JPS61190554A - Aromatic polyamide composition - Google Patents

Abstract

PURPOSE:To obtain a composition with improved dyeability and heat resistance, capable of being made into fibers suitable for beddings and clothings, by incorporating an aluminum complex compound in an aromatic polyamide having specific structure. CONSTITUTION:The objective composition can be obtained by incorporating (A) a polyamide containing >=80mol% of structural unit of formula (n is 0-2; R<1> is 2-4 valent aryl residue which may be substituted by group or atom unreactive with carboxyl group, etc.; R<2> is divalent aryl residue similar to R<1>) (e.g., polymethaphenylene isophthalamide) with (B) 0.5-10(pref. 1-6)wt% of an aluminum complex compound [e.g., tris(acetyl acetonate)aluminum].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to aromatic polyamide compositions having improved dyeability and heat resistance.

[Prior art]

Fully aromatic polyamide fibers, such as poly(metaphenylene isophthalamide), have excellent properties such as flame retardancy, heat resistance, and solvent resistance, and are used in a wide range of fields. In particular, taking advantage of its heat resistance and flame retardant properties, its use in the fields of bedding, clothing, and interior design is rapidly expanding. However, because the polymer molecular chains are extremely rigid, it is difficult to dye them using conventional methods, and it has been difficult to obtain products with high light fastness using a simple and economical method.

For this reason, various methods for improving dyeing properties have been proposed up to now. There are modification methods by introducing various functional groups into the polymer, improvements in fiber dyeing methods, and improvements in fiber manufacturing methods, but in general, modifying the polymer matrix results in a decrease in crystallinity and uniformity of the polymer. This resulted in a decrease in strength due to the decrease in , and furthermore, there were problems such as an increase in cost, and the results were not necessarily satisfactory.

[Problem that the invention seeks to solve]

The present inventors conducted intensive studies to solve the above-mentioned problems in wholly aromatic polyamides, and as a result, they discovered that the above-mentioned problems could be solved by adding an aluminum complex compound to wholly aromatic polyamides.The present invention I was able to complete it.

[Means for solving problems]

That is, the aromatic polyamide composition of the present invention has the following general formula (I) (wherein, n is an integer of O to 2, R1 is a group that does not substantially react with carboxyl groups and incyanate groups, or A divalent to tetravalent aryl residue that may be substituted with an atom, and R2 is a divalent 7-aryl residue that may be substituted with a group or an atom that does not substantially react with a carboxyl group and incyanate group. It contains a polyamide containing 80 mol% or more of the structural unit represented by (representing a residue) and an aluminum complex compound.

[Preferred mode for carrying out the invention]

The aromatic polyamide represented by the general formula CI) used as the substrate polymer in the composition of the present invention is R1
is a phenyl or naphthyl residue, R2 is a phenyl, methylphenyl or naphthyl residue, and n is preferably 0, particularly preferably poly(metaphenylene isophthalamide).

In addition, the substrate polymer must contain 80 mol% or more of the structural unit represented by the general formula (I), and for polymers containing less than 80 mol% of the structural unit, the substrate polymer itself Low crystallinity, flame retardant,
It is not preferable because heat resistance, solvent resistance, strength, etc. are reduced, and the excellent properties of a wholly aromatic polyamide cannot be exhibited.

Such aromatic polyamides can be produced according to conventionally known techniques, for example.

(1) A method using a high temperature solution polycondensation method from an aromatic polycarboxylic acid and an aromatic diisocyanate.

(2) A method using a low-temperature solution polymerization method or an interfacial polymerization method using an aromatic diamine and an aromatic polycarboxylic acid chloride.

The following methods are exemplified.

On the other hand, examples of the aluminum complex compound added to the composition of the present invention include aluminum acetyl complex compounds such as tris(7cetylacetonato)aluminum and tris(ethylacetylacetato)aluminum. Among these, tris(acetylacetonato)aluminum is preferred because it is inexpensive, easily available, and thermally stable.

The proportion of the aluminum complex compound in the aromatic polyamide composition of the present invention should be about 0.5 to 10% by weight, preferably about 1 to 8% by weight in order to exhibit a sufficient effect of improving dyeability. desirable.

