, the order of use when graft copolymerizing the vinyl spinning wheel body is arbitrary, and 2)! The above may be used simultaneously, or may be used separately for graft copolymerization without any problem.

As the methacrylic ester, alkyl esters having 1 to 4 carbon atoms are preferred, and methyl esters are particularly preferred. Examples of the aromatic monovinyl compound include styrene, vinyltoluene, α-methylstyrene, nuclear halogenated styrene, and vinylnaphthalene, with styrene being particularly preferred. Examples of vinyl cyanide compounds include acryloni].

Examples include methacrylonitrile and α-halogenated acrylonitrile, with acrylonitrile being particularly preferred. As the butadiene-based graft copolymer, ABS and MBS are preferably used.

In addition, the butadiene-based graft copolymer preferably has a graft ratio of 15 to 200% from the viewpoint of impact resistance and surface appearance. Here, the graft ratio is a value calculated from the following formula.

Grafting rate = weight of acetone insoluble fraction ffi/rubber component [(
b) Ingredients]! ! Agriculture x 100 However, in the formula, the acetone insoluble content is 8 enough to cover the graft copolymer with acetone! After crushing, the insoluble precipitate is strictly collected and determined by centrifugation.

Butadiene-based kraft copolymer (C
) can be produced by any method including bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. In particular, when producing a component with a high rubber content, it is desirable to produce it by emulsion graft polymerization.

The butadiene-based graft copolymer (C) of the present invention may be used in combination with a hard thermoplastic resin, but the butadiene-based polymer component (A) It is necessary that the amount is 10% or more with respect to the total amount. The hard thermoplastic resin may be one obtained by combining the same vinyl monomers as those used in the graft copolymer (C), or a thermoplastic resin obtained from a different monomer. Although resins can also be used, those obtained from the same monomer are preferred from the viewpoint of compatibility.

The ethylene copolymer (D) used in the present invention includes ethylene and propylene, butene-1°hexene-1,
α-olefins such as decene-1,4-methylbutene-1 and -4-methylpentene-1 or ethylenically unsaturated residues such as styrene, acrylonitrile, vinyl acetate, vinyl propionate, acrylic esters, and methacrylic esters Monomer, dicyclopentadiene, 1.4-
Examples include copolymers mainly composed of diene monomers such as hexadiene, ethylidenenorbornene, methylnorbornene, and 1,5-dicyclooctadiene, and the glass transition temperature of the copolymer is 0°C or lower. It is preferable that it is, and it is especially preferable that it is -20 degreeC or less.

The olefinic copolymer (
The α-olefin in E) includes ethylene, propylene, butene-1, etc., and ethylene is particularly preferred. Glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (in which R is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a glycidyl ester group), and specific examples thereof include contains glycidyl acrylate,
These include glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate, with glycidyl methacrylate being particularly preferred. α in glycidyl group-containing copolymers.

The copolymerization ratio of glycidyl ester of β-unsaturated acid is 0.
5-40! ! ! m% is preferred, and more preferably 1 to 30% by weight, more preferably 2 to 20% by weight. If the copolymerization amount is less than 0.5% by weight, the impact improvement effect will not be sufficient, and if it is more than 401121%, the fluidity during molding will decrease, which is not preferable. Alpha-olefins and glycidyl esters of alpha, beta-unsaturated acids can be copolymerized by standard copolymerization or grafting reactions. Also,
Further, if the amount is 40% by weight or less, unsaturated polymers copolymerizable with the above-mentioned copolymers, ie, vinyl ethers, and vinyl acetate.

Vinyl esters such as vinyl propionate, methyl,
Acrylic acid and methacrylic acid esters such as ethyl, propyl, butyl, acrylonitrile, styrene, -
It is also possible to combine 111 or more carbon oxides. Examples of preferred olefin copolymers include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl meccrylate copolymer, and ethylene/glycidyl acrylate copolymer. /W# acid vinyl copolymer and the like, among which ethylene/glycidyl methacrylate copolymer is most preferred.

A resin composition consisting of an aromatic polyester (A) and an aromatic boria J-bonate (B) contains <D) component and (E)
Even if the components are mixed together, the resulting molded product will suffer from layer peeling, resulting in poor surface appearance and insufficient impact resistance, especially impact resistance at low temperatures; however, by adding component (C), stripes will not appear and gloss will be improved. It is possible to obtain a molded product with excellent properties and low-temperature impact resistance. The reason for this is not clear, but it is presumed that polyolefins, polyesters, and polycarbonates are originally incompatible due to large differences in compatibility parameters, but chemically the glycidyl group of component (E) and the terminal carboxyl group of polyester The olefin component of the component (E) and the component (D), which is an ethylene co-merger, become compatibilized, the component (D) and the butadiene of the component (C) become compatible, and further the olefin component of the component (C) becomes compatible. It is believed that by making styrene compatible with polycarbonate, uniformity increases and a molded article with excellent surface properties without delamination is obtained.

The mixing ratio of such a thermoplastic resin composition is 4 to 95% by weight of component (A) and 4 to 95% by weight of component (B) per resin composition.
95ffiffi%, (C) component force 1~10ffi
lt1%, preferably 5 to 15% by weight, component (D) is 1%
~201%, preferably 5-15% and (E)
The ingredients must be mixed to contain 0.5 to 10% by weight, preferably 1 to 5% by weight. If the content of component (A) is less than 4rJm%, the resulting composition will have insufficient solvent resistance;
If it is more than 1%, the resulting composition will have insufficient dimensional stability. If the content of component (B) is less than 4 mm%, the dimensional stability of the resulting composition will be poor and the heat distortion temperature will not improve, resulting in an insufficient content, while on the other hand, if the content of component (B) is less than 95% heavy chain If the amount is too large, the resulting composition will not have good moldability.

