JP2002097268A - Polyamide resin composition and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for giving oxidation stability at a high temperature in the presence of oxygen, for example, to a dimeric-acid modified polyamide resin, using a less inexpensive and easier means greatly as compared with the method of hydrogenation. SOLUTION: The polyamide resin composition contains a polyamide resin wherein a polybasic carboxylic acid containing an unsaturated carbon-carbon bond, and a polyamine are constituent units. A few amount of an organic phosphorus compound is added to a usage of the polybasic carboxylic acid containing the unsaturated carbon-carbon bond of a raw material, and in the presence of a few amount of this organic phosphorus, the polyamide resin is formed by dehydrocondensing under heating. The polyamide resin composition contains a few amount of the organic phosphorus compound to be coexisted, as an accompanying component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyamide resin composition and a method for preparing the same, and more specifically, to suppress a change in resin color tone due to oxidation and an oxidative deterioration at high temperature, to obtain a color tone retention characteristic and a heating property. The present invention relates to a polyamide resin composition having excellent stability and a method for preparing the same, and more particularly to a polyamide resin composition using dimer acid as a dibasic acid as a raw material of a polyamide and a method for preparing the same. More specifically, the present invention relates to a polyamide resin composition synthesized in the presence of an organic phosphorus compound and a method for producing the same.

[0002]

2. Description of the Related Art Polyamide resins are synthesized by using polybasic acids and polyamine compounds as raw materials, performing dehydration condensation between amino groups and carboxyl groups under heating, forming amide bonds and stretching polymer chains. . Specifically, adipic acid, dibasic acid such as glutaric acid and ethylenediamine,
A resin in which both constituent units are linked by an amide bond using a polyamine such as hexamethylenediamine as a starting material has been conventionally known. By the way, tall oil fatty acids,
Among plant-derived natural fats and oils such as soybean oil fatty acids, a large amount of unsaturated fatty acids such as oleic acid and linoleic acid are contained, and dimer acid obtained by dimerizing the unsaturated fatty acids is converted into a polyamide resin raw material. Those selected as dibasic acids are particularly called dimer acid-modified polyamide resins. This dimer acid-modified polyamide resin is
Depending on the average molecular weight, those exhibiting various properties from those which are liquid at room temperature to those whose softening point reaches about 180 ° C. have been synthesized.

[0003] In the dimer acid-modified polyamide resin, in the design stage of the synthesis method, by selecting the raw material ratio and changing the equivalent ratio between amino groups and carboxyl groups, two reactive or non-reactive ones can be obtained. Each type of polyamide resin can be made separately. Specifically, if the equivalent ratio of amino groups to carboxyl groups is increased, the resulting polyamide resin becomes a reactive type resin in which amino groups remain at both ends. On the other hand, if the equivalent ratio between the amino group and the carboxyl group is substantially equal, a non-reactive type resin is obtained. Usually, the reactive type polyamide resin is used, for example, as a diamine type curing agent for an epoxy resin. In addition to the two-component adhesive between the epoxy resin and the reactive type polyamide resin, for example, as a coating resin or a structural adhesive for civil engineering and construction applications (use as a substitute for rivets and bolts, for concrete reinforcement), etc. used. On the other hand, non-reactive polyamide resins are thermoplastic resins and are therefore mainly used for hot melt adhesives. Further, taking advantage of the advantage of having excellent shear adhesive strength, it is widely used as a packaging adhesive, and also as a fixing adhesive for electric machines, electronic components, and the like because it has excellent electrical insulation properties. Further, by applying the properties of the hot melt type adhesive, it is also used as a vehicle for special gravure ink in the printing ink field.

As described above, although the polyamide resin has many uses, the disadvantage derived from its structure is that it is susceptible to oxidative deterioration. Particularly, the oxygen contained in the atmosphere under high temperature conditions or ultraviolet irradiation. Therefore, there is a problem that heat resistance and light resistance are poor. Although the polyamide resin itself has various characteristics, it is difficult to have heat resistance and light resistance,
As a result of the inability to maintain its excellent performance for a long period of time, it is a factor that limits its application range.

In the dimer acid-modified polyamide resin, particularly, the dimer acid itself has poor oxidation stability at high temperatures, and specifically, is severely oxidatively degraded at high temperatures in the presence of oxygen. This oxidation mechanism is roughly classified into the following two types of reactions.

The first reaction is a reaction caused by the cleavage of a carbon-hydrogen bond in a saturated hydrocarbon. The generated radical grows by a chain mechanism, reacts with oxygen molecules,
This gives the alkyl hydroperoxide (-OOH). Furthermore, when this hydroperoxide accumulates and reaches a certain amount (density), a radical chain branching reaction occurs, and the oxidation reaction proceeds abruptly autocatalytically, leading to deterioration of the resin.
In the oxidative deterioration involving the formation of the hydroperoxy group, the generation of radical species, which is an initial process, is promoted by light, heat, the presence of oxygen, a metal, and the like. This cleavage reaction is usually methyl (CH ₃ -) carbon, methylene (-C
It is less likely to occur with H _2- ) carbon and more likely with methine (> CH-) carbon. In dimer acid, the site where at least two fatty acids bind is methine carbon, which is more reactive than general fatty acids.

