JPS619457A - Light-resistant polyamide molding - Google Patents

Abstract

PURPOSE:A polyamide molding which maintains light resistance persistently for a long time and comprises solid particles of a zeolite retaining copper ions, a vehicle, and a polyamide. CONSTITUTION:0.005-10wt% solid particles of a zeolite (a) consisting of, for example, a powdered A-type zeolite having a specific surface of 150m<2>/g or greater, a mol ratio SiO2/Al2O3 of 14 or greater, and the particle diameter of 20mum or smaller are allowed to undergo ion exchange with a solution of CuSO4, etc. (b) to produce a copper-zeolite (A) retaining 0.001-0.5wt%, based on a molding, copper ions. Component A is kneaded with a vehicle (B) having a viscosity of 500-900cP (at 75 deg.C) and little reactivity with component C (e.g. diethylene glycol adipate) to give a slurry, which is added to a melted polyamide (C) (e.g. nylon 6) and mixed to disperse uniformly. This mixture is molded to give the titled molding in the form of particle, film, fiber, pipe, etc.

Description

[Detailed description of the invention] The present invention relates to a polyamide molded article having light resistance.

More specifically, it relates to a polyamide molded body comprising zeolite solid particles holding copper ions, a vehicle, and polyamide.

It has been known for a long time that copper has an effect on the heat oxidation resistance and light oxidation resistance of polyamide. The heat resistance of polyamide can be improved by adding a small amount of copper compound to polyamide.
French patent 9068 as a method to improve light resistance
98, British Patent No. 652,947, German Patent No. 883,644, etc.

However, using copper compounds alone cannot produce satisfactory effects, and at the same time, it is difficult to use W at the time of heating and heating during spinning, molding, etc.
Even when the amount of i is added, there is a drawback that metallic copper is precipitated. Therefore, in order to enhance the stabilizing effect of copper compounds,
There is a method of using iodine or an iodine compound in combination with a copper compound as proposed in Japanese Patent Publication No. 48-30956 and Japanese Patent Publication No. 48-7700, and a method proposed in Japanese Patent Publication No. 49-10987 and Japanese Patent Publication No. 49-28661. A method is known in which a mercapto compound is used in combination as described above.

Although the former method has a good stabilizing effect on the m compound in the polyamide, it has the following drawbacks. For example, iodine and gold
When using iodide, it will significantly corrode gold fp4 in the presence of water, so the inside of the containers, piping, and polymerization reaction containers used for storing and supplying iodine must be specially treated to prevent corrosion due to iodine. There is a complication in terms of equipment that must be used. In addition, nuclear-substituted aromatic iodine compounds and iodine-based aliphatic hydrocarbons are themselves unstable compounds, making it difficult to use them industrially.

In the latter method, heat resistance,
Although it has high light resistance, it has the disadvantage of being colored during spinning and molding.

The present inventors have completed the present invention as a result of intensive research to improve the above-mentioned drawbacks. An object of the present invention is to provide a light-resistant polyamide molded product, and more specifically, to provide a light-resistant polyamide molded product containing a vehicle and zeolite-based solid particles that retain copper ions. There is something to do.

That is, the present invention is a light-resistant polyamide molded article comprising zeolite solid particles, a vehicle, and polyamide, and the zeolite solid particles retain copper ions.

In the present invention, the zeolite-based solid particles holding copper ions are those obtained by treating the ion-exchangeable portion of natural or synthetic zeolite made of aluminosilicate with a solution of water-soluble copper salts to remove copper ions. It is something that is kept. Copper ions can be either in Cu or Cu'', but it is more advantageous to use Cu, which is stable as an ion and easily soluble in water.

Also, complex ions such as Ou (HHHf) may be used.

