KR20020091518A - PVC Compound And Method of Manufacturing Cord Using The Same - Google Patents

Abstract

PURPOSE: A poly(vinyl chloride) compound and a method for preparing a cord using the compound are provided to obtain a cord which is nontoxic to human body and nonpollutant and is used as a cord for an ear phone and a head phone. CONSTITUTION: The poly(vinyl chloride) compound comprises 100 parts by weight of a poly(vinyl chloride) resin; 1.0-2.0 parts by weight of a primary stabilizer containing no heavy metal component; 5-8 parts by weight of an epoxy compound prepared from the soy bean oil as a secondary stabilizer; and 45-78 parts by weight of a polymer plasticizer containing no phthalate-based compound. Preferably the primary stabilizer is a semisolid organic composite compound prepared by reacting calcium and zinc; and the epoxy compound is obtained by reacting the soy bean oil and hydrogen peroxide, thereby reacting the double bond of the soy bean oil with oxygen.

Description

Polyvinyl chloride compound and method of manufacturing the cord using the same {PVC Compound And Method of Manufacturing Cord Using The Same}

The present invention relates to a polyvinyl chloride (PVC) compound and a method for producing a cord using the same, and in particular, to a method for producing a non-toxic, environmental-free hormone PVC cord by preparing using a raw material harmless to the human body. will be.

PVC coated cords, which we use a lot, are used not only for cords but also for earphone earphones and headphones. As an example, earphones or headphones of a sounder will be described. 1 and 2 show schematic perspective views of earphones and headphones. Earphone 10 shown in Figure 1 has two earphone jacks (11a, 11b) having an appropriate size to be plugged into both ear holes, earphone jack (16) for connecting to the audio device, remote control 14 and connecting them It consists of a cord 18 with a conductor for giving. The headphone 20 shown in FIG. 2 also has two ear cover portions 21a and 21b formed to cover both ears similarly to earphones, a headphone jack 26 for connecting to an acoustic device, and a conductor for connecting them. Is composed of a built-in code (18).

As the cord described above, PVC coated on the conductor is mainly used. The PVC coated cord covering the conductor is usually manufactured by adding an additive, a stabilizer, a plasticizer, a surface treatment agent, or the like to PVC, which is a main material.

As a stabilizer in additives, the heavy metal component has been used so far with barium (Ba), zinc (Zn), lead (Pb), cadmium (Cd), calcium (Ca), tin (Sn) or combinations thereof. I use it. However, in particular, earphones or headphones are applied to a state of being plugged into or in contact with the ear, and the cord comes into contact with a specific part of the human body such as a cheek. In this case, various components included in the PVC cord may be absorbed into the human body. This is easier when the code is in contact with other substances, the higher the migration (migration) characteristic that the material contained therein dissolves or penetrates other substances in contact with it.

3 shows a state in which the earphone 10 shown in FIG. 1 is worn on the ear. As shown in the figure, when the earphone plugs 11a and 11b are plugged into the ear and used, a predetermined part of the human body comes into contact with the cord 18 such as a portion indicated by the hand and the like.

In general, most heavy metals tend to bind strongly to subcutaneous fat, and metals that bind to subcutaneous fat are not excreted. Therefore, continuous absorption of even a small amount accumulates in the body, and when its accumulation reaches a dangerous level, it can cause fatal problems. Heavy metals are strongly bound to enzymes related to the central nervous system and often cause abnormalities in the nervous system such as mental disorders, nerve paralysis and coma. Mercury, cadmium, and zinc are particularly harmful heavy metals. It is well known that mercury, Minamata disease, and cadmium, are the cause of the disease.

Accordingly, countries including Korea have regulated the amount of heavy metals in water and various industrial products. In Korea, heavy metals such as lead, mercury, hexavalent chromium, cadmium, etc. are regulated below a certain level in drinking water quality standards. In addition, some industrial items manufactured for the purpose of children's play, such as electric, inertial or self-winding toys, and some items such as automatic toys for children also apply the limits of heavy metals.

In the United States, heavy metals are also regulated in toys. In particular, the amount of heavy metals such as Sb, As, Ba, Cd, Cr, Pb, Hg, Se, etc. is regulated below a certain limit.

In addition to the heavy metal components described above, plasticizer components are also included for the manufacture of PVC sheathed cords, which are added to polymeric materials such as polyvinyl chloride (PVC) to increase the flexibility, workability, and elasticity of the polymeric materials. Organic ester compounds are mainly used. Plasticizers commonly used include phthalate plasticizers and adipate plasticizers. Phthalate plasticizers include di-ethyl hexyl phthalate (DEHP), di-hexyl phthalate (DHP), butyl benzyl phthalate (BBP), and di-butyl phthalate (di- butyl phthalate (DBP), di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP), and the like. The adipate-based plasticizer is di-2-ethylhexyl adipate ( di-e-ehtyl hexyl adipate (DOA). All these components are endocrine disruptors.

