KR20090121937A - Flame-retardant polymer resin composition resistant to naphthalenic and aromatic group oils and electric cable manufactured from the same - Google Patents

Abstract

PURPOSE: A flame-retardant polymer resin composition resistant to naphthalenic and aromatic group oils and an electric cable manufactured from the same are provided to extend service life, to prevent accidents which can be generated due to aging according to the reaction with oil. CONSTITUTION: A flame-retardant polymer resin composition resistant to naphthalenic and aromatic group oils comprises a polyvinylchloride(PVC) base resin 100 parts by weight, a high molecular weight plasticizer 30-80 parts by weight with a polar group, a flame retardant 10 - 150 parts by weight, and a stabilizer of 1 - 15 parts by weight. The viscosity of the high molecular weight plasticizer is 40 cPs or more at 25°C.

Description

Polymer flame retardant composition having resistance to naphthalene-based and aromatic oils and an electric wire manufactured using the same

The present invention relates to an oil resistant flame retardant resin composition having resistance to naphthalene-based and aromatic oils and an oil resistant flame retardant cable manufactured using the same. More specifically, the present invention relates to an oil-resistant flame retardant resin composition prepared by introducing a polymer plasticizer having high polarity and compatibility with the base resin in a polyvinyl chloride base resin to impart oil resistance, and an oil-resistant flame-retardant cable manufactured using the same. will be.

A typical power cable structure is a cross-linked polyethylene insulation layer 30 surrounding the conductor layer 10 at the center as shown in FIG. 1, and the insulation layer 30 is again replaced by the International Elecrotechnical Commission (IEC). ) IEC 60332-3 Cat. A sheath layer 40 of polyvinyl chloride resin material having a flame retardant grade of C is enclosed.

 In general, various oils are produced in oil refineries, petroleum refining plants, or chemical manufacturing plants. In the process, oils exposed to the outside are made of polyvinyl chloride (PVC). It can come in contact with the interior and exterior materials. The polymer flame retardant resin layer prepared using polyvinyl chloride resin as a main material, such as the sheath layer 40, has a plasticizer present in the polymer flame retardant resin composition at the contact interface between these materials when contact with naphthalene-based oil or aromatic oil occurs. The physical properties of the flame retardant resin eluted based on the polyvinyl chloride resin may be lowered. In particular, in the case of a polyvinyl chloride resin composition to which a phthalate-based plasticizer is generally used, elution of the plasticizer occurs severely, which causes a rapid decrease in elongation. In addition, when specific temperature conditions related to these physical property changes are appropriately formed, aging of a product manufactured using polyvinyl chloride resin as a main material proceeds. Due to this aging phenomenon, various physical conditions, for example, mechanical properties such as tensile strength and elongation can be drastically lowered.

In order to prevent naphthalene-based or aromatic oils from coming into direct contact with the wire sheath body or internal / exterior materials manufactured using PVC resin as a main material, the contact method is minimized by wrapping them in a special film from the outside or laying wires in a pipe. Although this is being used, this is because the additional installation of the protective member is greatly reduced work efficiency, it is not desirable in many economic aspects, such as the time and expense required for the related work.

The technical problem to be solved by the present invention may occur when the flame-retardant wire sheath body or the interior and exterior materials for the electric power made of polyvinyl chloride as the main material is exposed to naphthalene oil or aromatic oil in the environment of chemical plants and refineries, etc. It is to improve oil resistance so as to prevent deterioration of physical properties. The present invention provides an oil resistant flame retardant resin composition for such a problem.

In order to achieve the object of the present invention described above, the polymer resin composition of the present invention having resistance to naphthalene-based oil or aromatic oil has a polyvinyl chloride (PVC) base resin and a polyvinyl chloride base resin weight of 100 parts by weight. And 30 to 80 parts by weight of a high molecular weight plasticizer having a polar group, 10 to 150 parts by weight of a flame retardant and 1 to 15 parts by weight of a stabilizer.

