KR20130090233A - Non-crosslinked oil and mud-resistant composition - Google Patents

Abstract

PURPOSE: A non-crosslinked oil and mud-resistant composition is provided to satisfy flame retardance, cold resistance, oil resistance, and mud resistance without a crosslinking process. CONSTITUTION: A non-crosslinked oil and mud-resistant composition uses a polyester thermoplastic elastic polymer with a melt index of 4.5-6.0 g/10min as a base resin and includes 130-150 parts by weight of a surface-coated inorganic flame retardant or a mixture of the surface-coated inorganic flame retardant and a surface-non-coated inorganic flame retardant and 10-25 parts by weight of a flame retardant per 100.0 parts by weight of the base resin. The flame retardant is a material selected from a magnesium hydroxide, an aluminum a hydroxide, a calcium hydroxide, a huntite, a hydromagnesite, and a mixture thereof.

Description

Non-crosslinked oil and mud-resistant composition

The present invention relates to an oil resistant mud resistant composition and an electric wire using the same.

In order to be used as the sheath material of the electric wire, a certain degree of flame retardancy is required. In order to obtain such flame retardancy, a sheath material using a flame retardant containing a halogen element was developed. Since the insulating material prepared by using a halogen-based flame retardant or a basic resin containing a halogen atom is basically flame retardant, even if only a small amount of additives were used, the desired physical properties could be satisfied. Therefore, even when the additive was used, the viscosity of the sheath material was not caused to increase, so the extrusion workability was also excellent. However, halogen-containing plastics such as halogen-based flame retardants and polyvinyl chloride emit toxic gases during combustion, and thus are subject to environmental relief and will not be usable in the future or will be severely restricted.

The wires used for special applications are not only flame retardant, but also have difficulty in operation at low temperatures, and are resistant to oils such as oil and various muds. It is necessary to have resistance to mud resistance. In other words, the material constituting the sheath layer of the electric wire must be equipped with cold resistance, oil resistance and mud resistance in addition to flame retardancy.

In particular, in order to satisfy the resistance to lubricating oil and mud, the existing composition is inevitable crosslinking. However, there is a problem in that time and cost are added when the crosslinking process is performed. In addition, there is a problem of being pressed during the sheath extrusion operation such as CCV (Catenary Continuous Vulcanization), there is a limit of the insulating material.

Therefore, research has been conducted on non-crosslinking type insulating materials to satisfy sufficient flame retardancy, cold resistance and especially oil resistance and mud resistance in this field, and the present invention has been devised under such technical background.

Accordingly, an object of the present invention is to provide an insulating composition which is a non-crosslinking type, does not require a crosslinking process and satisfies flame resistance, cold resistance, and in particular oil resistance and mud resistance, and an electric wire including the insulating composition.

In order to solve the above problems, the present invention is a melt resin (MI) is 4.5 to 6.0 g / 10min polyester thermoplastic elastomer (thermoplastic polyester elastomer, TPEE); And 130 to 150 parts by weight of a mixture of an inorganic flame retardant coated with the surface or an inorganic flame retardant coated with the surface and an inorganic flame retardant not coated with the surface, and 10 to 25 parts by weight of a flame retardant aid based on 100 parts by weight of the basic resin. It provides an oil resistant mud resistant composition comprising.

In addition, the present invention is a base resin comprising 85% by weight or more of polyester thermoplastic elastomer (TPEE) having a melt index (MI) of 4.5 to 6.0g / 10min and 15% by weight or less of a polyolefin introduced with a polar group; And 130 to 150 parts by weight of a mixture of an inorganic flame retardant coated with the surface or an inorganic flame retardant coated with the surface and an inorganic flame retardant not coated with the surface, and 10 to 25 parts by weight of a flame retardant aid based on 100 parts by weight of the basic resin. It provides an oil resistant mud resistant composition comprising.

85% by weight or more of the 'polyester thermoplastic elastomer (TPEE)' means 85 to 100% by weight of the polyester thermoplastic elastomer, and '15% by weight or less of the polyolefin having a polar group 'means a polyolefin having a polar group. It means that it is included in 0 to 15% by weight or less. That is, the object of this invention is achieved even when 100 weight% of polyester thermoplastic elastomers are included (that is, when the polyolefin which introduce | transduced a polar group is not contained at all as 0 weight%).

The present invention also provides an electric wire including the oil resistant mud resistant composition.

Hereinafter will be described in detail with respect to the basic resin used in the present invention.

