KR100926928B1 - Polyamide copolymer composition with excellent transparency and flexibility and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a polyamide copolymer composition having excellent transparency and flexibility, and a method for preparing the same. More specifically, the polyamide copolymer composition according to the present invention includes (i) nylon 6, nylon 66 and nylon 6I, which is 82-98: 1. Copolymerized in a weight ratio of ˜6: 1 to 12, polyamide copolymer having an unreacted caprolactam content of 2 to 8% by weight, and (ii) bis (P-methylbenzilidene) sorbitol 0.05 ~ 0.15% by weight is characterized in that the mixture.

In the present invention, since 3 to 5% by weight of unreacted caprolactam remains in the polyamide copolymer, it plays a role as a plasticizer. Since the weight% is mixed, there is an advantage in that the transparency of the fishing net is greatly improved.

Fishnets, polyamides, copolymers, compositions, flexibility, transparency, unreacted, caprolactam.

Description

Polyamide copolymer composition with excellent transparency and flexibility and method for manufacturing the same

The present invention relates to a polyamide copolymer composition having excellent transparency and flexibility, and a method for producing the same, and more particularly, to a polyamide copolymer composition having excellent transparency and flexibility at the same time so as to be particularly suitable for the manufacture of fishing lines or fishing nets. It relates to a manufacturing method.

Fishing lines and fishing nets are polyamide monofilaments that require flexibility and transparency as well as mechanical properties such as nodular strength.

In general, polyamide monofilaments have been prepared by extruding (spinning) the melted polyamide in a first step, followed by stretching three to four times, followed by two step stretching at high temperatures, followed by heat setting.

In this case, in order to improve the transparency of the polyamide monofilament, the spun yarn is quenched.

On the other hand, in order to simultaneously improve the flexibility and transparency of the polyamide monofilament, various methods of adding and copolymerizing a third material to the existing polyamide polymer have also been proposed.

Specifically, Korean Patent Laid-Open Publication No. 1998-0056773 discloses a mixture of ε-caprolactam and adipic acid / hexamethylenediamine (the existing polyamide monofilament polymer) as a third component and 2-methylpentamethylenediamine as a third component. A method of adding and copolymerizing a salt of isophthalic acid and laulactam is disclosed.

In addition, Korean Patent Laid-Open Publication No. 1997-0042679 discloses a mixture of ε-caprolactam and adipic acid / hexamethylenediamine (existing polyamide monofilament polymer) as a third component (iii) hexamethylenediamine and / or Or a method of adding and copolymerizing 2-methylpentamethylenediamine and (ii) isophthalic acid.

However, the above conventional methods have a limitation in improving the flexibility of the polyamide monofilament as a method of simply adding and copolymerizing a third component to the composition of the polyamide monofilament.

In other words, the conventional methods have a limitation in that a plasticizer must be added to the composition separately in order to obtain the level of flexibility required for fishing nets or fishing lines.

The present invention is to maintain a residual amount of unreacted caprolactam in the polyamide copolymer to 2 to 8% by weight so as to solve the above conventional problems to prepare a polyamide copolymer composition excellent in flexibility without using a separate plasticizer .

In addition, the present invention is to produce a polyamide copolymer composition having excellent flexibility and significantly improved transparency than the conventional products by containing a specific nucleating agent.

The polyamide copolymer composition of the present invention for achieving the above problems is (i) nylon 6, nylon 66 and nylon 6I is copolymerized in a weight ratio of 82 ~ 98: 1 ~ 6: 1 ~ 12 and the unreacted caprolactam A polyamide copolymer having a content (residual amount) of 2 to 8% by weight and (ii) 0.05 to 0.15% by weight of bis (P-methylbenzylidene) sorbitol as a nucleating agent are characterized in that the mixture is mixed.

In addition, the method for preparing a polyamide copolymer composition according to the present invention includes (i) monomers, additives and pure water consisting of caprolactam, a mixed salt of hexamethylenediamine and adipic acid, hexamethylenediamine and isophthalic acid. Was added to the reaction tube and then copolymerized to prepare a polyamide copolymer, and then (ii) the polyamide copolymer was treated with hot water in an extraction bath to maintain 2 to 8 weight of unreacted caprolactam in the polyamide copolymer. Extract the unreacted caprolactam to%, and (iii) continue to dry and cool the polyamide copolymer treated in the extraction tank, and then add 0.05 to 0.15 weight of bis (P-methylbenzilidene) sorbitol, which is a nucleating agent. It is characterized by mixing the%.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, in the polyamide copolymer composition of the present invention, (6) nylon 6, nylon 66 and nylon 6I are copolymerized at a weight ratio of 94: 2: 4, and the content (remaining amount) of unreacted caprolactam is 2 to 8% by weight. It has a composition in which a polyamide copolymer and (ii) a bis (P-methyl benzylidene) sorbitol (Nu-500), which is a nucleating agent, are mixed at 0.05 to 0.15% by weight.

