KR100888178B1 - Shipboard cable having resistance to epoxy paint for shipboard - Google Patents

Abstract

A shipboard cable is provided to ensure excellent heat resistance, cold resistance, oil resistance, abrasion resistance, tear resistance, specifically resistance to solvent contained in paint. A shipboard cable(10) is equipped with a coble core conductor(1), an insulating layer(2) covering the coble core conductor, a first sheath(4) covering the aggregate combining the coble core conductor covered with the insulating layer, and a fabric layer(5) covering the first sheath and a second sheath(6) covering the fabric layer. The second sheath is formed from a composite resin composition. The composite resin composition comprises the mixed resin consisting of polyvinylchloride and thermoplastic urethane elastomer in a weight ratio of 2~8:8~2; maleic anhydride-modified ethylene vinyl acetate (EVA-g-MAH) 5-15 parts by weight; and surface-modified inorganic retardant 5-30 parts by weight or their mixture.

Description

SHIPBOARD CABLE HAVING RESISTANCE TO EPOXY PAINT FOR SHIPBOARD}

The present invention relates to a ship cable (Cable) that is resistant to paints, more specifically, solvents contained in the paint, improves the chemical resistance to the marine paint of the vinyl chloride resin previously used for the final coating for ships The present invention relates to a marine cable, which uses a composite resin composition capable of improving physical properties to form a final sheath.

In the conventional ships, since most of the structure of the ship is made of steel (steel) it was necessary to apply the paint for the ship (hereinafter 'paint'). Various electrical facilities are used in ships, which required the installation and installation of cables.

Most of the cables used in buildings on land, etc. are installed inside buildings or ducts and are not exposed to the outside, while cables installed on ships are exposed to the outside through the ship's blocks. Was universal.

As a result, when the cable is applied (painting) to prevent corrosion of the ship after the cable is installed, the cable may be painted or painted at all.

The applied paints include Alkyd paints and epoxy paints. These paints have a bad influence on the outer jacket of the cable (also called Sheath). There was a problem of causing a decrease in strength, elongation, and the like.

This is because the existing marine PVC compound, that is, a composition using polyvinyl chloride (PVC) is weak in solvent resistance, especially in the case of ketone solvents mainly used in epoxy paints, strong solvent permeability (driving force) Existing polyvinyl chloride is vulnerable to the ketone-based solvent, polyvinyl chloride (PVC) itself also shows a phenomenon that the retention of the kidney sharply (aging) after the aging due to the degradation of the molecular chain (degradation).

Therefore, shipbuilders (Maker), etc., who build ships, performed coating work by covering the cable in any form before painting work in order to prevent paint on the cable jacket to prevent this.

This work not only decreases the productivity of painting work but also increases the hourly labor cost for shipbuilding, affecting the cost of ship manufacturing, and if there is a part where vinyl tape is not covered before painting work, Marine paint is applied to the cable (Cable) is a problem that the physical properties of the wire is reduced. Because of these problems, the need for a marine cable having paint resistance to maintain the characteristics of the cable itself even if the marine paint is urgently emerged.

The present invention aims to provide a marine cable having resistance to marine paints, in particular epoxy paints. More specifically, it is an object to provide a marine cable having resistance to ketone solvents usually contained in epoxy paints.

The present invention has been made to solve the problems described above, and the thermoplastic polyurethane elastomer (TPU) having excellent compatibility with polyvinyl chloride (PVC) and excellent chemical resistance is made of polyvinyl chloride (PVC) and alloy ( alloy) and more preferably polymer molecular chains are broken down by paint or solvent by containing maleic anhydride modified ethylene vinyl acetate (EVA-g-MAH), surface modified inorganic flame retardants or mixtures thereof as compatibilizers. It is characterized in that the final sheath of the cable for ships is formed by using the composite cable composition for the cable coating that can completely improve the phenomenon that the elongation retention drops sharply after aging.

