JPH10120781A - Production of weather-resistant polyamide and weather-resistant polyamide and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable to obtain the subject polymer excellent in polymer-binding stability, weather resistance and molecular characteristics and useful for fibers, etc., by adding a specific piperidine compound and a phenol compound as stabilizer components to one or more monomers before or during their (condensation) polymerization. SOLUTION: This method for producing a weather-resistant polyamide comprises (condensation) polymerizing (A) one or two monomer such as a lactam or a dicarboxylic acid and a diamine in the presence of (B) 0.02-0.7wt.% of 4-amino-2,2,6,6-tetraalkylpiperidine, (C) 0-0.5wt.% of a primary or secondary amino group-containing aliphatic or alicyclic diamine and (D) 0.02-0.7wt.% of a compound of the formula [R<1> , R<2> are each a 1-6C alkyl; R<3> is H, CH3 ; A is a primary amino (A1 ), carboxyl (A2 ), etc.; (x) is 2 and (y) is 0, etc., when A is A1 ; and (x) and (y) are each 0, etc., when A is A2 ] in conditions satisfying relations comprising that the total amount of the components A, B, C and D is 100wt.% and that the total amount of components B, C and D is 0.05-1.3wt.%. The components B, C and D are bound to the polymer chain through amide bonds in the produced polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The invention relates to the subject-matter described in the claims. In particular, the present invention provides for the polymerization or polycondensation of the polyamide-forming monomer (I) in the presence of components II, III, IV and V as described in more detail below.
The present invention relates to a method for producing a polyamide. Also, the present invention
The invention relates to weatherable polyamides obtained from components I, II, III, IV and V in which the components II, III, IV and V are linked to the polymer chain via amide bonds. Further, the present invention provides injection molded parts, extruded parts, yarns, fibers, foils,
It relates to the use of these polyamides in the production of hot melt powders and hot melt fibers.

[0002]

BACKGROUND OF THE INVENTION The weatherability of polyamides, i.e., their resistance to ultraviolet light and high temperatures when exposed to ultraviolet light and high temperatures simultaneously or alternately in the presence of oxygen and humidity, is inadequate for various applications. This problem is caused by the so-called wholly aromatic polyamides (eg "Kevlar", trade name)
With the exception of virtually all known polyamides, PA-6,
This applies to homopolyamides such as PA-66, PA-12, PA-11, PA-69, PA-6.10, and also to copolyamides obtained by any combination of aliphatic monomers. Insufficient weather resistance may also lead to partially crystalline or amorphous and aromatic polyamides and aliphatic and / or cycloaliphatic diamines or salts thereof, or other polyamides which are possible. Partially aromatic polyamides derived from the forming monomers are adversely affected.

In the past, amines, monocarboxylic acids or dicarboxylic acids have been used for many years as chain terminators in the polymerization or polycondensation of polyamides. For example, carboxylic acids such as acetic acid, benzoic acid, or adipic acid are commonly used for the polymerization or polycondensation of polyamides. Other aliphatic or cycloaliphatic diamines may also be used, for example, to enhance the adhesion between the polyamide and the carboxyl- or carboxylic anhydride-functional polymer. The amine chain termination reaction is
A polymer mixture such as a blend of PA-6 or PA-12 and an anhydrous functional poly (2,6-dimethylphenyl oxide), or a polymer compound (composite) such as a multilayer tube or multilayer foil
Used effectively. Further effects can be obtained by adjusting the type and amount of the chain terminator. Adjusting the type and amount of chain terminator is much more than just adjusting the reaction rate during polymerization or polycondensation, or adjusting the molecular weight or degree of polymerization of a particular polyamide obtained by adjusting the reaction rate. Has a great influence.

Angewandte Makromolekulare Chemie 34
(1973), pp. 135-152 and 153-163.
As a result of the hydrolysis polymerization of phosphorus lactam, the molecular weight
Cloth M _W / M_N Is the function and amount of the chain stopper, and the conversion
And that it was found to be dependent on it. This sentence
Especially for PA-12 with monofunctional termination or unadjusted
Rather than using a bifunctional chain terminator such as adipic acid
Is actually more effective for all chain terminator concentrations and polymerization rates.
Is also relevant, but states that the distribution of polymerization degree is narrower.
You. These findings are at least qualitatively similar to those of PA-6.
It seems to apply also to the polyamide of the above. The results of this study
Is very valuable in practice. Because it is made of polyamide
Is it known that build stability is affected by its molecular weight distribution?
It is. Experience has shown that especially PA-6 and PA-66
When spinning polyamide, good spinning capacity (spinning speed
And spinning safety) and fiber properties (strength and uniformity)
), A relatively narrow molecular weight distribution is advantageous.

