JPS5815554A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. suitable for extensive applications ranging from high-viscosity and high-melt tension elastomer to heat-and cold-resistant flexible material, prepared by blending polyether ester amide and ionomer resin. CONSTITUTION:5-98wt% (A) polyether ester amide consisting of (a) 6C or higher aminocarboxylic acid or lactam, (b) poly(alkylene oxide) glycol with a number-average molecular weight of 300-6,000 and (c) 4-20C dicarboxylic acid, is blended with 2-95wt% (B) ionomer resin obtained by adding a mono- to tri-valent metallic ion to a copolymer of an alpha-olefn and a 3-8C alpha,beta-unsatd. carboxylic acid. Preferred component (a) are 11-aminoundecanoic acid and 12- amino-dodecanoic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyether ester amide composition which has a high viscosity by blending a polyether ester amide and an ionomer, a tough and flexible resin composition, and a resin composition which has excellent cold resistance and heat resistance. The present invention provides an excellent ionomer resin composition. Polyetheresteramide, which has polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain, is well known and, like polyetherester or polyesteramide, has excellent impact resistance and rubber elasticity, so it is a new material in the elastomer field. has been attracting attention in recent years.

In particular, polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and is also promising for injection molding applications because it does not easily cause flakes or sink marks during molding, but it has drawbacks such as easy discoloration and elastic recovery. There is a need for improvement. For example, manufacturing tubes, bellows, etc. by extrusion molding or blow molding requires high viscosity and high melt tension, but extending the polymerization time to obtain high viscosity tends to worsen coloring. Furthermore, polyether ester amide has a relatively low melting point, making solid phase polymerization difficult, forcing liquid phase polymerization, which tends to increase discoloration.

On the other hand, ionomers are known as resins with excellent impact resistance, but they have the disadvantage of lacking flexibility and cold and heat resistance properties.

The present invention solves the above-mentioned drawbacks and provides a resin composition suitable for a wide range of uses, from elastomers having high viscosity and high melt tension to flexible materials having heat and cold resistance.

That is, the present invention is based on aminocarboxylic acids or lactams having 6 or more carbon atoms (a), poly(alkylene oxide) glycols having a number average molecular weight of 600 to 6,000 (b), and dicarboxylic acids having 4 to 2D carbon atoms (C). 5 to 98% by weight of polyether ester amide (A),
α-olefin (X) and α, β having 3 to 8 carbon atoms
- A resin composition containing 2 to 95% by weight of an ionomer resin (B) in which a monovalent to hexavalent metal ion is added to a copolymer of an unsaturated carboxylic acid (y).

In the present invention, the aminocarboxylic acid or lactam (a) having 6 or more carbon atoms includes ω-abatsucaproic acid,
- Aminocarboxylic acids such as abanoenanthic acid, ω-aminocaprylic acid, ■-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or caprolactam, enantholactam, capryllactam, laurolactam There are lactams such as
Particularly preferred are 11-aminoundecanoic acid and 12-aminododecanoic acid, and these can also be used in combination depending on the purpose and use. It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness.

Examples of the poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000 in the present invention include polyethylene glycol, poly(1,2- and
Propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc., among others. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as heat resistance, water resistance, mechanical strength, and elastic recovery. poly(alkylene oxide)
The number average molecular weight of 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 properties and mechanical properties is selected, and this optimum molecular weight range is Oxide) Varies depending on the type of glycol. For example, in the case of polyethylene glycol, 300 to 6,00 CJ, particularly preferably i,
, ooo~4,000 is poly(propylene oxide)
In the case of glycol, 300 to 2,000, particularly preferably 5
In the case of poly(tetramethylene oxide) glycol, those having a molecular weight in the range of 500 to 2,500, particularly preferably 500 to 1.5.00 are preferably used.

Examples of dicarboxylic acids (0) having 4 to 20 carbon atoms in the present invention include terephthalic acid, inphthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'- dicarboxylic acid, diphenoxyethane dicarboxylic acid, aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid. Examples include alicyclic dicarboxylic acids such as hysuccinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedic acid (decanedicarboxylic acid).

