KR20130094406A

KR20130094406A - Resin composition for defense industry tube with excellent flexibility and oil resistance

Info

Publication number: KR20130094406A
Application number: KR1020120015612A
Authority: KR
Inventors: 이재익; 김선근
Original assignee: 엘에스전선 주식회사
Priority date: 2012-02-16
Filing date: 2012-02-16
Publication date: 2013-08-26

Abstract

The present invention relates to a resin composition for tubes. In particular, the present invention has a defense industry (hereinafter referred to as 'defense') or a military industry having excellent flexibility, oil resistance, heat resistance, cold resistance and flame retardancy according to VW-1 according to the munitions specification Mil-23053 / 1. It relates to a resin composition for tubes used in the military industry.

Description

Resin composition for defense industry tube with excellent flexibility and oil resistance}

Industrial or household tubes, in particular, tube for coating such as electric wire, tube for pipeline such as fluid or the like, and heat shrink tube used in the connection portion thereof may be made of a polymer material, and may be designed as polymer materials and additives of various specifications. . In addition, the polymer material should satisfy the test regulations for various physical properties required according to the use environment of the tube.

In particular, according to the design standards and various test regulations prescribed in the military standard Mil-23053 / 1, etc., since the dissipation tube is used in an extreme environment, the polymer material employed here requires high oil resistance, high heat resistance, and high cold resistance. In addition, the tube may be applied between complex electrical devices, so that the polymer material may further require high flexibility.

However, the properties required in the polymer material for the dissipation tube may be in a trade-off with each other, and the improvement of specific properties may cause deterioration of other properties. For example, when a resin having a low shore hardness is adopted to improve the cold resistance and flexibility of the polymer material, oil resistance and flame retardancy may be deteriorated, and when the content of the flame retardant is increased to secure the flame resistance of the polymer material, Physical properties, ie flexibility, cold resistance, heat resistance and the like may be lowered.

Conventionally, a combination of polyvinyl chloride (PVC) and lead-based flame retardant has been used as a polymer material for dissipation tubes. Polyvinyl chloride is characterized by excellent water resistance, chemical resistance, flame retardancy, etc., but incomplete combustion generates a dioxin, a mutagen suspected to be a carcinogen, has recently regulated its use. In addition, the use of lead-based flame retardants are also regulated due to environmental and safety issues.

In another prior art, a thermoplastic polyester resin is used in place of the polyvinyl chloride as a polymer material for a tube, but the thermoplastic polyester resin has excellent resistance to gas and oil, mechanical strength, etc. There is a problem that can be prematurely ruptured by hydrolysis, such as cracks when exposed to, and bursts when subjected to a humid temperature cycle.

In another prior art, a crosslinked polyethylene resin is used as the polymer material for the tube, but there is a problem in that heat resistance and flexibility are lowered when used as the material of the thin film tube due to the complexity of the apparatus and the increase in the number of tubes.

As described above, it is extremely difficult in the art to simultaneously satisfy the physical properties required in the dissipation tube, that is, excellent flexibility, oil resistance, heat resistance, cold resistance, flame resistance.

Accordingly, the resin composition for the dissipation tube that satisfies all properties such as excellent flexibility, oil resistance, heat resistance, cold resistance, and flame retardancy according to VW-1, and does not cause the problems of the prior art according to the munition specification Mil-23053 / 1 Development is required.

An object of the present invention is to provide a resin composition for a dissipation tube that satisfies all properties such as excellent flexibility, oil resistance, heat resistance, cold resistance, and flame resistance according to VW-1 according to Mil-23053 / 1.

In order to solve the above problems,

A mixture of a chlorinated polyethylene resin, an ethylene copolymer resin, and a modified polyolefin resin grafted with maleic anhydride as a base resin, and based on 100 parts by weight of the base resin, the content of the chlorinated polyethylene resin is 30 to 85 parts by weight, The content of the ethylene copolymer resin is 5 to 65 parts by weight, the content of the modified polyolefin resin grafted with the maleic anhydride is 5 to 10 parts by weight, to provide a resin composition for a tube.

