JPH0676549B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a resin composition having a high viscosity and excellent mechanical properties.

<Prior Art> Polyether ester amides having a polyamide repeating unit, a polyether repeating unit and an ester bond in the polymer main chain are known, and because they have excellent impact resistance and rubber elasticity like polyether ester or polyester amide. In recent years, it has attracted attention as a new material in the elastomer field.

In particular, polyetheresteramide has excellent lightness and transparency, and is less prone to burrs and sink marks during molding, and is therefore promising for injection molding applications.

Further, it is more flexible than polyamide resin and has excellent impact resistance at room temperature and low temperature.

Although the polyether ester amides have the above-mentioned characteristics, they are easily colored and have problems such as elastic recovery, and therefore, improvement is desired. For example, a high viscosity is required to manufacture a tube, a bellows, etc. by extrusion molding or blow molding, but when the polymerization time is extended to obtain a high viscosity, the coloring tends to be severe. Further, since polyether ester amide has a relatively low melting point and solid phase polymerization is difficult, liquid phase polymerization is unavoidable and there is a problem that coloration is promoted.

<Problems to be Solved by the Invention> An object of the present invention is to solve the above problems and provide a polyetheresteramide resin composition having high viscosity and excellent mechanical properties.

<Means for Solving Problems> The above-mentioned problems of the present invention are as follows: aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt (a) of diamine and dicarboxylic acid having 6 or more carbon atoms, number average molecular weight of 300 ~ 6,000
50 to 99% by weight of a polyether ester amide (A) composed of the poly (alkylene oxide) glycol (b) and a dicarboxylic acid (c) having 4 to 20 carbon atoms,
Olefin-based copolymer (B) 50 consisting of α-olefin (x) and glycidyl ester of α, β-unsaturated acid (y)
This can be achieved by using a resin composition containing 1 to 1% by weight.

Examples of the aminocarboxylic acid having 6 or more carbon atoms or lactam or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms (a) in the polyether ester amide (A) of the present invention include ω-aminocaproic acid and ω-aminoenanthic acid. , Ω-aminocaprylic acid, ω-aminopelargonic acid,
ω-aminocapric acid, 11-aminoundecanoic acid, 12-
Aminocarboxylic acids such as aminododecanoic acid or lactams such as caprolactam, enantolactam, capryllactam, laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylene There are diamine-dicarboxylic acid salts such as diamine-adipic acid salt and 4,4'-diaminodicyclohexylmethane-dodecanedioic acid salt, but 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferable, depending on the purpose and application. These may be used together.

Further, it is acceptable to use another amide-forming component as a copolymerization component for the purpose of lowering the melting point of the polyether ester amide or improving the adhesiveness, as long as it is in a small amount range.

The polyether ester amide (A) of the present invention has a number average molecular weight of 300 to 6,000 poly (alkylene oxide)
As the glycol (b), polyethylene glycol,
Poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide / propylene oxide block or random copolymer, ethylene oxide / tetrahydrofuran block or Random copolymers and the like can be mentioned. Among them, poly (tetramethylene oxide) glycol is preferable in order to obtain excellent physical properties of polyetheresteramide such as heat resistance, water resistance, mechanical strength and elastic recovery. Used. The number average molecular weight of poly (alkylene oxide) glycol can be used in the range of 300 to 6,000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature characteristics and mechanical properties is selected. Depends on the type of poly (alkylene oxide) glycol.

For example, in the case of polyethylene glycol, 300 to 6,000, particularly preferably 1,000 to 4,000, and in the case of poly (propylene oxide) glycol, 300 to 5,000, particularly preferably 500.
.About.3,000, and in the case of poly (tetramethylene oxide) glycol, those having a molecular weight range of 500 to 3,000, particularly preferably 500 to 2,500 are preferably used.

Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyether ester amide (A) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid naphthalene-2,7-dicarboxylic acid and diphenyl-4. , 4'-Dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'- Alicyclic dicarboxylic acid such as dicarboxylic acid, succinic acid,
Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid) can be mentioned. Especially terephthalic acid, isophthalic acid, 1,
Dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties of polymer.