[0005] In addition to the "typical" chain transfer agents mentioned above (benzoic acid, acetic acid, adipic acid), there are also substances which function as chain terminators. These substances have a special molecular structure and are therefore suitable for improving the thermal stability of the polyamide and, if applicable, the light stability. Examples of these materials include those in which the phenolic OH group is sterically shielded by one or two bulky alkyl groups, and which has a carboxyl- and ester- or amine-functionalized steric structure. There are hindered phenols, specifically 3,5-di-t-butyl-4-
Hydroxybenzoic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid or 3- (3,5-di-t-butyl-4-hydroxyphenyl) -1-aminopropane There is. In addition, examples of these substances include 4-amino-2,2,6,6
Tetraalkylpiperidines, for example 4-amino-2,2,6,6-tetramethylpiperidine, commonly called triacetonediamine, or 4-amino-1 having a C ₁ -C ₁₈ alkyl or benzyl group at the 1-position -There is alkyl-2,2,6,6-tetramethylpiperidine.

The use of sterically hindered phenols of the above structure in chain control or chain termination reactions is described in French Patent No. 1,558,350, published German Patent Application No.
237,849 (DE-OS 2,237,849) and Japanese Patent 4,159,
No. 327. French Patent No. 1,558,350 combines a sterically hindered phenol with a pentavalent phosphorus compound. The French patent states that, as can be seen from the examples, polyamide fibers have thermal stability even under thermal oxidative stress, and that anionic dyed fibers have good dyeing fastness. The purpose is. The French patent also mentions at the outset the resistance to light-induced degradation reactions, but the effect of combining individual stabilizers on the light-induced oxidative degradation of polyamides and only PA-66. There is no description based on experiments for the effect obtained by using. To test the heat and color stability of the polyamide, the dyed PA-66 fibers are exposed to high temperatures for a short period of time and the resulting reduction in the concentration of amino end groups and the reduction in color intensity are measured.

German Patent 1,919,021 describes the use of special phenolic acids, phosphoric acids and / or phosphorous acids for the hydrolytic polymerization of lauric lactams. German Patent 1,919,021 relates to the improvement of the heat, light and oxygen resistance of polylaurin lactams. The phenolic carboxylic acids used as stabilizers are obviously condensed at the end of the polyamide chain.

[0008] German Offenlegungsschrift 2,237,849 (DE-OS 2,2
37,849) use 3,5-dialkyl-4-hydroxyphenylcarboxylic acids to improve the thermal and oxidative stability of polyamide compositions. The amine salt is introduced into the polyamide before, during and after the polycondensation. Thus, it can be assumed that these amine salts, when added, act as chain stoppers before or during polycondensation (or before or during polymerization if lactams are used as monomers). During the oven aging test, the effect of the amine salt used is determined by the degree to which the stabilized viscosity and tarnish resistance of the stabilized polyamide are retained.

Japanese Patent No. 4,159,327 discloses, for example, 3,5-
Polyamide-12 hydrolyzed from laurin lactam in the presence of di-t-4-hydroxybenzoic acid and the like is described. This polyamide-12 differs from end-modified PA-12 in that it has better oil and "sour-gasoline" resistance. Also, sterically hindered phenolic acid acts as a chain terminator and binds to the polymer chain in the form of the corresponding terminal group.

EP-A-008431 A2 relates to a synergistic mixture of low and high molecular weight polyalkylpiperidines. These mixtures have a synergistic effect and can be added to various plastics, especially with the melt. These mixing processes are completed in a few minutes (approximately 1 to 3 minutes), and the residence time of the piperidine derivative in the melt is correspondingly short, so that it is likely that most of the physical mixture is contained.

German Offenlegungsschrift 44 13 177 (DE-OS 44)
13 177) and 44 29 089 (DE-OS 44 29 089) are based on 4-amino-2, in which the N atom of the piperidine ring can be substituted.
2,6,6-tetraalkylpiperidine. These patents further describe the dual action that heat stabilizers and chain terminators play in "essentially heat-stable polyamides", the method of stabilization being based on any aliphatic and partially aromatic Applicable to polyamides or copolyamides. However, what is actually exemplified is the stabilized polyamide-6 type used for spinning.

European Patent No. 345,648 (Applicant Ems-
Inventa) relates to branched, thermoplastically processable polyamides. This polyamide is obtained by the hydrolytic association of ω-aminocarboxylic acids and / or lactams. As a result, the amount of polymer having one or more branches is at least 50% by weight. This value can be obtained by adding components of the polycarboxylic acid and polyamine type having a branching action in a strictly defined molar ratio to the melt of the base monomer. These polyamides can be produced by a batch process over a relatively long time with good quality and good reproducibility, and the resulting polyamides have high flow resistance.

EP 0,345,648 also describes that 4-amino-2,2,6,6-tetraalkylpiperidine can be introduced at the end of the polymer chain by mixing it with the melt of the base monomer. I have. European Patent No.
According to 0,345,648 4-amino-2,2,6,6-tetraalkylpiperidine is particularly preferably used.

