JPH10140005A - Polyether-ester-amide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in hydration resistance and capable of providing a transparent molding product by formulating a specific amount of arbodiimide compound to a polyethe-rester-amide. SOLUTION: This composition comprises (A) 100 pts.wt. polyether-ester-amide, 0.01-5 pts.wt. carbodiimide compound [e.g. a high molecular weight substance of bis(2,6-diisopropylphenyl)carbodiimide] and, preferably, (C) 2-60 pts.wt. phenoxy resin. For example, the component A is preferably a reaction product of (i) polyamide component with (ii) a polyether-ester component composed of a polyoxyalkylene glycol and a dicarboxylic acid, and the component C is preferably constituted of a constituting unit of the formula (X1 to X4 are each H, a lower alkyl, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetheresteramide resin composition having excellent hydrolysis resistance.

[0002]

2. Description of the Related Art Polyetheresteramide is promising for various molding applications because of its excellent light weight, transparency, low-temperature impact resistance, elastic recovery, and good moldability. However, there is a problem in hydrolysis resistance, for example,
When used in a high-temperature, high-humidity environment, durability becomes a problem, and applications are often limited.

In order to improve these problems, Japanese Patent Application Laid-Open No. 58-53946 proposes a method of blending a polyether ester amide with a polyepoxide having two or more functional groups. This method improves hydrolysis resistance to some extent but is not sufficient. Further, there are problems such as a decrease in fluidity during injection molding and a decrease in mechanical properties of a molded product when the resin is retained in a molding machine for a long time.

[0004]

As a result of intensive studies to solve the above-mentioned problems, a specific amount of (C) a carbodiimide compound or (B) a carbodiimide compound or (B) a phenoxy resin and (C) a carbodiimide compound is mixed with polyetheresteramide. By doing so, it was found that a polyetheresteramide resin composition having excellent hydrolysis resistance and capable of giving a transparent molded product was obtained, and the present invention was accomplished based on this finding. That is, an object of the present invention is to obtain a polyetheresteramide resin composition capable of providing a molded article having excellent hydrolysis resistance, and the object of the present invention is to provide (A) 100 parts by weight of polyetheresteramide. (C) carbodiimide compound 0.01 to 5
It is achieved by mixing 2 to 60 parts by weight of (B) the phenoxy resin and 0.01 to 5 parts by weight of the carbodiimide compound (C).

The details of the present invention will be described below.

The polyetherester amide (A) in the present invention is obtained by reacting a polyamide component with a polyetheralkylene glycol and a diether ester component, and has an amide bond, an ether bond and It is a polymer having an ester bond.

As the polyamide component, specifically, tetramethylenediamine, hexamethylenediamine, 2,2
2,4 or 2,4,4-trimethylhexamethylenediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane,
Aliphatic, alicyclic or aromatic diamines having 4 or more carbon atoms such as phenylenediamines and xylylenediamines and adipic acid, azelaic acid, sebacic acid, dodecadioic acid,
Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, polyamides prepared from aliphatic, alicyclic or aromatic dicarboxylic acids having 6 or more carbon atoms, such as polymerized fatty acids, ω-aminocaproic acid, ω-aminoenanoic acid, ω-
Aminocaprylic acid, 11-aminoundecanoic acid, 12-
Polyamides produced from aminocarboxylic acids having 6 or more carbon atoms such as aminododecanoic acid, polyamides produced from lactams having 6 or more carbon atoms such as caprolactam, enantholactam, caprylactam, laurolactam, and copolymerized polyamides thereof Or a mixed polyamide thereof. In particular, polyamides produced from hexamethylenediamine and adipic acid, hexamethylenediamine and polymerized fatty acids and azelaic acid or sebacic acid, 12-aminododecanoic acid, and caprolactam are preferably used. The number average molecular weight of these polyamide components is preferably in the range of 500-5000.

As the polymerized fatty acid, an unsaturated fatty acid, for example, a polymerized fatty acid obtained by polymerizing a monobasic fatty acid having at least one double bond or triple bond having 10 to 24 carbon atoms is used. Specific examples include dimers such as oleic acid, linoleic acid and erucic acid.

Commercially available polymerized fatty acids usually contain a dimerized fatty acid as a main component, and also contain a raw material fatty acid and a trimerized fatty acid in addition to the dimerized fatty acid content of 70% or more. Preferably, the content is 95% by weight or more and the degree of unsaturation is reduced by hydrogenation. In particular, pre-pole 1009, pre-pole 1004, pre-pole 1010
Commercial products such as (all manufactured by Unichema) and Enpol 1010 (produced by Henkel) are preferred. Of course, mixtures thereof are also used.