Although there are no particular restrictions on the method of mixing the aromatic polyamide and aluminum complex compound to produce the composition of the present invention,
For example, an aluminum complex compound may be present and mixed with the raw materials during the polymerization of aromatic polyamide, or may be added after the polymerization is completed. Examples of the amide solvents to which an aluminum complex compound may be added to the solution include 1, for example, N, N-dimethylformamide,
Examples include N,N-dimethylacetamide, N-methyl-2-pyrrolidone, w,w,N7rr-tetramethylurea, and the like.

The aromatic polyamide composition of the present invention can be processed into various forms such as fibers and films in the same manner as conventionally known aromatic polyamides. Moreover, as for the dyeing method, a normal dyeing method for aromatic polyamide fibers can be applied without special pretreatment. As a dye used for dyeing.

Various dyes such as disperse dyes, basic dyes, acid dyes, and reactive dyes can be used.

〔Effect of the invention〕

The aromatic polyamide composition of the present invention is dyed in a deep color without uneven dyeing by the same dyeing method as conventional aromatic polyamide dyeing, has good light fastness, and also has excellent heat resistance properties. . Therefore, the fibers formed from the aromatic polyamide composition of the present invention have great utility value in bedding, clothing, interior decorations, and the like.

〔Example〕

EXAMPLES Hereinafter, the aromatic polyamide composition of the present invention will be explained with reference to Examples, but the present invention is not limited by these.

Example 1 Isophthalic acid and toluylene-2,4-diisocyanate/toluylene-2,6-diisocyanate (molar ratio 8
0:20) was mixed with 3 g of tris(acetonato)aluminum to 97 g of polyamide powder with a logarithmic viscosity (in 95% concentrated sulfuric acid, Q, 1% concentration by weight, 30°C) of 2.5, and The mixture was dissolved in N-methyl-2-pyrrolidone, degassed under reduced pressure, filtered, heated to 100°C, extruded into a heated air stream, and subjected to dry spinning. Subsequently, the extruded undrawn yarn was stretched 8 times in hot water and further heat set at 280° C. for 15 minutes to obtain a filament of 100 d/25 fil.

The obtained filament obtained in this way was Re5
oline Blue FBL (blue disperse dye) 3
%o, w, f, acetic acid 1ce/j, sodium acetate 0.
25g/1. Dyeing was carried out at 140°C for 60 minutes in a dye bath consisting of 1 g/l of hydrosulfide.
l, NaOHIg/7 surfactant 1 g/1. The sample was subjected to reduction cleaning in a bath at 80°C for 20 minutes, washed with water, and then dried. The dyeing rate after dyeing was 71%, and there was no uneven dyeing. Moreover, the light fastness of the dyed product was also good. Furthermore, this mis was subjected to a heat resistance deterioration test at 250°C for 500 hours.

The strength retention rate was 80%.

Reference Example 1 The filament obtained in Example 1 was dyed in the same manner as in Example 1 except that Basacryl Red GL was used as the dye. The dyeing rate was 68%, and the light fastness was also good.

Example 1 Terephthalic acid and toluylene-2,4-diisocyanate/toluylene-2,6-diisocyanate (molar ratio 8
A filament was prepared in the same manner as in Example 1, except that a polyamide with an logarithmic viscosity (0.1% concentration in 95% concentrated sulfuric acid, 30° C.) of 8.5:35) was used. Manufactured. This filament was dyed in the same manner as in Example 1.

The dyeing rate after dyeing was 67%, and there was no uneven dyeing.

Moreover, the light fastness of the dyed product was also good.

Further, this m-fiber was subjected to a heat deterioration test at 250° C. for 500 hours, and as a result, the strength retention rate was 83%.

Claims (1)

[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the above formula, n is an integer of 0 to 2, R^1 is a carboxyl group and The isocyanate group is a divalent to tetravalent aryl residue which may be substituted with a group or atom that does not substantially react with the isocyanate group, and R^2 is a group or atom that does not substantially react with the carboxyl group and the isocyanate group. An aromatic polyamide composition comprising a polyamide containing 80 mol% or more of a structural unit represented by the following formula (representing an optionally substituted divalent aryl residue) and an aluminum complex compound. 2) The aromatic polyamide composition according to claim 1, wherein the aluminum complex compound is tris(acetylacetonato)aluminum.