JPH08199065A - Aromatic polyamide composition - Google Patents

Abstract

(57) [Summary] [Objective] To provide an aromatic polyamide composition excellent in light resistance with little yellowing even when irradiated with ultraviolet rays. [Structure] 100 parts by weight of an aromatic polyamide containing metaphenylene isophthalamide as a main repeating unit, and 2-aminobenzophenone acyl derivative 0.1 to 10
And an aromatic polyamide composition. Clothing use,
It is useful as fibers, various films, sheets, etc. as interior materials for interiors and vehicles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polyamide composition, and more particularly to a novel aromatic polyamide composition containing a specific 2-aminobenzophenone acyl derivative and having excellent heat resistance and light resistance.

[0002]

2. Description of the Related Art A wholly aromatic polyamide containing poly (metaphenylene isophthalamide) as a main component is excellent in thermal stability at high temperatures, shape retention, self-extinguishing property, and chemical resistance.
Widely used as heat resistant fibers.

However, such an aromatic polyamide is inferior in stability to light (ultraviolet light), and when exposed to light, it is significantly discolored or colored, its molecular weight is lowered, and physical properties such as mechanical properties are lowered. This photo-deterioration is more remarkable than that of general organic polymer materials. When it is directly exposed to the sun's rays, it is significantly deteriorated in a short period of time. Even when it is used as an interior material, etc., it is greatly restricted.

Several attempts have been proposed to improve the light resistance of aromatic polyamides. For example, JP-A-50-343
No. 44 discloses a method of incorporating a piperidine derivative, and JP-A No. 53-120313 discloses a method of incorporating a benzotriazole type ultraviolet absorber. Further, JP-A-54-71192 discloses a method of partially copolymerizing a benzotriazole-based aromatic diamine.
Japanese Patent No. 178324 discloses a method of imidizing an aromatic polyamide by reacting it with an aromatic acyl halide. Further, JP-A-1-174680 discloses a method of treating an aromatic polyamide molded product with a polyethyleneimine compound. Although these methods each have an effect, their light resistance improving effect is insufficient, initial physical properties such as mechanical strength are deteriorated,
In addition, there are problems such as requiring complicated steps, which are not satisfactory.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel aromatic polyamide composition which does not have the above-mentioned problems and can give an aromatic polyamide molded article having excellent light resistance, mechanical properties and heat resistance. To do.

[0006]

Means for Solving the Problems The present inventors have found that the above-mentioned problems can be solved by blending an aromatic polyamide with a specific 2-aminobenzophenone acyl derivative in a specific ratio, and arrived at the present invention. did.

That is, the present invention relates to 100 parts by weight of an aromatic polyamide containing metaphenyleneisophthalamide as a main repeating unit, and a 2-aminobenzophenone acyl derivative 0.1 represented by the following formulas (I) and / or (II). It is an aromatic polyamide composition consisting of 10 to 10 parts by weight.

[0008]

[Chemical 4]

[0009]

Embedded image

[In the above formulas (I) and (II), R
₁, R₂, R_Four, R_Five, R₇And R ₈Is a hydrogen atom,
Toro group, hydroxyl group, carboxyl group, halogen source
Child, halogen-substituted or unsubstituted C1-C6 al
Kill group, alkoxy group, cycloalkyl having 5 to 10 carbon atoms
Group, aryl group having 6 to 12 carbon atoms, or phenoxy
Represents a group, which may be the same or different from each other
Yes. R₃Is an alkyl group having 1 to 6 carbon atoms, 5 to 10 carbon atoms
Cycloalkyl group, substituted or unsubstituted carbon number 6 to
12 aryl groups or the following formula (III)

[0011]

Embedded image —NHR ′ (III) [In the above formula (III), R ′ is a hydrogen atom and has 1 carbon atom.
Is an alkyl group having 6 to 6 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ]] Is selected. Also R
₃ may be the same as the structure in [] of the above formula (I). R ₆ is an alkylene group having 1 to 12 carbon atoms, 5 to 5 carbon atoms
It may be a cycloalkylene group having 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, or a direct bond. The numbers of substituents l, m, n, o, p and q each independently take a value of 1 to 4. The present invention will be described in detail below.