Zeolites are generally aluminosilicates with a three-dimensionally developed skeleton structure, and are generally Alx O3
Based on that, XM! 0-A40j-YSiO*
・Represented by ZH,O. M represents an ion-exchangeable metal ion and is usually a monovalent to divalent metal, and n corresponds to this valence. On the other hand, X and Y represent the coefficients of metal oxide and silica, respectively, and 2 represents the number of crystal water. Many types of zeolites are known, differing in their composition ratio, pore diameter, and specific surface area.

However, the specific surface area of the zeolite solid particles used in the present invention must be 150 frI/f (based on anhydrous zeolite) or more, and the bi02/A/(201 molar ratio of the zeolite components must be 14 or less, preferably 11 or less). Must be.

Since the water-soluble copper salts used can easily undergo ion exchange with the zeolite defined in the present invention, it is possible to utilize this phenomenon to retain the ions in the zeolite stationary phase. However, zeolite particles holding metal ions have a specific surface area of 150 m/f or more and
Two conditions must be met: the 5i02/A40s molar ratio is 14 or less. It has been found that if this is not the case, an effective lightfast object cannot be obtained. This is considered to be due to the fact that the absolute amount of copper ions in the zeolite is insufficient in a state where the effect can be exerted. In other words, this is considered to be due to the physicochemical properties of the zeolite, such as the amount of exchange groups, exchange rate, and accessibility.

Therefore, 510 is known as molecular sieve.
Zeolites with a large molar ratio of 2/A40s are completely unsuitable for the present invention. In addition, in zeolite with a 5i02/A40s molar ratio of 14 or less, it is possible to retain copper ions uniformly, and by using such a zeolite, a sufficient light resistance effect can be obtained for the first time. It turned out that it was possible.

In addition, the 5i02/Al2O5 molar ratio of zeolite is 1
The acid resistance and alkali resistance of zeolites with a high silica ratio exceeding 4 increase with increasing 5102, but on the other hand, this
The synthesis of zeolite takes a long time, and from an economic point of view, it is not advisable to use zeolite with such a high silica ratio. 5 mentioned above
Natural or synthetic zeolites with i02/A40s≦14 can be used satisfactorily from the viewpoint of acid resistance and alkali resistance in the fields in which the present polyamide composition is normally considered, and are also economically inexpensive. , is a good idea. Also from this meaning.

The 5i02/Ag2O3 molar ratio must be 14 or more.

The molar ratio of 5i02/An2'g used in the present invention is 1
As the zeolite material of 4 or less, natural or synthetic zeolites can also be used. For example, as a natural zeolite, analcime (8i0
．． /A#203=8.6~5.6), Chabazite: 850g/A#203=
88-6.0 and 6.4-7.6L Clinoptilolite: 5i02/
AA'20. = 8.5~10-5), Erionite (Erionite: sio, /A120g =
5.8-7.4), Faujasit
e: sio, /Az, o,, = 4.2 to 4.6
), mordenite (SiO
, B/A/103=8.84~10.0), Phillipsite: 810g/
AA'tOs ~2.6~4,4). These typical natural zeolites are suitable for the present invention.

- Typical synthetic zeolides include A-type zeolide (Si02/A40s=1.4-2.4);
X-type zeolite) (Si02/A403= 2~B
), Y-type zeolide (5i02 /1203 =
B~6), mordenite (SxO, /A/, 03=
9 to 10), and these synthetic zeolites are suitable as the zeolite material of the present invention. Particularly preferred are synthetic A-type zeolides, x-type zeolides, Y-type zeolides and synthetic or natural mordenites.

The shape of the zeolite is preferably in the form of powder particles, and the particle size may be appropriately selected depending on the application, but is preferably 20 μm or less.

When the average particle diameter exceeds 20 μm, the texture of the dispersed state tends to become rough, and the light resistance effect decreases. When applied to thick molded objects, such as various containers, pipes, granular objects, or thick denier JILS, the thickness may be from several μ to 20 μ, and -
When molding fine denier fibers or films, it is desirable to use a force with a small particle size, especially for clothing fibers, 5μ
Above, more preferably 2μ or more F.