In the present invention, the high molecular weight plasticizer is preferably at least one ester polymer selected from the group consisting of adipic acid-based polyesters, citric acid-based esters and mixed alcohol esters.

The plasticizer used in the oil-resistant flame retardant resin composition of the present invention may be a mixed plasticizer of the ester-based polymer and a non-high molecular weight plasticizer, wherein the mixed plasticizer is used in an amount of 30 to 80 parts by weight based on 100 parts by weight of the base resin, and a mixed plasticizer. It is preferable that the specific gravity of the said ester type polymer is at least 20 weight%, and a non-polymeric plasticizer is a phthalic acid plasticizer or a melic acid plasticizer.

Since the oil-resistant flame retardant resin composition of the present invention uses a high molecular weight plasticizer having poor compatibility with naphthalene oil or aromatic oil, the plasticizer cannot be eluted by reaction with oil at high temperature even when exposed to naphthalene or aromatic oil. Minimizing and reducing the reactivity of the polyvinyl chloride base resin and oil is excellent in preventing the mechanical properties of the flame retardant resin composition. The flame retardancy is also good or comparable to that of the general flame retardant resin composition. Oil-resistant flame retardant resin composition of the present invention can extend the service life when used as a power, control, instrumentation wire or interior materials with high exposure frequency to naphthalene oil or aromatic oil, aging phenomenon due to reaction with oil This can prevent various safety accidents that may occur, and lower the incidence rate.

Hereinafter, the present invention will be described in more detail with reference to the following examples and accompanying drawings. However, it is apparent that the present invention may be modified in various equivalent embodiments in addition to the embodiments according to the embodiments and the accompanying drawings, and thus the technical scope of the present invention is not limited to the embodiments and the accompanying drawings. do. Embodiment of the present invention is merely an example to help the average skilled person in the art.

The oil resistant flame retardant resin composition of the present invention includes a polyvinyl chloride (PVC) base resin, a high molecular weight plasticizer, a flame retardant, and a stabilizer. Polyvinyl chloride, which is a basic resin of the present invention, is a straight chain-like polymer that is a kind of thermoplastic resin that can be melted and reshaped when heated.

The oil-resistant flame retardant resin composition of the present invention contains a plasticizer which provides plasticity to the rigid polymer resin as an essential component. The plasticizer is composed of a part (polar part) that interacts with the polymer chain and a part (non-polar part) that facilitates the movement between the polymer chains by extending the distance between the polymer chains without interacting with the polymer chains. In the present invention, the plasticizer enters into the gap formed between the PVC polymer chains by heat, causing an interaction between the polarization portion of the polymer chain and the polar portion of the plasticizer.

The plasticizer for oil-resistant flame retardant resin compositions of the present invention is characterized by being a high molecular weight plasticizer having a polar group. High molecular weight plasticizers having polar groups have low compatibility with polyvinyl chloride resins, but have low solubility in nonpolar hydrocarbon solvents such as naphthalene or aromatic oils. The high molecular weight plasticizer used in the present invention is 40 cps or more at 25 ° C. The high molecular weight plasticizer having a viscosity of 40 cps or more at 25 ° C is preferable, and more preferably, the viscosity is 90 cps or more. Such high molecular weight plasticizers are not essential, but are suitable with specific gravity at 25 ° C. of about 1.0 to about 1.2. When the high molecular weight plasticizer of the present invention is less than 40 cps at 25 ° C., compatibility with naphthalene-based or aliphatic oils increases, so that the plasticizer may elute from the base resin when the polymer resin is exposed to oil, and the viscosity range is 40 cPs. If less than the above results, mechanical properties after infiltration, in particular, the tensile residual ratio and elongation residual ratio is a disadvantage that is sharply lowered.

Specific examples of the high molecular weight plasticizer of the present invention include, but are not limited to, the following examples, as non-phthalate plasticizers, particularly adipic acid polyesters, citric acid esters, mixed alcohol esters. and ester polymers such as (mixed alcohol ester). The high molecular weight plasticizer of the present invention is excellent in resistance to the oil because it is incompatible with naphthalene-based oils or aromatic oils, and does not depart from the polyvinyl chloride base resin even when the polymer resin is exposed to the oil.