In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. One of the present invention is the above-mentioned aminocarboxylic acid or lactam (a)
, poly(alkylene oxide) glycol) and dicarboxylic acid (q) and the polyether ester amide (A) obtained by polymerizing the ionomer resin (B) described below.
) is a resin composition blended with.

The ionomer resin FB+ will be explained below.

The α-olefin (X), which is a monomer component constituting the ionomer resin (B), includes ethylene, propylene, butene-1, etc., and among these, ethylene is preferred. Further, the α,β-unsaturated carboxylic acid (y) must have 6 to 8 carbon atoms, and for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, etc. are used. , these alkyl esters may be copolymerized.

Among these, acrylic acid and methacrylic acid are preferably used. The concentration of the α,β-unsaturated carboxylic acid component in the copolymer is 0.2 to 25 mol%, preferably 1 to 10 mol%. Ionomer resin (B) is produced by adding monovalent to hexavalent metal ions to a copolymer consisting of the above components.
It is an ionic copolymer in which ionic crosslinking occurs with the carboxylic acid groups in the copolymer. 1~ Suitable for generating ionic crosslinks
Examples of hexavalent metal ions include soot, lithium, potassium, lithium, magnesium, calcium, zinc, aluminum, ferrous and ferric ions. Introduction of ionic crosslinks into the copolymer is achieved by reacting the copolymer with a hydroxide, methoxide, ethoxide, carbonate, nitrate, acetate, formate, or oxide of a monovalent to hexavalent metal. Generally at least one of the carboxylic acid groups in the copolymer
It is necessary that 0% be interrupted by metal ions.

The method for polymerizing polyether ester amide (3) is not particularly limited, and any known method can be used. For example, an aminocarboxylic acid or lactam (a) and a dicarboxylic acid (0) are reacted in an approximately equimolar ratio to produce a polyamide prepolymer with carboxylic acid groups at both ends, and then poly(alkylene oxide) glycol is added to this under vacuum. Alternatively, a carboxylic acid-terminated polyamide prepolymer can be produced by charging the compounds (a), (b), and (C) above into a reaction tank and reacting them under pressure at high temperature in the presence or absence of water. A method is known in which the polymer is produced and then the polymerization is proceeded under normal pressure or reduced pressure.

Alternatively, there is also a method in which the compounds (a), (b), and (c) are simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum; this method is preferable because it causes less coloring of the polymer.

On the other hand, the ionomer resin (B) can be obtained by a generally known polymerization method, or a commercially available product such as "Surlyn" manufactured by Zorobon Co., Ltd. can also be used.

In the present invention, the blending ratio of polyether ester amide (A) and ionomer resin (B) must be such that (A) is 5 to 98% by weight and (B) is 2 to 95% by weight. Although the blending ratio should be appropriately selected depending on the purpose and use, the following blending ratio can usually be used as a guideline for the use.

(A) : (B) -9s~70:2~30 (weight)...This range is obtained with polyether ester amide ■, and a composition with high viscosity and high melt tension can be obtained. Since a composition with excellent blow moldability can be obtained, it is suitable for use in dust covers, boots, bellows, blow pins, and blow molded products of various shapes.

(A) : (B) -80 to 50: 20 to 50 (weight) Since a tough polyether ester amide composition is obtained, it can be used as various impact-resistant materials.

(A) : (B) -50 to 5:50 to 95 (weight)...This range is due to the fact that the ionomer resin (B) is made flexible by the addition of polyether ester amide, and the heat resistance and cold resistance are imparted. The resulting ionomer resin composition is useful for various industrial materials, golf ball shells, etc.

Of course, the physical properties of the compositions of the invention depend on the composition of the polyether ester amide <A), especially the poly(alkylene 7
It also depends on the amount of copolymerized glycol (C). The preferred copolymerization amount of component (0) is 5 to 90% by weight.