Here, based on 100 parts by weight of the base resin, the content of the chlorinated polyethylene resin is 40 to 80 parts by weight, characterized in that the content of the ethylene copolymer resin is 10 to 55 parts by weight, to provide a tube resin composition.

Here, the content of chlorine contained in the chlorinated polyethylene resin, 20 to 60% by weight based on the total weight of the chlorinated polyethylene resin, it provides a tube resin composition.

In addition, the content of chlorine contained in the chlorinated polyethylene resin, 25 to 50% by weight based on the total weight of the chlorinated polyethylene resin, it provides a resin composition for tubes.

And, the hardness of the chlorinated polyethylene resin provides a resin composition for tubes, characterized in that 40 to 95 in Shore (shore) A.

Here, the hardness of the chlorinated polyethylene resin provides a resin composition for tubes, characterized in that the Shore A is 50 to 85.

In addition, the content of the copolymer contained in the ethylene copolymer resin, 10 to 40% by weight based on the total weight of the ethylene copolymer resin, it provides a resin composition for tubes.

Here, the content of the copolymer contained in the ethylene copolymer resin, 15 to 35% by weight based on the total weight of the ethylene copolymer resin, it provides a tube resin composition.

And the copolymer contained in the said ethylene copolymer resin contains ethylene vinyl acrylate, ethylene methacrylate, ethylene ethyl acrylate, ethylene butyl acrylate, or a combination thereof. to provide.

Moreover, the melting point of the said ethylene copolymer resin is 40-110 degreeC, The resin composition for tubes is provided.

Here, the melting point of the said ethylene copolymer resin is 50-100 degreeC, The resin composition for tubes is provided.

In addition, the modified polyolefin-based resin to which the maleic anhydride is added may be a polyolefin elastomer, ethylene vinyl acrylate, ethylene ethyl acrylate, linear low density polyethylene, low density polyethylene, or resin grafted maleic anhydride to high density polyethylene, or a combination thereof. It provides, the resin composition for tubes characterized by including.

In addition, the content of maleic anhydride is 0.2 to 3% by weight based on the total weight of the modified polyolefin-based resin to which maleic anhydride is added, to provide a resin composition for a tube.

Here, the content of the maleic anhydride is 0.5 to 2% by weight, based on the total weight of the modified polyolefin-based resin to which the maleic anhydride is added, to provide a resin composition for a tube.

In addition, based on 100 parts by weight of the base resin, it characterized in that it further comprises 30 to 150 parts by weight of a flame retardant, provides a resin composition for tubes.

Here, based on 100 parts by weight of the total weight of the base resin, the content of the flame retardant is 40 to 130 parts by weight, to provide a tube resin composition.

The flame retardant is a brominated flame retardant, an antimony flame retardant, a metal hydroxide flame retardant, or a combination thereof, and provides a resin composition for a tube.

In addition, based on 100 parts by weight of the base resin, it provides a tube resin composition, characterized in that it further comprises 0.3 to 5 parts by weight of antioxidant.

Here, the content of the antioxidant is 1 to 4 parts by weight based on 100 parts by weight of the base resin, it provides a tube resin composition.

The antioxidant may include a hindered phenol-based antioxidant, an amine-based antioxidant, or a combination thereof, a primary antioxidant and a sulfur-based antioxidant, a phosphorus antioxidant, or a combination thereof. The content of each of the primary antioxidant and the secondary antioxidant is 0.5 to 2 parts by weight based on 100 parts by weight of the base resin, and provides a resin composition for a tube.

In addition, on the basis of 100 parts by weight of the base resin, it provides a tube resin composition, characterized in that it further comprises 3 to 20 parts by weight of cold-resistant plasticizer.

Here, the content of the cold-resistant plasticizer is based on 100 parts by weight of the base resin, 5 to 10 parts by weight, to provide a tube resin composition.

And, the cold-resistant plasticizer provides a resin composition for tubes, characterized in that the adipic acid-based cold-resistant plasticizer, sebacic acid-based cold-resistant plasticizer, or a combination thereof.

It also provides a tube produced from the resin composition for the tube.

Here, the defense industry provides a tube.

