JPH0615658B2 - Heat and impact resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition for molding which has improved impact resistance and moldability while maintaining the heat resistance of an aromatic polyester.

[Prior Art] As a polyester having improved impact resistance, JP-A 58-45225 discloses a composition comprising an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer and a polybutylene terephthalate resin. . Japanese Patent Application Laid-Open No. 59-11353 discloses a composition comprising polyester, polyester ether and a rubber-reinforced resin having a rubber component content of 30 to 70% by weight.

Further, JP-A-58-25352 discloses a composition comprising an aromatic polyester, an aromatic polycarbonate resin and an acrylic rubber. However, these are still insufficient in terms of the balance of heat resistance, impact resistance, and moldability.

[Problems to be Solved by the Present Invention] Aromatic polyester resins are used in structural parts and the like by taking advantage of their excellent heat resistance as engineering plastics, but they are inferior in impact resistance and moldability. There is. An object of the present invention is to provide a thermoplastic resin composition for molding in which these three properties are balanced.

[Means for Solving Problems] The present inventors searched for various polymers that improve the impact resistance and moldability of aromatic polyesters, and used polyamide elastomers and styrene resins as excellent improving agents. They found out the present invention, and came to the present invention. That is, the present invention is 30 to 90% by weight of the aromatic polyester resin (A),
A heat and impact resistant resin composition comprising 1 to 40% by weight of a polyamide elastomer (B) and 5 to 60% by weight of a styrene resin (C).

[Aromatic Polyester Resin] The aromatic polyester resin (A) used in the present invention is a condensation product containing an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and an aliphatic glycol (or an ester-forming derivative thereof) as main components. It is a polymer or copolymer obtained by the reaction. Examples of the aromatic dicarboxylic acid component include a dicarboxylic acid having a benzene nucleus such as terephthalic acid and isophthalic acid, a naphthalene nucleus such as naphthalene 1.5-dicarboxylic acid, naphthalene 2.7-dicarboxylic acid and naphthalene 2.6-dicarboxylic acid. And a dicarboxylic acid or ester-forming derivative thereof. The acid component may be replaced with a dicarboxylic acid (for example, adipic acid, sebacic acid) other than 20 mol% or less of aromatic dicarboxylic acid or an ester-forming derivative thereof. Examples of the diol component include aliphatic glycols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol and cyclohexanediol, and ester-forming derivatives thereof.

Further, the diol component may be substituted with 20 mol% or less of a diol other than the aliphatic glycol (for example, a diol having an aromatic group such as 1.4-bisoxyethoxybenzene or bisphenol A) or an ester-forming derivative thereof. .

The aromatic polyester resin (A) used in the present invention is 1
Not only one kind of aromatic polyester but also a mixture of two or more kinds of aromatic polyester can be used.

Preferred aromatic polyester resins are polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene 2.6-naphthalate and polytetramethylene 2.6-naphthalate, particularly preferably polyethylene terephthalate, polytrimethylene terephthalate. Methylene terephthalate and polytetramethylene terephthalate.

In the present invention, the compounding amount of the aromatic polyester resin (A) in the entire resin composition is 30 to 90% by weight. (A) is 3
If it is less than 0% by weight, the heat resistance is lowered, and if it exceeds 90% by weight, the moldability is lowered.

[Polyamide Elastomer] The polyamide elastomer (B) used in the present invention is a polyamide polymer having an ester bond. Specifically, it is composed of a polyamide block (a) and a polyester block (b).

The proportion of the component (a) in the polyamide elastomer (B) is 99 to 10, preferably 90 to 20, and more preferably 80 to 30% by weight.

When the ratio of the component (a) is 99% or more, the impact resistance improving effect is small, and when it is 10% or less, the heat resistance is lowered.

In the present invention, the polyamide block (a) is composed of a polyamide-forming compound and is composed of an aminocarboxylic acid having 6 or more carbon atoms, a lactam or a nylon mn salt having m + n ≧ 12.

The aminocarboxylic acid having 6 or more carbon atoms or the lactam or the nylon mn salt having m + n ≧ 12 includes ω-aminocaproic acid, ω-aminoenanthic acid, ω
-Aminocarboxylic acids such as aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, or lactams such as caprolactam and laurolactam and nylon 6.
6, 6/10, 6/12, 11/6, 11/10, 11
-Nylon salts such as 12, 12, 6, 12, 10, 12 and 12 are mentioned.