The polyoxyalkylene glycol used in the present invention includes, specifically, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, Examples include a block or random copolymer of ethylene oxide and tetrahydrofuran and a copolymer of a dihydric phenol compound and the above polyoxyalkylene glycol. The number average molecular weight of these polyoxyalkylene glycols is preferably in the range of 200-3000.

The dicarboxylic acid used in the present invention is preferably a dicarboxylic acid having 6 to 20 carbon atoms, specifically, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecadioic acid, and terephthalic acid. And aromatic dicarboxylic acids such as isophthalic acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. In particular, adipic acid, azelaic acid, sebacic acid, dodecaniic acid, terephthalic acid, and isophthalic acid are preferably used from the viewpoint of polymerizability and physical properties of polyetheresteramide.

The ratio of the polyamide component / polyether ester component of the polyetheresteramide (A) used in the present invention is preferably in the range of 95/5 to 20/80 by weight. When the amount of the polyamide component is larger than this range, the impact resistance of the resin composition decreases, and when the amount is small, the mechanical strength and the thermal properties of the resin composition decrease.

As the method for producing the polyetheresteramide (A), any method can be employed as long as a uniform high molecular weight polymer can be obtained. For example, it is obtained by first synthesizing a polyamide oligomer, adding a polyoxyalkylene glycol and a dicarboxylic acid thereto, and heating the mixture under reduced pressure to increase the degree of polymerization.

The phenoxy resin used as the component (B) of the present invention comprises epichlorohydrin and bisphenol A
Or, it is a polycondensate with its nuclear substituent, and comprises a structural unit represented by the following general formula (I).

[0015]

Embedded image (X _{1 to} X ₄ in the formula may be the same or different and represent a hydrogen atom; a lower alkyl group such as a methyl group or an ethyl group; or a halogen atom such as chlorine or bromine.) The phenoxy resin preferably used in the above is derived from epichlorohydrin and bisphenol A, and has a number average molecular weight of 10,000 to 75,000.

The carbodiimide compound (C) used in the present invention is a compound having a carbodiimide group in the molecule, and specifically, diisopropylcarbodiimide, dicyclohexylcarbodiimide, di-O-triylcarbodiimide, diphenylcarbodiimide, diphenylcarbodiimide,
2,6-dimethylphenylcarbodiimide, poly (hexamethylenecarbodiimide), poly (cyclohexylenecarbodiimide), poly (paraphenylenecarbodiimide), poly (metaphenylenecarbodiimide), poly (tricarbodiimide), poly (4,4′-biphenyl) Methanecarbodiimide), poly (3,3'-dimethyl-
Carbodiimide compounds such as 4,4′-biphenylmethanecarbodiimide), high molecular weight of bis (2,6-diisopropylphenyl) carbodiimide and high molecular weight of bis (2,4,6-triisopropylphenyl) carbodiimide. Among these, di-O
-High molecular weight of triylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, poly (triylcarbodiimide), poly (4,4'-biphenylmethanecarbodiimide), bis (2,6-diisopropylphenyl) carbodiimide, bis A high molecular weight substance of (2,4,6-triisopropylphenyl) carbodiimide is preferred.

In the first polyetheresteramide resin composition of the present invention, the mixing ratio of (A) the polyetheresteramide and (C) the carbodiimide compound is as follows:
The carbodiimide compound (C) is preferably used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the component. When the compounding ratio of the (C) carbodiimide compound is less than 0.01 part by weight, the hydrolysis resistance of the polyetheresteramide resin composition is insufficiently improved, and when it exceeds 5 parts by weight, the polyetheresteramide resin composition The melt viscosity of the product increases and the moldability deteriorates.

The mixing ratio of each component of the second polyetheresteramide resin composition of the present invention is as follows:
The phenoxy resin (B) is preferably 2 to 60 parts by weight and the carbodiimide compound (C) is preferably 0.01 to 5 parts by weight based on 0 part by weight. (B) If the blending ratio of the phenoxy resin is less than 2 parts by weight, the hydrolysis resistance of the polyetheresteramide resin composition is insufficiently improved, and if it exceeds 60 parts by weight, the polyetheresteramide resin composition It is not preferable because the flexibility and impact resistance of the product are reduced.

The method for producing the resin composition of the present invention includes:
A melt kneading method is preferable, and a known method can be used as the melt kneading method. For example, the resin composition can be melt-kneaded using a Banbury mixer, a rubber roll machine, a single-screw or twin-screw extruder, or the like.

