JPH06179814A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin composition excellent in all of plasticity, retention, and cold resistance by incorporating a specific hydroxylated aliphatic polycarboxylic ester as a plasticizer into a polyamide resin polyamide. CONSTITUTION:The composition contains a hydroxylated aliphatic polycarboxylic ester represented by formula I. In formula I, R<1> and R<2> are the same or different and each is hydrogen, a 1-18C alkyl, a 2-18C alkenyl, an optionally substituted cycloalkyl, an aryl, an aralkyl, or a group represented by formula II, provided that at least either of R<1> and R<2> is neither hydrogen nor any group represented by formula III; R<4> is hydrogen or hydroxy; R<3> and R<5> are the same or different and each is hydrogen, a 2-22C alkyl, a 2-22C alkenyl, an optionally substituted cycloalkyl, an aryl, or an aralkyl; A is a 2-4C alkylene; and m and n each is an integer of 0-20.

Description

Detailed Description of the Invention

[0001]

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, and
Since it also has excellent properties such as chemical resistance and heat resistance,
It is used for the production of molded products such as threads, thin plates, rods, films, gears, hoses, etc. When polyamide is used for pressure hoses etc., it is necessary to add a plasticizer for the purpose of imparting flexibility.

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

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polyamide resin composition capable of satisfying all of the various properties of plasticity, holding property and cold resistance, and by extension spreads a polyamide resin having excellent properties. It is intended to be usable under the environment.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have expected to use a hydroxyl group-containing polycarboxylic acid ester having a specific structure as a plasticizer for polyamide. It has been found that the object of (1) can be achieved, 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 a hydroxyl group-containing aliphatic polycarboxylic acid ester represented by the general formula (1) (hereinafter referred to as "the present ester"). .

[Chemical 4] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group which may have a substituent, or an aryl group. Group, aralkyl group or

[Chemical 5] Represents However, neither R ¹ nor R ² is a hydrogen atom,

[Chemical 6] Not even. R ⁴ represents a hydrogen atom or a hydroxyl group.
R ³ and R ⁵ are the same or different and each represents a hydrogen atom or a carbon number of 2 to 2.
2 represents an alkyl group having 2 to 2 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group which may have a substituent, an aryl group or an aralkyl group. A represents an alkylene group having 2 to 4 carbon atoms. m and n each independently represent an integer of 0-20. ]

The present ester has, for example, a predetermined hydroxyl group-containing aliphatic polycarboxylic acid as an acid component, and a saturated or unsaturated aliphatic alcohol having 2 to 22 carbon atoms, an alicyclic alcohol and an alkyl-substituted product thereof, and an aromatic compound. Group alcohols and their alkyl-substituted products, and one or more alcohols selected from the group consisting of ether-containing alcohols obtained by adding a predetermined amount of alkylene oxide having 2 to 4 carbon atoms to these alcohols as an alcohol component. It can be prepared by esterifying these according to a conventional method.

The hydroxyl group-containing aliphatic polycarboxylic acid according to the present invention is represented by the general formula (2).

[Chemical 7] [In the formula, R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group which may have a substituent, or an aryl group. Group, aralkyl group or

[Chemical 8] Represents However, neither R ⁶ nor R ⁷ is a hydrogen atom. R ⁸ represents a hydrogen atom or a hydroxyl group. R ⁹ represents a hydrogen atom, an alkyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group which may have a substituent, an aryl group or an aralkyl group. A has 2 carbon atoms
~ 4 alkylene groups are shown. p represents an integer of 0 to 20. ]

Among the above compounds, lactic acid, malic acid, tartaric acid and the like are exemplified as more preferable acid components.

As the saturated alcohol, 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), Lineball 7
9 and 911 (Shell Chemistry), Diadol 79 and 9
11 (Mitsubishi Kasei) and the like are exemplified, and among them, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol and the like are effective as the alcohol component.