That is, the present invention provides a marine cable having resistance to paint, more specifically, a solvent contained in the paint, and excellent in heat resistance, cold resistance, oil resistance, abrasion resistance, and tear resistance.

As shown in FIG. 1, the ship cable 10 includes a core conductor 1; An insulating layer (2) surrounding said core conductor; A primary sheath (4) surrounding the aggregate incorporating the core conductors covered with the insulating layer; A braided layer 5 surrounding the primary sheath; And a secondary sheath 6 surrounding the braided layer, in which case an outer circumference of the collection of the insulation layers 2 composed of a plurality of the insulation layers and an inner circumference of the primary sheath 4 are formed. It further comprises a filler layer (3) filling the space to be.

Currently, ship cables (wires) mainly used in container ships, oil tankers, cargo ships, etc. built in shipyards are cables manufactured according to Japanese Industrial Standard JIS C 3410 standard (hereinafter referred to as JIS TYPE name). JIS TYPE cable is insulated with EP rubber (Ethylene propylene rubber) on copper wire conductor, and after collecting several wire cores, primary sheath is made of polyvinyl chloride (PVC) and galvanized on it for external impact protection. It has a braided layer braided by an iron wire or the like, and has a structure in which a polyvinyl chloride (PVC) secondary sheath is added as necessary.

In addition, the filler layer 3 filling the space formed by the outer circumference of the aggregate in which the core conductors covered with the insulating layer and the inner circumference of the primary sheath 4 is formed usually has a primary sheath on the outer circumference of two or more core wire conductors. In the case of coating, the polypropylene filler may be used to form the cross section of the cable in a circular shape.

The ship cable according to the present invention is characterized in that the final coating layer is formed of a composite resin composition containing a mixed resin consisting of polyvinyl chloride (PVC) and thermoplastic polyurethane elastomer (TPU), and the mixing ratio is weight ratio (PVC: TPU) and 2-8: 8-2, More preferably, it is mixed with 3-7: 7-3. More preferably, the composite resin composition for forming the final coating layer contains maleic anhydride modified ethylene vinyl acetate (EVA-g-MAH), a surface-modified inorganic flame retardant, or a mixture thereof as a compatibilizer in addition to the mixed resin.

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

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

Existing marine PVC compound has polyvinyl chloride (PVC) average polymerization degree of 1,000 to 1,700 100 parts by weight, plasticizer 40 to 120 parts by weight, flame retardant 10 to 100 parts by weight, flame retardant aid 2 to 30 parts by weight, inorganic filler It consists of 30-120 weight part and a small amount of stabilizer, processing aid (lubricant), antioxidant, pigment, etc.

When coating the wire (mainly epoxy-based paint) used in shipyards with the existing PVC compound composed of such a composition, the tensile strength / elongation rate at room temperature and the residual value after aging are obtained. It is significantly below the aging specification value of cable for ships at 25 ~ -40% and elongation rate -50 ~ -80% (standard, ± 25% tensile, ± 25% elongation at 100 ℃ × 168hr aging). In addition, it does not fundamentally satisfy the properties of crosslinked rubber (IEC60092-359, SHF2) in oil resistance (IRM902 oil, 100 ℃ × 24hr), cold resistance (CSA test, -35 ℃ × 4hr), wear resistance, tear strength.

Aging property changes due to marine paints occur when epoxy paints are applied rather than alkyd paints used in shipyards. Alkyd paint is composed of alkyd resin and hydrocarbon solvent and volatilizes slowly. The PVC resin of PVC compound is relatively solvent resistant against hydrocarbon solvent. It doesn't have a big impact.

In the case of epoxy paints, methyl isobutyltone (MIBK) or methyl ethyl ketone (MEK) is used among xylene and ketone solvents, which are strong solvents. Used to improve workability such as coating and spraying.

In case of ketone solvent, the solvent permeability (driving force) is strong with respect to polyvinyl chloride resin, and in particular, the existing polyvinyl chloride resin shows a phenomenon in which the elongation residual ratio decreases rapidly after aging due to the degradation of molecular chain by ketone solvent. .