Nylon 6I is a polymer in which hexamethylenediamine and isophthalic acid are polymerized.

The polyamide copolymer contains 2 to 8% by weight of unreacted caprolactam, and more preferably 3 to 5% by weight. In other words, the content (remaining amount) of the unreacted caprolactam is higher than that of the conventional polyamide copolymer, thereby expressing excellent flexibility in preparing polyamide monofilament without adding a plasticizer.

When the content of unreacted caprolactam in the polyamide copolymer is less than 2% by weight, the flexibility is poor, and when it exceeds 8% by weight, mechanical properties such as strength are deteriorated, which is not preferable.

On the other hand, in the polyamide copolymer composition of the present invention, bis (P-methylbenzylidene) sorbitol, which is a nucleating agent, is mixed in an amount of 0.05 to 0.15% by weight, thereby expressing more excellent transparency than in the prior art.

Optionally, the polyamide copolymer may contain one or more additives selected from phosphoric acid, heat resistant and complementing agents.

The heat-resistant agent is Iganox B 1171 and the like, and the complementary agent is cobalt acetate (Cobalt Acetate) and the like.

Next, the method for producing the polyamide copolymer composition of the present invention will be described in detail.

First, monomer components, additives, and pure water (water) are added to a reaction tube, and nitrogen is charged into the reaction tube, and then, these are copolymerized with stirring to prepare a polyamide copolymer.

The prepared polyamide copolymer is cut while discharging in a spaghetti form to prepare a chip form.

It is preferable that the said copolymerization reaction conditions hold | maintain about 90 minutes by inputting the temperature of 260 degreeC, and 15 kg / cm <2>, and depressurizing-process to atmospheric pressure for 30 minutes, and depressurizing to 440 mmHg for 30 minutes continuously.

The monomer components introduced into the reaction tube are (i) caprolactam, (ii) mixed salt of hexamethylenediamine and adipic acid, (iii) hexamethylenediamine and (i) isophthalic acid. The amount of the monomer component is preferably 4 to 6 parts by weight of the mixed salt of hexamentylene diamine and adipic acid, and 6 to 7 parts by weight of hexamethylenediamine and isophthalic acid based on 100 parts by weight of caprolactam.

Next, the polyamide copolymer of the chip type prepared as described above is added to an extraction tank and treated with hot water so that the amount of unreacted caprolactam in the polyamide copolymer remains 2 to 8% by weight. Extract

In the above unreacted caprolactam extraction process, it is most preferable to treat the polyamide copolymer with hot water at 92 to 98 ° C. for 20 to 40 minutes.

Next, the polyamide copolymer treated in the extraction tank is dried and then cooled, and the polyamide copolymer composition of the present invention is prepared by mixing 0.05 to 0.15 wt% of a bis (P-methylbenzilidene) sorbitol which is a nucleating agent thereto. .

Drying in the process is treated for 4 to 6 hours at a temperature of 115 ~ 125 ℃ and a pressure condition of 550 ~ 650 mmHg in a vacuum dryer, cooled to 80 ℃, mixed with a nucleating agent for about 5 minutes by adding a supermixer It is preferable.

Nucleating agents and internal release agents can also be mixed together.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

620 kg of caprolactam, 31.0 kg of mixed salt of hexamethylenediamine and adipic acid, 41.0 kg of hexamethylenediamine and 40.5 kg of isophthalic acid, 67 kg of pure water, 0.126 kg of phosphoric acid as additive, 0.8 kg of Iganox B1171 and acetic acid 0.012 kg of cobalt was added to the reaction tube, the temperature was raised to 260 ° C. while stirring, the pressure was maintained at 15 kg / cm 2 for 90 minutes, and the pressure was maintained at 270 ° C. to reduce the pressure to copolymerize the monomer components. An amide copolymer is prepared and cut while discharging it in a spaghetti form to prepare a polyamide copolymer in the form of a chip.

Next, the prepared polyamide copolymer was added to an extraction tank and treated with 95 ° C. hot water for 30 minutes to extract unreacted caprolactam in the polyamide copolymer such that the content (remaining amount) of the unreacted caprolactam was 4% by weight. do.

Next, the polyamide copolymer extracted as described above is introduced into a vacuum dryer and then dried for 5 hours at a temperature of 120 ° C. and a pressure of 600 mmHg, and then cooled to 80 ° C.