Until now, phthalate-based plasticizers, which are heavy metals and environmental hormones, as described above, have been used because of their good physical properties and are easy to purchase, but recently, heavy metals and environmental hormones (or endocrine-disrupting substances) have been used in human body, environment and ecosystem. Has become a big problem. The US Environmental Protection Agency (EPA) regulates the highest permissible water limit of 6 mg / l for the most used DEHP and 0.4 mg / l for the DOA. In the future, not only the US but also all countries are expected to establish and regulate the regulation of these endocrine disruptors.

The present invention excludes the use of the heavy metals and endocrine-disrupting substances described above, and by using a raw material that is harmless to the human body when adding additives such as stabilizers, plasticizers, etc. to the PVC, PVC can produce a non-toxic, environmental-free PVC coating cord The purpose is to provide a compound.

Another object of the present invention is to provide a method for producing a PVC coating cord that is a non-toxic, environmental-free hormone by using the above PVC compound.

It is still another object of the present invention to provide a method of using such a PVC sheathed cord, particularly for cords such as earphones or headphones of an audio device having a lot of contact with human body.

1 is a perspective view of a conventional earphone.

2 is a perspective view of a conventional headphone.

3 is a view schematically showing a state when wearing the conventional earphone shown in FIG.

Figure 4 is a cross-sectional view showing the PVC cord of the present invention applied for the bending test.

5 is a schematic cross-sectional view for illustrating a bending test method.

<Explanation of symbols for the main parts of the drawings>

18, 28: PVC cord

A: Where the PVC cord and skin touch

In order to achieve the above object, in the present invention, 100 parts by weight of PVC resin, 1.0 to 2.0 parts by weight of the first stabilizer containing no heavy metal components, 5 to 8 parts by weight of the epoxy compound prepared from soybean oil as the second stabilizer and phthalate system It provides a PVC compound comprising 45 to 78 parts by weight of a polymeric plasticizer containing no compound.

In particular, the first stabilizer is a semi-solid organic composite compound obtained by reacting calcium (Ca) and zinc (Zn), and an epoxy compound prepared from the soybean oil is obtained by reacting oxygen with a double bond in soybean oil by reacting soybean oil with hydrogen peroxide. It is preferable that it is an epoxy compound.

In addition, the polymer plasticizer preferably contains 40 to 70 parts by weight of an adipic acid-glycol polyester compound. Specifically, P-2600 (Songwon Industry) may be used.

In addition, the polymer plasticizer may include 5 to 8 parts by weight of tri-octyl trimellitate, and the PVC compound may further include a pigment and an insulation additive.

In order to achieve the above object of the present invention, in the present invention

100 parts by weight of the PVC resin, 1.0 to 2.0 parts by weight of the first stabilizer containing no heavy metal components, 5 to 8 parts by weight of the epoxy compound prepared from soybean oil as the second stabilizer and 45 to 78 parts by weight of the polymeric plasticizer containing no phthalate compound. Mixing the parts;

Melting the resulting mixture at a temperature of 170 ± 10 ° C., and then extruding to produce a PVC compound; And

It provides a method for producing a PVC cord comprising the step of coating the PVC compound on the conductor.

In particular, it is preferable to further perform the steps of cutting the extruded PVC compound into a PVC compound chip and melting the PVC compound chip and coating it on the conductor, followed by cooling.

Another object of the present invention described above is achieved by a method of using a PVC cord manufactured according to the above method as an acoustic cord of one of earphones and headphones.

According to the present invention, it is possible to manufacture a PVC cord having excellent physical properties without any harm to the human body, the environment and the ecosystem because no heavy metal material or endocrine disruption material is used.

Hereinafter, the present invention will be described in more detail.

45-78 weight part of polymer plasticizers which do not contain a phthalate type compound are mixed with PVC resin which is a main raw material. If the addition amount thereof is less than 45 parts by weight, the plasticity is not imparted to the resin does not have a suitable strength, if the addition amount thereof exceeds 78 parts by weight, the resin is too soft and the transition is not preferable, the addition amount thereof is in the above range To be

Specifically, 40 to 70 parts by weight of an adipic acid-glycol polyester compound, which is nonvolatile and has excellent aging resistance, cold resistance, heat resistance, electrical insulation, and transferability, is preferably used. Specifically, P-2600 (Songwon Industry) can be used. In addition, it is preferable to use tri-octyl trimellitate, for example, 5 to 8 parts by weight of TOTM of Songwon Industries, as the polymer plasticizer.