The aromatic polyamide used in the present invention is
The main repeating unit is metaphenylene isophthalamide. Specifically, it is an aromatic polyamide in which metaphenylene isophthalamide is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more based on all repeating units. The repeating unit other than metaphenylene isophthalamide is not particularly limited, but examples thereof include paraphenylene isophthalamide, metaphenylene terephthalamide, 2,4-tolylene isophthalamide, and metaphenylene-4,4'-.
Diphenyldicarboxamide, metaphenylene-2,
6-naphthalene dicarboxamide, 4,4'-phenylene methylene phenylene isophthalamide, 4,4'-
Phenylene sulfonyl phenylene isophthalamide,
4,4'-phenyleneoxyphenylene isophthalamide, 3,4'-phenyleneoxyphenylene isophthalamide and the like can be mentioned. Of these, those containing metaphenylene terephthalamide in an amount of about 10 mol% or less based on all repeating units are preferable as the aromatic polyamide.

The above aromatic polyamides may be used alone or in combination of two or more kinds.

The above aromatic polyamide is N-methyl-2.
-Intrinsic viscosity (η _{SP / C} ) of a polymer solution prepared by dissolving 100 mg of pyrrolidone in 10 ml at 30 ° C.
Is preferably 1.3 to 2.5.

The aromatic polyamide used in the present invention is
It can be produced by a conventionally known method such as an interfacial polymerization method.

The 2-aminobenzophenone acyl derivative used in the present invention is a compound represented by the following formulas (I) and (II).

[0017]

[Chemical 7]

[0018]

Embedded image

In the above formulas (I) and (II), R ₁ , R
₂ , R ₄ , R ₅ , R ₇ , and R ₈ are hydrogen atoms, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms such as Cl and Br, halogen-substituted or unsubstituted methyl, ethyl, propyl, isopropyl, butyl, An alkyl group having 1 to 6 carbon atoms such as pentyl and hexyl, an alkoxy group having 1 to 6 carbon atoms such as methoxy and ethoxy, cyclopentyl,
Cycloalkyl group having 5 to 10 carbon atoms such as cyclohexyl, and 6 to 1 carbon atom such as phenyl, diphenyl, naphthyl and the like.
2 aryl groups and phenoxy groups. These may be the same as or different from each other. Among these, a hydrogen atom and a hydroxyl group are preferable.

R ₃ is an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl and hexyl groups, a cycloalkyl group having 5 to 10 carbon atoms such as cyclopentyl and cyclohexyl, and an unsubstituted group such as phenyl and naphthyl. Carbon number 6
~ 12 aryl groups, methyl, ethyl, etc., having 1 to 6 carbon atoms
Alkyl group of 1 to 6 carbon atoms such as methoxy and ethoxy, a halogen atom such as Cl and Br, or an aryl group of 6 to 12 carbon atoms substituted with a nitro group,
Or the following formula (III)

[0021]

Embedded image —NHR ′ (III) [In the above formula (III), R ′ is a hydrogen atom and has 1 carbon atom.
Is an alkyl group having 6 to 6 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ] An amino group or an alkylamino group represented by R ₃ may have the same structure as the structure in [] of the above formula (I). Among them, R ₃ is preferably a phenyl group.

R ₆ is methylene, ethylene, propylene,
C1-C12 alkylene groups such as tetramethylene, decamethylene, dodecamethylene groups, etc., C5 carbon atoms such as cyclopentylene, cyclohexylene, cyclododecamethylene groups, etc.
-10 cycloalkylene group, phenylene, unsubstituted arylene group having 6 to 12 carbon atoms such as naphthylene, methyl,
An alkyl group having 1 to 6 carbon atoms such as ethyl, an alkoxy group having 1 to 6 carbon atoms such as methoxy and ethoxy, a halogen atom such as Cl and Br, or an arylene group having 6 to 12 carbon atoms substituted with a nitro group or the like. Indicates. Further, R ₆ may be a direct bond (an omitted oxalyl bond). Of these, ethylene, tetramethylene, phenylene, or a direct bond is preferable.

The numbers of substituents l, m, n, o, p and q each independently take a value of 1 to 4, preferably 1 to 2.

The following compounds can be exemplified as the 2-aminobenzophenone acyl derivative used in the present invention.