Specific examples of the unsaturated alcohol include octenyl alcohol, undecenyl alcohol, hexadecenyl alcohol, octadecenyl alcohol, linoleyl alcohol, and linolenyl alcohol. Octadecenyl alcohol is effective as the alcohol component.

As the alicyclic alcohol, cyclohexyl alcohol, methylcyclohexyl alcohol,
2,3,5-trimethylcyclohexyl alcohol, n
Examples thereof include octylcyclohexyl alcohol and nonylcyclohexyl alcohol, and among them, cyclohexyl alcohol, methylcyclohexyl alcohol, n-octylcyclohexyl alcohol and nonylcyclohexyl alcohol are effective as the alcohol component.

Examples of the aromatic alcohol include benzyl alcohol, methylbenzyl alcohol, butylbenzyl alcohol and the like. Among them, benzyl alcohol, butylbenzyl alcohol and the like are effective as the alcohol component.

Examples of the alcohol-containing alcohol include the alkylene oxide adducts of the above aliphatic alcohols, the alkylene oxide adducts of alicyclic alcohols, and the alkylene oxide adducts of phenols such as phenol, cresol, octylphenol and nonylphenol, among which nonylphenol. The ethylene oxide 2 mol adduct and the like are effective as the alcohol component.

Examples of the alkylene oxide constituting the alcohol-containing compound include ethylene oxide, propylene oxide, butylene oxide, etc., which may be used alone or in combination of two or more kinds.

At this time, the added mole number of alkylene oxide is 0 to 20 moles, and preferably about 0 to 10 moles.

Specific preferred examples of the present ester include lactic acid (n-butyl), lactic acid (2-ethylhexyl), stearyl lactate, lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl) and ditartrate. (N-
Octyl), tartrate (n-octyl) (nonylphenoxyethyl), di (2-ethylhexyl) tartrate, di (2-ethylhexyloxypropyl) tartrate, di (octoxyethoxyethyl) tartrate, di (octoxypropoxyethyl) tartrate. , Di (n-octyl) malate, di (2-ethylhexyl) malate, dibutoxyethyl malate, di (n-butoxyethoxyethyl) malate,
Di (n-decyl) malate, distearyl malate, dioctadecenyl malate, tri (n-octyl) citrate, tributoxyethoxyethyl citrate, di (n-octyl) citrate (nonylphenoxyethyl), citric acid Examples include di (n-octyl) cyclohexyl and trimyristyl citrate.

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

The above-mentioned 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 have excellent compatibility with the present ester.

The amount of the ester used is appropriately selected depending on the application, but is usually about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, relative to 100 parts by weight of the polyamide.
It is about the weight. If the amount is less than 1 part by weight, it is difficult to obtain the desired plasticizing effect. If the amount is more than 50 parts by weight,
Bleed to the resin surface is severe, which is not preferable in any case.

The ester can be added to the polyamide by a known method, for example, by mixing a desired amount of the ester with polyamide powder or pellets at a temperature not higher than the softening point of the polyamide, and then extruding at a temperature not lower than the softening point of the polyamide. Alternatively, a method of adding and mixing into the monomer before the polymerization or at a stage during the 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, an antioxidant, etc. Alternatively, it may be mixed with an additive such as an ultraviolet absorber or an antistatic agent.

Examples of the colorant include carbon black and various dyes.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylenebisstearic acid amide, butyl stearate, calcium stearate and the like.

As the filler, metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth and ferrite, fibers and powders such as glass, metal and carbon,
Examples thereof include glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium silicate, calcium silicate and the like.

As the antioxidant, 2,6-di-tert-
Butylphenol, tetrakis [methylene-3- (3,3
5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone and other phenolic compounds, alkyl disulfides, thiodipropionic acid esters, benzothiazole and other sulfur compounds, trisnonylphenylphosphine Phosphate compounds such as phyto, diphenylisodecyl phosphite, triphenyl phosphate, tris (2,4-di-tert-butylphenyl) phosphate, and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. Etc. are illustrated.

Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, and benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone. , 5-methyl-
In addition to benzotriazole compounds such as 1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified.