In the present invention, a polyester thermoplastic elastomer (TPEE) is used as one component of the base resin. Polyester thermoplastic elastomer is composed of hard segment and soft segment. The hard segment is composed of aromatic polyester, and the soft segment is aliphatic polyester, polyester. Or polyether. Polyester thermoplastic elastomer is composed of hard and mechanically strong hard segments and soft and rubbery soft segments, which have rubber properties at room temperature, and thermoplastic properties at high temperature. It has possible properties, and also has excellent heat, weather, oil and flex resistance and high hardness.

In general, in the case of the thermoplastic elastomer, its properties vary depending on the composition ratio of the hard and soft segments.

The polyester thermoplastic elastomer which can be used in the present invention preferably has a melt index (MI) of 4.5 to 6.0 g / 10 min at 190 degrees. If the MI is less than 4.5g / 10min, there is difficulty in molding during cable extrusion due to poor flowability, and if it is more than 6.0g / 10min, the tensile strength may be less than room temperature.

 The hardness of the polyester thermoplastic elastomer is preferably 38 to 42D on the Shore D scale. Hardness is an important representative property of TPEE, and when the hardness is 38 or more, the wear resistance and tear resistance are good, and when the hardness is 42 or less, the flexibility of the cable is prevented by appropriate modulus.

In the present invention, the polyester thermoplastic elastomer is preferably included in the 85 to 100% by weight relative to the total base resin. When the polyester thermoplastic elastomer is 85% by weight or more, the oil or mud has an advantage of satisfying the standard of tensile residual rate or normal temperature tensile strength after oil resistance.

In the present invention, a polyolefin having a polar group may be included as another component of the basic resin. Polyolefins with polar groups increase the compatibility between the inorganic flame retardant and the polyester thermoplastic elastomer, helping to evenly disperse the inorganic flame retardant. Materials to provide polar groups are, for example, maleic anhydride, ethylene acetic acid, glycidyl methacrylate, or mixtures thereof, and polyolefins into which the polar groups are to be introduced are, for example, polyethylene, polypropylene, polybutadiene, Ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer or mixtures thereof, and the like. Preferably, as the polyolefin having a polar group according to the present invention, an ethylene-vinyl acetate copolymer having a maleic anhydride introduced therein may be used.

The polyolefin introduced with a polar group according to the present invention may be included in 0 to 15% by weight relative to the total base resin. If the polyolefin containing the polar group is included in excess of 15% by weight does not satisfy the oil resistance properties, there is a problem that does not satisfy the elongation at room temperature elongation and the tensile and elongation remaining after aging.

Hereinafter, the inorganic flame retardant and the flame retardant aid used in the present invention will be described in detail.

In the present invention, an inorganic flame retardant surface-treated with a polymer material or a mixture of the surface-treated inorganic flame retardant and surface untreated inorganic flame retardant is used as the flame retardant. The inorganic flame retardant may include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, huntite, hydromagnesite or mixtures thereof, but is not limited thereto. Preferably, the inorganic flame retardant in the present invention may include magnesium hydroxide, because magnesium hydroxide can ensure the desired level of flame retardancy by minimizing changes in tensile strength and elongation at room temperature. The surface-treated inorganic flame retardant is characterized in that the surface is coated with a material selected from the group consisting of organosilanes, organic acids, organic polymers and the like. Examples of coating materials that can be used as the organosilane include vinylsilane, aminosilane and methacrylatesilane. In addition, materials that can be used as the organic acid include fatty acids, stearic acid and oleic acid, amino polysiloxane and the like. The kind of the coating material is not limited to the kind as long as it can be used within the scope of not impairing the object of the present invention. When only the inorganic flame retardant not surface-treated as the inorganic flame retardant is used, the modulus decreases and the elongation decreases, so that room temperature properties of the standard cannot be satisfied, and oil resistance cannot be exhibited due to oil absorption phenomenon and transition phenomenon of the flame retardant.

Inorganic flame retardant in the present invention includes 130 to 160 parts by weight relative to 100 parts by weight of the base resin. If it is less than 130 parts by weight, the oxygen index is not satisfactory for flame retardancy, and if it is more than 160 parts by weight, the modulus is lowered, the tensile strength is not extended to elongation at room temperature, the oil resistance is lowered, and the appearance is poor during extrusion.

In the present invention, a flame retardant aid is included to reduce the amount of the inorganic flame retardant and increase the flame retardancy. For example, silica-based, phosphorus-based flame retardant adjuvant or zinc borate, antimony trioxide, or the like is used alone or in combination, but is not limited to the above kind. Preferably, in the present invention, a flame retardant adjuvant includes zinc borate, antimony trioxide alone or in combination.

Flame retardant auxiliary agent in the present invention includes 10 to 25 parts by weight relative to 100 parts by weight of the base resin. More preferably 10 to 20 parts by weight. If it is 10 parts by weight or less, flame retardancy is not satisfied due to a decrease in the oxygen index, and when it is 25 parts by weight or more, the physical properties are lowered at room temperature.