The plasticizer used in the composition of the present invention may be composed of only the polymeric plasticizer (s) satisfying the above molecular weight and viscosity standards, or may be composed of a mixture (mixed plasticizer) of the ester-based polymer and a general plasticizer (non-high molecular weight plasticizer). In the case of the mixture of the ester polymer and the general plasticizer, the oil-resistant effect by the polymer plasticizer is exhibited when the content of the ester polymer is 20% or more by weight in the plasticizer mixture.

Non-molecular weight plasticizers that can be mixed with the ester polymers are preferably phthalate-based or mellitate-based plasticizers. As a specific example, the phthalate plasticizer, DINP (Diisonony Phthalate), DIDP (Diisodecyl Phthalate), DUP (Diundecyl phthalate), Dibutyl phthalate (DBP), Diisobutyl phthalate (DIBP), Disoothyl phthalate (DIOP), C9-based phthalic acid plasticizer, DTDP (Ditridecyl phthalate) and BBP (Butyl Benzyl Phthalate) is preferably any one or more materials selected from the above, Is preferably one or more materials selected from Tri-2-ethylhexyl Trimellitate (TOTM), Tri-2-ethylhexyl Trimellitate (TOTM), Tri-isononyl Trimellitate (TINTM), and Tri-isodecyl Trimellitate (TIDTM).

In the present invention, a plasticizer containing a high molecular weight plasticizer (both in case of a plasticizer only in a high molecular weight plasticizer and a mixture with a general plasticizer) is preferably 30 to 80 parts by weight based on 100 parts by weight of the polyvinyl chloride base resin. When the plasticizer content is less than 30 parts by weight, the plasticizing effect on the PVC, a role of the plasticizer, is lowered, thereby increasing the hardness of the composition, thereby lowering the flexibility and the extrudability of the extrusion. . On the other hand, when the plasticizer content exceeds 80 parts by weight, not only the tensile strength of the mechanical properties is lowered and the heat resistance is lowered, but also the flame retardancy required in the case of the polymer composition of the present invention is not preferable. In addition, when an excessive amount of plasticizer is used, a part of the plasticizer in the polymer flame retardant composition is inevitably eluted when prolonged exposure to naphthalene-based oil or aromatic oil at a high temperature. When the plasticizer is eluted, an elongation rate is drastically reduced. It is also not desirable to maintain stable physical properties.

In the present invention, the stabilizer is included in 1 to 15 parts by weight based on 100 parts by weight of the base resin. The stabilizer is preferably any one selected from lead-based, lead-free, epoxy stearate and metal soap-based materials or a mixture of two or more optionally selected from these. If the stabilizer is less than the lower limit of the content, it is not preferable because the heat resistance of the material is rapidly lowered to satisfy the required properties. On the other hand, when the stabilizer exceeds the upper limit of the content is not preferable because the effect on the heat resistance improvement due to excessive use is not expected.

The resin composition of the present invention contains 10 to 150 parts by weight of a flame retardant based on 100 parts by weight of the base resin. The flame retardant is preferably any one selected from the group consisting of metal hydroxides such as aluminum hydroxide, magnesium hydroxide, magnesium hydroxide, and metal hydroxides and hydrotalcite, or a mixture of two or more selected arbitrarily. If the flame retardant does not meet the lower limit of the content, it is not preferable because the flame retardancy of the oxygen index and the cable, which are required flame retardant properties, are not sufficiently secured, and if the flame retardant exceeds the upper limit, the improvement of the flame retardancy according to the amount of use is sufficient. Although it can be expected, the addition of excess inorganic material is not preferred because of poor extrusion processability and lowered tensile strength, elongation and heat resistance.