Furthermore, when the content of component (C) is less than 11% by weight, the impact strength and surface appearance of the resulting composition are not improved, while when it is more than 20% by weight, the thermal deformation of the composition is 2 g.
! This is not desirable because the degree of Regarding the content of component (D), if it is less than 1% by weight, the impact strength of the resulting composition will not be improved, while if it is more than 20 Iffi%, it will not only lower the heat distortion temperature of the composition. , (C
Even in the presence of component ), the surface appearance is impaired, which is undesirable. Furthermore, if the content of component (E) is less than 0.5% by weight, the impact strength of the composition will not be improved, while if it is more than 10% by weight, it will become a gel state and the surface properties will deteriorate, which is not preferable.

The composition of the present invention may contain various additives (e.g., various stabilizers, fl additives, flame retardants, mold release agents, inorganic fillers) within the range that does not impair the purpose of the present invention. Also good.

As a method for preparing the thermoplastic resin composition of the present invention, any method of mixing solid substances (for example, a method using a Banbury mixer 9 heated roll or a single-screw or multi-screw extruder) can be applied.

[Example] The effects of the present invention will be explained in further detail with reference to Examples below.

In the Examples, "parts" and "%" are all based on weight, and impact strength was measured by the method of ASTM-256, and molding shrinkage rate was measured by the method of ASTM-955. The surface appearance was evaluated by the striped pattern and gloss of the surface. Also,
Reduced specific viscosity is Asisochro 07 x / -) Lt 10
0ad! This is the value measured at 35° C. by dissolving 1.2 g of m-coalescence in water.

Examples 1-5. and Comparative Examples 1 to 5 Polyethylene terephthalate (reduced specific viscosity 0.71) dried at 130°C for 5 hours as aromatic polyester
, “Panlite L-1250” (product name; manufactured by Yojin Kasei KK) dried at 130°C for 5 hours as an aromatic polycarbonate, and methyl ester in the presence of butadiene-styrene co-m polymer rubber 6or11 as a butadiene-based graft copolymer. 24 parts of methacrylate.

Butadiene-based graft copolymer obtained by emulsion graft copolymerization of 16 parts of styrene (grafting rate 57.3%),
An ethylene copolymer and an olefin copolymer consisting of an .alpha.-olefin and a glycidyl ester of an .alpha., .beta.-unsaturated acid were uniformly mixed in various proportions shown in Table 1 in a V-type blender.

The resulting mixture was heated to a barrel temperature of 2 using a 65J11φ extruder.
The mixture was melt-kneaded at 10° C., and the thread discharged from the die was cooled and cut to obtain a pellet for molding.

Next, this pellet was dried with hot air at 130°C for 5 hours, and a test piece mold for measuring physical properties was attached to a 5-ounce injection molding machine, and the cylinder temperature was 270°C.

Mold temperature 90℃, 11i1 pressure cuff 0039/d
, a cooling time of 20 seconds and a total cycle of 35 seconds.

The resulting test pieces were evaluated for impact strength and surface appearance.

The results are shown in Table 1.

(Left below) As shown in Table 1, by using components (C), (D), and (E) in combination, a molded product with excellent surface appearance and good 1I411i impact resistance can be obtained. Recognize. Furthermore, the molding shrinkage rate of polyethylene terephthalate is 0.
．． 019α/aS, whereas that of the example is 0.0
It was 06-0.007 cm/cm.

Examples 6-10. and Comparative Examples 6 to 10 Polytetramethylene terephthalate (reduced specific viscosity i 1.1G) was used as the aromatic polyester, Panlite L-1225'' (trade name: manufactured by Yojin Kasei KK) and butadiene-based graft were used as the aromatic polycarbonate. As a polymer, a graft copolymer obtained by emulsion graft copolymerization of 50 parts of styrene and 20 parts of acrylonitrile in the presence of 30 parts of polybutadiene (grafting rate 82.5%), an ethylene copolymer, and an α-olefin The olefinic copolymer consisting of glycidyl ester and α,β-unsaturated acid was evaluated by the same method as in Example 1 at the ratios shown in Table 2.

The results are shown in Table 2.

(Left below) Note that while the molding shrinkage rate of polytetramethylene terephthalate is 0.021α/aR, that of the present invention is 0.
．． It was 008 to 0.009 cm+/α.

Claims (1)

[Scope of Claims] (A) Aromatic polyester 4 to 95% by weight, (B) Aromatic polycarbonate (B) 4 to 95% by weight, (C) Butadiene polymer (a) and methacrylic acid ester (b) , 1 to 20% by weight of a butadiene-based graft copolymer obtained by graft copolymerizing one or more vinyl monomers selected from the group consisting of aromatic monovinyl compounds (c) and vinyl cyanide compounds (d), (D) 1 to 20% by weight of ethylene copolymer, and (E
) A thermoplastic resin composition comprising 0.5 to 10% by weight of an olefin copolymer comprising an α-olefin and a glycidyl ester of an α,β-unsaturated acid.