In addition to the above components, the oil-resistant mud composition of the present invention may include other additives such as antioxidants, lubricants and hydrolysis agents commonly used in the art within the scope of not impairing the object of the present invention.

The antioxidant may be a phenol-based, amine-based antioxidant alone or mixed, but is not limited thereto. The lubricant may include, but is not limited to, stearic acid, polyethylene or silicone lubricant. Preferably the lubricant includes 1 to 2 parts by weight based on 100 parts by weight of the base resin. The hydrolysis agent is carbodiimide type and is not limited to powder or master batch form. Preferably the hydrolysis agent comprises 1 to 3 parts by weight relative to 100 parts by weight of the base resin.

The composition consisting of a combination of the base resin, inorganic flame retardant, flame retardant adjuvant and other additives including the polyester thermoplastic elastomer and the polyolefin incorporating the polar group of the present invention has the resistance to major oils and muds to meet international requirements. .

The composition of the present invention satisfies the requirements of IRM 902, IRM 903 industrial lubricants and oil-based mud (oil-based mud), the oil is more than 70% of tensile and elongation, 30% of volume and mass change, the mud is tensile · Satisfaction rate of more than 75% of elongation, less than 20% of volume change and less than 15% of mass change. In addition, flame retardants are mixed to meet IEC 60332-3 cat.A and can be extruded.

The present invention is a non-crosslinking type that does not require a crosslinking process, and when the crosslinking process is performed in order to satisfy oil resistance, additional problems of time and cost, and the problem of being pressed through the sheath extrusion operation such as Catalytic Continuous Vullcanization (CCV) Overcoming problems such as crosslinking problems and crosslinking efficiency can be excluded.

That is, the present invention does not require a crosslinking step and can provide an insulation composition that satisfies flame resistance, cold resistance, and in particular oil resistance and mud resistance.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example

<Preparation of oil resistant mud resistant composition>

In order to compare the performance of the electric wire according to the present invention, the compositions of Examples and Comparative Examples were prepared as shown in Table 1 and Table 2 below.

Description of Tables 1 and 2

Resin a: Polyester thermoplastic elastomer having MI 5.6 (g / 10min), Tm 150 ° C

Resin b: Vinyl acetate type resin which introduced maleic anhydride

Resin c: vinyl acetate resin (vinyl acetate content 28%)

Resin d: Polyester thermoplastic elastomer having MI 6.3 (g / 10min), Tm 147 ° C

Inorganic flame retardant a: Magnesium hydroxide coated with vinyl silane

Inorganic flame retardant b: surface untreated magnesium hydroxide

Flame Retardant A: Zinc Borate, Specific Gravity 2.7

Flame retardant adjuvant b: antimony trioxide, specific gravity 5.2

After kneading in an open roll according to the examples and comparative examples according to Tables 1 and 2 were molded under pressure and heating at 170 ° C. for 20 minutes, and specimens were prepared according to IEC 60811-1-1.

<Evaluation Method of Oil-Resistant Mud Mud Composition>

㉠ room temperature

  Tensile strength and elongation at room temperature were measured at a rate of 250 mm / min in accordance with IEC 60811-1-1. Evaluation criteria are based on tensile strength of 0.9kgf / mm2 or more and elongation of 120% or more according to IEC 60092-359.

㉡ heating characteristics

Tensile and elongation after heating were measured in the same manner as the standard for measuring room temperature characteristics after aging at 100 ° C. × 168 h in accordance with IEC 60092-359. Evaluation criteria are tensile residual rate and elongation residual rate of 75% or more.

㉢ oil resistance

 Tensile and elongation residual tests after oil resistance were prepared in the same size as the test specimens of room temperature properties and measured at a speed of 250 mm / min according to IEC 60811-1-1. The volume change and mass change after oil resistance were tested by preparing a 3.5 mm long 2.7 mm rectangular shape. The test temperature and test duration of the specific oils were based on the specifications.

The evaluation criteria and test temperatures and test periods for specific oils are shown in Table 2.

Description of Table 3

IRM 903: mineral oils, paraffinic and naphthenic hydrocarbons

Oil based-mud 1: Drilling fluid

Oil based-mud 2: polyester type mud, Accolade mud

사다리 vertical ladder flame retardant test

The vertical ladder flame retardant test is based on IEC 60092-3 cat.A. Evaluation criteria are 40 minutes of flame application time and less than 2.5m of 3.5m should be burned.

<Evaluation result of oil-resistant mud composition>

Table 4 is the results of the experiment for Table 1, Table 5 is the result of the experiment for Table 2.