According to all these prior art methods for heat stabilizing polyamides and the heat-stabilized polyamides obtained therefrom, the addition of a stabilizing component before or during the production of the polymer makes it possible, It is clearly advantageous because no stabilizers need to be added and a product which is already ready for processing can be obtained. Further, since the molecular group of the stabilizer and the polymer chain are bonded, the stabilizer is not lost due to migration, evaporation, or extraction. Therefore, the effect of the stabilizer is maximized during the production, processing and use of the polyamide.

[0015]

However, when it is intended to produce usable polyamides having weatherability, i.e., a high resistance to ultraviolet light, high temperature and humidity simultaneously or over time, it is necessary to use a stabilizer. Permanent binding of the molecule to the chain ends is a problem. When used outdoors,
Polyamide undergoes photo-oxidative and thermo-oxidative degradation,
In order to minimize damage to such polymers of polyamide over a long period of time, relatively large amounts of stabilizer must be added. In this case, the use of the above-mentioned polymer bond stabilizer inevitably increases the chain termination reaction. As the chain termination reaction increases, the molecular weight reached by polymerization and / or polycondensation of the polyamide decreases. At the same time, the viscosity also decreases. For this reason, there is a limit in using the conventional polymer-bonded stabilizer, and the above-mentioned stabilizer cannot satisfy the molecular properties, molecular weight, end group balance, and weather resistance required for polyamide. For example, when the viscosity of the polyamide is set to be higher than the average, the amount of the stabilizer to be used must be limited to an amount that does not achieve the required weather resistance, and the applicable range is limited.

Therefore, there is a problem in obtaining a weather-resistant polyamide and a method for producing the same in the above-mentioned invention. There is a need to develop a polymer bond stabilization system. This allows
At the same level of use, a stabilizer with equal or better effect can be developed and the weather resistance and molecular properties of the polyamide are improved.

[0017]

This problem is solved by the method according to claims 1 and 2 and the use of the polyamide according to claims 12 and 13 by the use according to claim 15.

The problem is surprisingly that, according to one embodiment, 4-amino-2,2,6,6-tetraalkylpiperidine (II) is used before or during polymerization or polycondensation. And adding a 2,6-dialkylphenol (IV) having an OH group at the 4-position represented by the following formula.

[0019]

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(R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group, An ester with a C ₁ -C ₄ alcohol or a primary amino group, and in the case of a primary amino group, x
And the values of y are x = 2 and y = 1, x = 2 and y = 0, x
Is 1 and y is 0 and x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which both x and y are 0 is further possible. )

In addition to the stabilizer components II and IV, aliphatic or alicyclic diamines (III) having primary and tertiary amino groups can also be added.

Accordingly, the present invention relates to a method for producing a polyamide. In the method, the polyamide-forming monomer (I)
Polymerization or polycondensation of 0.02-0.7% by weight of 4-amino-
2,2,6,6-tetraalkylpiperidine (II), 0 to 0.5% by weight of an aliphatic or alicyclic diamine (III) having primary and tertiary amino groups and 0.02 to 0.7% by weight of 2,6-dialkylphenol (IV) having an OH group at the 4-position represented by the formula,

[0023]

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(R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group, An ester with a C ₁ -C ₄ alcohol or a primary amino group, and in the case of a primary amino group, x
And the values of y are x = 2 and y = 1, x = 2 and y = 0, x
Is 1 and y is 0 and x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which both x and y are 0 is further possible. ).

The components I to IV complement each other so that the total amount is 100% by weight. Components II, III and
The sum of IV is 0.05-1.3% by weight and components II, III and IV are linked to the polymer chain via amide bonds.

According to another embodiment, the present invention relates to a process for producing a weatherable polyamide obtained from a lactam and an ω-aminocarboxylic acid. In the method, the polycondensation of the polyamide-forming monomer (I) is carried out in an amount of 0.02-0.7% by weight of 4-
Amino-2,2,6,6-tetraalkylpiperidine (II), 0-
0.5% by weight of an aliphatic or cycloaliphatic diamine (III) having primary and tertiary amino groups, optionally from 0.02 to 0.
7% by weight of 2,6-having an OH group at the 4-position represented by the following formula:
Dialkylphenol (IV),

[0027]

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(R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group, An ester with a C ₁ -C ₄ alcohol or a primary amino group, and in the case of a primary amino group, x
And the values of y are x = 2 and y = 1, x = 2 and y = 0, x
Is 1 and y is 0 and x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which both x and y are 0 is further possible. ) And 0.1 to 1.2% by weight of tricarboxylic acid, tetracarboxylic acid or polycarboxylic acid (V).

The components I to V complement each other so that the total amount is 100% by weight. The sum of components II, III, IV and V is 0.2-2.5% by weight,
, IV and V are linked to the polymer chain via an amide bond. Preferred embodiments of the invention are described in the dependent claims 2-1.
As described in No. 5.