As the antistatic agent, an alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agent, nonionic antistatic agents such as poly (ethylene glycol) derivatives, sorbitan derivatives and diethanolamine derivatives are used. Agents, quaternary ammonium salts such as alkylamidoamine type, alkyldimethylbenzyl type, etc., cationic antistatic agents such as organic acid salts or hydrochlorides such as alkylimidazoline type, alkylpyridinium type, etc., alkylbetaine type, alkylimidazoline type etc. An amphoteric antistatic agent is illustrated.

The polyamide resin composition thus obtained is molded by a conventionally known method such as injection molding, extrusion molding, powder molding and blow molding, and is used for general machine parts, automobile parts, electric parts, construction material parts, textile machine parts. In addition to miscellaneous goods, it is useful as a material for extruded products such as films, tubes, round bars, sheets, monofilaments, and coating agents.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples. The characteristics of the resin composition in each example were measured and evaluated by the following methods.

Mechanical properties : Based on JIS K-6301.

Cold resistance : Crashberg method (ASTM-
D-1043).

Compatibility : The press sheet of the compounded resin is 25
After being left in a constant temperature and humidity room at a temperature of 60% RH for 48 hours, the amount of bleeding of the plasticizer on the surface of the sheet was visually observed and evaluated according to the following criteria. ○: No bleed, △: Slight bleed, ×: Surface wet with plasticizer

Oil resistance : A press sheet obtained from a compounded resin is dipped in insulating oil and left in a constant temperature bath at 50 ° C. for 70 hours, and the ratio (% by weight) of weight loss before and after immersion of a test piece is measured. .

Example 1 Nylon 12 (trade name "UBE Nylon 3030B",
A polyamide resin composition prepared by mixing 100 parts by weight of Ube Industries, Ltd. and 15 parts by weight of lactic acid (n-decyloxyethoxyethyl) (hereinafter referred to as "main ester 1") was prepared. The mechanical properties, cold resistance, compatibility and oil resistance of the product were evaluated. The results obtained are shown in Table 1.

Example 2 A polyamide resin composition prepared by mixing 100 parts by weight of "nylon 12" and 15 parts by weight of di (n-butoxyethoxyethyl) malate (hereinafter referred to as "main ester 2") was prepared, The mechanical properties, cold resistance, compatibility and oil resistance of this product were evaluated. The results obtained are shown in Table 1.

Example 3 A polyamide resin composition prepared by mixing 100 parts by weight of "nylon 12" and 15 parts by weight of (n-octyl) nonylphenoxyethyl tartrate (hereinafter referred to as "present ester 3") was prepared. The mechanical properties, cold resistance, compatibility and oil resistance of the product were evaluated. The results obtained are shown in Table 1.

Example 4 100 parts by weight of "nylon 12" and octadecenyl isononyl malate (hereinafter referred to as "the present ester 4") 15
A polyamide resin composition prepared by blending parts by weight is prepared,
The mechanical properties, cold resistance, compatibility and oil resistance of this product were evaluated. The results obtained are shown in Table 1.

Comparative Example 1 The mechanical properties, cold resistance and oil resistance of "nylon 12" itself were evaluated. The results obtained are shown in Table 1.

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

[Table 1]

[0041]

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

Claims (1)

[Claims] 1. A polyamide resin composition comprising a hydroxyl group-containing aliphatic polycarboxylic acid ester represented by the general formula (1). [Chemical 1] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group which may have a substituent, or an aryl group. Groups, aralkyl groups or Represents However, neither R ¹ nor R ² is a hydrogen atom, and Not even. R ⁴ represents a hydrogen atom or a hydroxyl group.
R ³ and R ⁵ are the same or different and each represents a hydrogen atom or a carbon number of 2 to 2.
2 represents an alkyl group having 2 to 2 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group which may have a substituent, an aryl group or an aralkyl group. A represents an alkylene group having 2 to 4 carbon atoms. m and n each independently represent an integer of 0-20. ]