Examples 1 to 6 showed satisfactory temperature and heating characteristics, three types of oil resistant mud, and flame retardant characteristics.

Comparative Example 1 is a basic resin not using a resin, Under normal temperature tensile strength and three types of oil resistance are not enough for tensile / elongation residual and volume / mass change.

Comparative Example 2 was 100 parts by weight of a MI 6.3 (g / 10min) polyester thermoplastic resin, which is less than room temperature tensile strength due to its small molecular weight.

Comparative Example 3 was a weight loss test of the flame retardant aid compared to Example 4, and did not satisfy the conditions in the vertical ladder flame retardancy test.

In Comparative Example 4, as compared with Example 4, the content of the flame retardant aid a increases, which hinders the role of the resin having oil resistance or the phenomenon of transition from the resin to the oil. Accordingly, the tensile strength was lower than room temperature due to the decrease in modulus, and the tensile residual elongation was lower than that of oil based-mud 1.

Comparative Example 5 is low in the content of TPEE resin having a high melting point, while increasing the content of maleic anhydride, which increases the compatibility of the resin with the flame retardant and the filler, the heating characteristics are lowered. In addition, the two oil-based muds did not satisfy all items.

Comparative Example 6, while lowering the ratio of the inorganic flame retardant was satisfactory oil and heating characteristics, but did not satisfy the conditions in the vertical ladder flame retardant test.

Comparative Example 7 was a test applied to 150 parts by weight of untreated magnesium hydroxide, which could not satisfy the room temperature properties of the standard due to the decrease in modulus and elongation, and the oil-resistant phenomenon and the transition phenomenon of the flame retardant did not satisfy all three conditions. .

Claims (11)

A polyester resin (TPEE) having a melt index (MI) of 4.5 to 6.0 g / 10 min is used as the base resin,
100 parts by weight of the base resin, 130 to 150 parts by weight of the surface-treated inorganic flame retardant or a mixture of the inorganic flame retardant and the surface-coated inorganic flame retardant and 10 to 25 parts by weight of flame retardant aids Oil resistant mud resistant composition. The oil-resistant mud resistant composition according to claim 1, wherein the inorganic flame retardant is a material selected from the group consisting of magnesium hydroxide, aluminum hydroxide, calcium hydroxide, huntite, hydromagnesite and mixtures thereof. The oil-resistant mud resistant composition according to claim 2, wherein the surface-treated inorganic flame retardant is coated with a material selected from the group consisting of organosilanes, organic acids, organic polymer materials, and the like. The oil-resistant mud-resistant composition according to claim 3, wherein the flame retardant adjuvant is one or a mixture of zinc borate and antimony trioxide. A base resin comprising 85% by weight or more of polyester thermoplastic elastomer (TPEE) having a melt index (MI) of 4.5 to 6.0 g / 10min and 15% by weight or less of a polyolefin having a polar group; And
130 to 150 parts by weight of a mixture of the inorganic flame retardant coated with the surface or the inorganic flame retardant coated with the surface and an inorganic flame retardant not coated with the surface and 10 to 25 parts by weight of the flame retardant aid based on 100 parts by weight of the basic resin; Oil resistant mud resistant composition comprising a. The oil-resistant mud resistant composition according to claim 5, wherein the polyolefin having a polar group is an ethylene-vinyl acetate copolymer having a maleic anhydride introduced therein. 7. The oil resistant mud resistant composition according to claim 6, wherein the inorganic flame retardant is a material selected from the group consisting of magnesium hydroxide, aluminum hydroxide, calcium hydroxide, huntite, hydromagnesite and mixtures thereof. The oil-resistant mud resistant composition according to claim 7, wherein the surface-treated inorganic flame retardant is coated with a material selected from the group consisting of organosilanes, organic acids, organic polymer materials, and the like. The oil-resistant mud-resistant composition according to claim 8, wherein the flame retardant adjuvant is any one or a mixture of zinc borate and antimony trioxide. A base resin comprising 85% by weight or more of polyester thermoplastic elastomer (TPEE) having a melt index (MI) of 4.5 to 6.0 g / 10min and 15% by weight or less of an ethylene-vinyl acetate copolymer introduced with maleic anhydride; And
130 to 150 parts by weight of an inorganic flame retardant, which is a mixture of magnesium hydroxide whose surface is coated with vinyl silane or magnesium hydroxide whose surface is coated with vinyl silane, and magnesium hydroxide which is not coated with the surface, based on 100 parts by weight of the basic resin. And 10 to 25 parts by weight of a flame retardant adjuvant consisting of any one or a mixture of zinc borate and antimony trioxide. Insulated wire provided with the sheath consisting of the oil-resistant mud-resistant composition of any one of Claims 1-10.