JPS61183352A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent impact resistance, durability and toughness, by blending a polyether ester amide with a linear arom. polyester. CONSTITUTION:At least one compd. (a) (e.g. 12-amino-dodecanoic acid) selected from among 6C or higher aminocarboxylic acids and lactams and salts of 6C or higher diamines with dicarboxylic acids, a poly(alkylene oxide) glycol (b) having a number-average MW of 300-6,000, such as poly(tetramethylene oxide) glycol, and a 4-20C dicarboxylic acid (c) such as dodecanedioic acid are solution-polymerized and the polymerization is then accelerated under high vacuum to obtain a polyether ester amide (A). 1-50wt% component A is blend ed with 99-50pts.wt. linear arom. polyester (e.g. polybutylene terephethalate) obtd. by condensing an arom. dicarboxylic acid with a diol as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyester resin compositions.

[Conventional technology]

Conventionally, polyether ester amide resins have been known (
US Patent No. 5,044,987 Akirabutsu 1゜Aromatic linear polyester μ is also known as a general-purpose resin such as PBT resin or PICT resin.

[Problem that the invention seeks to solve]

Aromatic linear polyester is known as a general-purpose resin with durability and toughness, but it has the drawback of lacking impact resistance.

[Means for solving problems]

Therefore, as a result of intensive studies aimed at improving the above-mentioned problems, the present inventors found that at least one type (a) selected from Amizuka μ-boxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms; Number average molecular weight 500~
6000 poly(alkylene oxide) glyco-/L/
('b) and polyether ester amide (A) derived from carbon & 4-20 dicarboxylic acid Ca) 1 or more 5
Less than 0% by weight, aromatic linear polyester/I/(B)5
We have now discovered that the above object can be achieved by creating a polyester rho resin composition in which the polyester rho resin composition is blended in a proportion of more than 0 and less than 99% by weight.

Hereinafter, the resin composition according to the present invention will be explained in detail.

Polyether ester amide (at least one selected from aminocarboxylic acids or lactams having 6 or more carbon atoms for inducing AJ or salts of diamines and dicarboxylic acids having 6 or more carbon atoms (aJ is ω-amitsukagulonic acid, ω- Aminoenanthate, ω-aminocaprylic acid, ω
-7 Minovera Gonic acid, ω-1 Minocapric acid, 11-
Aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid, or lactams such as cabloctam, enanthuctam, cabloctam, laurolactam, and hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylene Diamine-isophthatvrllll salt, undecamethylenediamine-adipate, 4,4'-diaminodicyclohexyμ
For forming polyamides such as salts of diamine-dicarboxylic acids such as methanedodecanedate, the above-mentioned components may also be used in combination.

Also, lowering the melting point of polyether ester amide,
It is also permissible to use amide-forming components other than the above-mentioned components as copolymerization components in small amounts for the purpose of increasing adhesion.

The poly(alkylene oxide) glyco-tv (b) in the polyether ester amide (A) of the present invention includes polyethylene glycol, poly(b,2- and 1
, 3-propylene oxide) glyco-〃, poly(tetramethylene oxide fuglycol), poly(hexamethylene oxide) glyco-〃, block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydro7 Among them, poly(tetramethylene oxide) has excellent physical properties such as heat resistance, water resistance, mechanical strength, and elastic recovery. Glyco is preferably used.Poly(7μ
The number average molecular weight of Kylene Oxytone Glyco-μ is 300~
It can be used in the range of 000 to 500 to 500, but preferably 500 to 500
Those having a molecular weight in the range of 0 to 40, more preferably 500 to 40, and even more preferably 3,000 to 3,000 are preferably used.

The polyether ester amide of the present invention (the dicarboxylic acid (0) having 4 to 20 carbon atoms in AJ is terephthalic acid, isophthalic acid, naphthalene-2,6-dicabonic acid, naphthalene-2゜7-dicabonic acid) , Jihueni/L/
- Aromatic dicarboxylic acids such as 4,4'-cicaμboxylic acid, diphenoxyethanedicarboxylic acid, 3-μsodium dicarboxylate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl/ Alicyclic acidic acids such as l/-4,4'-dicarboxylic acids and succinic acids, oxalic acids, adipic acids,
Mention may be made of aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid (dacanedicaponic acid).In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sepaconic acid, and dogcanedic acid are polymerized. It is preferably used from the viewpoints of color, color tone, and physical properties of the polymer.