The second reaction is an oxidation reaction for a double bond or an aromatic ring. Dimer acid has 1 to 4 double bonds in the molecule derived from the unsaturated carboxylic acid on which it is based, and may be partially aromatic. . Oxygen oxidation to this unsaturated bond,
This reaction is the main reaction mechanism of the oxidative deterioration. The oxidation reaction further includes (a) a reaction in which direct oxidation occurs on the double bond to form an epoxide; and (b) a carbon adjacent to the double bond, that is, an allylic position (—CH ＝ CH—CH ₂ — methylene) (-CH ₂ -) carbon or the carbon adjacent to the aromatic ring, i.e., the benzyl position _{(-C 6 H 4 -CH 2 -} ; α -position)
Methylene (-CH ₂ -) by the addition of the carbon, there are two kinds of reactions in the reaction to produce a hydroperoxide (-OOH). In this reaction, it is known that, as the size of the ring increases, the formation of an epoxide by addition to the double bond takes precedence in the reaction for the double bond present in the ring. Conversely, in the case of a six-membered ring having a small ring size contained in dimer acid, in most cases, the carbon at the allylic position is oxidized to generate hydroperoxide (—OOH) and the like. In addition, when the molecule has an aromatic ring, the oxidation reaction of oxygen to benzylic carbon also proceeds to generate hydroperoxide (—OOH) and the like. The generated hydroperoxide undergoes further oxidation, and various peroxides,
Alternatively, an active molecular species such as a radical species is generated. This active molecular species causes a chain reaction and reacts with a functional group such as an amide group in the polyamide, resulting in polymerization of the resin, cleavage of the molecular chain, formation of an oxide, etc., resulting in coloring of the resin,
Or deterioration occurs. This series of oxidation reactions is more likely to occur as the number of unsaturated bonds contained in the molecule increases, and more specifically, increases as the iodine value, which is an index indicating the amount of unsaturated bonds, increases. Thus, the unsaturated bond derived from dimer acid affects the oxidative stability of the polyamide obtained therefrom. That is, in the dimer acid-modified polyamide resin, although there is an oxidation reaction involving the methine (> CH—) carbon, the dimer acid-modified polyamide resin has a greater influence on the oxidation stability of the polyamide resin. It is an oxidation reaction involving a double bond and an aromatic ring contained in itself.

In order to suppress oxidative deterioration, there is a method in which hydrogenation is performed on dimer acid which leaves an unsaturated bond to reduce unsaturated bonds such as a double bond and an aromatic ring, thereby improving oxidative stability. However, in the reaction for converting into a hydrogenated dimer acid having excellent stability by hydrogenation, for example, in a catalytic hydrogenation reaction, the pressure of hydrogen used needs to be increased to 10 atm or more, preferably to about 100 atm. Reactions under high pressure require special production equipment. In order to ensure sufficient oxidation stability, it is preferable to use conditions that can reduce all of the unsaturated carbon-carbon bonds contained.As the hydrogenation catalyst, palladium, platinum, rhodium,
It is desirable to use a noble metal catalyst such as ruthenium. In that case, these catalysts are expensive and increase the cost required to convert the raw material dimer acid to the desired hydrogenated dimer acid, and as a result, a dimer acid-modified polyamide resin synthesized from the hydrogenated dimer acid It is also an economic factor that hinders the widespread expansion of its production cost.

Therefore, in order to develop a means for imparting good oxidation stability to a dimer acid-modified polyamide resin instead of a technique for converting dimer acid itself to hydrogenated dimer acid by hydrogenation and improving the oxidation stability. Many efforts have been made. The most common attempt is to add an oxidation stabilizer to the dimer acid-modified polyamide resin. However, to date, this method of adding an oxidation stabilizer has not yet provided excellent oxidation stability comparable to that of a dimer acid-modified polyamide resin derived from hydrogenated dimer acid.

[0010]

As described above,
The dimer acid-modified polyamide resin has a problem in oxidation stability at high temperatures due to the unsaturated bond contained in the dimer acid itself, and takes advantage of its characteristic good adhesiveness.
This is a major factor that hinders development in various fields. Indeed, by using hydrogenated dimer acid,
Although excellent oxidative stability can be achieved, it is used only in limited applications for economic reasons because of the significant increase in production costs. In other words, at present, even in many fields where the use of the resin does not progress for economic reasons, in order to enable the use of the dimer acid-modified polyamide resin, it is much cheaper and simpler than the hydrogenation method. There is a demand for a method for imparting oxidative stability to a dimer acid-modified polyamide resin in the presence of oxygen at a high temperature by using the above.

[0011] The present invention solves the above-mentioned problems, and an object of the present invention is to use, for example, a dimer acid-modified polyamide resin by using a far cheaper and simpler means than a hydrogenation method. To provide a method for imparting oxidative stability at high temperature in the presence of oxygen, and to provide a novel polyamide resin composition imparted with excellent oxidative stability by employing such a method. It is in.

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied on the mechanism of oxidative degradation of a polyamide resin such as the dimer acid-modified polyamide resin described above, which has an unsaturated carbon-carbon bond in the molecule. Based on the knowledge, as a result of further intensive research, instead of adding a oxidizing stabilizer to a synthesized polyamide resin to form a polyamide resin composition as in the past, a polyamide using an unsaturated carboxylic acid as a raw material When synthesizing a resin, for example, a dimer acid-modified polyamide resin, an organic phosphorus compound, more specifically, an organic phosphorus compound having an unshared electron pair on a phosphorus atom, for example, a trisubstituted phosphine derivative, or a phosphorus suboxide When an acid triester derivative is added and a polyamide resin is prepared in the presence of these organic phosphorus compounds,
In the polyamide resin obtained from the obtained unsaturated carboxylic acid, for example, a dimer acid-modified polyamide resin, that is, in the polyamide resin composition accompanied by these organic phosphorus compounds, the color change of the polyamide resin due to oxidation is small, and It has been found that there is little oxidative deterioration at the time and a polyamide resin composition having excellent oxidative stability is obtained. In addition, the present inventor, the polyamide resin composition prepared by such a method, even immediately after synthesis,
The resin color tone, without the presence of an organic phosphorus compound, was also found to be significantly improved when compared with a polyamide resin produced by a conventional synthesis method.Based on these findings, it was found that the present invention was completed. Reached.

