JP3200966B2 - Polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition having excellent plasticity, retention and cold resistance.

[0002]

2. Description of the Related Art Polyamide has extremely excellent mechanical properties such as toughness, rigidity, impact resistance, and abrasion resistance.
Because it has excellent properties such as chemical resistance and heat resistance,
It is used for the production of molded products such as yarns, thin plates, rods, films, gears, hoses and the like. When polyamide is used for pressure-resistant hoses and the like, it is necessary to add a plasticizer for the purpose of imparting flexibility.

Hitherto, as this type of plasticizer, dibenzyltoluenes, p-hydroxybenzoic acid esters, benzenesulfonamides and the like have been known. However, these have problems in compatibility with the polyamide, plasticization efficiency, and the like, and in particular, have a problem that the flexibility of the plasticized polyamide cannot be maintained at a low temperature.

[0004]

SUMMARY OF THE INVENTION The present invention provides a polyamide resin composition which satisfies all of the various properties of plasticity, retention and cold resistance. It is intended to be usable under the environment.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, as a plasticizer for polyamide, tetrahydrofurfuryl alcohol (hereinafter "THF").
A ". It has been found that the intended purpose can be achieved by using the prescribed ester of (1), and the present invention has been completed based on such findings.

That is, the polyamide resin composition according to the present invention is characterized by containing an ester compound represented by the general formula (1) (hereinafter referred to as “the present ester”).

Embedded image [Wherein, X represents a 1 to 4 carboxylic acid residue, and k represents 1 to 4
4, 1 represents an integer of 0 to 3. m and n show the integer of 0-20. A represents an alkylene group having 2 to 4 carbon atoms, and R represents a hydrogen atom, an alkyl group, a cycloalkyl group which may have a substituent, an aryl or an aralkyl group. ]

[0007] The present ester is used as an ester of THFA, an alkylene oxide having 2 to 4 carbon atoms of THFA (ethylene oxide,
One or more alcohols selected from adducts such as propylene oxide) as essential components, and if necessary, a predetermined aliphatic alcohol, an aromatic alcohol, or a mixed alcohol thereof and a predetermined carboxylic acid are mixed by a usual method. It is a compound obtained by esterification.

Examples of the aliphatic alcohol include linear or branched saturated or unsaturated alcohols.
More specifically, ethyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl Alcohol, stearyl alcohol, behenyl alcohol, Alfol 610 (Vista Chemical Far East),
Saturated alcohols such as Lineball 79, 911 (Shell Chemical), Diadol 79, 911 (Mitsubishi Chemical); octenyl alcohol, undecenyl alcohol, hexadecenyl alcohol, octadecenyl alcohol, linoleyl alcohol, Examples include unsaturated alcohols such as linolenyl alcohol; and ether-containing alcohols obtained by adding ethylene oxide or propylene oxide to these alcohols.

Examples of the aromatic alcohol include benzyl alcohol, methyl benzyl alcohol, and butyl benzyl alcohol; ether alcohols obtained by adding ethylene oxide or propylene oxide to phenols such as phenol, cresol, octylphenol, and nonylphenol.

As the carboxylic acid, monovalent or polyvalent,
Aliphatic, alicyclic or aromatic carboxylic acids are exemplified,
More specifically, aliphatic monovalent carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid; adipic acid, azelaic acid, sebacic acid, citric acid, thiodipropionic acid, butane Aliphatic polycarboxylic acids such as tetracarboxylic acid; alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, and nadic acid; benzoic acid, p-hydroxybenzoic acid, salicylic acid, and benzyl Aromatic monocarboxylic acids such as acetic acid; and aromatic polycarboxylic acids such as phthalic acid, trimellitic acid, pyromellitic acid and diphenylsulfonetetracarboxylic acid are exemplified.

Preferred specific examples of the present ester include di (tetrahydrofurfuroxyethyl) thiodipropionate, di (tetrahydrofurfuroxyethyl) phthalate, dioctyl citrate (tetrahydrofurfuroxyethyl), tetrahydrofurfuryl oleate, Examples thereof include butanetetracarboxylic acid-dioctyl-di (tetrahydrofurfuryl), and esters of p-hydroxybenzoic acid with a 2 to 8 mol adduct of tetrahydrofurfuryl alcohol / ethylene oxide.