Next, the vehicle used in the present invention is preferably a viscous liquid that is kneaded with zeolite solid particles to form a slurry and has poor reactivity with polyamide.

Examples include polyethylene glycol, polytetramethylene glycol, polyoxyethylene triglyceride, polybutylene adipate, diethylene glycol adipate, etc., which have a viscosity of 500 to 900 c at 75°C.
ps level is preferable. The method of kneading the zeolite solid particles with the vehicle is not particularly limited, and any method that can form a slurry, such as an automatic mortar or a three-roll mixed kneader, may be used.The concentration of the zeolite solid particles in the slurry is 50. It is preferable that the amount is less than % of the vehicle volume. When the acceptance rate exceeds 50%, thixotropy occurs and it becomes difficult to form a slurry.

The slurry is added to and mixed with the bath-melted polyamide. For example, in the case of spinning, there is a method of pressurizing the slurry with a gear pump into the polyamide that is melted with a screw and fed into a spinning head. On the other hand, when zeolite solid particles are melt-spun in a powder state without slurrying, for example, in a chip blend with polyamide, secondary agglomeration of the zeolite solid particles occurs, resulting in the formation of fine particles in the polyamide. Mixing as is may be difficult, and uniform dispersion is also difficult. - The method of kneading zeolite solid particles with Bihiwan to form a slurry and adding this to molten polyamide prevents secondary agglomeration of zeolite solid particles, maintains a fine particle state, and improves uniform dispersibility. It can be improved.

By adding the slurry to the molten polymer and then kneading it with a static mixing element or the like, more uniform dispersion can be achieved. Being able to maintain the zeolite solid particles in a fine state makes it possible to reduce the increase in filtration pressure when passing through the filtration medium in the spinneret pack, for example, and to improve uniform dispersibility. This means that the dispersibility of copper ions also improves, which is extremely effective for improving light resistance.

Polyamides used in the present invention include Na-flon 6, nylon 66, nylon 11. These include nylon 12 and copolyamides thereof.

The zeolite-based solid particles and vehicle-containing polyamide molded article of the present invention is composed of the zeolite-based solid particles, the vehicle, and the polyamide, and retains at least a portion of the zeolite-based solid particles; ing. The proportion of zeolite solid particles in the whole is 0.
．． 01 to 10% by weight (based on anhydrous zeolite). 0
．． 01! If it is less than 1%, it is an in-house method to retain enough copper ions to have a light resistance effect, and even if it exceeds the 10% market weight, the light resistance effect remains unchanged (3 points, and The physical properties of polyamide are greatly deteriorated, and polyamide formation J1>
Its use as a salary is limited. From this point of view, the more preferable self-containing base range I11 is 001 to 6%, and more preferably 001 to 4% when the particle-containing polyamide molded article of the present invention is used after being made into fibers. .

Copper ions must be retained in the zeolite solid particles by an ion exchange reaction. Mere absorption or adhesion without ion exchange does not provide sufficient light resistance and its durability.

There are two possible methods for retaining copper ions.

The first method is to add and mix a slurry of copper-zeolide and vehicle to polyamide, and the second method is to
This is a method in which a slurry of zeolite and vehicle is added to and mixed with polyamide and molded, and then the polyamide molded body is subjected to ion exchange treatment to cause copper ions to be retained in the zeolite within the polyamide composition.

First, the first method will be explained. This method utilizes a button-zeolide, and the copper-zeolide can be prepared using an ion exchange reaction as described above. Each yuzu zeolite defined in the present invention is
When converting to zeolide, a solution of a water-soluble copper salt such as copper sulfate is usually used, but care must be taken not to increase the concentration of this solution. For example, by ion exchange reaction, AN or X type zeolite (sodium type) is
When converting to zeolite, when i M -CuSO4 is used, Cu''i is replaced with Na+ in the solid phase, but at the same time, basic precipitates such as Cua(SO4)(OR)4 are precipitated in the same phase of the zeolite. As a result, the porosity of zeolite becomes fuzzy and the specific surface area decreases significantly.In order to prevent such excessive copper from being deposited on the zeolite phase, the concentration of the aqueous preparation used must be diluted. state, e.g. 0.0
It is desirable to keep it below 5M.