In addition, according to the present invention, as the stabilizer which is one of the additives, the PVC resin includes a first stabilizer which does not contain a heavy metal component and a second stabilizer composed of an epoxy compound prepared from soybean oil, wherein the first stabilizer is 1.0 to 2.0 parts by weight. The second stabilizer is to be used in the range of 5 to 8 parts by weight. The amount of each stabilizer component used is the range obtained by the inventor's repeated experiments, and when added in the range given above, stability to heat is imparted. Specifically, CZ-122 (manufactured by Wittco, Germany) is used as the first stabilizer, and EPOXY (Songwon Industry) is used as the second stabilizer. Preferably, the semi-solid mixture obtained by adding a small amount of CaCO ₃ as an insulation additive and carbon black as a pigment is stirred in the PVC compound by stirring for about 35 minutes at a temperature range of 170 ± 10 ° C. The extruded PVC compound is made into a noodle shape and finely cut to produce a small PVC compound chip. Here, the term PVC compound refers to a material obtained by extruding a mixture obtained by mixing various additives with a PVC resin under predetermined conditions.

Next, a PVC cord is manufactured using the manufactured PVC compound chip. First, it is coated with urethane enamel and coated with a synthetic fiber yarn which is resistant to copper wire giving insulation and color, and the manufactured PVC compound is heated and melted. The molten compound is coated on the conductor and cooled to produce a PVC cord. At this time, the cooling is performed by using the cooling water, and the cooling water should be replaced frequently to maintain the 30 ± 5 ℃ range. The resulting cord is wound on a spinning wheel, cut into suitable lengths, and packed.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

<Example 1>

100 kg of P-1700 (manufactured by Hanyang Chemical) with a polymerization degree of 1700 as a main raw material, 65 kg of P-2600 (manufactured by Songwon Industrial Company) as a plasticizer, 6 kg of TOTM (manufactured by Songwon Industry Company) as a plasticizer, and CZ-122 (manufactured by Wittco, Germany) ) 1.5 kg, 6 kg of EPOXY (Songwon Industrial Co., Ltd.) was put into a mixer as an epoxy compound prepared from soybean oil, and mixed. To this was added trace amounts of CaCO ₃ as insulation additive and carbon black as pigment. Stir well for 35 minutes while maintaining the mixer at a temperature of about 170 ℃. This was extruded with an extruder to prepare a PVC compound. It was cut into appropriate lengths, made of PVC compound chips, and packaged.

<Example 2>

Synthetic fiber yarn which is strong against urethane enamelled copper wire (manufactured by Hankuk Ilsun Co., Ltd., diameter: 0.06 mm), coated with Kevlar yarn (manufactured by Dupont), and sheathed the PVC compound prepared according to Example 1 on the conductor. To do so.

At this time, the extruder temperature was set to screw No. 1 is 150 ± 3 ° C, No. 2 was maintained at 170 ± 3 ℃, head 170 ± 3 ℃, die 140 ± 3 ℃, and the PVC cord was manufactured so that the temperature of the cooling water is about 30 ± 5 ℃ to about 120m per minute while replacing frequently. Depending on the purpose of use, the size of the wheel was adjusted to adjust the length of the wire to be wound.

Flexibility tests were performed on a PVC cord prepared according to Example 2 using a cord bending tester manufactured by Intrinsic Engineering. This test is to observe the presence of breakage by connecting both terminals and the negative terminal at both ends of the cord and performing a ± 90 ° bend in both directions at room temperature at a speed of 40-50 times / minute. The structure and the flexural test method of the PVC cord used for the test are shown in FIGS. 4 and 5. In FIG. 4, RED, NAT, GRN, RED + GRN and the like represent the color of the insulator provided by the coating on the urethane enamel, respectively, red, colorless, green, red + green. The results of the two tests were more than 12270 times and the results are shown in Table 1.

Number of tests RED NAT RED + GRN GRN 1 time 12,270 ↑ 12,270 ↑ 12,270 ↑ 10,421 ↑ Episode 2 12,270 ↑ 12,270 ↑ 12,270 ↑ 12,270 ↑

Also, a performance test was performed on the PVC cords prepared according to Example 2. This is a test to check the compound appearing in the panel after placing the PVC cord between the panel and left for 72 hours under a load of 1 kg at a temperature of 60 ℃. The results are shown in Table 2.

sample Adjacent Panel (Test Panel) result PVC code according to Embodiment 2 ABS none PS none AS none

In Table 2, ABS represents acrylnirobutadiene styrene, PS represents poly styrene, AS represents acrylnitryl styrene, it can be confirmed that no chemical composition was detected in the panel because no transition occurs.