The resin composition for the dissipation tube according to the present invention is required for use as a polymer material for the dissipation tube, but satisfies all of the physical properties in the trade-off, that is, excellent flexibility, oil resistance, cold resistance, heat resistance, flame resistance, etc. Excellent effect.

The resin composition for a dissipation tube according to the present invention contains a mixture obtained by blending a modified polyolefin resin grafted with chlorinated polyethylene resin, ethylene copolymer resin and maleic anhydride as a base resin.

The chlorinated polyethylene resin improves the flame retardancy of the tube produced from the base resin. In the above chlorinated polyethylene resin, the polyethylene resin includes various polyethylene resins according to various known polymerization methods. That is, the polyethylene resin may be linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene resin (HDPE), or a combination thereof, polyethylene homopolymer, polyethylene copolymer, or It may be a combination thereof.

Processes for chlorination of polyethylene are known in the art. For example, the polyethylene may be dissolved in trichloroethylene, chloroform, carbon tetrachloride, or the like to be in solution or as a suspension, and chlorinated at 60 ° C. or lower.

In the chlorinated polyethylene resin, the content of chlorine may be 20 to 60% by weight, preferably 25 to 50% by weight. If the content of the chlorine is less than 25% by weight may be insufficient flame retardancy of the tube produced, if more than 50% by weight may lower the cold resistance and oil resistance of the tube.

In addition, based on 100 parts by weight of the base resin, the content of the chlorinated polyethylene resin may be 30 to 85 parts by weight, preferably 40 to 80 parts by weight. If the content of the chlorinated polyethylene resin is less than 40 parts by weight may be insufficient flame retardancy of the tube produced, if more than 80 parts by weight may be insufficient cold resistance and flexibility of the tube.

The hardness of the chlorinated polyethylene resin may be 40 to 95, preferably 50 to 85, in Shore A. When the Shore A hardness is less than 50, the flexibility of the manufactured tube may be excellent, but heat resistance and oil resistance may be lowered, and when the Shore A hardness is greater than 85, flexibility and cold resistance of the tube may be reduced.

In addition, the ethylene copolymer resin improves filler loading of the base resin, cold resistance and flexibility of a tube made from the base resin.

The ethylene copolymer resin may include a copolymer of ethylene or repeating units derived from ethylene and repeating units derived from α-olefins or α-olefins other than the repeating units derived from ethylene or ethylene, and also cyclic olefins. It may include a copolymer by repeating units derived from.

Specific examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 1-octene, 3-ethyl-1-hexene, 1-decene, 1-dode Sen, 1- tetradecene, 1-hexadecene, 1-octadecene, eicosene and the like.

Preferably, the ethylene copolymer resin may comprise ethylene vinyl acetate (EVA), ethylene methacrylate (EMA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), or combinations thereof. .

On the other hand, the ethylene copolymer resin may include substantially 10 to 40% by weight, preferably 15 to 35% by weight of the copolymer. When the content of the copolymer contained in the ethylene copolymer resin is less than 15% by weight, the flexibility and filler loading of the produced tube is lowered, and when the content is greater than 35% by weight, the flexibility of the tube is improved but the price is increased. Done.

Based on 100 parts by weight of the base resin, the content of the ethylene copolymer resin may be 5 to 65 parts by weight, preferably 10 to 55 parts by weight. When the content of the ethylene copolymer resin is less than 10 parts by weight, the flexibility of the manufactured tube may be insufficient and filler loading may be lowered and thus mechanical strength may not be secured. Flexibility is good, but flame retardancy may be insufficient.

In addition, the melting point (Tm) of the ethylene copolymer may be 40 to 110 ℃, preferably 50 to 100 ℃. When the melting point is less than 50 ° C., even when a little heat is applied during the extrusion process for producing a tube, the resin composition in the form of pellets may be entangled and the resin composition may not be transferred between the extruder screw and the barrel. As the extrusion amount of the raw material is changed, the productivity is lowered, and the manufactured tube may not exhibit sufficient elastic modulus and strength to satisfy sufficient room temperature strength, and when the temperature is higher than 100 ° C., the flexibility of the tube may be reduced.