That is, the polyamide resin composition of the present invention is a polyamide resin composition containing, as a main component polyamide, a polyamide resin whose constituent units are a polybasic carboxylic acid having an unsaturated carbon-carbon bond and a polyamine. When the polyamide resin is dehydrated and condensed under heating from the polybasic carboxylic acid having an unsaturated carbon-carbon bond of its constituent unit and a polyamine to form an amide bond, the unsaturated carbon as a raw material is used. A polyamide resin formed by adding a small amount of an organic phosphorus compound to the amount of the polybasic carboxylic acid having a carbon bond, and coexisting with the small amount of the organic phosphorus compound, by dehydration condensation under heating; A polyamide resin composition containing the small amount of the organic phosphorus compound coexisting as an accessory component.

In the polyamide resin composition of the present invention, the organic phosphorus compound contained as an accessory component is preferably a phosphine derivative. Alternatively, the organic phosphorus compound contained as an accessory component is
It is also preferable to use a phosphorous acid derivative. In addition, it is more preferable that the content of the organic phosphorus compound contained as an accessory component is selected in the range of 0.1 to 5.0 parts by mass per 100 parts by mass of the polyamide resin.

[0015] In the polyamide resin composition of the present invention, the unsaturated carbon-
When the polybasic carboxylic acid having a carbon bond is a polyamide resin composition characterized by being a dimer acid having an unsaturated carbon-carbon bond, the effect becomes more remarkable.

Further, the method for preparing the polyamide resin composition of the present invention is a method for efficiently preparing the above-described polyamide resin composition of the present invention. More specifically, the method for preparing a polyamide resin composition of the present invention is a method for preparing a polyamide resin containing, as a main component polyamide, a polyamide resin having a polybasic carboxylic acid having an unsaturated carbon-carbon bond and a polyamine as its constituent units. A method for preparing a resin composition, wherein the polyamide resin is obtained by using, as raw materials, a predetermined amount of the polybasic carboxylic acid having a unsaturated carbon-carbon bond and a predetermined amount of polyamine having a structural unit thereof, and With respect to the amount of the polybasic carboxylic acid having a carbon-carbon bond, a small amount of an organic phosphorus compound is added, and in the presence of the small amount of the organic phosphorus compound, dehydration condensation is performed under heating to form an amide bond; A polyamide resin, without removing the small amount of the organic phosphorus compound to be coexisted, characterized in that it is a composition containing as an accessory component, It is a manufacturing method.

The method for preparing a polyamide resin composition of the present invention is a suitable method when the organic phosphorus compound contained as an accessory component in the target polyamide resin composition is a phosphine derivative. . Alternatively, a suitable preparation method is also used when the organic phosphorus compound contained as an accessory component in the target polyamide resin composition is a phosphorous acid derivative. In addition, in the preparation method of the present invention, in the target polyamide resin composition, the addition amount of the organic phosphorus compound contained as an accessory component is such that the raw material is a polybasic carboxylic acid having an unsaturated carbon-carbon bond. A more preferable method is selected when it is selected in the range of 0.1 to 5.0 parts by mass per 100 parts by mass of the polyamide resin obtained in the ratio of the amounts of the polyamine and the polyamine.

In the preparation method of the present invention, the target polyamide resin composition is such that the polybasic carboxylic acid having an unsaturated carbon-carbon bond, which is a structural unit of the polyamide resin, has an unsaturated carbon-carbon bond. When it is a dimer acid, it becomes a more preferable preparation method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide resin composition of the present invention is characterized in that, when the polyamide contained as the target main component has the above-mentioned polybasic carboxylic acid containing an unsaturated carbon-carbon bond as its constituent unit, the unsaturated resin is In order to prevent oxidative deterioration due to carbon-carbon bonds, a polybasic carboxylic acid containing the unsaturated carbon-carbon bond and a polyamine are used to form an amide bond to form a polyamide resin, and a polyamide formed in advance. By adding a small amount of an organic phosphorus compound having the property of forming a uniform miscible material with the resin, and performing a dehydration condensation reaction by heating in the coexistence of the organic phosphorus compound, the coexisting organic phosphorus compound is used as an additional component. By making the composition of the polyamide resin contained, even in this heating reaction, the oxidation caused by oxygen is suppressed, and in addition, the generated polyamide Also in fat, then the oxygen contained in the air, in which are effectively suppressed even oxidative degradation to proceed the heating or light irradiation as incentive. The suppression of such oxidative deterioration is achieved by the action of an organic phosphorus compound attached to the polyamide resin molecule, thereby suppressing the introduction of a hydroperoxy group (-OOH) by the addition of oxygen and the accumulation thereof in the above-described radical reaction. Has been achieved by that.