In the case of the compound represented by the above formula (I): 2
-Acetylaminobenzophenone, 2-propionylaminobenzophenone, 2-cyclohexanoylaminobenzophenone, 2-benzoylaminobenzophenone,
2- (4-methylbenzoyl) aminobenzophenone,
2- (4-bromobenzoyl) aminobenzophenone,
2- (4-nitrobenzoyl) aminobenzophenone,
2- (4-methoxybenzoyl) aminobenzophenone, 2-naphthoylaminobenzophenone, 2-acetylamino-4-methoxybenzophenone, 2-propionylamino-4-methoxybenzophenone, 2-cyclohexanoylamino-4-methoxybenzophenone, Two
-Benzoylamino-4-methoxybenzophenone, 2
-Benzoylamino-4-ethylbenzophenone, 2-
(4-Methylbenzoyl) amino-4-methoxybenzophenone, 2- (4-nitrobenzoyl) amino-4-
Methoxybenzophenone, 2- (4-methoxybenzoyl) amino-4-methoxybenzophenone, 2-naphthoylamino-4-methoxybenzophenone, 2-acetylamino-2'-carboxybenzophenone, 2-propionylamino-2'-carboxybenzophenone Two
-Cyclohexanoylamino-2'-carboxybenzophenone, 2-benzoylamino-2'-carboxybenzophenone, 2- (4-methylbenzoyl) amino-
2'-carboxybenzophenone, 2- (4-nitrobenzoyl) amino-2'-carboxybenzophenone,
2- (4-methoxybenzoyl) amino-2'-carboxybenzophenone, 2-naphthoylamino-2'-carboxybenzophenone, 2- (4'-methylbenzoyl) amino-4-methylbenzophenone, 2- (4'-
Hydroxybenzoyl) amino-4-hydroxybenzophenone, 2- (4′-ethoxybenzoyl) amino-
4-ethoxybenzophenone, N- (2-benzoylphenyl) urea, N, N'-di- (2-benzoylphenyl) urea, N-phenyl-N '-(2-benzoylphenyl) urea and the like.

In the case of the compound represented by the above formula (II):
N, N'-bis {2- (benzoyl) phenyl} oxamide, N, N'-bis {2- (benzoyl) phenyl}
Maloamide, N, N'-bis {2- (benzoyl) phenyl} succinamide, N, N'-bis {2- (benzoyl) phenyl} glutaramide, N, N'-bis {2
-(Benzoyl) phenyl} adipamide, N, N'-bis {2- (benzoyl) phenyl} terephthalamide,
N, N'-bis {2- (benzoyl) phenyl} naphthamide, N, N'-bis {2- (benzoyl) -4-methoxyphenyl} maloamide, N, N'-bis {2-
(Benzoyl) -4-methoxyphenyl} oxamide,
N, N'-bis {2- (benzoyl) -4-methoxyphenyl} succinamide, N, N'-bis {2- (benzoyl) -4-methoxyphenyl} glutaramide,
N, N'-bis {2- (benzoyl) -4-methoxyphenyl} terephthalamide, N, N'-bis {2- (benzoyl) -4-methoxyphenyl} naphthamide and the like.

Among the above compounds, 2-benzoylaminobenzophenone, 2- (4-methylbenzoyl) aminobenzophenone, 2- (4-nitrobenzoyl) aminobenzophenone, 2- (4-methoxybenzoyl) aminobenzophenone, N, N'-bis {2- (benzoyl) phenyl} terephthalamide, N-phenyl-N'-
(2-Benzoylphenyl) urea is preferably used.

The 2-aminobenzophenone acyl derivatives represented by the above formulas (I) and (II) can be used alone or in combination of two or more kinds.

These compounds can be produced by a known method by using 2-aminobenzophenone or a substituted derivative thereof and a corresponding carboxylic acid chloride or phosgene as raw materials.

The aromatic polyamide composition of the present invention is obtained by adding 0.1 to 10 parts by weight of a 2-aminobenzophenone acyl derivative to 100 parts by weight of the above aromatic polyamide. If the amount of the 2-aminobenzophenone acyl derivative added is less than 0.1 part by weight, the effect of improving the light resistance is insufficient, and if it is more than 10 parts by weight, the mechanical properties are deteriorated and the moldability and thermal stability are deteriorated. It is not preferable because it may have an adverse effect. The amount of the 2-aminobenzophenone acyl derivative added is preferably 0.2 to 8 parts by weight, more preferably 0.5 to 6 parts by weight, and particularly preferably 1 to 5 parts by weight, relative to 100 parts by weight of the aromatic polyamide.

The method of mixing the aromatic polyamide and the 2-aminobenzophenone acyl derivative is not particularly limited, but a method of adding and dissolving the 2-aminobenzophenone acyl derivative in an organic solvent solution of the aromatic polyamide can be mentioned.

The organic solvent may be any one that can dissolve the aromatic polyamide and the 2-aminobenzophenone acyl derivative without decomposing or reacting with them. As such an organic solvent, N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Examples thereof include dimethylacetamide and 1,3-dimethyl-2-imidazolidinone. These may be a mixed solvent of two or more kinds. According to this method, the obtained solution, so-called dope, can be formed into a fiber, film or sheet by a dry method or a wet method, which is preferable.