The weatherable polyamides according to the invention may also be substantially selected from specific polyamide-forming monomers (I), from 0.02 to 0.7.
Wt% 4-amino-2,2,6,6-tetraalkylpiperidine
(II) (preferably 4-amino-2,2,6,6-tetramethylpiperidine), 0 to 0.5% by weight of an aliphatic or cycloaliphatic diamine having primary and tertiary amino groups (III) And 0.
02 to 0.7% by weight of a 2,6-dialkylphenol (IV) having an OH group at the 4-position represented by the following formula:

[0031]

Embedded image

(R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group, An ester with a C ₁ -C ₄ alcohol or a primary amino group, and in the case of a primary amino group, x
And the values of y are x = 2 and y = 1, x = 2 and y = 0, x
Is 1 and y is 0 and x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which both x and y are 0 is further possible. ).

The components I to IV complement each other so that the total amount is 100% by weight. Components II, III and
The sum of IV is 0.05-1.3% by weight and components II, III and IV are linked to the polymer chain via amide bonds.

The invention further relates to weatherable polyamides obtained from lactams and ω-aminocarboxylic acids.
The polyamide is substantially comprised of 0.02-0.7% by weight of a polyamide-forming monomer (I) of 4-amino-2,2,6,6-tetraalkylpiperidine (II), 0-0.5% by weight of primary and primary polyamides. 3
Aliphatic or alicyclic diamine (III) having a secondary amino group
If necessary, 0.02 to 0.7% by weight of a 2,6-dialkylphenol having an OH group at the 4-position represented by the following formula (I
V),

[0035]

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(R ¹ and R ² are an alkyl group having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group, An ester with a C ₁ -C ₄ alcohol or a primary amino group, and in the case of a primary amino group, x
And the values of y are x = 2 and y = 1, x = 2 and y = 0, x
Is 1 and y is 0, and x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, x
Combinations where both and y are 0 are further possible. ) And 0.1-1.2% by weight of tricarboxylic acid,
It can be obtained from tetracarboxylic acid or polycarboxylic acid (V).

The components I to V complement each other so that the total amount is 100% by weight. The sum of components II, III, IV and V is 0.2-2.5% by weight,
, IV and V are linked to the polymer chain via an amide bond.

According to a particular embodiment of the invention, when a polyfunctional carboxylic acid, for example a trifunctional carboxylic acid, is added to the melt of the base monomer of pure amino acids (and / or lactams), the polymer molecule Always grows in predetermined three directions while having a COOH group at the terminal of its main chain. In ordinary condensation, the COOH groups do not react with each other, so that no crosslinking reaction occurs.

By using the chain stopper of the present invention and further adding a trifunctional carboxylic acid such as nitrilotriacetic acid, nitrilotripropionic acid or trimethylnitrilotripropionic acid, 6-lactam, ω-aminoundecanoic acid and When producing copolyamides from, for example, ω-aminododecanoic acid, the melting point of the copolyamide is determined systematically by selecting the termination system, the type and concentration of end groups (syste
matic selection), which is given by the mixing ratio of the base monomers. Also, by increasing the concentration of the functional end group as much as possible, the adhesive force to various adherends can be systematically adjusted according to the application.
It is possible to change.

For this reason, the above-mentioned trifunctional compound must always have three functional groups of the same type. The trifunctional compound needs to be dissolved in the melt of the monomer in advance, and can be made into a solution by forming a salt. Suitable trifunctional or tetrafunctional carboxylic acids include nitrilotriacetic acid, ethylenediaminetriacetic acid, and trimesic acid. Nitrilotripropionic acid or trimethylnitrilotripropionic acid can be used as well. Examples of particularly preferred tricarboxylic acids are nitrilotriacetic acid and nitrilotripropionic acids represented by the following formula.

[0041]

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R = H; n = 0: nitrilotriacetic acid R = H; n = 1: nitrilotripropionic acid R = CH ₃ ; n = 1: trimethylnitrilotripropionic acid Finally, the invention relates to injection-molded parts or extrusions. Molded parts,
It relates to the use of weatherable polyamides for producing yarns, fibers or foils or hot-melt powders or hot-melt fibers.

[0043]

DETAILED DESCRIPTION OF THE INVENTION The combination of two different groups of stabilizer molecules whose movements are restricted due to polymer binding is novel and unpredictable in the art, and is important in achieving weatherability. Very preferred, simply 1
The effect is higher than using one stabilizer molecule group.

In addition to components II and IV, which simultaneously function as both a stabilizer and a chain terminator, other chain transfer agents can be used with the diamine component III. However, as is evident from the examples, other chain transfer agents have no effect on weatherability.
Thus, the diamine component III only functions as a chain terminator, reducing the total amount of amine end groups in a particular polyamide to:
It serves to adjust the value to suit a particular application.
For example, in the case of polyamide-6 fibers which are dyed with a dye having a high affinity for basic moieties on polymer molecules, the use of diamine component III is theoretically unavoidable. Preferred diamine components III are 3- (dialkylamino) -1-propylamine, 2- (dialkylamino) -1-ethylamine, piperidino- and pyrrolidinoalkylamine, and the preferred amount is 0 to 0.4% by weight. is there.