Next, the cooled polyamide copolymer is added to a supermixer and mixed with a nucleating agent bis (P-methyl benzylidene) sorbitol for 5 minutes to prepare a polyamide copolymer composition.

At this time, the content of the nucleating agent in the polyamide copolymer composition was 0.1% by weight.

The sheet-like specimens were prepared using the polyamide copolymer composition thus prepared, and the results of measuring flexibility (flexural strength / flexural modulus) and transparency (light transmittance) are shown in Table 2.

Comparative Example 1-Comparative Example 2

A polyamide copolymer composition or a polyamide copolymer was prepared in the same manner as in Example 1 except that the extraction conditions of the unreacted caprolactam and the mixing amount of the bis (P-methylbenzylidene) sorbitol as nucleating agents were changed as shown in Table 1. Manufacture.

The sheet-like specimens were prepared using the polyamide copolymer composition thus prepared, and the results of measuring flexibility (flexural strength / flexural modulus) and transparency (light transmittance) are shown in Table 2.                     

Manufacture conditions division Extraction conditions of unreacted caprolactam (unreacted caprolactam content after extraction) Mixing amount of nucleating agent Example 1 30 minutes treatment with warm water at 95 ℃ (4% by weight) 0.1 wt% Comparative Example 1 1 hour treatment with 100 ℃ hot water (0.5% by weight) 0.1 wt% Comparative Example 2 30 minutes treatment with warm water at 95 ℃ (4% by weight) 0% by weight

Property evaluation result division flexibility Transparency (light transmittance) Flexural Strength (㎏ / ㎠) Flexural modulus (㎏ / ㎠) Example 1 1,000 24,400 92% Comparative Example 1 1,700 26,800 92% Comparative Example 2 1,100 24,800 86%

The flexural strength and flexural modulus were measured by ASTM D790 method, and the light transmittance was measured using a specimen having a thickness of 2 mm.

The present invention is excellent in transparency and flexibility at the same time is useful for the manufacture of fishing nets or fishing lines.

Claims (9)

(Iii) Nylon 6, Nylon 66 and Nylon 6Ⅰ are copolymerized in a weight ratio of 82 to 98: 1 to 6: 1 to 12, and a polyamide copolymer having an unreacted caprolactam content of 2 to 8% by weight; (Ii) A polyamide copolymer composition having excellent transparency and flexibility, wherein 0.05 to 0.15% by weight of bis (P-methylbenzilidene) sorbitol as a nucleating agent is mixed. The polyamide copolymer composition having excellent transparency and flexibility according to claim 1, wherein the polyamide copolymer contains at least one additive selected from phosphoric acid, a heat resistant agent and a complementary agent. The polyamide copolymer composition having excellent transparency and flexibility according to claim 2, wherein the heat resistant agent is an iganox compound. The polyamide copolymer composition having excellent transparency and flexibility according to claim 2, wherein the complementing agent is cobalt acetate. (Iii) A mixture of caprolactam, hexamethylenediamine and adipic acid salt (Salt), hexamethylenediamine and isophthalic acid, monomers, additives and pure water (water) are added to the reaction tube and copolymerized therewith, After the copolymer was prepared, (ii) the polyamide copolymer was treated with hot water in an extraction tank to extract unreacted caprolactam so that the residual amount of unreacted caprolactam in the polyamide copolymer was 2 to 8% by weight, and (iii) Subsequently, the polyamide copolymer treated in the extraction tank is dried and then cooled, followed by mixing 0.05 to 0.15% by weight of a bis (P-methylbenzilidene) sorbitol, which is a nucleating agent, with excellent transparency and flexibility. Process for the preparation of amide copolymer composition. The method for producing a polyamide copolymer composition having excellent transparency and flexibility according to claim 5, wherein the polyamide copolymer is treated with hot water at 92 to 98 ° C. for 20 to 40 minutes to extract unreacted caprolactam. The polyamide having excellent transparency and flexibility according to claim 5, characterized in that the polyamide copolymer treated in the extraction tank is dried for 4 to 6 hours at a temperature of 115 to 125 ° C. and a pressure of 550 to 650 mmHg in a vacuum dryer. Process for the preparation of amide copolymer composition. The amount of each monomer introduced into the reaction tube is 4 to 6 parts by weight of a mixed salt of hexamethylenediamine and adipic acid, 6 to 7 parts by weight of hexamethylenediamine and 6 to isophthalic acid based on 100 parts by weight of caprolactam. A method for producing a polyamide copolymer composition excellent in transparency and flexibility, characterized in that 7 parts by weight. The method for producing a polyamide copolymer composition having excellent transparency and flexibility according to claim 5, wherein the additive is phosphoric acid, diganox compound and cobalt acetate.