The aromatic linear polyester μ (B) used in the present invention is a polyester μ that has an aromatic ring in the chain unit of the polymer, and is mainly composed of an aromatic dicarboxylic acid or its ester derivative and di-μ. It is a polymer or copolymer obtained by a condensation reaction.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, 7-μ acid, 2,6-naphthalene dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid! Bonic acid, bis(p-
Carboxy p-phenylene/L/) methane, antofcene dicarboxylic acid, 4.4'-diphenic acid μ-boxylic acid 4.4
Examples include 7-diphenylaminic acid, esteric acid, and derivatives thereof. Preferred dicarboxylic acids are terephthalic acid and isophthalic acid.

In addition, as an acid component, if it is 404μ% or less, aliphatic dicarboxylic acids such as adipic acid, sepacic acid, azelaic acid, dodecanedioic acid, 1°4-cyclohexanedicarboxylic acid% L,! - Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and ester derivatives thereof may be substituted.

In addition, as the diol component, aliphatic diols having 2 to 10 carbon atoms, ie, ethylene glycol, clobylene glycol, 1,4-butanedio-〃, neopentyl glyco-A/, 1, 5-pentanedio-A/, 1 .6-hexanediol, decamethylene glyco-μ, etc. or,
Long chain glyco with a number average molecular weight of 300 to 6000, i.e. polyethylene glyco! , polypropylene glycol, poly(tetramethylene oxide) glyco-μ, and mixtures thereof. A preferred diol is ethylene! l: ff-ol, 1,4-butanedi-〃 Examples of preferable aromatic linear polyester μ used in the present invention include polyethylene terephthalate, polyprolylene terephthalate, polygethylene terephthalate, polyhexamethylene Terephthalate, polyethylene 2.6
- Natsutarenshika〃poquinate, etc., and more preferably polyethylene terephthalate and polybutylene terephthalate.

Polyether ester amide (A) used in the present invention
The polymerization method is not particularly limited, and any known method can be used. For example, Amitsuka μponic acid, lactam,
and diamine and dicarboxylic acid salts (a) are reacted with dicarboxylic acid (oJ) to produce a polyamide prepolymer having acid groups at both ends, and poly(alkyl V oxide) glyco-N (b)) in a vacuum, or the above (LJ, (b)
), (0) is added to a reactive species, and a carboxylic acid-terminated polyamide prepolymer is produced by heating the reaction at high temperature in the presence or absence of water, and then polymerization is carried out under normal pressure or reduced pressure. There are known ways to proceed. Alternatively, there is a method in which the compounds (AJ, (b) J, and (c) above are simultaneously introduced into the reactants, melt polymerized, and then polymerized all at once under high vacuum. Rather, this method also reduces the coloring of the polymer. Less is preferable.

Polyether ester amide (AJ
The relative viscosity of is preferably in the range of 1.2 to &5, particularly 1.
The range of 5 to 2-a is preferable.

In the present invention, polyether ester amide (A)
The blending ratio of polyether ester amide (A) and aromatic linear polyester (B) is 1 or more and less than 50% by weight, whereas the aromatic linear polyester (B) is more than 50 and less than 99% by weight.
It is necessary to make the proportion less than 5% by weight, and preferably the proportion is 50 to 95% by weight of the aromatic linear polyester (EJ) to 5 to 50% by weight of the polyether ester amide (A).

Butylation ratio of polyether ester amide (A) is %
If it is less than that, the impact resistance of the aromatic linear polyester ρ(B) will not be improved at all. Furthermore, if the blending ratio of polyether ester amide (A) exceeds 50% by weight, the heat resistance, tensile strength, etc. will decrease, and the properties of the aromatic linear polyester μ will be impaired.

The physical properties of the resin composition of the present invention are also influenced by the copolymerization ratio of the soft component and hard component that constitute the polyether ester amide (A). The copolymerization amount of the soft component, that is, poly(akylene oxide) glyco-μ in polyether ester amide (A) is 5 to 90% by weight.
is desirable.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for the melt-kneading method. For example, the resin composition can be prepared by melt-kneading the resin composition using a Banbury mixer, a rubber roll machine, a screw-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C.

The resin composition of the present invention may also contain known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, Any amount of reinforcing agent, filler, lubricant, nucleating agent, mold release agent, plasticizer, adhesion aid, adhesive, etc. can be contained.

〔Example〕

Hereinafter, the present invention will be explained with reference to Examples. In addition, unless otherwise specified in the examples, parts mean parts by weight.