Therefore, the effect of effectively suppressing the oxidative deterioration of the polyamide resin composition of the present invention can be obtained by applying it to a dimer acid-modified polyamide resin in which the oxidative deterioration is remarkable unless any measures are taken. The effect becomes clearer. In addition, in the heating reaction for synthesizing the amide resin, the oxidation caused by oxygen mixed in the reaction system increases in frequency as the heating temperature in the dehydration condensation reaction increases, but in the present invention, In the reaction system, a polybasic carboxylic acid containing an unsaturated carbon-carbon bond as a raw material, a small amount of an organic phosphorus compound is allowed to coexist, so that the progress of this oxidation is also suppressed, The reaction temperature of the dehydration condensation reaction is 150 ° C.
As described above, the oxidation reaction by oxygen can be sufficiently suppressed even when the polymerization reaction is promoted by setting the temperature to preferably 200 ° C. or higher, so that more preferable reaction conditions can be achieved. As a matter of course, the degree of oxidation of the formed polyamide resin composition itself is kept low, and the color tone is more preferable. As the organophosphorus compound, specifically, a trisubstituted phosphine derivative or a phosphite triester derivative is used, and these two kinds of organophosphorus compounds have an unshared electron pair (lone electron pair) on a phosphorus atom. Have a structural commonality. Utilizing this structural feature, for example, an organic phosphorus compound is derived from a polybasic carboxylic acid containing an unsaturated carbon-carbon bond, and is oriented to a carbon-carbon double bond skeleton, whereby the organic phosphorus compound is converted into a polyamide resin molecule. It will be attached. As a result, the hydroperoxy group (—OOH) due to the addition of oxygen can be effectively eliminated or the generation thereof can be suppressed. Specifically, with respect to such a polyamide resin, the configuration of the organophosphorus compound that is additionally located is a carbon atom at which generation of a hydroperoxy group (—OOH) is likely to occur by addition of an oxygen molecule, that is, mentioned allylic position (-CH = CH-CH ₂
-) methylene (-CH ₂ -) carbon, or carbon adjacent to the aromatic ring, i.e., the benzyl position (-C ₆ H ₄ -CH
_2- ; α-position) methylene (-CH _2- ) carbon or the like, and the phosphorus atom is selectively generated when the phosphorus atom is oriented. By utilizing the fact that this position is occupied by a tri-substituted phosphine derivative or a phosphite triester derivative, the above-described action and effect are achieved. In addition, it is more efficient to perform such selective arrangement of the organic phosphorus compound while the polyamide resin itself is in a state of exhibiting sufficient fluidity, that is, in advance in the process of synthesizing the polyamide resin. By making the organic phosphorus compound coexist, it is necessary to perform the above-mentioned additional orientation.

Hereinafter, the polyamide resin composition of the present invention and its preparation method will be described in more detail.

The polyamide resin as the main component contained in the polyamide resin composition of the present invention is a polyamide resin having a polybasic carboxylic acid having an unsaturated carbon-carbon bond and a polyamine as its constitutional units, preferably, It is a polymer obtained by reacting a diamine having an unsaturated carbon-carbon bond with a polyamine.

For example, examples of the dibasic acid having an unsaturated carbon-carbon bond include dimer acid obtained by dimerizing an unsaturated fatty acid among natural fatty acids derived from plants such as tall oil fatty acid and soybean oil fatty acid. Is preferably used. In addition, in addition to the dimer acid, a polybasic carboxylic acid such as a trimer acid which is incidentally generated in the dimerization reaction may be contained. In addition, in order to achieve the desired resin characteristics of the polyamide resin, in addition to a dibasic acid having an unsaturated carbon-carbon bond such as dimer acid which is a main component, saturated A basic carboxylic acid, for example, adipic acid, alaisenic acid, sebacic acid and the like may be used in combination.

On the other hand, as the polyamine serving as the remaining structural unit, diamines are usually used in many cases. For example, diamines having a chain-like saturated hydrocarbon group; ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, etc. Saturated cyclic diamine containing an imino nitrogen atom in the ring; diamine having a ring structure such as piperazine; xylene diamine, isophorone diamine, 4,
4'-methylenebis (cyclohexylamine), 4,
Various diamines, such as 4'-methylene dianiline, can be used depending on the desired resin properties of the polyamide resin.

The polymerization reaction for synthesizing a polyamide resin having a polyamine and a polybasic carboxylic acid having an unsaturated carbon-carbon bond, which is a main component polyamide resin, as a constituent unit is carried out by heating the raw material polybasic acid with heating. This is a reaction for forming an amide bond with a polyamine.
The temperature is selected in the range of from 300C to 300C, preferably in the range of from 200C to 270C. In this reaction, the starting compound, for example, a polybasic carboxylic acid having an unsaturated carbon-carbon bond itself, and an oxygen-free atmosphere in the reaction system, for example, in order to prevent oxidative deterioration of the generated polyamide resin itself, for example, It is necessary to carry out the reaction under an inert gas atmosphere such as nitrogen gas or argon gas. In addition, even when replacement is performed in an inert gas atmosphere, slight oxidative deterioration proceeds in such a synthesis reaction process due to unavoidable slight residual oxygen. However, in the present invention, it will be described later. By adding a small amount of the organic phosphorus compound to the reaction system together with the raw material compound in advance, oxidation in the synthesis process is suppressed. On the other hand, the reaction is usually carried out at normal pressure.
It is also possible to carry out under reduced pressure of up to 500 mmHg. Alternatively, after completion of the reaction, 10-500 mmH
While maintaining the reduced pressure of g, these unnecessary substances can be distilled off. The reaction time is determined according to the reaction conditions such as the type of raw material used, the reaction temperature, and the ratio of the amount of the polybasic acid to the polyamine used as the raw material. Usually, the reaction is almost complete within 1 to 10 hours.

The preparation of the polyamide resin composition of the present invention comprises:
In the process of synthesizing the polyamide resin, a small amount of an organic phosphorus compound is added in advance to the reaction system together with the raw material compound, an amide bond is formed in the coexistence of the organic phosphorus compound, and the polyamide resin formed by this reaction is formed. To
The composition is a state in which the coexisting organic phosphorus compound is attached. As an organic phosphorus compound to coexist, it does not cause unnecessary reaction to the raw material polybasic carboxylic acid itself or polyamine, and by heating reaction,
Satisfies these two requirements not to cause thermal decomposition, etc. In addition, it has an affinity for the polybasic carboxylic acid having an unsaturated carbon-carbon bond as a raw material, and has a phase with the generated polyamide resin. Those excellent in solubility are preferably used. Specific examples of the organophosphorus compound that satisfies the above four requirements and has excellent ability to suppress oxidative deterioration due to oxygen molecules at high temperatures or during light irradiation include phosphine (phosphane) derivatives, Or a phosphorous acid (phosphonic acid) derivative.