This problem can be improved to some extent by factors such as compatibility of plasticizer and vinyl chloride resin, molecular weight size of plasticizer and polyvinyl chloride resin, but cannot be a fundamental prescription and completely exclude polyvinyl chloride resin. In this case, the cable extrusion workability is poor, if the chlorine (Cl) disappears, the flame retardancy, fire resistance is sharply dropped and the char formation in the fire test worsens. In addition, the vinyl chloride resin is advantageous in terms of cost, and therefore, the vinyl chloride resin should be properly used. Therefore, it is necessary to introduce other polymers resistant to xylene and ketones to vinyl chloride resin and copolymerize or alloy them to have a solvent resistance to ketone solvents.

The present invention is a mixed resin in which the weight ratio (PVC: TPU) of polyvinyl chloride (PVC) and thermoplastic polyurethane elastomer (TPU) is 2 to 8: 8 to 2, and maleic anhydride is modified based on 100 parts by weight of the mixed resin. Provided is a marine cable having a final coating layer formed of a composite resin composition containing 5 to 15 parts by weight of ethylene vinyl acetate (EVA-g-MAH), 5 to 30 parts by weight of surface-modified inorganic flame retardant, or a mixture thereof. The marine cable according to the present invention has excellent resistance to marine paints, in particular epoxy paints, and has excellent cold resistance, oil resistance, abrasion resistance, and tear resistance characteristics that can be comparable to crosslinked rubber, and thus is suitable for use in various marine cables. .

The composite resin composition for forming the outermost sheathing layer of the ship cable according to the present invention will be described in detail.

1) Resin

The composite resin composition of this invention contains the mixed resin which consists of polyvinyl chloride (PVC) and a thermoplastic polyurethane elastomer (TPU). The thermoplastic polyurethane elastomer (TPU) is generally a thermoplastic high-elastic material having a urethane group (-NHCOO-) in its molecular structure, and the polyol and hard segment constituting the soft segment (amorphous or rubbery region). It is a block copolymer made of a three-component combination of glycol and diisocyanate constituting the crystal phase region), and a polymer having a very high polarity due to hydrogen bonding and strong electronegativity in a molecule. Due to the strong binding force inside the polymer, it has high elasticity, oil resistance, solvent resistance, abrasion resistance, tear strength, cold resistance, and excellent compatibility with polyvinyl chloride, a conventional polar polymer. TPU of polyether or polyester ester is good, but there is no problem of water resistance when blending with PVC and polyester-based TPU is suitable for economic reasons because of its excellent properties of urethane group (-NHCOO-) itself. . In the case of hardness, Shore A hardness 75 ~ 90 is preferred. If the hardness is higher than 90, the ratio of the crystalline region of the polymer is high, so it is incompatible with PVC, and the possibility of interfacial separation during processing is increased due to the difference in processing temperature between the two resins. Abrasion resistance, tear strength is lowered and disadvantageous.

Polyvinyl chloride (PVC) is inexpensive, has excellent extrusion processability, and has high chlorine group (Cl) in polymer. It has excellent flame retardancy. Also, it has good adsorption compatibility with general plasticizers. If the TPU is added after 20 minutes of plasticization, the plasticizer adsorbed on the PVC can be minimized from the PVC matrix to the TPU matrix, thereby maximizing the properties of the composite resin composition.

The mixing ratio of the polyvinyl chloride (PVC) and the thermoplastic polyurethane elastomer (TPU) is preferably 2 to 8: 8 to 2, and more preferably 3 to 7: 7 to 3, by weight ratio (PVC: TPU). If the PVC content is too small and too much TPU out of the above range, the cable extrusion workability is poor, the flame retardancy and fire resistance may be reduced, on the contrary, if the PVC content is too high and the TPU is too low, The resistance decreases and becomes undesirable.