In order to show the effect of the present invention most remarkably, the copolymerization amount of the poly (alkylene oxide) glycol (b) in the polyether ester amide (A) is 5 to 90% by weight.
Is preferred. When the amount of copolymerization is less than 5% by weight, flexibility and elastic recovery are lost, and when it exceeds 90% by weight, high temperature characteristics,
Mechanical strength is not sufficient.

The method for polymerizing the polyether ester amide (A) is not particularly limited, and a known method can be used. For example, a method in which an aminocarboxylic acid or lactam (a) is reacted with a dicarboxylic acid (c) to form a polyamide prepolymer having carboxylic acid groups at both ends, and a poly (alkylene oxide) glycol (b) is reacted with this under vacuum. Alternatively, the compounds (a), (b) and (c) described above are charged into a reaction tank and heated at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then A method of promoting polymerization under normal pressure or reduced pressure is known.

There is also a method in which the compounds (a), (b) and (c) are simultaneously charged in a reaction tank, melt polymerization is performed, and then the polymerization is carried out at once in a high vacuum. preferable.

The olefin copolymer (B) composed of α-olefin (x) and glycidyl ester (y) of α, β-unsaturated acid used in the present invention contains at least two components (x) and (y). A copolymer in which α-olefin (x)
Is ethylene, propylene, butene-1, etc., but ethylene is preferably used. Further, the glycidyl ester (y) of α, β-unsaturated acid has the general formula (In the formula, R is a hydrogen atom or a lower alkyl group.)
Are specifically glycidyl acrylate, glycidyl methacrylate, glycidyl ethagilate, and the like, and glycidyl methacrylate is preferably used. The copolymerization amount of glycidyl ester (y) of α, β-unsaturated acid in the olefin copolymer is 0.1 to 5
A range of 0 mol%, preferably 0.5 to 5 mol% is suitable. Further, if it is 40 mol% or less, preferably 30 mol% or less (in this case, the total of the three or more copolymerization components is 100 mol%), an unsaturated monomer copolymerizable with the above-mentioned copolymer, that is, Vinyl ethers, vinyl acetate, vinyl propionate and other vinyl esters, methyl, ethyl, propyl and other acrylic acid and methacrylic acid esters, acrylonitrile, styrene and the like may be copolymerized. Of these, vinyl acetate is preferably used.

In the present invention, the mixing ratio of the polyether ester amide (A) and the olefin copolymer (B) is such that (A) is 50 to 99.
It is necessary to make the weight% and (B) 50 to 1% by weight. If (B) is less than 1% by weight, the thickening effect of the present invention is small, and if it exceeds 50% by weight, the excellent mechanical properties of the polyether ester amide are impaired, which is not preferable.

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

In addition, the resin composition of the present invention includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents. Agents, fillers, lubricants, nucleating agents, release agents, plasticizers, adhesion aids,
An adhesive or the like can be optionally contained.

Further, the composition of the present invention can be used by blending an ionomer resin and as a material having excellent mechanical properties, particularly impact resilience, in applications requiring such properties.

The ionomer resin referred to here is α-olefin and α,
It is a β-unsaturated carboxylic acid salt copolymer, and is an ionic copolymer containing a monovalent to trivalent metal ion.

<Effects of the Invention> According to the present invention, a high-viscosity composition can be obtained while maintaining the excellent mechanical properties of the polyether ester amide (A), and a tube, a dust cover, a bellows, Suitable for forming various shapes such as boots.

<Examples> Unless otherwise specified, the numbers of parts mean parts by weight.

Reference Example Polymerization of Polymer (A-1) 81.9 parts of ω-aminododecanoic acid, 6.8 parts of dodecanedioic acid and 19.3 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 650 are added to “IRGANOX” 1098 0.5 part (antioxidant) A reaction vessel equipped with a helical ribbon impeller was charged together with it, and after purging with N ₂ and heating and stirring at 260 ° C. for 1 hour to form a homogeneous transparent solution, antimony trioxide catalyst 0.01
5 parts, monobutyl monohydroxytin oxide catalyst 0.015
Parts, 0.005 parts phosphoric acid (tinting agent) were added and brought to a polymerization condition of <1 mmHg in 1 hour according to a vacuum program. After reacting for 2.5 hours under these conditions, a viscous colorless transparent molten polymer was obtained, and when this polymer was discharged as a gut into water, it was crystallized and whitened.