The composition of the present invention may contain a known antioxidant, thermal decomposition inhibitor, ultraviolet absorber, pigment, antistatic agent, conductive agent, flame retardant, reinforcing agent, lubricant, nucleating agent, mold release. Agents, adhesion aids, pressure-sensitive adhesives and the like can be arbitrarily contained.

[0021]

EFFECT OF THE INVENTION The polyetheresteramide resin composition of the present invention can provide a molded article having no deterioration in transparency and moldability and having improved hydrolysis resistance. It is suitably used for applications such as

[0022]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Each property in Production Examples and Examples was measured by the following methods.

(1) Melt viscosity Using a flow tester CFT-500 manufactured by Shimadzu Corporation,
Measurement temperature 230 ° C or 250 ° C, die 1mm (diameter) x 1.0mm
(Long), measured under the condition of a load of 10 kg.

(2) Acid value and amine value The acid value was determined by dissolving 1 g of a sample in 50 g of benzyl alcohol and using a phenolphthalein indicator in a 1 / 10N NaOH methanol solution. It was dissolved in 50 g of a mixed solution of methanol = 1/1 and titrated with a 1 / 10N methanolic hydrochloric acid solution using a bromophenol blue indicator.

(3) Melting point and crystallization temperature Using a differential scanning calorimeter (DSC), the temperature was raised at a rate of 10 ° C. /
The melting point was measured in minutes, the temperature was lowered at 10 ° C./minute, and the crystallization temperature was measured.

(4) Hydrolysis resistance Length (L) 60 m produced at 240 ° C. by an injection molding machine
mx height (h) 2 mm x width (W) 15 mm
It was immersed in warm water at 0 ° C., dried 7 days and 14 days later at 50 ° C. under vacuum, and formed into chips. The melt viscosity at 230 ° C. was measured, and the hydrolysis resistance was evaluated based on the retention.

(A) Polyetheresteramide Production Example 1 Synthesis of TPAE-1 1000 ml of 4 equipped with a stirrer, a nitrogen inlet and a distilling tube.
In the neck flask, the composition of the resulting polyamide copolymer is
Hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-azelaic acid polycondensate = 5 by weight ratio
0/50 hydrogenated polymerized fatty acid (carbon number
36, trade name: Pripol 1009, manufactured by Unichema)
7 g, azelaic acid 70.1 g, and hexamethylene diamine 61.1 g were charged, and the temperature was raised while flowing a fixed amount of nitrogen to advance a dehydration polycondensation reaction. Finally, the acid value and the amine value are adjusted so as to have an equivalent relation, and the terminal group concentration is adjusted to 41.
A transparent polyamide oligomer having a number average molecular weight of 1362 and 2 mgKOH / g was obtained. At a reaction temperature of 190 ° C., 48.1 g of azelaic acid was charged, and when the contents became transparent, polyoxyethylene glycol 26 having a number average molecular weight of 510 was used.
After the addition of 1.1 g, the temperature was raised to 250 ° C. while removing the reaction water. After adding 0.75 g of the zirconium catalyst, the pressure was reduced to 1 mmHg and the reaction was further promoted.
0 ° C., melting point 146 ° C., crystallization temperature 132 ° C., hard segment (polyamide copolymer) / soft segment (azelaic acid to polyoxyethylene glycol) = 40 /
60 (by weight) of a clear polyetheresteramide (TPAE-1) was obtained.

(B) Phenoxy resin: PKHH manufactured by Union Carbide Co., USA was used. (C) Carbodiimide compound A high molecular weight substance of bis (2,6-diisopropylphenyl) carbodiimide, Sudavacol P manufactured by Rhine Chemie, Inc. was used.

Examples 1 to 7, Comparative Examples 1 to 4 Polyetheresteramide (TPA) synthesized in Production Examples
E-1), a phenoxy resin and a carbodiimide compound were blended in the proportions shown in Table 1 and melt-kneaded at 200 ° C. using a 35 mmφ kneader ruder (manufactured by Kasamatsu Chemical Industry Research Institute) to form pellets.

After drying the obtained pellets, the acid value and the melt viscosity at 230 ° C. were measured. In addition, a predetermined test piece was prepared by injection molding, and the hydrolysis resistance was evaluated using the test piece. These results are summarized in Table 1.

[Table 1]

Claims (2)

[Claims] 1. A polyetheresteramide (A) 100
(C) carbodiimide compound 0.01 parts by weight
A polyetheresteramide resin composition, which is blended in an amount of 5 to 5 parts by weight. 2. (A) Polyetheresteramide 100
A polyetheresteramide resin composition comprising (B) 2 to 60 parts by weight of a phenoxy resin and (C) 0.01 to 5 parts by weight of a carbodiimide compound, based on parts by weight.