2) Compatibilizer

The compatibilizer is used to improve the compatibility of the blended resin blending two or more polymers, in the present invention, as the compatibilizer, EVA-g-MAH (maleic anhydride modified ethylene vinyl acetate) based on 100 parts by weight of the mixed resin It is used at 5 to 15 parts by weight. MAH (maleic anhydride) modified on EVA is a polar group with strong electronegativity, and has the property of making ring-opening condensation reaction when it meets -OH group to make strong hydrogen bond.It reacts in PVC and TPU, especially inorganic flame retardant and high temperature extruder. There is an effect of increasing the compatibility between the components. When the amount of EVA-g-MAH used is in the range of 5 to 15 parts by weight, the compatibility or mechanical properties are better, so it is more suitable. The EVA is preferably a VA (vinyl acetate) content of 40 to 70% by weight, when the VA content is less than 40% by weight, the effect of increasing the compatibility between PVC / TPU / inorganic materials is insignificant and the VA content If it exceeds 70% by weight, amorphousness is maximized and mechanical or chemical properties are lowered, which is undesirable.

3) Flame retardant

The flame retardant contained in the composite resin composition according to the present invention preferably uses the surface-modified inorganic flame retardant in an amount of 5 to 30 parts by weight based on 100 parts by weight of the mixed resin. As the inorganic flame retardant, metal hydroxides such as magnesium hydroxide and aluminum hydroxide are used. Surface modification treatment is to react the silane-based compound of Formula 1 and the metal hydroxide particles to be coated on the surface of the metal hydroxide particles.

[Formula 1]

HS-R ¹ -Si (OR ² ) ₃

[In Formula 1, R ¹ represents (C1-C30) alkylene, (C6-C20) arylene, (C6-C20) ar (C1-C30) alkylene or (C1-C30) alkyl (C6-C20) aryl And alkyl is linear or branched and may include unsaturated bonds in the carbon chain, and the carbon atoms of the aryl may be substituted with one or more heteroelements selected from N, O, S, P and Si;

R ² is selected from linear or branched (C 1 -C 7) alkyl.]

Aryl in R ¹ of Chemical Formula 1 may include phenyl, naphthyl, anthryl, biphenyl, etc. as an aromatic ring, and alkyl in R ¹ and R ² may include methyl, ethyl, propyl, butyl, and the like. Can be mentioned.

The silane-based compound of Formula 1 has a mercapto group (-SH) in addition to the alkoxy group (-OR ² ) to increase the chemical bonding strength between the TPU and the inorganic flame retardant to improve the chemical resistance, tensile strength and Improve oil resistance more.

As an inorganic flame retardant, magnesium hydroxide is preferably used by surface modification with a silane-based compound of Chemical Formula 1, and as the silane-based compound of Chemical Formula 1, 3-mercaptopropyl trimethoxysilane is used as an example. Can be mentioned.

When the surface-modified inorganic flame retardant is used in an amount less than 5 parts by weight based on 100 parts by weight of the mixed resin, not only the effect of improving flame retardancy but also the expression of the chemical resistance, tensile strength and oil resistance improving effect as described above are insignificant. If the content is more than 30 parts by weight, the compatibility is lowered, so it is preferable to use it in the above range.

4) plasticizer

Phthalic acid-based plasticizers are the most widely used phthalic acid plasticizers due to their excellent compatibility with PVC. They are DBP (Di-butyl-phthalate), DOP (Di-2-ethylhexyl phthalate), DINP (Di-isononyl phthalate), DIDP (Di-isodecyl phthalate), Butyl benzyl phthalate (BBP) is used, and DINP and DIDP are low volatility plasticizers and are used in artificial leather and film.

The compatibility and plasticization efficiency is slightly lower than phthalic acid plasticizers, while the low volatility, oil resistance and heat resistance are particularly excellent. Thus, the trimellitic acid ester plasticizer, which is widely used for heat resistant wires, is TOTM (Tri). -ethylhexyl trimellitate), Tri-isononyl trimellitate (TINTM), and Tri-iso decyl trimellitate (TIDTM), among which TOTO is the most widely used. In the present invention, it is more preferable to use DIDP (Diisodecyl Phthalate) as a phthalate plasticizer in consideration of cost and compatibility with TPU.