When using a CuSO4 solution with such a concentration, the Cu obtained
-The specific surface area of zeolite is almost the same as that of zeolite, which is the conversion material, and the light resistance effect can be fully exhibited.

Theoretically, the maximum amount of Cu in the copper-zeolide (based on anhydrous zeolite) is approximately 221% by weight for A-type zeolite, approximately 20% by weight for X-type zeolite, and approximately 16% by weight for Y-type zeolite. For mordenite, it is approximately s/m%, with a preferred range of 0.01 to 15% by weight.

Also, metal ions other than copper, such as sodium.

The coexistence of potassium, calcium, or other Kanejima ions does not impede the light resistance effect, so the residual or coexistence of these ions cannot be questioned.

Next, the copper zeolite is mixed with a vehicle to form a slurry, and the slurry is added to the polyamide in the above-mentioned content number to obtain the composition of the present invention. The fft of copper relative to copper-zeolide (A m, KL%) and the amount of copper-zeolide relative to the polyamide composition (B weight 1;%) are also related to the lightfastness effect; If there is a large amount, B needs to be small, and if A is small, B needs to be large. In order to effectively demonstrate the light resistance effect, AXBxIAI)
(i.e. 41% by weight of the total polyamide composition of copper ions retained in the zeolite solid particles) is 0.00
It must be adjusted so that it is between 1 and 0.1. 0001
The light resistance effect is poor in the uncoated steel, and the light resistance effect is almost unchanged in the range of 0.671 m, and furthermore, depending on the temperature conditions during molding or melt spinning, the precipitation of Kinho copper may be slightly affected. [I think it's because of this], a certain impression occurs.

The timing and method of addition and mixing are not particularly limited. For example, there are a method of adding it to a raw material monomer for mixed layer polymerization, a method of adding it to a reaction intermediate and adding it to the polymer, a method of adding it to a polymer at the end of polymerization, a method of adding it to a molding dope such as a spinning stock solution, and the like. In the following, for the sake of simplicity, Kowara's method will simply be referred to as ``adding and mixing with polyamide.'' In short, the most suitable method may be adopted depending on the properties of the polyamide used, characteristics of the process, etc. Usually, a method of adding and mixing just before molding is suitable. Further, the copper-zeolide is subjected to a drying treatment if necessary before being turned into a slurry. The drying conditions may be arbitrarily selected from the range of normal pressure or reduced pressure of 10°C to 500°C. Preferred drying conditions are reduced pressure of 100 to 850°C. Next, the second method of the present invention will be described. Second
Although the method differs in the timing of the ion exchange treatment, it is basically similar to the first method in many respects. If the zeolite defined above is mixed with a vehicle without ion exchange,
It is made into a slurry and mixed into polyamide. The content range of zeolite is the same as in the first method. The timing and method of addition and mixing are not particularly limited. As in the first method, the additives may be added and mixed at any stage from the preparation of polyamide raw materials to molding. Furthermore, if it is necessary to dry the zeolite, the method described above may be followed. In the second method, the zeolite-containing molded body thus obtained is subjected to ion exchange efficiency. The type and shape of the molded product are not particularly limited; for example, it may be an intermediate molded product such as a pellet, or it may be in the form of a final product. In order to increase the ion exchange efficiency, a molded body with a large specific surface area is suitable. Therefore, molded bodies with small diameter and thickness are preferable, such as granular bodies,
Films or fibers are preferred. The method of ion exchange treatment is basically similar to the method of ion exchange treatment of zeolite described above, in which the zeolite-containing polyamide molded body is treated with a solution of water-soluble copper salts. In this case, the concentration range of copper salt is 0.05 for 0u304
M or less is desirable. If the concentration of Cu salt is too excessive, basic copper precipitates will be deposited, reducing the light resistance effect.