The polyester (b) referred to in the present invention is polycaprolactone-based polyester synthesized from ε-caprolactone, ω-oxycaproic acid, or its C ₁ -C ₃ alkyl ester.

The polycaprolactone-based polyester can be obtained, for example, as follows. That is, when ε-caprolactone is polymerized to form a polycaprolactone-based polyester, water or a compound having hydroxyl groups at both ends is used as the polymerization initiator.

As the polymerization initiator, resorcin, pyrocatechol, hydroquinone, pyrogallol, chloroglucine,
Benzenetriol, bisphenol-A, bisphenol-F and ethylene oxide adducts thereof, dimethylolbenzene, cyclohexanedimethanol, tris (2-hydroxyethyl) isocyanurate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol. , 1,4-butanediol, 1,8-butanediol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 1,5-pentanediol, glycerin, trimethylolpropane, 1,6-hexanediol , Pentaerythritol, sorbitol, glucose, sucrose and dicarboxylic acid components such as terephthalic acid, isophthalic acid, adipic acid, sepacic acid, undecanedioic acid, dodecanedioic acid, etc. Len glycol, diethylene glycol, triethylene glycol, poropylene glycol, 1,4-butanediol, meopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc. Polyester polyol having an average molecular weight of 200 to 600 and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block of ethylene oxide and tetrahydrofuran produced from a polyol component. Alternatively, a random copolymer can be used.

Production of Polyesteramide Containing Polyamide Block (a) and Polyester Block (b) (Polycondensation Reaction)
May be performed by a usual method. That is, the polycondensation reaction is 5 mmHg or less with stirring in the presence of a catalyst,
220 to 280 ° C, preferably under high vacuum of 1 mmHg or less
At the reaction temperature of.

As a manufacturing method, a polyester block is synthesized,
Next, there is a method of forming a polyesteramide, but it is also possible to simultaneously supply a polyester monomer and a polyamide monomer to a polymerization vessel to form a polyesteramide.

Titanium-based catalysts give good results in the production of polyesteramides. Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and titanium oxalate metal salts such as potassium oxalate. Other catalysts include tin compounds such as dibutyltin oxide, dibutyltin laurate, and lead compounds such as lead acetate.

In the method for producing a polyesteramide composed of a polyamide block and a polyester block of the present invention, it is possible that both ends of the polyester component are diols or diacids.

When both ends are diols, a dicarboxylic acid having 4 to 20 carbon atoms can be used.

Examples of the dicarboxylic acid having 4 to 20 carbon atoms in the present invention include phthalic acid, isophthalic acid, terephthalic acid, naphthalene 2,6-dicarboxylic acid, naphthalene 2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid. Acids, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sepacic acid and dodecanedioic acid Mention may be made of acids. Especially terephthalic acid, isophthalic acid, 1,4
-Cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid are preferably used.

When the terminal is diacid, diamine is used.

As the diamine, aromatic, alicyclic, or aliphatic diamine is used. Specifically, hexamethylenediamine is considered as the aliphatic diamine.

In the present invention, a part of the polyester component (b) that can be used as a soft component other than polyester, such as polyalkylene polyol, for example, polytetramethylene glycol, polypropylene glycol, can exhibit the characteristics of the present invention. Can be used in a range.

In the present invention, the content of the polyamide elastomer (B) in the total resin composition is 1 to 40% by weight, preferably 5 to 35%.
% By weight. If (B) is less than 1% by weight, the impact resistance improving effect is small, and if it exceeds 40% by weight, the heat resistance decreases.

[Styrene Resin] In the present invention, the styrene resin (C) means (a) a homopolymer or copolymer of an aromatic vinyl monomer, (b) an aromatic vinyl monomer as an essential component, and an aromatic compound. A copolymer of a group vinyl monomer and another vinyl monomer copolymerizable with the group vinyl monomer, and (c) the above (ii) or (ii) is reinforced with a rubber component. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and the like, and a typical example is styrene. Examples of other vinyl monomers copolymerizable with the aromatic vinyl monomer include acrylonitrile, maleic anhydride, methyl methacrylate, ethyl methacrylate, methyl acrylate and the like. Examples of the rubber component include polybutadiene rubber, butadiene styrene copolymer rubber, ethylene propylene copolymer rubber, ethylene propylene diene terpolymer rubber, acrylonitrile butadiene copolymer rubber, and acrylic rubber, and these are usually the above-mentioned monomers. Can be used by graft polymerization.