5) Other additives

The composite resin composition according to the present invention may further contain fillers, flame retardant aids, stabilizers, processing aids and antioxidants as other additives, and additives commonly used in the formulation of PVC or TPU resins may be used, which are described in the art. It is well known in the art.

Examples of the filler include calcium carbonate, magnesium carbonate, huntite, hydromagnesite, and the like, and antimony trioxide (Sb ₂ O ₃ ) having a good flame retardant effect in a formulation containing a halogen-containing resin as a flame retardant aid. It is preferable to use, and as a stabilizer, an organic acid metal salt containing zinc, calcium, magnesium, etc. as a metal component or a mixture thereof is preferable as a lead-free stabilizer, and zinc stearate is mentioned as said organic acid metal salt. . As a processing aid, a hydrocarbon-based substance such as paraffin wax (P / Wax) or a fatty acid-based substance such as stearic acid may be used. As the antioxidant, it is preferable to use a phenolic antioxidant for thermal oxidation stability of the matrix of the TPU resin.

In general, when manufacturing PVC compound for electric wire, vinyl chloride resin, plasticizer, and other chemicals are added in a batch, followed by heating and mixing in a Henschel mixer or supermixer, and then processed into pellet after extrusion mixing in a single screw or twin screw extruder. In the case of the composite resin composition, the resin, plasticizer and other flame retardants, chemicals, etc. are polyvinyl chloride (PVC) and TPU, or three composite alloy systems of PVC / TPU / MA-g-EVA. Since the properties of the final compound may change depending on the order of injection and processing temperature, the equipment and process conditions may also be a major factor. In the present invention, PVC, plasticizer, flame retardant, and other additives except TPU were added and plasticized, and then TPU resin was continuously added, mixed, and extruded and cooled in an extruder. Putting the TPU resin into the super mixer later can minimize the plasticizer adsorbed on the PVC transition from the PVC matrix to the TPU matrix, further improving the physical properties of the PVC composite. The extruder is preferably a twin screw but may be a single screw extruder, but the L / D of the extruder is preferably 34/1 or more, and the compression ratio of the screw is preferably 3.5 / 1 or more. This is to allow the heterogeneous polymer and various chemicals to be mixed well and the PVC / TPU matrix to be well alloyed.

The preferred form of the ship cable according to the invention is shown in FIG. Ship cable according to the invention is a ship cable 10 is a plurality of core conductor (1); An insulating layer (2) surrounding said core conductor; A primary sheath (4) surrounding the aggregate incorporating the core conductors covered with the insulating layer; A braided layer 5 surrounding the primary sheath; And a secondary sheath 6 surrounding the braided layer, in which case an outer circumference of the collection of the insulation layers 2 composed of a plurality of the insulation layers and an inner circumference of the primary sheath 4 are formed. It further comprises a filler layer (3) to fill the space, characterized in that the secondary sheath, which is the final coating layer is formed by the composite resin composition as described above, the primary sheath is to be made of a general PVC compound However, the composite resin composition used to form the secondary sheath may be used.

In the method for manufacturing a ship cable of the present invention, the formation method up to the braided layer can proceed in a conventional manner. Extrude and coat the composite resin composition used for forming the secondary sheath on the combined wire rod having the braided layer is formed to manufacture a ship cable according to the present invention. More specifically, for example, the extrusion operation is to put the composite resin composition into the hopper, and then rotate the screw to melt the composite resin composition in the state capable of extruding, and then extruded through the extruder head on the braided layer formed with the braided layer do. At this time, the speed of the ship is adjusted to 3 ~ 30m / min according to the outer diameter of the cable, screw RPM is adjusted to 50 ~ 70RPM, the cable passed through the extruder is cooled by passing through the cooling water tank installed in front of 0.3 ~ 2m.