Of course, the known chain transfer agents mentioned at the outset may be used simultaneously in amounts which correspond to the specific guidelines concerning the molecular weight and the end group concentration of the polyamide. These additional chain transfer agents include aromatic dicarboxylic acids and monocarboxylic acids such as terephthalic acid, isophthalic acid and benzoic acid, adipic acid, sebacic acid, acetic acid, propionic acid, cyclohexane-1,4-dicarboxylic acid and the like. And di- and monocarboxylic acids of the aliphatic or cycloaliphatic type, and also include monoamines and diamines having two primary amino groups. When a tricarboxylic acid having a branching action is used as a chain transfer agent instead of a dicarboxylic acid, it is preferable to use one of the above-mentioned nitrilotricarboxylic acids.

In the process for producing a weather-resistant polyamide of the present invention, the polyamide-forming monomer (I), ie, lactam, ω-aminocarboxylic acid, dicarboxylic acid, and diamine, aliphatic or monocarboxylic acid obtained from diamine salt of dicarboxylic acid are used. Partially aromatic polyamides or copolyamides can be used.

The lactam preferably has 6 to 12 carbon atoms, particularly preferably caprolactam and laurin lactam. The ω-aminocarboxylic acid has 6 to 12 carbon atoms, and ε-aminocaproic acid and ω-aminolauric acid are particularly preferred.

[0048] Linear or branched C6-C36 aliphatic or cycloaliphatic dicarboxylic acids can be used with substituted or unsubstituted C8-C18 aromatic dicarboxylic acids. The two subgroups of dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, dodecandioic acid,
Trimethyladipic acid, cis- or transcyclohexane-1,4-dicarboxylic acid and dimerized fatty acids (eg, PRIpol types from UNICHEMA)
And terephthalic acid, isophthalic acid, and naphthalene
1,6-dicarboxylic acid can be preferably used.

The diamines which can be used include aliphatic diamines which are linear or branched and have 4 to 13 carbon atoms and two primary amino groups, and 6 to 26 carbon atoms and two primary amino groups.
Alicyclic diamine having a quaternary amino group, and C8-C
It is a partially aromatic araliphatic having two primary amino groups bonded to 26 aliphatic carbon atoms.

Examples of the three sub-groups of the above diamines are hexamethylenediamine (1,6-diaminohexane), 1,10-diaminodecane, 1,12-diaminododecane, 1,4-diaminobutane, 2, 2,4- or 2,4,4-trimethyl-1,6-diaminohexane, cis- or trans-1,4
-Cis- or trans with diaminocyclohexane etc.
-1,4-bis (aminomethyl) -cyclohexane, 3-amino-3,5,5-trimethylcyclohexylamine, isomer bis- (4-amino-3-methylcyclohexyl) methane, isomer 2,2 -Bis (4-aminocyclohexyl) propane; and 1,3- or 1,4-bis- (aminomethyl) benzene.

The diamine salt of dicarboxylic acid used in the present invention is a salt obtained by reacting the above-mentioned dicarboxylic acid with a diamine in a substantially stoichiometric amount. Hexamethylene diammonium adipate obtained from hexamethylene diamine and adipic acid is particularly preferred. All other salts which may be included are usually prepared immediately from the dicarboxylic acid and the diamine in aqueous solution immediately before the polycondensation and added as such to the polycondensation. In addition, diamines that can be used as a fourth subgroup include diamino-poly (oxyalkylenes) having terminal primary amino groups. Particularly preferred polyether diamines are α, ω-diamino-poly (oxy-1,2-propylene), α, ω-diamino-poly (oxy-1,3-propylene), α, ω-bis (3-amino Propyl) -poly (oxy-1,3-propylene), α,
ω-bis (3-aminopropyl) -poly (oxy-1,4-butylene).

Many homopolyamides, copolyamides and block copolyamides can be produced from the above-mentioned polyamide-forming monomer (I). Preferred homopolyamides for application of the method for producing a weather-resistant polyamide of the present invention include polyamide-6, -11, -12, -66, -69, -610,-
6.12, -6I (I represents an isophthalamide unit),
And -MXDA.6 (MXDA is metaxylylenediamine and 1,3-
Bis- (aminomethyl) benzene).

The copolyamide and the block copolyamide include CoPA-6 / 12, -6/66, -66/12, -6/66/12,
-6/69, -6/610, -66 / 6I or ternary and quaternary copolyamides obtained from these monomers, having less than 40 mol% of hexamethylene terephthalamide (6T) units
CoPA-6T / 6I, laurin lactam, ω-aminolauric acid, isophthalic acid, terephthalic acid, and the isomer bis- (4-amino-3-methylcyclohexyl) -methane, 2,2-bis- (4-
Copolyamide obtained from (aminocyclohexyl) -propane, dodecanedioic acid, and a copolyamide obtained from isomer bis- (4-amino-3-methylcyclohexyl) -methane, and caprolactam, laurinlactam, and dicarboxylic acid, and block copolyetheramides obtained from α, ω-diaminopoly (oxy-1,2-propylene).