In addition, the modified polyolefin resin grafted with maleic anhydride improves the oil resistance of the tube produced from the base resin and increases the interfacial bonding force of the resin with the flame retardant added further below.

In the modified polyolefin resin grafted with maleic anhydride, the polyolefin resin includes polyethylene, polypropylene, and the like, and is not particularly limited, and may be a homopolymer, a copolymer, or a combination thereof. Preferably, the polyolefin resin is a polyolefin elastomer, ethylene vinyl acrylate (EVA), ethylene ethyl acrylate (EEA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), or their Combinations may be included.

Methods for grafting maleic anhydride to polyolefinic resins are known in the art. For example, a polyolefin-based resin grafted with maleic anhydride can be obtained by reacting maleic anhydride with a polyolefin resin in the presence of oxygen, air, hydrogen peroxide or other free radical initiator and under heating conditions.

Based on 100 parts by weight of the base resin, the content of the polyolefin resin grafted maleic anhydride may be 5 to 10 parts by weight. If the content is less than 5 parts by weight oil resistance of the tube to be produced may be insufficient, if more than 10 parts by weight the price of the tube may rise and cold resistance may be lowered.

In addition, in the polyolefin resin grafted maleic anhydride, the content of maleic anhydride is 0.2 to 3% by weight, preferably 0.5 to 2 weight based on the total weight of the polyolefin resin grafted maleic anhydride May be%. When the content of the maleic anhydride is less than 0.5% by weight, the strength and oil resistance of the tube produced by the interfacial bonding strength between the filler and the resin may decrease, and when the content of the maleic anhydride exceeds 2.0% by weight, the tube price increases and elongation and cold resistance decrease. Can be.

The resin composition for a dissipation tube according to the present invention may further include a flame retardant to improve the flame retardancy of the tube to be produced. The flame retardant may be a bromine-based, antimony-based, metal hydroxide-based flame retardant, or a combination thereof, preferably a combination of bromine-based flame retardant and metal hydroxide-based flame retardant. Here, as said metal hydroxide type flame retardant, aluminum hydroxide, magnesium hydroxide, etc. are mentioned, for example.

In particular, the metal hydroxide flame retardant may be used by surface treatment or non-surface treatment with a silane such as vinyl silane, an amine such as vinyl amine, stearic acid, fatty acid, or the like, or may be used alone or in combination of two or more thereof. . In addition, the metal hydroxide flame retardant may be used with auxiliary flame retardants such as melamine cyanurate, zinc borate, tin flame retardant and the like. Preferably, the particle size of the metal hydroxide inorganic flame retardant may be 0.5 to 30㎛, specific surface area (BET) may be 3 to 20 mm 2 / g.

For example, the untreated magnesium hydroxide is commercially available from Konoshima Chemical Co. Ltd. under the product names Magseeds N1, N2 and N3, and the surface treated magnesium hydroxide is Albe From Albemarle Corporation to MAGNIFIN, from Kyowa Chemical Industry to KISUMA, from Sakai Chemical to MGZ, from Martin Marietta Magnesia Specialties It is marketed under the product name of Magshield.

Based on 100 parts by weight of the base resin, the total content of the flame retardant may be 30 to 150 parts by weight, preferably 40 to 130 parts by weight. If the content of the flame retardant is less than 40 parts by weight, the flame retardancy of the tube produced may be lowered. If it is more than 130 parts by weight, the flexibility, cold resistance, oil resistance of the tube may be reduced.

In addition, the resin composition for a dissipation tube according to the present invention may further include an antioxidant to improve the heat resistance of the tube to be produced. The antioxidant is directly involved in the oxidation reaction, such as hindered phenol-based, amine-based primary antioxidants to prevent oxidation, and secondary, such as sulfur-based, phosphorus-based, etc. to inactivate the metal that serves as the catalyst of the oxidation reaction Antioxidants. In addition, the primary antioxidant and the secondary antioxidant may be a mixture of two or more antioxidants.