As the processing method, either a batch method or a continuous method is possible. In order to increase the amount of metal ions retained, the number of batch treatments can be increased, or in the case of a continuous process, the treatment time can be increased.

The second method shows that the zeolite entrapped within the cylindrical body still retains ion exchange capacity, and that by appropriate ion exchange treatment, the zeolite can be made to retain copper ions.

The proportion of zeolite within the polyamide that is ion-exchanged depends on the nature of the polyamide. However, since most polyamides are hydrophilic, as water permeates, copper ions permeate into the interior, and the zeolite in the polyamide circle is also ion-exchanged. In the second method as well, the amount of copper ions retained in the zeolite solid particles is preferably 0.001 to 0.5% by weight based on the entire polyamide composition. In the second method, even if the proportion of lead is extremely increased, the precipitation of metallic copper will not occur or it will take too much time, so the optimum upper limit is 0.5% by weight. or,
There is no problem with the remaining or coexistence of other metal ions.

The zeolite particles and vehicle-containing polyamide molded article of the present invention may contain a fourth component other than the copper zeolite and the vehicle. Examples include polymerization catalysts, stabilizers, matting agents, brighteners, organic or inorganic pigments, inorganic fillers, and various plasticizers. Furthermore, a liquid or an organic solvent may be contained as a fourth component. Moreover, the shape, size, etc. of the zeolite particles and vehicle-containing molded article of the present invention are not particularly limited. Distribution of copper-zeolide in the molded body
You may devise an appropriate method to do so. For example, there is a method in which the outer layer of the multilayer structure contains the zeolite and the vehicle according to the present invention. In the case of fibrils, there is a method of incorporating zeolite and vehicle into the sheath component of a core-sheath cross-section yarn using a known conjugate spinning technique.

The bonding force between zeolite and copper ions defined in the present invention is
Unlike the method of simply holding it by physical adsorption on an adsorbent material such as activated carbon or alumina, it is extremely large. Therefore, the light resistance effect of the polyamide composition containing such copper zeolite and its durability over time should be particularly mentioned as a characteristic advantage of the present invention. The zeolite defined as in the present invention has the advantage of high reactivity with Cu. For example, A-type zeolide, X-21 zeolite, Y-? zeolite,
Ion exchange in chabasite is a powerful metal ion (Na+
) easily undergoes ion exchange with Cu'' and retains copper ions Ff in the matrix of zeolite 1, and has a high retention ability.
It has the advantage of high selective adsorption for u"+. This fact indicates that even when the polyamide molded article containing zeolite particles of the present invention is used in liquids containing yuzu metal ions or in water for the purpose of light resistance, it does not adsorb Cu"+. is stably maintained in the zeolite matrix for a long period of time, meaning that the light resistance is maintained for a long period of time.

In addition, the zeolite limited as in the present invention has a large parent exchange valley B, which has the advantage of increasing the Ou retention group. Another advantage is that the amount of Cu contained in the zeolite solid particles can be easily adjusted by ion exchange depending on the intended use of the zeolite particle-containing molecular weight of the present invention.

In addition, the zeolite obtained at a fixed rate in the present invention hardly deteriorates the physical properties of the molecular body, and a wide variety of types of high-strength molecules can be selected. Because of this, it can be molded into various shapes and sizes.

For example, it can be made into granules, films, fibers, various containers, pipes, or any other molded product, and can be used in an extremely wide range of applications requiring light resistance.

Moreover, since the zeolite particles and the polyamide molded article containing bicarbonate of the present invention also have the functions inherent to zeolite, it is possible to utilize both the luminous properties and the functions inherent to zeolite. For example, the combined effect of zeolite's original functions of moisture absorption and adsorption and light resistance can be utilized.