In addition, tensile load, elongation, and bending tests were performed on the PVC compound and the PVC cord. The test conditions and results are shown in Table 3 below. The bending tester was a cord bending tester of Jinsung Engineering. The test speed was 45 times / minute and the test temperature was room temperature.

Test Items unit Test result PVC compound PVC cord Tensile load kgf - 14.3 Elongation % 190 - Bending test: cap tire structure (balance), 10000 times - - No crack, burst, disconnection of conductor wire Test Methods According to KS C 3004-98

Next, the heavy metal content was analyzed. Remove the copper wire from the PVC sheathed cord, chop it to a particle size of 6 mm or less, place the sample in a 0.07M HCl solution at 50 times the sample weight, stir at 37 ° C for 1 hour, allow to stand for 1 hour, and then filter and remove heavy metals from the solution. Was analyzed. The experiments were carried out using an atomic absorption spectrometer (AAS) and an inductively coupled plasma-emission spectrometer. It was examined whether it met the requirements and the results are shown in Table 4.

ingredient Content (mg / kg) Limit value (mg / kg) Total lead amount (Pb) <10 <600 Dissolved lead (Pb) <10 <90 Dissolved arsenic (As) <5 <25 Molten antimony (Sb) <10 <60 Amount of dissolved barium (Ba) <10 <1000 Cadmium dissolved (Cd) <5 <75 Amount of dissolved chromium (Cr) <10 <60 Dissolved mercury (Hg) <5 <60 Dissolved selenium (Se) <25 <500

Next, Table 5 shows the results of the gas chromatography / mass spectrometer (GC / MS) analysis test on the phthalate- and adipate-based plasticizer components in PVC chips.

ingredient content Butyl benzyl phthalate (BBP) n.d Di-n-butyl phthalate (DBP) n.d Dicyclohexyl phthalate (DCHP) n.d Diethyl phthalate (DEP) n.d DE (2-ethylhexyl phthalate) n.d Dihexyl phthalate (DHP) n.d Di-n-pentyl phthalate (DPP) n.d Dipropyl phthalate (DPrP) n.d DEHA (di (2-ethylhexyl) adipate) n.d

n.d: not detected

Through the above test results it can be confirmed that the PVC compound and PVC cord prepared according to the present invention can provide good physical properties without containing heavy metal components and no environmental hormones.

As described above, the PVC cord according to the present invention is a product that is harmless to the human body, the environment, and the ecosystem, and is a non-toxic, environmental-free hormone that does little harm to the user even after long-term use. In particular, when applied to earphones, hair phones, ear microphones, portable hands-free earphones, operator headsets, microphone cords of sound equipment, users can use it with confidence, and it does not pollute the environment during waste disposal.

Although the present invention has been described above according to an embodiment of the present invention, it will be apparent to those skilled in the art that various modifications may be made without departing from the spirit of the present invention.

Claims (10)

100 parts by weight of a polyvinyl chloride (PVC) resin, 1.0 to 2.0 parts by weight of a first stabilizer that does not contain heavy metal components, 5 to 8 parts by weight of an epoxy compound prepared from soybean oil as a second stabilizer and a polymer that does not contain a phthalate compound PVC compound containing 45-78 weight part of plasticizers. The PVC compound according to claim 1, wherein the first stabilizer is a semisolid organic composite compound in which calcium (Ca) and zinc (Zn) are reacted. The PVC compound according to claim 1, wherein the epoxy compound prepared from soybean oil is an epoxy compound obtained by reacting soybean oil with hydrogen peroxide to react oxygen with a double bond in soybean oil. The PVC compound according to claim 1, wherein the polymer plasticizer comprises 40 to 70 parts by weight of an adipic acid-glycol polyester compound. The PVC compound according to claim 1, wherein the polymer plasticizer comprises 5 to 8 parts by weight of tri-octyl trimellitate. The PVC compound according to claim 1, further comprising a pigment and an insulation additive. 100 parts by weight of the PVC resin, 1.0 to 2.0 parts by weight of the first stabilizer containing no heavy metal components, 5 to 8 parts by weight of the epoxy compound prepared from soybean oil as the second stabilizer and 45 to 78 parts by weight of the polymeric plasticizer containing no phthalate compound. Mixing the parts; Melting the resulting mixture at a temperature of 170 ± 10 ° C., and then extruding to produce a PVC compound; And Coating the PVC compound on a conductor. The method of claim 7, further comprising the step of cutting the extruded PVC compound to produce a PVC compound chip. The method of claim 8, further comprising melting the PVC compound chip, coating the conductor, and cooling the PVC compound chip. A method of using a PVC cord according to claim 7 for a cord of either earphones or headphones.