The obtained polyether ester amide (A-1) had a relative viscosity (ηr) of 1.81 measured in orthochlorophenol at 25 ° C. and a 0.5% concentration, and had a crystal melting point by DSC of 167 ° C.

Polymerization of polymer (A-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid, 48.8 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 1020, 0.5 part of "Irganox" 1098, 0.015 part of antimony trioxide, Monobutyl monohydroxytin oxide 0.015 parts and phosphoric acid 0.005 parts from a polymer (A-
Polymerization was performed under the same conditions as in 1) to obtain a polyetheresteramide (A-2) having a relative viscosity of 1.93 and a melting point of 154 ° C.

Polymerization of polymer (A-3) ω-aminododecanoic acid 27.3 parts, terephthalic acid 5.7 parts, poly (tetramethylene oxide) glycol having a number average molecular weight of 2060 70.5 parts, "Irganox" 1098 0.5 part, antimony trioxide 0.015 part, Polymerized from 0.015 parts of monobutylmonohydroxytin oxide and 0.005 parts of phosphoric acid under the same conditions as polymer (A-1), relative viscosity 1.92, melting point 145
Polyether ester amide (A-3) having a temperature of ℃ was obtained.

Polymerization of Polymer (A-4) Undecamethylenediamine-adipic acid salt 44.9 parts, terephthalic acid 12.8 parts, poly (tetramethylene oxide) glycol having a number average molecular weight of 650 50.0 parts, "Irganox" 1098 0.5 part, antimony trioxide. 0.015 parts, monobutyl monohydroxytin oxide 0.015 parts, and phosphoric acid 0.0
Polymerization from 05 parts under the same conditions as polymer (A-1), polyether ester amide (A with relative viscosity 1.80, melting point 209 ° C)
-4) got.

Olefin Copolymer The copolymer composition and abbreviations of the olefin copolymer (B) used in the examples are as follows.

Examples 1 to 10 and Comparative Example 3 (Comparative Examples 1 and 2 will be described later) Polyether ester amide block copolymer (A-
1), (A-2), (A-3) and (A-4) are mixed with the olefin copolymers shown in the table and optionally an ionomer resin, and (A-1), (A- 200 for 2) and (A-3)
(A-4) was melt-kneaded with a 30 mmφ extruder heated to 240 ° C. and pelletized. Using an injection molding machine having an injection capacity of 50Z, the obtained pellets (A-
For 1), (A-2) and (A-3) at 200 ° C, (A-
4) is 240 ℃, mold temperature is 40 ℃, JIS 2
No. 10 tensile test pieces were molded.

Tensile properties were measured according to ASTM D-638, hardness according to ASTM D-2240 and melt index according to ASTM D-1238. The results are shown in the table.

Comparative Examples 1, 2, 4, 5 Polyetheresteramide (A-1), (A-2), (A-
For 3) and (A-4), tensile properties, hardness, and melting index were measured in the same manner as in Examples 1 to 10 and Comparative Example 3. The results are shown in the table.

As can be seen from Examples 1 to 10, it can be seen that the resin composition of the present invention has a reduced melt index and a high viscosity while maintaining the excellent mechanical properties of polyetheresteramide.

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Claims (1)

[Claims] 1. An aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a dicarboxylic acid and a dicarboxylic acid having 6 or more carbon atoms (a), a poly (alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000, And 50 to 99% by weight of a polyetheresteramide (A) composed of a dicarboxylic acid (c) having 4 to 20 carbon atoms, a glycidyl ester of an α-olefin (x) and an α, β-unsaturated acid (y). A resin composition comprising 50 to 1% by weight of an olefin copolymer (B).