Furthermore, it is also possible to incorporate other functional substances to exhibit a combined function of the above effects and other functions. Other functional substances include activated carbon and silica gel.

In the case of activated carbon, the deodorizing and adsorption effect is enhanced, and in the case of silica gel, the adsorption effect is enhanced.

Examples of the present invention will be described below, but the present invention is not limited to these examples unless the gist thereof is exceeded.

Reference Examples] Table 1 shows unconverted natural and synthetic IJk zeolite particles that are conveniently used in the examples of the present invention. Each zeolite was obtained by crushing and classifying Japanese raw materials to obtain the desired particle size.

The A-type zeolide in Table 1 is 27, the X-type zeolide'
e Z2, Y-type zeolide is abbreviated as z3, natural mordenite 2 is abbreviated as zli, and natural chabasite is abbreviated as z6. The particle size, water content, and specific surface area of these zeolites are as shown in Table 1. Amata.

Next, 2500 each of fine powder dried products of each yuzu zeolite listed in Table 1
A 1/20M aqueous solution of copper sulfate was added to each sample, and the resulting mixture was kept under stirring at room temperature for 5 hours to perform ion exchange. After filtering the copper-zeolide obtained by this ion exchange method, it is washed with water to remove excess copper ions, and then the washed copper-zeolide is
It was dried at 105°C and then ground to obtain a fine powder of copper-zeolide. The copper-containing paper and specific surface area of the dried copper-zeolide product obtained were as shown in Table 2. (K, 27-2
1. ) Reference Example 2 Collect dry powder 2502 of Y-type zeolite (2,) shown in Table 1, add 1/200M copper sulfate solution to it,
The resulting mixture was stirred at room temperature for 5 hours.

The copper-zeolide obtained by this ion exchange method was filtered and washed with water. (Zrs) Separately, dry powder 25 of Y-type zeolite (2,) shown in Table 1
02 was collected, 1/20M copper sulfate solution 14 was added thereto, and the mixture was stirred at room temperature for 5 hours, and the obtained copper-zeolide was separated by centrifugation. Next, the same process as above was repeated eight times. The finally obtained converted product was washed with water to remove excess copper ions. (z14) The above two samples of copper-zeolide were dried at 100 to 105°C and then ground to obtain finely powdered steel-zeolide.

Table 8 shows the copper content and specific surface area of this n.

Example 1 The copper-zeolides (Zy, ~z1.) shown in Table 2 were each dried at 200°C under reduced pressure for 7 hours. Next, take 50 f of each of these, and each has a viscosity of 80 at 75°C.
0 cps diethylene glycol adipate 100f
were mixed and kneaded in an automatic mortar for 24 hours to form a slurry.

At this time, while irradiating with an infrared lamp, the slurry
It was maintained at 0'C.

05V15 in 95% sulfuric acid using a conventional melt spinning machine.
0 CIaa concentration, relative viscosity measured at 25°C 2.3 6
Dry nylon chips were melted with a screw, and the above copper-zeolide-containing slurry was forced into the molten nylon 6 polymer fed into the spinning head using a gear pump.

At this time, the slurry was 8% by weight based on the entire mixed polymer.
I made it so that After passing through 20 stationary intermixing elements in the spinning head, the yarn was extruded from the spinneret and wound up, and the obtained undrawn yarn was drawn to obtain a drawn yarn of 50 denier/12 filaments and a 6-hole type.

Separately, take 50 of each of the vacuum-dried powders of copper-zeolide shown in Table 2, add and mix them to nylon 6 dry chips so that the total copper-zeolide content is 1% by weight, and melt-spun according to a conventional method. did. At this time as well, the first undrawn yarn passed through the 20 stationary intermixing elements in the throat is stretched for spinning.
Six types of drawn yarns of 0 denier/12 filaments were obtained.