Based on 100 parts by weight of the base resin, the total content of the antioxidant may be 0.3 to 5 parts by weight, preferably 1 to 4 parts by weight. If the total content of the antioxidant is less than 1 part by weight, the heat resistance of the tube to be produced may be insufficient, and if more than 4 parts by weight, blooming may occur on the surface of the tube.

In addition, the content of each of the primary antioxidant and the secondary antioxidant may be 0.5 to 2 parts by weight based on 100 parts by weight of the base resin.

The resin composition for a dissipation tube according to the present invention may further include a cold-resistant plasticizer to improve the cold resistance of the tube to be produced. The properties required as the cold-resistant plasticizer is, in addition to cold resistance and flexibility, compatibility with the polymer constituting the base resin, high boiling point, non-toxic, natural fats and oils such as triglycerides, phthalic anhydride, maleic anhydride, adipic acid, Sebacic acid type or the like or a combination thereof is used as a plasticizer.

In the present invention, the cold-resistant plasticizer preferably includes an adipic acid-based, sebacic acid-based plasticizer, or a combination thereof.

Based on 100 parts by weight of the base resin, the content of the cold-resistant plasticizer may be 3 to 20 parts by weight, preferably 5 to 10 parts by weight. When the content of the cold-resistant plasticizer is less than 5 parts by weight may be insufficient cold resistance of the produced tube, when the content of more than 10 parts by weight may reduce the strength of the tube, oil resistance, heat resistance and the like.

The resin composition for a dissipation tube according to the present invention is a high molecular weight wax, a low molecular weight wax, a polyolefin wax, a paraffin wax, a paraffin oil, a stearic acid, a metal soap, an organic silicone, a fatty acid ester, a fatty acid amide, Other additives such as lubricants, crosslinking aids, reinforcing agents, mold release agents, UV absorbers, stabilizers, pigments, dyes, colorants, antistatic agents, foaming agents, metal deactivators, and the like, or combinations thereof, such as fatty alcohols, fatty acids, and the like.

A typical method for producing a resin composition for a dissipation tube according to the present invention is a modified polyolefin resin grafted with a chlorinated polyethylene resin, an ethylene copolymer and maleic anhydride constituting the base resin, a flame retardant, an antioxidant and a cold-resistant plasticizer, and other additives. And melt mixing in a melt mixing apparatus such as a compounding extruder or a banbury mixer.

In addition, the melt mixed mixture is melt filtered through at least one filter having an opening having a diameter of 20 to 150 micrometers, preferably 30 to 130 micrometers, more preferably 40 to 110 micrometers to remove particulate impurities. Can be. The melt filtration process may be performed through a single melt filtration system or may be performed through multiple melt filtration systems.

The melt filtered mixture is directly made into a tube by extrusion or the like, or pelletized by strand pelletization or underwater pelletization through a die head and then again. It can be melted and made into a tube by a suitable method such as extrusion molding.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the present invention to those skilled in the art.

[Example]

The chlorinated polyethylene resins, ethylene copolymers, modified polyolefin resins grafted with maleic anhydride, antioxidants, flame retardants, and cold-resistant plasticizers used in the following Examples and Comparative Examples are as follows.

1) Chlorinated Polyethylene Resin

CPE1: YASHING, CPE 6235

CPE2: Dupont Dow, CPE CM631

CPE3: Showa-denko, 202 KB

2) Ethylene Copolymer

EC1: Mitsui-dupont, EVA 421

EC2: Mitsui-Dupont, EVA 422

EC3: Michi-Dupont, EEA-A1150

3) Modified polyolefin resin grafted with maleic anhydride

Modified PO1: DuPont, Fusabond 250D

Modified PO2: Modchem, MOD-157

4) antioxidant

Primary antioxidants: CIBA-Specialty, Irganox-1010

Secondary Antioxidants: Ciba-Specialty, Irganox-PS-802

5) Flame retardant

Albemarle, Magnefine H5A

6) Coldproof plasticizer

Geoyoung, DOS

Through the compounding extruder, the resin compositions for tubes of Examples 1 to 4 and Comparative Examples 1 to 9 shown in Table 1 below, and tubes having an outer diameter of 5.5 mm and a thickness of 0.48 mm were prepared.