In the present invention, by using a TPU and a PVC having a urethane bond (-NHCOO-) with a compatibilizer, a surface-modified inorganic flame retardant or a mixture thereof, the final coating layer is formed by using a composite resin composition resistant to the marine paint Provide a cable. The ship cable according to the present invention is embodied in the resistance to the ship paint by the strong polarity and hydrogen bonding of the TPU and at the same time has oil resistance, cold resistance, tear resistance equivalent to the crosslinked rubber.

The ship cable according to the present invention does not affect the physical properties even if the paint is applied to the coating of the wire can effectively solve the problems such as productivity decrease, manufacturing cost, etc. currently occurring in the shipyard. In addition, the ship cable of the present invention can provide an example of the specification and specifications of the new type of Korean ship wire in the future by implementing excellent oil resistance, cold resistance and tear strength. In particular, high tear resistance values (not more than 2.5kgf / mm), which were not seen in the existing ship compound, can prevent damage such as tearing and chipping when installing ship wires.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by the following Examples.

[Production example]

The composite resin composition was prepared by adjusting the resin composition and the content of the additive as shown in Table 1 below, and the sum of the polyvinyl chloride resin and the TPU resin was 100 parts by weight, and the content of the additive was expressed in parts by weight based on 100 parts by weight of the resin. It was. As a comparative example, a PVC compound used solely with polyvinyl chloride resin was prepared in the composition shown in Table 1 below.

Each component contained in the composition of this manufacture example is as follows specifically. Each component contained in a composition is as follows specifically.

-Polyvinyl chloride resin: LG Chemical, degree of polymerization 1,300

-TPU resin: Noveon, Eastane 58213

-Compatibilizer: EVA-g-MAH (VA content 45wt%, 1.5% MAH, Dupon-Mistui, 45LX)

Magnesium Hydroxide: Powder with an average particle diameter of 1.5㎛

Surface-Modified Magnesium Hydroxide: Magnesium Hydroxide (Nanotec Cemix Co., Ltd.) surface-modified with mercaptopropyltrimethoxysilane (content: 1 wt%)

-Filler: CaCO _{3 with} average particle diameter of 1㎛ (OMYA 1T)

Complex stabilizer: ADK, Rup-144

Processing aid: paraffin wax (P / Wax) or stearic acid (S / A)

-Antioxidant: Phenolic antioxidant (Shibagaiki Co., 1010)

Manufacturing Process of Specimen

Specimens were prepared in the same pilot plant as the mass production plant. First, all plasticizers, flame retardants and other additives except TPU are added to a 50-liter supermixer and heated at 60 ° C. for plasticization for 20 minutes. After continuously injecting the TPU resin and mixed for 5 minutes and extruded in a T-Die form in a 40mm single screw extruder and left for 24 hours after cooling, it was punched into a specimen. In this case, the TPU resin is introduced later into the super mixer in order to maximize the physical properties of the PVC composite resin because the plasticizer adsorbed on the PVC can be minimized from the PVC matrix to the TPU matrix.

TABLE 1

[Test Example 1]

The physical properties of the specimens prepared in Preparation Examples 1 to 4 and Comparative Examples 1 and 2 were tested before and after applying paint for ships as described below, and in addition, the oil resistance, cold resistance, and tear strength were tested and the results are shown in Table 2 below. .

1) Physical properties before paint application were measured according to IEC60811-1-1. Tensile strength over 1.25kgf / mm2 and over 150% elongation rate is the standard.

2) The change of physical property after heating (100 ℃) was tested according to IEC60811-1-2 after application of epoxy paint for ships to the specimen. According to the standard, tensile strength 1.25kgf / mm2 and elongation rate 150% Abnormal Tensile Residual Elongation Residuals should be within ± 25%, but this test was conducted to 100 ℃ × 14 days to verify the long-term reliability of the polymer and to confirm the difference between the properties.

