JPS61221261A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent impact strength, consisting of an arom. polyester resin and a polyamide elastomer. CONSTITUTION:0.5-100pts.wt. polyamide elastomer consisting of 99-10wt% polyamide block and 1-90wt% polyester block and optionally, additives such as dispersant, stabilizer, pigment, flame retarder, antistatic agent, filler, etc., are blended with 100pts.wt. arom. polyester resin such as polyethylene terephthalate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a moldable thermoplastic resin composition comprising an aromatic polyester (hereinafter abbreviated as polyester) and a polyamide elastomer.

Nowadays, polyester is used as an engineering plastic in structural parts and other products that take advantage of its excellent properties such as chemical resistance and heat resistance, but it is said to have problems with its impact resistance. The present invention relates to a polynisal-containing thermoplastic resin composition for molding, which has improved W impact resistance using a polyamide elastomer.

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

Furthermore, Japanese Patent Application Laid-Open No. 58-25352 discloses a composition comprising an aromatic polyester, an aromatic polycarbonate resin, and an acrylic rubber.

[Problem to be Solved by the Present Invention 1] However, the effect of improving impact strength is still insufficient, and a technique for improving impact strength using a polyamide elastomer as in the present invention has not yet been disclosed. Also,
As shown in Comparative Example 1-2, polyester has low impact strength and, because of its low impact properties, its excellent chemical resistance, heat resistance, etc. as an engineering plastic is not fully utilized. Therefore, the present inventor attempted to improve the impact strength, and discovered that polyamide elastomer improves the impact strength of polyester, and completed the present invention.

[Means for Solving the Problems] The present inventor's object is to provide a resin composition consisting of 100 parts by weight of aromatic polyester and 0.5 to 100 parts by weight of polyamide elastomer.

[Polyester] The aromatic polyester resin used in the present invention is a polymer obtained by a condensation reaction 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 combination or a copolymer.

Examples of the aromatic dicarboxylic acid component include dicarboxylic acids having a benzene nucleus such as arephthalic acid and isophthalic acid, naphthalene 1.5-dicarboxylic acid, and naphthalene 2.7-dicarboxylic acid.
-dicarboxylic acid, dicarboxylic acid having a naphthalene nucleus such as naphthalene 2°6-dicarboxylic acid, or an ester-forming derivative thereof. Further, as the acid component, 20 mol % or less of dicarboxylic acids other than aromatic dicarboxylic acids (for example, adipic acid, cepatic acid) or ester-forming derivatives thereof may be substituted. Examples of diol components include ethylene glycol, trimethylene glycol, tetramethylene glycol, heximethylene glycol,
These include fatty glycols such as diethylene glycol and cyclohexanediol, or their ester-forming derivatives.

In addition, as a diol component, it may be substituted with 20 mol% or less of a diol other than fat bottom 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 used in the present invention is not limited to one type of aromatic polyester, but may be a mixture of two or more types of aromatic polyester.

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, polytetramethylene terephthalate, Methylene terephthalate and polytetramethylene terephthalate.

[Polyamide elastomer] The polyamide elastomer used in the present invention includes: ■Polyamide block (a) and polyester block (
b) Consisting of ■Polyamide block (a) and polyol block (
Examples include those having an ester bond with C).

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

If the ratio of component (a) is 99% or more, the effect of improving impact resistance will be small, and if it is less than 10%, the heat distortion temperature will decrease.

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

The aminocarboxylic acids or lactams having 6 or more carbon atoms or the nylon mn salts with m+n≧12 include ω-aminocaproic acid, ω-aminoenanthate, ω-
Aminocarboxylic acids such as aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, lactams such as caprolactam and laurolactam, and nylon 6.6.
6・1016・12.11・6.11・10111・1
Examples include nylon salts such as 2.12, 6.12, 10.12, and 12.

The polyester (b) referred to in the present invention refers to (1) a polyester synthesized from cyazide and a diol; (2) a polycaprolactone system synthesized from ε-caprolactone, ω-oxycaproic acid, or a C-03 alkyl ester thereof; There is polyester.

Examples of polyesters synthesized from cyazide and diol include phthalic acid, isophthalic acid, terephthalic acid, naphthalene 2,6-dicarboxylic acid, and naphthalene 2,6-dicarboxylic acid.
, 7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, 1°4-cyclohexanedicarboxylic acid, 1
, 2-cyclohexanedicarboxylic acid, dimeta-0hexyl-4゜4'-dicarboxylic acid and other alicyclic dicarboxylic acids, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid, Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-bentanediol, 1
, 6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol.
Each of these ester-forming components can be used alone or in the form of a copolymer.

The polycarbolactone polyester can be obtained, for example, in the following manner. 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 a polymerization initiator.