As the organic phosphorus compound as an additional component in the polyamide resin composition of the present invention, the above-mentioned phosphine (phosphane) derivative or phosphorous acid (phosphonic acid) derivative is preferably selected. The range is obtained by adding a small amount of the organic phosphorus compound to the amount of the polybasic carboxylic acid having an unsaturated carbon-carbon bond as the raw material. Therefore, it is preferable that about 0.002 to 0.05 molecules of the organic phosphorus compound coexist per molecule of the raw material polybasic carboxylic acid having an unsaturated carbon-carbon bond, the molecular weight of the organic phosphorus compound used, and The average molecular weight of the polyamide resin to be produced depends on the molecular weight of the polybasic carboxylic acid having an unsaturated carbon-carbon bond as a constituent unit thereof, but the content of the organic phosphorus compound contained as an accessory component is determined by polyamide. Resin 10
More preferably, it is selected in the range of 0.1 to 5.0 parts by mass per 0 parts by mass. Particularly, in the polyamide resin composition, when the polyamide resin contained as a main component is a dimer acid-modified polyamide resin, about 1 to 2 carbon-carbon double bonds remain in the molecule of the dimer acid. In this case, per 100 parts by mass of the polyamide resin,
More preferably, it is selected in the range of 0.1 to 5.0 parts by mass.

The phosphine (phosphane) derivative used in the present invention includes the following general formula (I):

[0029]

Embedded image

(Wherein, R1, R2 and R3 each represent a hydrocarbon group and may be the same), or a trisubstituted phosphine (phosphane) derivative represented by the following formula: Bis (disubstituted phosphino) hydrocarbon derivatives are preferred. Examples of trisubstituted phosphine (phosphane) derivatives include, for example, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, and tri-t. -Butylphosphine, tricyclohexylphosphine, tri-n-octylphosphine, triphenylphosphine, triorthotolylphosphine, trimetatrilyphosphine, triparatolylphosphine, tribenzylphosphine, tris- (4-methoxyphenyl) phospho Fin, diphenylcyclohexylphosphine, such as Pallas styryl diphenyl phosphine,
Examples of bis (disubstituted phosphino) hydrocarbon derivatives include 1,2-bis (diphenylphosphino) ethane,
1,3-bis (diphenylphosphino) propane, 1,
4-bis (diphenylphosphino) butane and the like.

The phosphorous acid derivative used in the present invention includes the following general formula (II):

[0032]

Embedded image

Wherein R 4, R 5 and R 6 each represent a hydrocarbon group and may be the same, or a phosphite (phosphonic acid) moiety Are preferably esterified diphosphonic acid derivatives and the like, and examples of the phosphite triester derivatives include, for example, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, and tri-n-butyl phosphite. Phyte, triisobutyl phosphite, tri-t-butyl phosphite, tricyclohexyl phosphite, trioctyl phosphite, tridecyl phosphite, tris (dodecyl) phosphite, tris (triisodecyl) phosphite, tris (tetradecyl) phosphite , Tris (hexade Phosphite, tris (octadecyl) phosphite, triphenyl phosphite, triortho tolyl phosphite, trimetatrile phosphite, triparatolyl phosphite, tribenzyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, bis (2,4-di-t-butyl-6) -Methylphenyl) monoethyl phosphite, bis (nonylphenyl) mono (dinonylphenyl) phosphite, 2,2′-methylene-bis (4,6
As an esterified diphosphorous acid derivative such as -di-t-butylphenyl) octyl phosphite, for example, tetra (tridecyl) -4,4'-isopropylidenediphenyl diphosphite, 4,4'-butylidene-
As an esterified triphosphorous acid derivative such as bis [3-methyl-6-t-butylphenylbis (tridecyl)] phosphite, for example, 2,4,4′-butanetriyl-tris [3-methyl-6 As an esterified tetraphosphorous acid derivative such as -t-butylphenylbis (tridecyl)] phosphite, for example, phosphorous acid forming an intramolecular ring structure such as tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite As triester derivatives, for example, didecylpentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (octadecyl)
Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (4-methyl-2,6-di-
(t-butylphenyl) pentaerythritol diphosphite and the like.

In the preparation method of the present invention, these trisubstituted phosphine derivatives or phosphite triester derivatives (phosphonate triesters) are used in an amount of 0.1 to 0.1 parts by mass per 100 parts by mass of the total amount of polybasic acid and polyamine. It is preferable to select an addition amount in a range of 5.0 parts by mass, preferably in a range of 0.2 to 2.0 parts by mass, and to add the raw materials together with the raw materials in advance to the reaction system to carry out the polymerization reaction.

As described above, various phosphine derivatives or phosphorous acid derivatives can be used. However, in order to further improve the heat stability of the dimer acid-modified polyamide resin composition, the above-mentioned phosphine derivative or phosphorous acid derivative is used. From the derivatives, not only one kind may be selected, but also two or more kinds may be mixed and used. That is, two or more compounds classified as either a phosphine derivative or a phosphorous acid derivative can be used in combination. Alternatively, two or more compounds can be selected from both the phosphine derivative and the phosphorous acid derivative and used in combination.

In the polyamide resin composition of the present invention, its excellent oxidation stability is achieved by the action of the above-mentioned organic phosphorus compound attached to the polyamide resin molecule. Alternatively, at the time of use, a phenol-based, amine-based, sulfur-based, or phosphorus-based antioxidant can be further added. The polyamide resin composition of the present invention contains the organic phosphorus compound added at the time of the synthesis reaction, and the sum of the organic phosphorus compound and an antioxidant added later is a polyamide resin of the main component. , for example, 100 parts by weight per dimer acid modified polyamide resin, within a range not exceeding 10.0 parts by weight, preferably in a range not exceeding 4.0 parts by weight, the addition of additional antioxidants described above You can also.