The method of applying paint to the specimen is to remove foreign substances on the surface of the specimen with isopropyl alcohol, and then JOTUN's SAFEGUARD TF KS and Xylene content 35% with 30% by weight of methyl isobutyl ketone (MIBK). Mix the yarn curing agent in a 3: 1 weight ratio and apply it to the surface of the specimen with a spray gun (nozzle diameter: 0.4 ~ 0.7mm, spray pressure: 130 ~ 160atm, spray angle: 65 degrees). After drying for 4 hours at room temperature it was applied once more under the same conditions and dried for 24 hours to form a coating layer of 200㎛ thickness.

3) The oil resistance test was conducted according to IEC60811-2-1 SHF2 standard. The test standard is a relatively harsh test standard that is mainly applied to crosslinked rubber, and all tensile elongation residuals after tension of 120 ℃ × 24 hours (IRM902 oil) should be within ± 40%. do.

4) Cold resistance test was carried out by applying CSA C22.2 No38, and if it is impacted after standing at -35 ℃ × 4 hours and crack occurs in more than 20% of the sample, it fails.

5) Tear strength test was tested according to ASTM D470 and the standard value is more than 1.2Kgf / mm.

TABLE 2

As can be seen from the results of Table 2, in case of Preparation Examples 1 to 4, the tensile strength and elongation were measured by aging for one week (168 hours) and two weeks (336 hours) by applying marine paint. It exceeds the standard temperature of 1.25kgf / mm2 and 150%, and the residual value of the 1st week aging test also satisfies the standard value of ± 25%.

As described above, the oil resistance, cold resistance, and tear resistance were all applied to a high specification test method applied to the crosslinked rubber, but all of Production Examples 1 to 4 satisfied the reference values. This phenomenon is caused by the urethane group (-NHCOO-) of TPU, which shows hydrogen bond and strong electronegativity in the molecule. TPU has strong viscoelasticity and shows good chemical resistance, oil resistance, cold resistance and tear strength. In addition, the strong polarity of the TPU has good compatibility with the polar polymer PVC, and by alloying the TPU / PVC / EVA-g-MAH, PVC offsets the weak part of the TPU so that the TPU, Synergistic effect than when used as a PVC alone, it is realized more excellent physical properties.

On the other hand, in the case of Preparation Example 3 and Preparation Example 4, but satisfies the requirements until the 2nd week of aging test, the value shows a low value for Preparation Example 1, which does not have a compatibilizer EVA-g-MAH (Preparation Example 3) By using unmodified general magnesium hydroxide (Production Example 4), it is recognized that the compatibility and electrochemical bond between each polymer matrix and inorganic material are relatively weak, and the compatibilizer, EVA-g-MAH or mercaptopropyltrime It can be seen that it has better physical properties when it contains magnesium hydroxide surface-modified with oxysilane.

EXAMPLE

The ship cable of JIS TYPE as shown in FIG. 1 was manufactured.

Core image conductor (1) consisting of tin-plated copper wire, insulation layer (2) composed of EP rubber (Ethylene-Propylene copolymer), three core conductors coated with insulation layer, and polypropylene filler layer (3) To cover the primary sheath layer (4) and galvanized wire braided layer (5) made of PVC to produce a wire rod. The resin composition of the above production example is extruded and cooled through an extruder, respectively, to form the secondary sheath 6 on the wire rod.

Secondary sheath formation is performed under the conditions of extruder (manufacturer: polisher, model name: PVC 100Φ EXTRUDER).

1) dice and nipple selection

   -Die diameter: Nipple diameter + 6 x nipple thickness + 4 x sheath thickness

   Nipple diameter: Wire diameter + 2 mm

2) Working temperature condition

3) Extrusion operation is to insert the composition of the production example into the hopper, and then rotate the screw to melt the composition of the production example in a state capable of extrusion, and then extrude the compound on the wire rod through the extruder head. At this time, the line speed was 15 m / min, screw RPM was adjusted to 60 RPM, the cable passed through the extruder was passed through the cooling water tank installed in front of 1 m to cool and wound on the take-up roll to complete the ship cable.