Ingredients Example Comparative Example One 2 3 4 One 2 3 4 5 6 7 8 9 CPE1 (Cl: 42%, S: 81) 70 40 70 40 90 70 70 70 70 CPE2 (Cl: 50, S: 84) 60 40 15 CPE3 (Cl: 16, S62) 70 EC1 (Co: 28%, Tm: 76 ° C) 25 50 35 25 50 5 80 25 25 25 35 EC2 (Co: 20%, Tm: 85 ° C) 55 EC3 (Co: 12%, Tm: 102 ° C) 25 Modified PO1 (M: 1.5%) 5 10 5 5 5 5 5 5 5 5 5 25 Modified PO2 (M: 0.3%) 10 Primary antioxidants 2 2 2 2 2 2 2 2 2 2 2 2 2 Secondary antioxidant One One One One One One One One One 0 One One One Flame retardant 60 100 60 90 60 60 60 60 100 60 160 60 60 Cold-free plasticizer 5 8 5 5 5 5 5 5 5 5 8 20 8 Cl: chlorine amount; S: Shore A hardness; Co: copolymer content ratio; Tm: Melting Point
M: Maleic Anhydride Content Ratio

The method for evaluating the cold resistance, heat resistance, oil resistance, flame retardancy and flexibility of the resin composition prepared in the above Examples and Comparative Examples and the tube prepared therefrom is as follows.

1) cold resistance evaluation

The cold resistance of the tube manufactured from the resin composition for the tube was measured by the test method specified in the Military Standard Mil-23053 / 1, that is, maintaining the tube to be tested at -70 ° C for 4 hours and then applying a predetermined round rod to observe cracks. The method was evaluated by the test method specified in ASTM D746 in place of the method. Specifically, the specimen of the tube prepared in each Example and Comparative Example was mounted in the apparatus specified in ASTM D746, and maintained at -70 ° C. for 3 minutes, and then the test was repeated five times to lower the striking edge. The number of crack occurrences was recorded.

2) oil resistance evaluation

The oil resistance of the tube manufactured from the resin composition for tubes was evaluated by the test method prescribed | regulated by the munitions standard Mil-23053 / 1. Specifically, the tensile strength and elongation of the tube specimens prepared in each of Examples and Comparative Examples were stretched at a rate of 500 mm / min after soaking in a predetermined oil at room temperature for 24 hours. It was judged that the tensile strength was 0.7 kgf / mm 2 or more and the elongation was 175% or more, so that it had excellent oil resistance.

3) Heat resistance evaluation

The heat resistance of the tube manufactured from the resin composition for tubes was evaluated by the test method prescribed | regulated by the munitions standard Mil-23053 / 1. Specifically, the tensile strength and elongation rate of the tube specimens prepared in each of Examples and Comparative Examples were stretched at a rate of 500 mm / min after holding at 121 ° C. for 168 hours. It was judged that the said tensile strength was 0.84 kgf / mm <2> or more and the elongation rate is 175% or more and it had excellent heat resistance.

4) Flexibility Assessment

The flexibility of the electric wires prepared from the resin composition for tubes was evaluated according to ASTM D638. Specifically, the tube specimens prepared in each example and comparative example are tensioned in a defined device to measure the modulus of elasticity at the point where 2% strain of the specimen length occurs or breaks 2% before.

5) Flame retardancy evaluation

The flame retardance of the tube produced from the resin composition for tubes was evaluated according to VW-1. Specifically, the tube specimens prepared in Examples and Comparative Examples were arranged vertically, and the predetermined flame in the vertical direction at the bottom was applied five times at intervals of 15 seconds for 15 seconds. It was judged that the flame retardancy of the tube was excellent when the combustion length of the electric wire after flame application was 600 mm or less.

Evaluation results of the cold resistance, oil resistance, heat resistance, flame retardancy and flexibility of the resin composition for tubes or tubes prepared according to Examples 1 to 4 and Comparative Examples 1 to 9 described in Table 1, respectively, are as described in Table 2 below.