The oil-resistant flame retardant resin composition of the present invention may include a filler in an amount of 3 to 100 parts by weight based on 100 parts by weight of the base resin in addition to the base resin, stabilizer, flame retardant, and high molecular weight plasticizer. The filler is preferably a single substance of any one selected from calcium carbonate, clay and talc or a mixture of two or more optionally selected thereof. Such a filler is an inexpensive material and has an effect of saving cost by increasing the volume of the oil-resistant flame retardant resin composition of the present invention. If the filler is less than the lower limit of the content, the cost saving effect of applying a low-cost filler is insignificant, and if the filler exceeds the upper limit of the filler content, the tensile strength and elongation rate are drastically lowered due to the excess of inorganic material, and compression processing is performed. The property is also lowered, which is not preferable.

The resin composition of the present invention may further include a flame retardant aid in addition to the flame retardant in order to further increase the flame retardancy. The flame retardant aid is preferably any one selected from the group consisting of antimony-based compounds, boron-based compounds, tin-based compounds and molybdenum-based compounds or a mixture of two or more selected arbitrarily. In the flame retardant aid used in the present invention, the antimony compound is antimony trioxide, and the tin compound is more preferably a zinc hydroxide compound or a zinc tin compound.

The present invention also provides a wire having a sheath or an internal and external material manufactured using the oil-resistant flame retardant resin composition. Since the sheath of the electric wire or the internal / exterior materials have a high risk of exposure to naphthalene-based oils or aromatic oils, it is highly preferable to use the oil-resistant flame retardant resin composition of the present invention in manufacturing. The sheath material for wires, the internal and external materials, including the oil-resistant flame retardant resin composition of the present invention, can be easily manufactured as a power cable having an insulating layer material, a conductive layer, an internal and external semiconducting layer, and a sheath through a single screw extruder for wire production.

2 is a cross-sectional view of an electric wire having a sheath layer manufactured using the oil-resistant flame retardant resin composition of the present invention. The wire of FIG. 2 includes a conductor layer 50 through which an inner current flows, an inner semiconducting layer 61 surrounding the conductor layer 50, an insulating layer 70 surrounding the inner semiconducting layer 61, and the insulating layer. An outer semiconducting layer 62 surrounding 70 and a sheath 80 surrounding the outer semiconducting layer 62 and made from an oil resistant flame retardant resin of the present invention. In Fig. 2, the sheath layer 80 made of the resin composition of the present invention is shown in dark color. The sheath layer 80 prepared from the oil-resistant flame retardant resin composition of the present invention or the wire having internal and external materials has excellent resistance to naphthalene and aromatic oils.

The present invention will be described in more detail with reference to the following Examples. The embodiments of the present invention are provided by way of illustration in order to explain the present invention to the average skilled in the art more fully, and the scope of the present invention should not be construed as being limited to the embodiments described below. It will be apparent to those skilled in the art that the present invention may be modified in various other equivalent forms besides the embodiments described in the Examples below.

Example compositions according to the present invention having a high molecular weight plasticizer and a comparative example composition having only a general plasticizer were prepared as in Table 1 below to compare physical properties.

Example (1-6) and Of Comparative Example (1-3)  Composition and Manufacturing

The flame retardant resin compositions of the compositions shown in Table 1 below were kneaded in an openron of about 130 ° C., and then molded in a press at 170 ° C. for 5 minutes, and then test specimens of the wire sheath body for physical property measurement were prepared. In this example, adipic acid polyester was used as Olicizer-20N of Aekyung Emulsifier, Citrocizer-A of the same company was used as citric acid ester, and Pyrocizer of the same company was used as mixed alcohol ester.

division Example (1-6) Comparative Example (1-3) One 2 3 4 5 6 One 2 3 Polyvinyl chloride 100 100 100 100 100 100 100 100 100 Adipic acid polyester 50 25 25 25 Citric acid ester 50 Mixed alcohol ester 50 DINP 25 50 DIDP 25 50 TOTM 25 50 Lead-based stabilizer 5 5 5 5 5 5 5 5 5 Calcium Carbonate (Filling Agent) 50 50 50 50 50 50 50 50 50 Magnesium Hydroxide 30 30 30 30 30 30 Antimony trioxide 15 15 15 15 15 15 15 15 15

Physical characterization

For each of the test specimens prepared as described above, the following tests were carried out to determine their respective physical properties, such as tensile strength and elongation rate as the standard temperature properties, tensile strength and elongation rate as the heat-based property criteria, heating loss standard, oxygen index and Flame retardancy was measured and evaluated according to each criterion, and the results are shown in Table 2 below.