Representative examples of the above item (a) include polystyrene, styrene α-methylstyrene copolymer, and styrene p-methylstyrene copolymer. Examples of (b) include styrene acrylonitrile copolymer, styrene maleic anhydride copolymer, styrene acrylonitrile maleic anhydride terpolymer, styrene α-methylstyrene acrylonitrile terpolymer, styrene methyl methacrylate. Many copolymers can be exemplified in addition to the copolymer. Specific examples of (c) above include HIPS resin and AB
In addition to S resin and rubber-reinforced styrene maleic anhydride resin, many resins can be exemplified.

The styrenic resins represented by these may be used alone or in combination of two or more.

In the present invention, the amount of the styrene resin (C) compounded in the entire resin composition is 5 to 60% by weight. If the content of (C) is less than 5% by weight, the moldability will decrease, and if it exceeds 60% by weight, the heat resistance will decrease.

[Additives] The resin composition of the present invention may further contain a reinforcing agent or filler such as glass fiber, a crystal nucleating agent such as talc, a stabilizer, if necessary.
A dispersant, a pigment, a flame retardant, an antistatic agent, etc. may be added.

[Production Method] The composition of the present invention can be produced by various known methods. For example, the aromatic polyester resin (A), the polyamide elastomer (B), the styrene resin (C), and other additives are dry-mixed with a mixer such as a tumbler mixer, and then supplied to a single-screw or twin-screw extruder. Then, the mixture is melt-kneaded and then shredded to form pellets for molding. Alternatively, a dry-mixed product may be directly molded by injection molding or the like. The molding can be selected from various known methods applied to the thermoplastic resin composition. For example, when polytetramethylene terephthalate is used as (A), it can be injection-molded at a normal cylinder temperature, for example 250 ° C., and a normal mold temperature, for example 60 ° C., while polyethylene terephthalate is used as (A). When used, a crystal nucleating agent such as talc may be added to enable injection molding at a standard mold temperature of about 60 to 80 ° C. In these extrusion, injection molding, etc., it is desirable to thoroughly dry the raw material in advance.

[Effects of the Invention] As seen in the following examples, the present invention provides a resin composition having excellent heat resistance, impact resistance, and moldability.

[Examples 1 to 6 and Comparative Examples 1 to 4] As a polyethylene terephthalate resin, "523" manufactured by Nippon Unipet Co., Ltd., and as a polytetramethylene terephthalate resin, "Duranex 2000" manufactured by Polyplastics Co., Ltd., styrene. HIPS resin "Topolex 83" manufactured by Mitsui Toatsu Chemicals, Inc. as the resin (1)
0 "as the styrene resin (2), ABS resin" Cevian V-500 "manufactured by Daicel Chemical Industries, Ltd., and as the styrene resin (3), styrene maleic anhydride copolymer resin" Dylark 332 "manufactured by Arco Co., Ltd. The rubber-reinforced styrene-maleic anhydride copolymer resin "Dylark250" manufactured by Arco Co., Ltd. is used as the styrene resin (4), and "Daiamide PAE-F62L" manufactured by Daicel Chemical Industries, Ltd. is used as the polyamide elastomer (1). 12-aminodecanoic acid 4 as elastomer (2)
6.5% by weight, adipic acid 3.5% by weight, average molecular weight 2
Of polycaprolactone diol having an average molecular weight of 1,000 was used as a polyamide elastomer (3) in an amount of 62.5 wt% of 12-aminododecanoic acid, 4.5 wt% of adipine sun, and 33 wt% of polycaprolactone diol having an average molecular weight of 1000. The compound synthesized from and was used as a talc, "PH Talc" manufactured by Takehara Chemical Co., Ltd., was melt-kneaded by a uniaxial extruder with a compounding recipe shown in Table 1, and then a test piece was molded by an injection molding machine. . For Comparative Example 2,
Although the allowable range of the cylinder temperature and mold temperature of the injection molding machine at the time of injection molding were narrow and the moldability was poor, the other compositions had good moldability. The test pieces thus obtained were used to measure notched Izod impact strength according to ASTM D-256 and heat distortion temperature (4.6 kg / cm ² ) according to ASTM D-648, and the results are shown in Table 1.

Claims (1)

[Claims] 1. An aromatic polyester resin (A) 30 to 90.
Polyamide elastomer (B) composed of a polyamide block and a polylactone-based polyester block in a weight percentage of 1
A heat and impact resistant resin composition comprising -40% by weight and styrene resin (C) 5-60% by weight.