After forming the secondary sheath using the compositions of Preparation Examples 1 to 4 and Comparative Examples 1 to 2 to produce a marine cable as shown in FIG. 1, the secondary sheath of the manufactured cable was peeled off (size: 75 mm X 4 mm, thickness: 1 to 2 mm) was measured, and the physical properties before and after the coating of the paint were measured in the same manner as the test example, and are shown in Table 3 below.

TABLE 3

As can be seen from the results of Table 3, when the secondary sheath was formed using the conventional PVC composition, the retention value of the aging property test after the paint was applied was -35 to -40% of tensile strength and -50 to -60 of elongation. Although it is less than the aging standard value (100 ° C × 7 days tensile residual rate ± 25%, elongation residual rate ± 25%) of the ship cable to about%, 7 days when the secondary sheath is formed with the composition of the preparation according to the present invention In all of the aging conditions, the aging standard was satisfied. Particularly, in the case of forming the second sheath with the resin compositions of Preparation Examples 1 and 2, more excellent results were obtained.

The above examples are intended to illustrate the present invention, and a large amount of experimental results have been representatively selected and displayed. The terminology or compound names of the examples do not limit the claims, and the present invention is defined based on the appended claims. It can be modified or modified by those skilled in the art within the scope of. For example, the shape and structure of the elements of each component specifically shown in the embodiment of the present invention can be modified.

1 is a perspective view showing the structure of a ship cable.

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

DESCRIPTION OF SYMBOLS 1 Core conductor 2 Insulation layer 3 Filler layer

4: primary sheath 5: braided layer 6: secondary sheath

10: ship cable

Claims (5)

A core sheath, an insulating layer surrounding the core conductor, a primary sheath surrounding the aggregate incorporating the core conductor covered with the insulating layer, a braided layer surrounding the primary sheath, and a braided layer surrounding the braided layer In a marine cable having a secondary sheath, The secondary sheath is a mixed resin in which a weight ratio (PVC: TPU) of polyvinyl chloride (PVC) and thermoplastic polyurethane elastomer (TPU) is mixed in a range of 2 to 8: 8 to 2; And 5 to 15 parts by weight of maleic anhydride modified ethylene vinyl acetate (EVA-g-MAH), 5 to 30 parts by weight of surface-modified inorganic flame retardant, or a mixture thereof, based on 100 parts by weight of the mixed resin; Ship cable, characterized in that formed from a composite resin composition containing. delete The method of claim 1, Maleic anhydride modified ethylene vinyl acetate (EVA-g-MAH) is a marine cable having a vinyl acetate (VA) content of 40 to 70% by weight. The method of claim 1, The surface-modified inorganic flame retardant is a marine cable is magnesium hydroxide surface-modified with a silane-based compound of formula (1). [Formula 1] HS-R ¹ -Si (OR ² ) ₃ [In Formula 1, R ¹ is (C1-C30) alkylene, (C6-C20) arylene, (C6-C20) aryl (C1-C30) alkylene or (C1-C30) alkyl (C6-C20) aryl And alkyl is linear or branched and may include unsaturated bonds in the carbon chain, and the carbon atoms of the aryl may be substituted with one or more heteroelements selected from N, O, S, P and Si; R ² is selected from linear or branched (C 1 -C 7) alkyl.] The method according to any one of claims 1 and 3 to 4, The composite resin composition is a polyvinyl chloride (PVC) and the thermoplastic polyurethane elastomer (TPU) weight ratio (PVC: TPU) of 3 to 7: 7 to 3 mixed resin mixed with a vinyl acetate (VA) content A marine cable comprising 5 to 15 parts by weight of maleic anhydride modified ethylene vinyl acetate (EVA-g-MAH), which is 40 to 70% by weight, and 5 to 30 parts by weight of magnesium hydroxide surface-modified with mercaptopropyltrimethoxysilane.

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