Evaluation item Example Comparative Example One 2 3 4 One 2 3 4 5 6 7 8 9 Cold resistance (cutting / normal) 0/5 0/5 0/5 0/5 0/5 0/5 0/5 4/1 0/5 0/5 5/0 0/5 3/2 Oil resistance
Tensile strength (kgf / ㎡)
Elongation (%)
0.85280
0.91
220
0.80
340
0.86
245
0.93
214
0.94
412
0.68
432
0.55
360
0.85
260
0.86
290
0.72
120
0.44
540
0.94
230 Heat resistance
Tensile strength (kgf / ㎡)
Elongation (%)
1.2
350
0.92
300
1.1
310
1.13
390
1.43
280
1.3
290
0.95
390
0.85
220
1.34
270
0.62
95
1.54
195
0.43
15
1.48
230 Flame retardancy (mm) 2/2/0/0/0 2/0/0/0/0 4/3/0/0/0 3/1/0/0/0 9/5/2/0/0 68/98 / burnout 3/6/2/0/0 2/3/2/0/0 24/92/70 / burnout 2/5/0/0/0 1/0/0/0/0 12/5/6/0/0 7/2/0/0/0 Flexibility (kgf / mm2) 7.9 9.2 8.3 9.4 31.4 4.3 6.3 16.7 10.8 7.8 21.9 4.3 11.3

As shown in Table 2, the resin composition for a tube of Examples 1 to 4 according to the present invention or a tube prepared therefrom is cold-resistant, oil-resistant, heat resistance, flexibility, VW-1 according to the munition standard Mil-23053 / 1 It was confirmed that the equivalent has an excellent effect of satisfying flame retardancy at the same time.

On the other hand, Comparative Example 1 was confirmed that the copolymer content ratio of the ethylene copolymer resin of the component is low, the melting point is high, the elastic modulus is increased, thereby reducing the flexibility of the tube,

Comparative Example 2 was confirmed that the flame retardancy is lowered because the chlorine content ratio of the chlorinated polyethylene resin among the components,

In Comparative Example 3, the maleic anhydride content ratio of the modified polyolefin-based resin grafted with maleic anhydride in the constituents was low, and the interfacial bonding force between the resin and the flame retardant was lowered, whereby the oil resistance of the tube was lowered.

Comparative Example 4 was found to be excellent in flame retardancy of the tube due to the high content of chlorinated polyethylene resin in the components, but lower oil resistance and cold resistance,

Comparative Example 5 was confirmed that the flame retardancy is lowered despite the low content of the chlorinated polyethylene resin in the component of the flame retardant content of 100 parts by weight,

Comparative Example 6 was confirmed that the heat resistance of the tube is lowered by not adding a secondary antioxidant,

Comparative Example 7 was found to have a high flame retardant content so that the tube is excellent in flame retardancy, but cold resistance and flexibility is reduced,

Comparative Example 8 was found to be excellent in the cold resistance and flexibility of the tube because the content of the cold-resistant plasticizer is too high, oil resistance and heat resistance is reduced,

Comparative Example 9 was found to have a high content of the modified polyolefin resin grafted maleic anhydride among the components, excellent oil resistance but low cold resistance.

While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. . It is therefore to be understood that the modified embodiments are included in the technical scope of the present invention if they basically include elements of the claims of the present invention.

Claims

A mixture of a chlorinated polyethylene resin, an ethylene copolymer resin, and a modified polyolefin resin grafted with maleic anhydride as a base resin, and based on 100 parts by weight of the base resin, the content of the chlorinated polyethylene resin is 30 to 85 parts by weight, The content of the ethylene copolymer resin is 5 to 65 parts by weight, the content of the modified polyolefin resin grafted with the maleic anhydride is 5 to 10 parts by weight, the resin composition for a tube.

The method of claim 1,
Based on 100 parts by weight of the base resin, the content of the chlorinated polyethylene resin is 40 to 80 parts by weight, the content of the ethylene copolymer resin, characterized in that 10 to 55 parts by weight, the resin composition for tubes.

3. The method according to claim 1 or 2,
The content of chlorine contained in the chlorinated polyethylene resin, based on the total weight of the chlorinated polyethylene resin, characterized in that 20 to 60% by weight, the resin composition for a tube.