The aromatic polyamide composition of the present invention can be preferably used as a fiber. As the method of fiberizing, as described above, wet spinning with an aromatic polyamide dope containing a 2-aminobenzophenone acyl derivative,
Dry spinning or semi-dry semi-wet spinning methods can be used. For these, methods known in the art can be used as they are.

In the aromatic polyamide composition of the present invention,
In addition to the above ingredients, oxidation stabilizers, optical brighteners, matting agents,
You may mix | blend various additives, such as a pigment.

[0035]

The aromatic polyamide composition of the present invention has excellent stability against ultraviolet rays, especially yellowing.
It is considered that this is because it works effectively as a UV absorber and that the compatibility between the aromatic polyamide and the 2-aminobenzophenone acyl derivative is good.

[0036]

INDUSTRIAL APPLICABILITY The aromatic polyamide composition of the present invention shows little yellowing even when irradiated with ultraviolet rays, exhibits excellent stability against ultraviolet rays, and is a fiber as an interior material for clothing applications, interiors, vehicles and the like. It can be preferably used as various films, sheets and the like.

[0037]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. "Part" in the examples
Means "parts by weight". The yellowing degree (YI) is JIS
According to K7103, it was measured by a transmission method using a color meter (Z-300A manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples 1 to 3 and Comparative Example 1 Polymetaphenylene isophthalamide prepared by copolymerizing a metaphenylene terephthalamide component in an amount of 3 mol% (intrinsic viscosity 1.37 measured at 30 ° C. in N-methyl-2-pyrrolidone). ) 100
Parts, a predetermined amount of the 2-aminobenzophenone acyl compound shown in Table 1 was dissolved in 400 parts of N-methyl-2-pyrrolidone.

The resulting solution (dope) was left standing at 50 ° C. for 24 hours for defoaming, and the blade clearance was 200 μm.
It was cast on a glass plate using a doctor knife of m. When this was desolvated in a hot air dryer at 100 ° C. for 30 minutes and then immersed in cold water, the film peeled from the glass plate. After thoroughly washing this film with water, it was fixed in a metal frame to a fixed length and treated in a hot air dryer at 100 ° C. for 3 hours. The obtained film had a thickness of 30 to 35 μm and was pale yellow and transparent.

Yellowing of the Film Obtained by UV Irradiation 10 KW UV Lamp (KUV manufactured by Toshiba Corp.)
Type) accelerated test by irradiation. The ambient temperature of the sample during this test was about 100 ° C. Table 1 shows YI of the film before irradiation with ultraviolet rays and YI after irradiation with ultraviolet rays for 4 hours. For comparison, Table 1 also shows the results when the 2-aminobenzophenone acyl compound was not added, but the aromatic polyamide composition of the present invention has an extremely excellent resistance to ultraviolet irradiation. Recognize.

[0041]

[Table 1]

Claims (1)

[Claims] 1. Mainly composed of metaphenylene isophthalamide
100 parts by weight of aromatic polyamide as a repeating unit
And 2 represented by the following formula (I) and / or (II)
-Aminobenzophenone acyl derivative 0.1 to 10 weight
And an aromatic polyamide composition. [Chemical 1][Chemical 2][In the above formulas (I) and (II), R₁, R₂, R
_Four, R_Five, R₇And R ₈Is a hydrogen atom, nitro group,
Droxyl group, carboxyl group, halogen atom, halogen
Substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms,
Lucoxy group, cycloalkyl group having 5 to 10 carbon atoms, carbon
Represents an aryl group or a phenoxy group of the formulas 6 to 12,
They may be the same or different from each other. R₃Is carbon
C1-C6 alkyl group, C5-C10 cycloalkyl
Group, substituted or unsubstituted aryl having 6 to 12 carbon atoms
Or a group represented by the following formula (III) —NHR ′ (III) [In the above formula (III), R ′ is a hydrogen atom or a carbon number 1
~ 6 alkyl group, or substituted or unsubstituted carbon number
6 to 12 aryl groups. ]] Is selected. Also R
₃May be the same as the structure in [] of the above formula (I)
Yes. R₆Is an alkylene group having 1 to 12 carbon atoms, and 5 to 5 carbon atoms.
10 cycloalkylene groups, substituted or unsubstituted carbon
It is selected from the arylene groups of the formulas 6 to 12. Also R₆Is straight
It may be a contact bond. The number of substituents l, m, n,
o, p, and q each independently take a value of 1 to 4. ]