As the phenolic antioxidant, for example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) commercially available from Ciba Specialty Chemicals under the trade names ) Propionate] (Irganox 1010),
N, N'-hexane-1,6-diylbis [3- (3,
5-Di-t-butyl-4-hydroxyphenyl) propionamide] (Irganox 1098), thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 103
5), octadecyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate (Irganox 1076), ethylenebis (oxyethylene) bis [3- (3,5-di-t-butyl-4-hydroxy-m
-Tolyl) propionate] (Irganox 24
5), hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 259), 2,6-di-t-butyl-4-
[4,6-bis (octylthio) -1,3,5-triazin-2-ylamino] phenol (Irganox 5
65), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ( Irganox 3114), 3,4-dihydro-2,5,7,
8-Tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol (Irganox E201), commercially available from Sumitomo Chemical Co., Ltd. under their respective trade names, 6-di-t-butyl-4-methylphenol (Sumilyzer BHT), 4,4′-butylidenebis (3-methyl-6-t-butylphenol (Sumilyzer BBM-S), 3,9-bis [1,1-
Dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,
5] Undecane (Sumilyzer GA-80), 2-t-
Butyl-6- (3-tert-butyl-2-hydroxy-5-
Methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GM), commercially available from Asahi Denka Kogyo KK under the trade names, 1,3,5-trimethyl-2,4,
6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (Adecastab AO-330),
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane (ADK STAB AO-3)
0) can be used.

Examples of the amine-based antioxidant include a reaction product (Irganox 505) of N-phenylbenzeneamine and 2,4,4-trimethylpentene which is commercially available from Ciba Specialty Chemicals under the trade names.
7) Octylated diphenylamine (Nocrack AD) commercially available from Ouchi Shinko Chemical Industry Co., Ltd.
-F), N, N'-diphenyl-p-phenylenediamine (Nocrack DP), N-phenyl-N'-isopropyl-p-phenylenediamine (Nocrack 810-N
A), N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (Nocrack 6C),
N, N'-di-2-naphthyl-p-phenylenediamine (Nocrack White), 2,2,4-trimethyl-
1,2-dihydroquinoline polymer (Nocrack 22
4), 6-ethoxy-1,2-dihydro-2,2,4-
Trimethylquinoline (Nocrack AW) and the like can be used.

Examples of the sulfur-based antioxidant include didodecyl- commercially available from Sumitomo Chemical Co., Ltd. under the trade names.
3,3-thiodipropionate (Sumilyzer TPL-
R), ditetradecyl-3,3-thiodipropionate (Sumilyzer TPM), dioctadecyl-3,3-thiodipropionate (Sumilyzer TPS), pentaerythryltetrakis (3-dodecylthiopropionate) (Sumilyzer TP) -D), ditridecyl-3,3-thiodipropionate (Adecastab AO-503A), which is commercially available from Asahi Denka Kogyo Co., Ltd. under each trade name, can be used.

As the phosphorus antioxidant, various phosphine derivatives or phosphorous acid derivatives exemplified above can be used.

After synthesizing the amide resin, if necessary, the polyamide resin composition of the present invention may be further added with various antioxidants within a range not exceeding the above-mentioned total amount range. At this time, in order to further improve the heating stability of the polyamide resin, for example, the dimer acid-modified polyamide resin, not only one kind is selected from the above-described antioxidants but also two More than one kind can be mixed and added. For example, as an antioxidant to be added additionally, any one group of phenolic antioxidant, amine antioxidant, sulfur antioxidant, phosphorus antioxidant is selected, and the antioxidant Two or more compounds classified into groups can be used in combination. Alternatively, from the group of phenolic antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants, select two or more compounds classified into different antioxidants, They can be used in combination.

The polyamide resin composition of the present invention, for example,
The dimer acid-modified polyamide resin composition is a polyamide resin, for example, per 100 parts by mass of the dimer acid-modified polyamide resin, the trisubstituted phosphine-type derivative or the phosphite triester-type derivative described above is allowed to coexist during the reaction. The sum of the amount and the amount added after the synthesis is 0.1 to
The composition may be contained in a range of 5.0 parts by mass, preferably in a range of 0.2 to 2.0 parts by mass. Naturally, the concentration of the organic phosphorus compound contained in the polyamide resin composition decreases, and the effect of improving the oxidative stability of the polyamide resin also decreases. Therefore, the phosphine derivative, the phosphite derivative, or the like The content of the organic phosphorus compound is, per 100 parts by mass of the polyamide resin,
If the amount is less than 0.1 part by mass, the oxidation stability provided by the organic phosphorus compound will be reduced in a short period of time.

On the other hand, when the content of the organic phosphorus compound such as the phosphine derivative or the phosphorous acid derivative exceeds 5 parts by mass per 100 parts by mass of the polyamide resin, the polyamide resin composition, for example, the dimer acid-modified polyamide resin For example, when the composition is applied to the surface of a material, dried, and used as an adhesive, as the ratio of the organic phosphorus compound contained increases, this becomes a factor in lowering the adhesive performance of the adhesive layer. Therefore, in many applications, the content of the above-mentioned phosphine derivative, or an organic phosphorus compound such as a phosphorous acid derivative, per 100 parts by mass of the polyamide resin,
If it is selected within a range not exceeding 5.0 parts by mass, for example, within a range not exceeding 2.0 parts by mass, the original excellent adhesive performance can be sufficiently exhibited, and the content is at this level. As long as it is sufficient oxidation stability can be maintained for a long period of time, a more preferable resin composition is obtained from a functional aspect.

Further, the polyamide resin composition of the present invention,
For example, a dimer acid-modified polyamide resin composition can be used as an epoxy resin curing agent, a resin for coatings, or a vehicle for gravure inks, as well as adhesives for civil engineering and construction applications, packaging applications, electrical and electronic component applications, and hot melt adhesives. When applied and developed for various uses, such as an agent, a polyamide resin, for example, 100 parts by mass of a dimer acid-modified polyamide resin, and a high amount of polyolefin, polyester, polyimide, thermoplastic rubber, etc. The molecular compound may be compatibilized in the range of 1 to 100 parts by mass, preferably 5 to 50 parts by mass to obtain a composition containing a plurality of resin components.