As the polyamide according to the present invention, a polymer having an amide group in the molecular chain is generally used. Specifically, adipic acid, aminoundecanoic acid, aminocaproic acid, aminododecanoic acid, isophthalic acid, ε-caprolactam 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, sebacic acid, terephthalic acid,
Polymers starting from one or more of α, ω-dodecanoic acid, hexamethylenediamine and ω-laurolactam; mixtures of the above polymers; starting materials starting from adipic acid and 1,3-benzenedimethanamine And polymers starting from adipic acid, 1,3-benzenedimethanamine, and bis (aminopropyl) poly (ethylene oxide).

The above polyamide is, for example, nylon 6,
Nylon 66, nylon 610, nylon 11, nylon 12, and copolymerized nylon are commercially available. Among them, nylon 11 and nylon 12 are excellent in compatibility with the present ester.

The amount of the present ester is appropriately selected according to its use, but is usually about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the polyamide.
It is about weight. When the amount is less than 1 part by weight, a predetermined plasticizing effect is hardly obtained, and when the amount exceeds 50 parts by weight,
Bleeding on the resin surface is severe, which is not preferable in any case.

As a method for adding the present ester to the polyamide, a known method, for example, a method in which a desired amount thereof is mixed with a polyamide powder or pellet in a mixer at a temperature lower than the softening point of the polyamide and then extruded at a temperature higher than the softening point of the polyamide. Alternatively, a method of adding and mixing into a monomer before polymerization or at a stage during polymerization can be used.

Further, the present ester can be used in combination with other known plasticizers, and if necessary, a coloring agent, a processing aid, a filler, a crosslinking agent, and the like, as long as the predetermined effect is not impaired.
You may mix with additives, such as an antioxidant or an antistatic agent.

The polyamide resin composition thus obtained is useful as a material for tubes and hoses for automobiles.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the following examples.
You. The properties of the resin composition in each example were determined by the following method.
Was measured and evaluated. Mechanical properties : Based on ASTM D-638.

Cold resistance : Crashberg method (JIS K)
6745).

Compatibility : Pressed sheet of compounded resin
After leaving for 48 hours in a constant temperature and humidity room at 60 ° C. and 60% RH, the amount of bleeding of the plasticizer on the sheet surface was visually observed and evaluated according to the following criteria. ：: No bleed, Δ: Slight bleed, ×: Surface wet with plasticizer

Oil resistance : A press sheet obtained from the compounded resin is immersed in gasoline, and the ratio (% by weight) of the weight loss before and after immersion of the test piece when left in a constant temperature room at 25 ° C. for 48 hours is measured.

Example 1 100 parts by weight of nylon 12 (UBE Nylon 3030B, manufactured by Ube Industries, Ltd., the same applies hereinafter) and a diester of thiodipropionic acid and a 1-mol adduct of tetrahydrofurfuryl alcohol EO (hereinafter referred to as "product 1 of the present invention") A polyamide resin composition containing 15 parts by weight was prepared, and its mechanical properties, cold resistance, compatibility and oil resistance were evaluated.
Table 1 shows the obtained results.

Example 2 A polyamide resin composition comprising 100 parts by weight of "nylon 12" and 15 parts by weight of a di-n-octyl citrate-mono THFA / EO 3 mol adduct (hereinafter referred to as "product 2 of the present invention"). The product was prepared and its mechanical properties, cold resistance, compatibility and oil resistance were evaluated. Table 1 shows the obtained results.

Comparative Example 1 The mechanical properties, cold resistance, compatibility and oil resistance of "Nylon 12" itself were evaluated. Table 1 shows the obtained results.

Comparative Example 2 A polyamide resin composition was prepared by mixing 100 parts by weight of “Nylon 12” and 15 parts by weight of 2-ethylhexyl p-hydroxybenzoate (hereinafter abbreviated as “EHPB”). The mechanical properties, cold resistance, compatibility and oil resistance were evaluated. Table 1 shows the obtained results.

[Table 1]

[0026]

By blending the ester according to the present invention with polyamide, a polyamide resin composition having excellent plasticity, retention and cold resistance can be obtained.

──────────────────────────────────────────────────の Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 CA (STN)

Claims (1)

(57) [Claims] 1. A polyamide resin composition comprising an ester compound represented by the general formula (1). Embedded image [Wherein, X represents a 1 to 4 carboxylic acid residue, and k represents 1 to 4
4, 1 represents an integer of 0 to 3. m and n show the integer of 0-20. A represents an alkylene group having 2 to 4 carbon atoms, and R represents a hydrogen atom, an alkyl group, a cycloalkyl group which may have a substituent, an aryl group or an aralkyl group. ]