Examples of the polymerization initiator include resorcinol, pyrocatechol, hydroquinone, pyrogallol, chloroglucine, benzenetriol, bisphenol-A1 bisphenol-F and their ethylene oxide adducts, dimethylolbenzene, cyclohexane dimetatool, and 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-bentanediol, glycerin, trimethy0-rubroban, 1,6-hexanediol, pentaerythritol, sorbitol, glucose,
Sucrose and terephthalic acid, isophthalic acid, adipic acid,
Dicarboxylic acid components such as sebacic acid, undecanedioic acid, dodecanedioic acid, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
1.4-butanediol, neopentyl glycol, 1
．． 5-bentanediol, 1,6-hexanediol,
Polyester polyols with an average molecular ff of 1,200 to 6,000 produced from polyol components such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide, and propylene oxide with an average molecule of ff of 1,200 to 6,000. Examples include block or random copolymers, block or random copolymers of ethylene oxide and tetrahydrofuran, and the like.

Polyamide plotter (a) and polyester block (b)
) may be produced by a conventional method (polycondensation reaction). That is, the polycondensation reaction is carried out in the presence of a catalyst with stirring,
Preferably at 220 to 280°C under a high vacuum of 1 or less Hg.
The reaction temperature is .

In addition, the manufacturing method is to synthesize polyester blocks,
Next, there is a method of making polyester amide, but it is also possible to make polyester amide by simultaneously feeding polyester monomers and polyamide monomers into a carrier can.

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

In addition, in the method for producing a polyester amide comprising a polyamide block and a polyester block according to the present invention, it is possible that both ends of the polyester component are diol or cyazide.

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

In the present invention, dicarboxylic acids having 4 to 20 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, naphthalene 2,6-dicarboxylic acid, naphthalene 2,7-dicarboxylic acid, diphenyl-4,4'- dicarboxylic acid, aromatic dicarboxylic acids such as diphenoxyethane dicarboxylic acid, alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid can be mentioned. Especially terephthalic acid, isophthalic acid,
1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferably used.

Moreover, when the terminal is cyazide, diamine is used.

As the diamine, aromatic, alicyclic, and aliphatic diamines are used. Specifically, hexamethylene diamine is considered as the aliphatic diamine.

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

In the present invention, the polyol block (C) includes polyols having a number average molecular weight of 500 to 3,000, such as poly(alkylene oxide) glycol.

Poly(alkylene oxide) glycols include polyethylene glycol, poly(1,2 and 1,3 propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, blocks of ethylene oxide and propylene oxide. Or a random copolymer, a block or random copolymer of ethylene oxide and tetrahydrofuran, and the like.

Polyamide block (a) and polyol block (C)
The above-described method for synthesizing polyesteramide can be applied to the polymerization with.

The amount of polyamide elastomer blended into polynisdel is 0.5 to 101 fa parts, more preferably 0.5 to 101 fa parts.
It is 50 parts by weight. If the amount is less than 0.5 parts by weight, no improvement in W impact strength will be observed. When the number is higher than 100 times, the heat distortion temperature decreases.

[Other additives] The resin composition used in the present invention may further contain a dispersant,
Of course, stabilizers, pigments, flame retardants, antistatic agents, and fillers or reinforcing agents such as glass fibers may be added.

[Manufacturing method] The composition of the present invention can be manufactured by various known methods. For example, there are methods such as mixing resins in a tumbler, Henschel mixer, etc., and then making them into pellets for molding using a single- or twin-screw extrusion machine, or using a Banbury mixer 1 Niki roll, etc., to mix the resins and then making pellets for molding. Can be used.

[Effects of the Invention] By blending the aromatic polyester with a polyamide elastomer, the impact strength could be greatly improved.

[Examples 1 to 7, Comparative Examples 1 to 21 The formulations shown in Table 1 were melt-kneaded in a single screw extruder equipped with a dullage screw, and injection molded into Izot impact test pieces. Using the obtained test piece, ASTM
Impact strength was measured using D-256. In addition, each component used is as follows.

Polyethylene terephthalate resin: [] This Unibet (
"523"' polybutylene terephthalate resin: "DURANEX 2000" polyamide elastomer (1), manufactured by Polyplastics Co., Ltd.: '1 Diamide PAEE-621' polyamide elastomer (2), manufactured by Daicel Chemical Industries, Ltd.: 12-aminododecanoic acid 46.5% by weight Adipine 113.5% by weight Polycaprolactone diol with an average molecular weight of 12,000 50
Polyamide elastomer (3) synthesized from weight%: 12-aminododecanoic acid 62.511% Adipine! 114.5% by weight polycaprolactone diol 3 with average molecular weight mi ooo
Synthesized from 3% by weight

Claims (1)

[Claims] Resin composition consisting of 100 parts by weight of aromatic polyester resin and 0.5 to 100 parts by weight of polyamide elastomer