(1) Room temperature standard

Tensile strength should be more than 1.25 kgf / mm2 and elongation should be more than 150% when measured by tensile speed 500mm / min according to IEC 60811-1-1.

(2) Property standard after heating

After leaving the specimen at a temperature of 100 ° C. for 168 hours, the rate of change in tensile strength and elongation should be greater than 70%.

(3) heating loss standard

After leaving the specimen at a temperature of 100 ° C. for 168 hours, the weight lost after heating to the unit surface area of the specimen should be 1.5 mg / cm 2 or less.

(4) Characteristics criteria after oil resistance 1

After the specimen was precipitated for 4 hours at a temperature of 70 ° C. in ASTM # 2 or IRM 902 oil, which is naphthalene oil, when the change in tensile strength and elongation was measured, the tensile residual ratio was 60% or more and the elongation residual value was 60% or more. Should be indicated.

(5) Characteristics criteria after oil resistance 2

After the specimen was precipitated in an ASTM # 3 or IRM 903 oil, which is an aromatic oil, at a temperature of 70 ° C. for 4 hours, when the tensile strength and elongation change rate were measured, the tensile residual ratio was 60% or more, and the elongation residual value was 60% or more. Should be indicated.

(6) Oxygen index measurement

Flame retardancy of the material is measured according to ASTM D 2863, and its oxygen index should be at least 28%.

(7) flame retardancy test

Tested according to IEC 332-3 Cat.C Flame Retardant Test Specification

division Example (1-6) Comparative Example (1-3) One 2 3 4 5 6 One 2 3 Room temperature Tensile Strength? BR /> (kg / mm2) 1.6 1.71 1.54 1.63 1.72 1.74 1.8 2.1 1.92 Elongation (%) 212 207 278 195 201 223 284 225 216 heating Tensile Residual (%) 99 89 87 93 94 91 58 41 67 Elongation Retention (%) 82 85 90 81 89 88 34 53 46 Loss of heating (mg / ㎠) 1.12 1.07 1.17 1.22 0.99 0.91 1.7 1.5 1.3 Oilproof 1 Tensile residual 104 84 80 89 86 87 77 78 77 Elongation 103 68 72 73 82 80 50 47 48 Oilproof 2 Tensile residual 97 75 78 87 87 89 82 69 72 Elongation 92 62 68 74 77 78 54 48 45 Oxygen index 35 34 35 35 36 35.5 25 26 25 Flame retardant pass pass pass pass pass pass fail fail fail

As can be seen through Table 2, in the case of Comparative Example 1, after adding the non-polymeric general plasticizer to the polyvinyl chloride resin, the durability of the naphthalene oil or the aromatic oil was evaluated, and the tensile residual and elongation residual after precipitation. This phenomenon is rapidly lowered. Meanwhile, in the case of Comparative Example 2, a general plasticizer having a higher molecular weight was applied to the same resin as Comparative Example 1, but it was found that durability of the oil was not secured. In the case of Comparative Example 3, naphthalene oil or aromatic oil Plasticizers having high heat resistance were applied for the purpose of improving durability against the oil, but this also shows that the durability against the oil is poor.

On the contrary, in the case of Examples 1 to 6 according to the present invention, it can be seen that excellent oil resistance properties for naphthalene oil and aromatic oil. In addition, the heating loss measured for the specimens according to all the examples (1-6) satisfies the reference value of 1.5 mg / cm 2 or less, and in all the examples (1-6), the reference value for the oxygen index It can be confirmed that it is satisfied. In addition, the example specimens using the high molecular weight plasticizer of the present invention also showed satisfactory flame retardancy. This shows that deterioration of flame retardant properties does not occur due to the addition of a high molecular weight plasticizer for improving oil resistance.