Furthermore, even if only 6 nylon is used, 5o denier/
A drawn yarn of 12 filaments was also collected.

The drawn yarns of these 13 citrus fruits were irradiated with an ultraviolet fade meter for 200 hours, and then the strength was measured.
Shown in the table.

As shown in the table above, the Noni method in which slurry was formed and press-fitted had better strength retention after ultraviolet irradiation than the method in which it was added and mixed by chip blending. Regarding the type of zeolite, all of the ones in the above table were good even if they were slurry type, but type A, type X, YIM zeolite and mordenite 1 were particularly good.

Example 2 South of Table 2 - Y-type zeolite (2,) and mud pile of Table 3 -
Y-type zeolite (z, 3, z14) was reduced by 2C.
) Dry at 0°C for 7 hours. Next, each of these is 1 (+
Each OV was taken and mixed with polyoxyethylene triglyceride 15 (1') at 600 cps at 75°C and kneaded with eight mixed wire rolls heated to 80°C to form a slurry. The relative viscosity measured with % sulfuric acid was 2.dO'). The 6-nylon chips were melted with a screw, and the above copper-zeolide slurry was pressurized with a gear pump into the molten 6-nylon polymer fed into the spinning head, and the mixture was held stationary. After passing through 15 kneading elements, it was extruded from the die, wound up, and drawn to obtain a drawn yarn of 120 denier/4 filaments.

Table 5 shows the amount of indentation of each slurry into the whole at this time, and the strength results after 120 hours and 400 hours of irradiation of the drawn yarn obtained by this method with an ultraviolet fade meter are also shown. .

From the results in Table 5, the content range of copper in the drawn yarn is 1)
0 (,11 City NL'h It was found that the light resistance was poor if the amount was less than the amount of shavings.Also, when the amount of copper in the polymer was more than the amount of 05 cells removed, slight coloring was observed in the polymer. However, the light resistance was good.

In addition, the copper-zeolide particles in the tar fine thread accounted for 10% by weight/
It was also found that the strength of the drawn yarn is considerably lower than that of the less drawn yarn.

Procedural amendment document July 1980-2S Mr. Manabu Shiga, Commissioner of the Patent Office Week 1, Case indication 1982 Patent Application No. 129882 2, Title of invention Light-resistant polyamide molded article 8, Person making the amendment Relationship to the case Patent applicant address: Sumida 5-chome @17-4, Sumida-ku, Tokyo Contact address: 6-90, Tomobuchi-cho 1-chome, Bejima-ku, Osaka 684, Kanebo Co., Ltd. Patent Department 6, Contents of amendment The description of the description shall be amended as follows.

Written amendment to the above procedure October 8, 1980 Patent Application No. 129882 2, Name of the invention Light-resistant polyamide molded article 8, Relationship to the case of the person making the amendment Patent applicant Address Sumida, Tokyo 5-17-4 Sumida 584
Kanebo Co., Ltd. Patent Department, 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka Telephone: (06) 921-125-1 4. Date of amendment order: September 5, 1980 (shipment date) 7. Contents of amendment +11 Table 1 on page 22 of the specification is amended as shown in the attached sheet.

that's all

Claims (4)

[Claims] (1) A polyamide molded article consisting of zeolite-based solid particles, a vehicle, and polyamide, and in which the zeolite-based solid particles retain copper ions. (2) The molded article according to claim 1, wherein the zeolite solid particles have a specific surface area of 150 m^2/g or more and a SiO_2/Al_2O_3 molar ratio of 14 or less. (3) The molded article according to claim 1, wherein the zeolite solid particles are composed of A-type zeolite, X-type zeolite, Y-type zeolite, or mordenite. (4) The content of zeolite solid particles is 0.005 to 1
0% by weight, and the copper ions contained in the zeolite solid particles are 0.001 to 0.5% by weight based on the entire molded object.
A molded article according to claim 1.