The method of claim 3,
The content of chlorine contained in the chlorinated polyethylene resin is 25 to 50% by weight based on the total weight of the chlorinated polyethylene resin, the resin composition for a tube.

3. The method according to claim 1 or 2,
The hardness of the chlorinated polyethylene resin is Shore (shore) A, characterized in that 40 to 95, the resin composition for a tube.

The method of claim 5,
The hardness of the said chlorinated polyethylene resin is 50-85 in Shore A, The resin composition for tubes.

3. The method according to claim 1 or 2,
The content of the copolymer contained in the ethylene copolymer resin is 10 to 40% by weight based on the total weight of the ethylene copolymer resin, the resin composition for a tube.

The method of claim 7, wherein
The content of the copolymer contained in the ethylene copolymer resin is 15 to 35% by weight based on the total weight of the ethylene copolymer resin, the resin composition for a tube.

The method of claim 7, wherein
The copolymer composition contained in the said ethylene copolymer resin contains ethylene vinyl acrylate, ethylene methacrylate, ethylene ethyl acrylate, ethylene butyl acrylate, or a combination thereof.

3. The method according to claim 1 or 2,
Melting | fusing point of the said ethylene copolymer resin is 40-110 degreeC, The resin composition for tubes.

The method of claim 10,
Melting | fusing point of the said ethylene copolymer resin is 50-100 degreeC, The resin composition for tubes.

3. The method according to claim 1 or 2,
The modified polyolefin-based resin to which maleic anhydride is added includes polyolefin elastomer, ethylene vinyl acrylate, ethylene ethyl acrylate, linear low density polyethylene, resin grafted maleic anhydride to low density polyethylene or high density polyethylene, or a combination thereof. A resin composition for tubes, characterized in that.

The method of claim 12,
Based on the total weight of the modified polyolefin-based resin to which the maleic anhydride is added, the content of maleic anhydride is 0.2 to 3% by weight, the resin composition for a tube.

The method of claim 13,
Based on the total weight of the modified polyolefin-based resin to which the maleic anhydride is added, the content of maleic anhydride is 0.5 to 2% by weight, the resin composition for a tube.

3. The method according to claim 1 or 2,
Based on 100 parts by weight of the base resin, characterized in that it further comprises 30 to 150 parts by weight of a flame retardant, the resin composition for a tube.

16. The method of claim 15,
Based on 100 parts by weight of the base resin, the content of the flame retardant is 40 to 130 parts by weight, the resin composition for a tube.

16. The method of claim 15,
The flame retardant is a brominated flame retardant, antimony flame retardant, metal hydroxide flame retardant, or a combination thereof, a resin composition for a tube.

3. The method according to claim 1 or 2,
Based on 100 parts by weight of the base resin, characterized in that it further comprises 0.3 to 5 parts by weight of antioxidant, the resin composition for a tube.

19. The method of claim 18,
Based on 100 parts by weight of the base resin, the content of the antioxidant is 1 to 4 parts by weight, the resin composition for a tube.

20. The method of claim 19,
The antioxidants include hindered phenolic antioxidants, amine antioxidants, or combinations thereof, primary and sulfur antioxidants, phosphorus antioxidants, or combinations thereof, secondary antioxidants. The content of each of the primary antioxidant and the secondary antioxidant is 0.5 to 2 parts by weight based on 100 parts by weight of the base resin, the resin composition for a tube.

3. The method according to claim 1 or 2,
On the basis of 100 parts by weight of the base resin, the resin composition for tubes, further comprising 3 to 20 parts by weight of cold-resistant plasticizer.

The method of claim 21,
Based on 100 parts by weight of the base resin, the content of the cold-resistant plasticizer is 5 to 10 parts by weight, the resin composition for a tube.

The method of claim 21,
The cold-resistant plasticizer is an adipic acid-based cold-free plasticizer, sebacic acid-based cold-free plasticizer, or a combination thereof.

A tube made from the resin composition for tubes according to claim 1.

The tube of claim 24 wherein the defense industry tube.