That is, as can be seen from the characteristics evaluation results of Comparative Examples 1 to 3, when applying various conventional non-high molecular weight plasticizer to the polyvinyl chloride resin, it was not possible to secure the resistance to naphthalene oil or aromatic oil, It was found that the reliability of the cable for a long time could not be secured.

Through the above results, the oil-resistant flame retardant resin composition according to the present invention and the electric wire manufactured using the same have superior or at least comparable effects to the flame retardant resins of the prior art in terms of flame resistance as well as excellent resistance to naphthalene oil or aromatic oil. It can be expected to indicate.

As described above, optimal embodiments of the present invention have been disclosed. Although specific terms have been used in the specification including this embodiment, it is used only for the purpose of describing the invention in detail to those skilled in the art and used to limit the meaning or limit the scope of the invention described in the claims. It is not.

1 is a cross-sectional view illustrating a typical power cable consisting of a conductor layer, an inner semiconducting layer, an outer semiconducting layer, an insulating layer and a sheath.

2 is a cross-sectional view of a power cable having a sheath layer made of the oil-resistant flame retardant resin composition of the present invention. The power cable further comprises a conductor layer, an inner semiconducting layer, an outer semiconducting layer, and an insulating layer.

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

10 ... conductor layer 21 ... inside semiconducting layer

22 External semiconducting layer 30 Insulating layer

40 ... sheath

50 ... conductor layer 61 ... inside semiconducting layer

62.External semiconducting layer 70 ... Insulating layer

80. A Sheath Prepared from the Oil Resistant Flame Retardant Resin Composition of the Present Invention

Claims (7)

100 parts by weight of a polyvinyl chloride (PVC) base resin; High molecular weight plasticizers having 30 to 80 parts by weight of a polar group; 10 to 150 parts by weight of flame retardant; And Containing 1 to 15 parts by weight of a stabilizer, The high molecular weight plasticizer has a viscosity of at least 40 cPs at 25 ℃ oil-resistant flame-retardant resin composition. The method according to claim 1, wherein the high molecular weight plasticizer, Oil-resistant flame retardant resin composition, characterized in that any one or more ester polymer selected from the group consisting of adipic acid-based polyesters, citric acid esters and mixed alcohol esters. 100 parts by weight of a polyvinyl chloride (PVC) base resin; 30 to 80 parts by weight of mixed plasticizer; 10 to 150 parts by weight of flame retardant; And Containing 1 to 15 parts by weight of a stabilizer, The mixed plasticizer is a mixture of a high molecular weight plasticizer and a non-high molecular weight plasticizer containing at least 20% by weight of a high molecular weight plasticizer selected from the ester-based polymer group of claim 2. The method of claim 3, The non-molecular weight plasticizer is an oil-resistant flame-retardant resin composition, characterized in that the phthalate (methate) or mellitate (mellitate). The method according to claim 1 or 3, The oil-resistant flame retardant resin composition further comprises 3 to 100 parts by weight of the filler based on 100 parts by weight of the polyvinyl chloride base resin. The method of claim 2, The high molecular weight plasticizer has a viscosity of at least 40 cPs at 25 ℃ oil-resistant flame-retardant resin composition. Optionally include internal and external materials for wires, A conductor layer 50 positioned therein and through which a current flows; An inner semiconducting layer 61 surrounding the conductor layer 50; An insulating layer 70 surrounding the inner semiconducting layer 61; An outer semiconducting layer 62 surrounding the insulating layer 70; And In the electric wire comprising a sheath 80 surrounding the outer semiconducting layer 62, At least one of the sheath layer (80) and the inner, outer material for the electric wire is made from the oil-resistant flame retardant resin composition of claim 1 for the electric cable.

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