The compositions (A) and (B) can be blended by a conventional melt-kneading method.

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 materials, fillers,
A lubricant, a nucleating agent, a mold release agent, a plasticizer, an adhesion aid, an adhesive, etc. can be optionally contained.

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

Example 1 54.57 parts of ω-aminododecanoic acid, 1 part of dodecanedioic acid
Poly(tetramethylene oxide) glycol 3 with 3.42 parts and a number average molecular weight of 665 determined by end group determination method
8.68 parts of 1 Irganox' 1098 0.2 parts (antioxidant) and 0.2 parts of tetrabutyl titanate catalyst.
05 parts into a reaction vessel equipped with a helical ribbon stirring blade, purged with N2, heated and stirred at 220°C for 30 minutes to obtain a homogeneous transparent solution, and then polymerized at 250°C < lIMHg in 60 minutes according to the temperature increase and pressure reduction program. brought to the conditions. When the reaction was carried out under these conditions for 5 hours, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyetheresteramide (A) had a relative viscosity (ηr) of 1.80 as measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point by DSC of 154°C.

Separately, products (B) (0) in which the polymerization time was extended to 10 hours and 20 hours were produced under the same reaction conditions. The melt viscosity index (M
I) and the polymer color tone were as shown in the following table.

Table-1 On the other hand, Surlyn 1 is a copolymer of ethylene, methacrylic acid and methyl methacrylate and is neutralized with Na ions.
707 (manufactured by DuPont) was prepared, and these were added to the polyether ester amide obtained in Example 1 in the proportions shown in Table 2.
After tri-blending the pellets with A), they were introduced into an extruder heated to 220° C. and melt-blended to form blended pellets.

The melting properties of these blended polymers were evaluated using a melt indexer set at 200°C and a melt tension measuring device set at 190°C. It can be said that the smaller the melting index of melting properties and the larger the melt tension and extensibility, the smaller the drawdown during blowing and tube forming, and the better the extensibility and other formability.

For comparison, the results of (B)% (0) were also evaluated at the same time. These have good extensibility but low tension relative to their melting index.

Example 2 In the same manner as in Example 1--aminododecanoic acid 65'
Starting materials were 4 parts II, 6.01 parts of terephthalic acid, and 35.29 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 974, and ηr 1.86.
, a colorless and transparent (when melted) block polyether ester amide with a Tm of 166°C (Dl was prepared).
557 was melt-blended at the ratio shown in Table 4, and the thermal and mechanical properties of the blended polymer were measured. As is clear from the results in Table 4, 20% polyether ester amide
And the ionomer resin it contains becomes soft at room temperature,
It can be seen that while maintaining flexibility and impact resistance even at low temperatures, it becomes difficult to soften and flow even at high temperatures, giving it heat resistance.

Table 4 Example 6 ω-Aminododecanoic acid 43.6% by the same method as Example 1
5 parts of dodecanedioic acid and 4 parts of poly(tetramethylene oxytone glycol) having a number average molecular weight of 666.
Using 6.42 parts as starting material, ηr1.99, Tm 14
A colorless and transparent (when melted) block polyether ester amide (B) was prepared at 5°C.

This polyether ester amide (B) was melt-blended with the ionomer resin "Surlyn" 1555 at a blending ratio of 20% or 40%, and the mechanical properties of the blended polymer were measured.The results are shown in Table 5. It can be seen that the composition has increased rigidity without impairing the excellent mechanical strength, elongation, elastic recovery, and cold resistance of polyether ester amide (E).

Margin below

Claims (1)

[Claims] Aminocarboxylic acids or lactams having 6 or more carbon atoms (
a), poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000 and having 4 to 2 carbon atoms;
5 to 98% by weight of polyether ester amide (A) composed of 0 dicarboxylic acid (C), α-olefin (x) and α, β-unsaturated unsaturated carboxylic acid having 6 to 8 carbon atoms. A resin composition containing 2 to 95% by weight of an ionomer resin (B) obtained by adding monovalent to trivalent metal ions to a polymer.