Examples 1 to 7, Comparative Examples 1 to 7 Production of polyether ester amide Production of polyether ester amide (A-1) 81.9 parts of ω-aminododecanoic acid, &8 parts of dodecanedioic acid, and (Tetramethylene oxide) Glyco! 19.5 parts + Irganox” + 098
115 parts (antioxidant) were charged into a reaction vessel equipped with a helical ribbon stirrer, purged with nitrogen, and heated and stirred at 260°C for 1 hour to obtain a homogeneous transparent solution. 1015 parts of monobutyl monohydroxytin oxide catalyst and 005 parts of phosphoric acid α (coloring inhibitor) were added, and I
The polymerization conditions were brought to below iolFIg. A viscous, colorless and transparent molten polymer was obtained by reacting under these conditions for 2.5 hours, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) is orthochloropheno-p
The relative viscosity (ηr) measured at medium temperature at 25°C and LL5% concentration was 1.81, and the crystal melting point according to Di90 was 167°C.

Production of polyether ester amide (A-2) 49.1 parts of ω-7 minododecanoic acid, 7.9 parts of terephthalic acid, poly(tetramethylene oxide) having a number average molecular weight of 1020
Glyco) v 4 & 8 parts, l Irganox 111
0913, 971,015 parts of antitrioxide, 1,015 parts of 7-nopti μ monohydroxide V tin oxide, and phosphoric acid (polymerized from 5 parts of LOO under the same conditions as A-13, with a relative viscosity of 1.95 and a melting point of 154°C). Polyetheresteramide (A-2) was obtained.

Production of polyether ester amide (A-3) 27.5 parts of ω-7 minododecanoic acid, 5.7 parts of terephthalic acid, poly(tetramethylene oxide) with a number average molecular weight of 2060
Glico-1v715 part, ■Irganox”1098
15 parts, antimony dioxide [1015 parts, monobutyμ monohydroxytin oxide 1015 parts, and phosphoric acid (L
Polyether ester amide (A-3) having a relative viscosity of t 92 and a melting point of 145°C was obtained by polymerizing 5 parts of OO under the same conditions as the polymer (A-13).

Production of polyether ester amide (A-4) 44.9 parts of undecamethylene diamine adipate, 12.8 parts of terephthalic acid, poly(tetramethylene oxide) glycerol having a number average molecular weight of 650:I-)vS CLG club,
+1 Irganox" 109al 15 parts, antimony trioxide 1 (b15 parts, monobutyl monohydroxytin oxide a, 015 parts, and phosphoric acid (b005 parts) were polymerized under the same conditions as polymer (A-1), and the relative viscosity was 1. 80
, polyether ester amide (A-4) with a melting point of 209°C
) was obtained.

Polybutyline terephthalate (hereinafter referred to as PBT and uf) and polyethylene terephthalate (hereinafter referred to as PRiT) were added to the polyether ester amide obtained by the above production method as aromatic linear polyesters.

PBT and PmT used in this example had a relative viscosity (
ηr) were 1.62 and 1.72, respectively. Polyether ester amide and PBT or PET were combined at the ratio shown in the table, and in the case of PBT, the temperature was 250°C;
In the case of PET, it was melted and kneaded at 280°C to form pellets. The obtained pellets were then molded into J-Ko S2 tensile test pieces and 1 part 2 using an injection molding machine with an injection capacity of 5 oz.
Izot impact test specimens with inch V notches were molded. The temperature during injection molding is 200℃ and pm'r for PBT.
In this case, the temperature was set at 240°C, and the mold temperature was set at 80°C in both cases.

The tensile properties and V-notched Izot impact value are respectively A.
Measured according to STMD-658 and ASTM D-256.

〔Effect of the invention〕

As is clear from the V-notched Izo impact values in Examples 1 to 7 and Comparative Examples 6 to 7, PET or P
By blending polyether ester amide with ET, the impact resistance of FB'L' or PET was significantly improved.

However, as shown in Comparative Examples 1 to 5, when the blending amount of polyether ester amide exceeds 50% by weight, the tensile modulus decreases extremely, and FB'l' or P
The characteristics of IIIiT are lost.

Claims (1)

[Claims] At least one type (a) selected from aminocarboxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms, (b) poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6000, and carbon atoms A polyether ester amide (A) derived from a dicarboxylic acid (c) of 4 to 20% by weight or more and less than 50% by weight is blended with an aromatic linear polyester (B) in a proportion of more than 50% and less than 99% by weight. A polyester resin composition.