The polyamide resin composition of the present invention, for example,
Dimer acid-modified polyamide resin composition, during the synthesis of the polyamide resin, or after finishing the synthesis, in addition to the additional components introduced above, depending on the purpose of use, additives having a specific use, for example, In addition, an antistatic agent, a defoaming agent, and the like, and a light stabilizer, a UV absorber, and the like can be appropriately added for the purpose of further suppressing oxidative deterioration due to light irradiation.

[0046]

The present invention will be described more specifically with reference to the following examples. In addition, although the example shown below is an example of the best embodiment of the present invention, the present invention
It is not limited to these specific examples.

Example 1 A stirrer, a drain tube with a cooling tube attached to the top, a thermometer, and a nitrogen conduit tube were attached.
In a 1-liter reactor, dimer acid (Halidimer 3)
00; Harima Chemicals, Inc.) 100 parts, tall oil fatty acid (Hartor FA-1; Harima Chemicals, Inc.) 1 part, sebacic acid 5 parts, ethylenediamine 10 parts, hexamethylenediamine 5 parts, and triphenylphosphine 0.2
4 parts are added, the inside of the system is set to a nitrogen atmosphere, and the temperature is gradually increased to 200 ° C. while stirring for uniformity under a nitrogen stream. Subsequently, while stirring, dehydration condensation was performed at 200 ° C. for 5 hours to obtain a dimer acid-modified polyamide resin composition.

The color of the resin composition immediately after preparation and the oxidation stability of the prepared dimer acid-modified polyamide resin composition were evaluated by the following procedure. Table 2 shows the evaluation results.

(Evaluation of Color of Resin Composition) The color of the dimer acid-modified polyamide resin composition was measured using a Gardner apparatus.

(Oxidation stability test) 30 g of the prepared resin composition was put into a 100 ml glass bottle, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-) was added as an antioxidant to be additionally added. 4-Hydroxyphenyl) propionate] (Irganox 1010) 1
Add 50 mg and mix homogeneously. The resin composition placed in the glass bottle is left in an oven at 160 ° C. for 2 days. Before and after the heat treatment, the viscosity of the resin composition is measured to evaluate the change in viscosity before and after.

The evaluation was based on the viscosity before the treatment, where the change in viscosity (increased viscosity) was within 20%, the change in viscosity (increased viscosity) was 20 to 50%, and the resin composition was partially solidified. The result is indicated by x.

In addition, the color of the resin composition was measured after the heat treatment.

(Example 2-12) At the time of the synthesis reaction, the organic phosphorus compounds shown in Table 1 were used as the organic phosphorus compounds coexisting in the reaction system, and the addition amount shown in Table 1 per 100 parts of dimer acid was used. The other conditions were the same as in Example 1 to synthesize a dimer acid-modified polyamide resin to obtain a dimer acid-modified polyamide resin composition.
In Table 1, with respect to the organic phosphorus compound contained in the polyamide resin composition, per 1 mol of the raw material dimer acid,
The added molar amount (molar ratio) is also shown.

In the same manner as in Example 1, the prepared dimer acid-modified polyamide resin composition was evaluated by the above-described procedure with respect to the color of the resin composition immediately after preparation and the oxidation stability thereof. The evaluation results are also shown in Table 2.

(Example 13) For the resin composition prepared in Example 3, an antioxidant additionally added during the oxidation stability test: pentaerythritol tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate] (Irganox 101
Heat treatment was performed without adding 0), and the change in viscosity before and after the heat treatment was evaluated. After the heat treatment, the color of the resin composition was measured. The evaluation results are also shown in Table 2.

(Comparative Example 1-4) In the synthesis reaction, an antioxidant shown in Table 1 was used in place of the organic phosphorus compound as an antioxidant previously added to the reaction system. A dimer acid-modified polyamide resin was synthesized under the same conditions as in Example 1 except for the addition amount shown in Table 1 to obtain a dimer acid-modified polyamide resin composition. Table 1 also shows the molar amount (molar ratio) of the antioxidant contained in the polyamide resin composition per 1 mol of the raw material dimer acid.

In the same manner as in Example 1, the prepared dimer acid-modified polyamide resin composition was evaluated by the above-described procedure with respect to the color of the resin composition immediately after preparation and its oxidation stability. The evaluation results are also shown in Table 2.

(Comparative Example 5) An antioxidant added to the resin composition prepared in Comparative Example 1 during the oxidation stability test: pentaerythritol tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate] (Irganox 1010)
Was added and heat treatment was performed, and the change in viscosity before and after the heat treatment was evaluated. After the heat treatment, the resin composition was solidified, and the color could not be measured. The evaluation results are also shown in Table 2.

[0059]

[Table 1]

[0060]

[Table 2]

From the evaluation results shown in Table 2, the dimer acid-modified polyamide resin compositions of Examples 1 to 12, which are the polyamide resin compositions of the present invention, are all comparative examples in which an organic phosphorus compound is not present at the time of synthesis. Compared with the composition of No. 1, the color of the resin composition is improved immediately after the synthesis. Also, in the heating stability test at 160 ° C., the increase in viscosity due to oxidative deterioration and the change in color tone are also within good ranges. Also in the comparison between Example 13 and Example 3, the oxidation stability is comparable, and the action of only the organic phosphorus compound coexisted from the beginning can be achieved without adding an additional antioxidant. It is determined that the suppression of oxidative degradation has been sufficiently achieved.