The weatherable polyamides according to the invention obtained by the process according to the invention can basically be produced by polymerization or polycondensation using a reactor operating in batch or continuous mode. The process of the present invention differs from the many known processes of the prior art in that a relatively small amount of two or three different raw materials, together with components II, IV and optionally III,
It can be introduced into a specific manufacturing process at an appropriate position. These components can be added without any problem and can be added simultaneously or continuously before, during, or after polymerization or polycondensation.

The weatherable polyamide of the present invention can be variously modified depending on the application. When molding polyamide into parts of required shape by injection molding, multi-component injection molding, injection molding welding, extrusion, co-extrusion, blow molding, deep drawing, and similar processing methods, , Glass fiber, carbon fiber, or reinforcing materials or fibers such as minerals, or, for example, flame retardants, lubricants,
It is common to add other modifiers such as release agents.
When processing polyamide into fibers or filaments,
In this case, polyamide-6 and -66 are mainly used, but it is preferable to add a general matting agent based on titanium dioxide before or during polymerization or polycondensation.

[0056]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments. In Examples and Comparative Examples, only polyamide-6 having a low viscosity to a medium viscosity, which is mainly suitable for producing fibers and injection molded parts, is used.

The weatherable polyamide-6 stabilized according to the process of the invention and the conventional polyamide-6 used as a comparative example were polymerized batchwise in a 130 liter stirrable autoclave. For the polymerization, in a stirred vessel inerted with nitrogen, 45 kg of liquid caprolactam, 7 l of water and the other components in the amounts given in Table 1 were mixed at 90 ° C. Thereafter, the homogenized mixed solution is transferred to the autoclave, and the mixture is rendered inactive (N ₂ ).
Was polymerized. The state during the polymerization was almost as follows throughout.

First stage (pressurization stage) Raw material temperature: 270 ° C. Pressure: 19 bar Time: 3 hours Second stage (expansion stage) Raw material temperature: 270 ° C. to 260 ° C. Pressure: 19 bar to 1 bar Time: 1.5 hours Third stage (degassing stage) Raw material temperature: 260 ° C Pressure: 1 bar Time: about 5 hours

When the desired viscosity was achieved, the individual batches were pressed into polymer strands, granulated from a water bath, extracted with water and dried. According to the torque display of the stirring mechanism of the autoclave, polyamide-6
A basic measurement of the viscosity of the melt was obtained.

The extraction was carried out at 80 ° C. for 16 hours using 2400 liters of fresh water per hour for 40 kg of each batch. Drying was performed at 110 ° C. for 24 hours under vacuum. The solution viscosity of the extracted and dried polyamide-6 was measured at 20 ° C. with a 0.5% by weight solution of m-cresol.

The end group concentration was determined by acid titration. The amino terminal groups were determined by using 0.1-N ethanolic perchloric acid using m-cresol / isopropanol at a weight ratio of 2: 1 as a solvent. The determination of the carboxyl terminal group was carried out using benzyl alcohol as a solvent and 0.1 N benzyl alcoholic potassium hydroxide.

In order to test the weather resistance, an artificial weather test was performed on each PA-6 type. Individual PA-6 types
An injection-molded tensile test piece having a thickness of 1 mm was used. The artificial weather test uses an Atlas Ci35 type weatherometer,
The test was performed under the following conditions in accordance with American Society for Testing and Materials (ASTM) D2565. Radiation intensity at a wavelength of 340 nm: 0.35 W / m ² cycles: 102/18 minutes Temperature (Schwarztafel = black panel): 63 ± 2 ° C

A mechanical test was performed on the test piece after the exposure time shown in Table 3. The degree of weatherability and resistance to photo-oxidative and thermo-oxidative damage of individual products can be measured by the degree to which the impact tensile strength decreases as the effect of exposure increases. The impact tensile strength test was carried out using a Zwick REL type high-speed tensile strength tester according to German Industrial Standard (DIN) 53448 B1.2 (June 1984).
Month) at 23 ° C. at a speed of 4 m / s. After 50 hours of exposure, some products had higher impact tensile strength compared to the initial state, and partially retained this high value for a relatively long time. This is because the test piece absorbed water because the water was periodically supplied to the test piece in the weatherometer, resulting in high toughness or impact tensile strength.