Further, since the color of the resin immediately after the synthesis is good, it can be seen that the oxidation is suppressed even in the heating step of forming an amide bond. That is, an organic phosphorus compound that coexists from the process of synthesizing a polyamide resin, which is a feature of the polyamide resin composition of the present invention, specifically, a trisubstituted phosphine derivative or a phosphite triester derivative (phosphonic acid triester) Derivatives)
Is considered to have a function of suppressing the oxidation of the synthesized dimer acid-modified polyamide resin by capturing oxygen slightly remaining in the reaction system during the synthesis and oxidizing itself.

In addition, in the polyamide resin composition of the present invention, an organic phosphorus compound coexisting with a carbon atom in the synthesized polyamide resin molecule which is liable to be oxidized, specifically, trisubstituted phosphine Derivatives or phosphite triester derivatives (phosphonic acid triester derivatives) take a coordinative orientation by utilizing lone pairs (unshared pairs) present on the phosphorus atom. By inhibiting the proximity of oxygen molecules, the progress of the oxidation reaction is suppressed. By adding a tri-substituted phosphine derivative or a phosphite triester derivative (phosphonic acid triester derivative) after the synthesis, such a sufficient orientation cannot be achieved. By coexisting, sufficient orientation can be achieved. As a result, in the polyamide resin composition prepared by the method of the present invention, even if the polyamide resin composition is left at a high temperature in an atmosphere containing oxygen, its oxidative deterioration is more effectively suppressed, and excellent oxidative stability is exhibited.

[0064]

When the polyamide resin composition of the present invention, for example, a dimer acid-modified polyamide resin composition is synthesized, an organic phosphorus compound, specifically, a phosphine derivative, for example, a tri-substituted phosphine type A derivative or a phosphorous acid derivative, for example, a phosphonic acid triester type derivative or the like, is prepared by a method in which a dehydration condensation reaction is carried out under heating in the presence of a small amount to form an amide bond, and the phosphine derivative, Alternatively, by the action of the phosphorous acid derivative, the resulting resin composition can eliminate oxidation during the synthesis and have an improved color of the resin. In addition, in the obtained polyamide resin composition, in the polyamide resin as a main component, there is an unsaturated carbon-carbon bond derived from a polybasic carboxylic acid having an unsaturated carbon-carbon bond as a raw material. The above-mentioned phosphine derivative or phosphorous acid derivative coexisting from the synthesis process is additionally contained, and due to its oxidation suppressing action, even when heated to about 160 ° C. in the atmosphere, oxidation by oxygen is caused. Deterioration is remarkably suppressed, and excellent oxidation stability is imparted.

Continued on the front page F-term (reference) 4J001 DA01 DB01 DC01 EB08 EB09 EB71 EC02 EC05 EC08 EC09 EC14 EC15 EC16 EC47 EC48 EE74E EE76E FA01 FB03 FC03 GA11 JA17 JA18 JA20 JB18 4J002 CL041 EW016 EW066 FD036 GH01 GJ01

Claims (10)

[Claims] 1. A polyamide resin composition comprising, as a main component polyamide, a polyamide resin containing a polybasic carboxylic acid having an unsaturated carbon-carbon bond and a polyamine as constituent units thereof, wherein the polyamide resin is When a polybasic carboxylic acid having a unsaturated carbon-carbon bond and a polyamine having a structural unit are dehydrated and condensed under heating to form an amide bond,
A small amount of an organic phosphorus compound is added to the used amount of the polybasic carboxylic acid having an unsaturated carbon-carbon bond as a raw material, and is formed by dehydration condensation under heating in the presence of the small amount of the organic phosphorus compound. A polyamide resin composition, which is a polyamide resin and contains the small amount of the organic phosphorus compound to be coexistent as an accessory component. 2. The polyamide resin composition according to claim 1, wherein the organic phosphorus compound contained as an accessory component is a phosphine derivative. 3. The polyamide resin composition according to claim 1, wherein the organic phosphorus compound contained as an accessory component is a phosphorous acid derivative. 4. The content of the organic phosphorus compound contained as an accessory component is selected in the range of 0.1 to 5.0 parts by mass per 100 parts by mass of the polyamide resin. The polyamide resin composition according to any one of 1-3. 5. The polybasic carboxylic acid having an unsaturated carbon-carbon bond, which is a structural unit of a polyamide resin, is a dimer acid having an unsaturated carbon-carbon bond. The polyamide resin composition according to any one of the above. 6. A method for preparing a polyamide resin composition containing, as a main component polyamide, a polyamide resin having a polybasic carboxylic acid having an unsaturated carbon-carbon bond and a polyamine as constituent units thereof, The resin is prepared by using a predetermined amount of the polybasic carboxylic acid having an unsaturated carbon-carbon bond and a predetermined amount of a polyamine as its raw materials, and the amount of the polybasic carboxylic acid having an unsaturated carbon-carbon bond in the raw material. , A small amount of an organic phosphorus compound is added, and in the coexistence of the small amount of the organic phosphorus compound, dehydration condensation is performed under heating to form an amide bond to form a polyamide resin. A method for preparing a polyamide resin composition, wherein the composition is not removed but is contained as an accessory component. 7. The method for preparing a polyamide resin composition according to claim 6, wherein the organic phosphorus compound contained as an accessory component is a phosphine derivative. 8. The method for preparing a polyamide resin composition according to claim 6, wherein the organic phosphorus compound contained as an accessory component is a phosphorous acid derivative. 9. The amount of the organic phosphorus compound contained as an accessory component is such that the amount of the polyamide resin 100 obtained is based on the ratio of the amount of the polybasic carboxylic acid having an unsaturated carbon-carbon bond to the amount of the polyamine used as the raw material. The method for preparing a polyamide resin composition according to any one of claims 6 to 8, wherein the amount is selected from the range of 0.1 to 5.0 parts by mass per part by mass. 10. The polybasic carboxylic acid having an unsaturated carbon-carbon bond, which is a constituent unit of a polyamide resin, is a dimer acid having an unsaturated carbon-carbon bond. A method for preparing the polyamide resin composition according to any one of the above.