The abbreviations used in the embodiments have the following meanings. LC-6: caprolactam TPS: terephthalic acid AcOH: acetic acid NTE: nitrilotriacetic acid TAD: triacetonediamine = 4-amino-2,2,6,6-tetramethylpiperidine DEAPA: 3-dimethylamino-1-propylamine DBHPP : 3- (3,5-di-t-4-hydroxyphenyl) -propionic acid SZZ: at 23 ° C, German Industrial Standard (DIN) 53443 B1.2
(C): carboxyl end group concentration (meg / kg) (A): amino end group concentration (meg / kg) RV: relative solution viscosity of 0.5% m-cresol solution at 20 ° C. ber : Calculated value Source material manufacturer: NTE: Fluka; Buchs (Switzerland) TAD: Huls; Marl (Germany) DEAPA: Fluka; Buchs (Switzerland) DBHPP: Ciba Geigy; Basel (Switzerland)

EXAMPLES The polyamide-6 type according to the invention and the polyamide-6 type according to the comparative example are listed in Table 1 for comparison. All polymers except the product of Comparative Example 1 terminated with acetic acid contain a polyfunctional carboxylic acid as a polymerization degree terminator. At the end of the polymerization, the equilibrium water content at 260 ° C of the polyfunctional product adjusted with the carboxylic acid at the end of the polymerization should be set at about 260 ° C in order to make the conditions such as polymerization rate, polymerization time, and average molecular weight almost the same. The dicarboxylate used in each sample was 0.153% by weight at a total end group concentration of 108.6 meq / kg and 0.187% by weight at a total end group concentration of 120 meq / kg for the extracted product. The amount of acid or tricarboxylic acid was calculated. Thus, the fraction extractable by water was estimated to be about 9.5% by weight based on the unextracted product. At 260 ° C
PA-6 amide formation equil
The equilibrium constant for ibrium weight) was calculated to be 403 from data presented by Ramesh et al. (Polymer,
1993, Vol. 34, No. 8, page 1716 et seq.).

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

Comparing Example 1 with Comparative Examples 2 and 3, it can be seen that by combining component II and component IV, very good results can be obtained as compared to the case of single use. This is evident from the behavior of the PA-6 of Example 3 containing twice the amounts of component II and component IV at an exposure time of 250 to 300 hours. Weathering tests were performed on the products of Examples 1 and 2 and the results were virtually identical.
This indicates that the addition of component III in Example 2 has no noticeable effect on weather resistance. Based on this data, it can be seen that terephthalic acid also has no stabilizing effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 77:00

Claims (15)

[Claims] Claims 1. A lactam, ω-aminocarboxylic acid, a dicarboxylic acid and a diamine, obtained from a diamine salt of a dicarboxylic acid, are weather-resistant, partially crystalline aliphatic polyamide or partially amorphous partially polyamide. A method for producing an aromatic polyamide, wherein the polymerization or polycondensation of the polyamide-forming monomer (I) is carried out in an amount of 0.02-0.7% by weight of 4-amino-2,2,6,6-tetraalkylpiperidine (II), 0.5% by weight of an aliphatic or cycloaliphatic diamine (III) having primary and tertiary amino groups, and 0.02 to 0.2.
7% by weight having an OH group at the fourth position represented by the following formula:
6-dialkylphenyl (IV), (R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group or a C ₁ to C It is an ester with an alcohol at C ₄ or a primary amino group.In the case of a primary amino group, the values of x and y are x = 2 and y = 1, x = 2 and y = 0, x is A combination of 1 and y is 0 and a combination of x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which x and y are both 0 is additionally provided. The components I to IV complement each other to give a total amount of 100% by weight, the sum of the components II, III and IV being 0.05 to 1.3% by weight, II, III and IV are linked to polymer chains via amide bonds A method for producing a weather-resistant polyamide. 2. A process for producing a weatherable polyamide obtained from a lactam and an ω-aminocarboxylic acid, wherein the polycondensation of the polyamide-forming monomer (I) is carried out in an amount of 0.02-0.7% by weight of 4-amino-2,2,6,4. 6-tetraalkylpiperidine (II), from 0 to 0.5% by weight of an aliphatic or cycloaliphatic diamine (III) having primary and tertiary amino groups and, if necessary, from 0.02 to 0.7% by weight of the formula 2,6-dialkylphenol (IV) having an OH group at the 4-position represented by the formula: (R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group or a C ₁ to C It is an ester with an alcohol at C ₄ or a primary amino group.In the case of a primary amino group, the values of x and y are x = 2 and y = 1, x = 2 and y = 0, x is A combination of 1 and y is 0 and a combination of x is 0 and y is 1. In the case of a free carboxyl group or an esterified carboxyl group, a combination in which x and y are both 0 is additionally provided. And in the presence of from 0.1 to 1.2% by weight of tricarboxylic, tetracarboxylic or polycarboxylic acids (V), the components IV being in a total amount of 100% by weight. Supplements each other with ingredients II, III, IV and The sum of the fine V is 0.2 to 2.5
% By weight, wherein the components II, III, IV and V are linked to the polymer chain via an amide bond. 3. The method for producing a weather-resistant polyamide according to claim 2, wherein a tricarboxylic acid represented by the following formula is used as the component V. Embedded image (When R is H or CH ₃ , n is 0 or 1,
When R is CH ₃ , n is 1.) 4. The process for producing a weatherable polyamide according to claim 1, wherein the amount of the component II is 0.03 to 0.6% by weight. 5. The process for producing a weatherable polyamide according to claim 1, wherein the amount of the component III is 0 to 0.4% by weight. 6. The method for producing a weather-resistant polyamide according to claim 1, wherein the amount of the component IV is 0.03 to 0.6% by weight. 7. The total amount of said components II, III and IV is 0.06
The method for producing a weather-resistant polyamide according to any one of claims 1 to 6, wherein the amount is 1.0 to 1.0% by weight. 8. The R¹ And R^Two Are all C (CH_Three)_Three 
Or R ¹ Is C (CH_Three)_Three In R^Two Is methyl
The method according to claim 1, 2, 6, or 7, wherein
For producing a weather-resistant polyamide. 9. The process for producing a weatherable polyamide according to claim 1, wherein 4-amino-2,2,6,6-tetramethylpiperidine is used as component II. 10. The method according to claim 10, wherein A is -COOH or -COOC.
H ₃ or NH ₂ , R ³ is H, x is 2 and y is 1
8. The method for producing a weather-resistant polyamide according to claim 1, wherein a compound selected from the group of compounds is used as Component IV. 11. Polyamide 6, 11 by condensation polymerization
, -12, -66, -69, -610, -6.12, -6I, -MXDA6 or
Copolyamide-6 / 12, -6 / 66, -66 / 12, -6 / 66/12, -6 / 6
The method for producing a weather-resistant polyamide according to any one of claims 1 to 10, wherein 9, 6, -6/610, -66/610, and 6T / 6I are obtained. 12. A lactam, ω-aminocarboxylic acid, dicarboxylic acid and a diamine, obtained from a diamine salt of a dicarboxylic acid, which are weather-resistant, partially crystalline aliphatic polyamide or partially amorphous partially polyamide. The aromatic polyamide is substantially a polyamide-forming monomer (I), 0.02-0.7% by weight of 4-amino-2,2,6,6-tetraalkylpiperidine (II), 0-0.5% by weight of primary And an aliphatic or alicyclic diamine (III) having a tertiary amino group;
% By weight of 2,6-having an OH group at the 4-position represented by the following formula:
Dialkyl phenyl (IV), (R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group or a C ₁ to C It is an ester with an alcohol at C ₄ or a primary amino group.In the case of a primary amino group, the values of x and y are x = 2 and y = 1, x = 2 and y = 0, x is 1 and y is 0
And combinations where x is 0 and y is 1 are possible.
In the case of a free carboxyl group or an esterified carboxyl group, a combination in which both x and y are 0 is further possible. Components I to IV complement each other to give a total of 100% by weight, the sum of components II, III and IV being 0.05 to 1.3% by weight, and components II, III and IV comprising amide linkages. A weather-resistant polyamide which is bonded to a polymer chain via a polymer. 13. The weatherable polyamide obtained from a lactam and an ω-aminocarboxylic acid is substantially composed of a polyamide-forming monomer (I), 0.02-0.7% by weight of 4-amino-2,2,6,6-tetracarboxylic acid. Alkylpiperidine (II), 0 to 0.5% by weight of an aliphatic or alicyclic diamine (III) having primary and tertiary amino groups, optionally 0.02 to 0.7% by weight represented by the following formula: 2,6-dialkylphenol (IV) having an OH group at the 1-position, (R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms which may be the same or different, and R ³ is a hydrogen atom or a methyl group. The functional group A is a free carboxyl group or a C ₁ -C Represents an ester with a C ₄ alcohol or a primary amino group, and in the case of a primary amino group, the values of x and y are such that x is 2 and y is 1, x is 2 and y is 0, and x is 1 and y is 0
And combinations where x is 0 and y is 1 are possible.
In the case of a free carboxyl group or an esterified carboxyl group, a combination in which x and y are both 0 is additionally possible. ) And 0.1 ~
1.2% by weight of tricarboxylic acid, tetracarboxylic acid or polycarboxylic acid (V), wherein components I to V complement each other to give a total amount of 100% by weight, and that of components II, III, IV and V Total is 0.2 to 2.5
A weatherable polyamide characterized in that, by weight, components II, III, IV and V are attached to the polymer chain via amide bonds. 14. A tricarboxylic acid represented by the following formula:
The weatherable polyamide according to claim 13, which is used as Component V. Embedded image (When R is H or CH ₃ , n is 0 or 1,
When R is CH ₃ , n is 1). 15. An injection molded part or an extruded part may be formed by using a yarn,
Use of the polyamide according to claim 12, 13 or 14 for producing fibers, foils, hot-melt powders or hot-melt fibers.