KR20070102155A - Composition of polyamide resin for band cable - Google Patents

Abstract

A polyamide resin composition for a band cable is provided to ensure long-term heat resistance and flexibility comparable to conventional resin compositions even without additional processes. A polyamide resin composition for a band cable comprises (1) 100 parts by weight of a polyamide resin, (2) 0.2-0.8 parts by weight of a phosphorus-based compound represented by the formula 1, (3) 0.2-0.8 parts by weight of a fluorine-based compound represented by the formula 2: (-CF2-CF2)n; (4) 4-9 parts by weight of a sulfonamide-based plasticizer and (5) 8-15 parts by weight of an impact resistant containing a maleic anhydride-grafted ethylene-propylene-diene terpolymer. In the formulae 1 and 2, Ar1 and Ar2 are a substituted or unsubstituted aryl group having 6-7 carbon atoms, in which the aryl substituent is selected from hydrogen and a C1-C6 alkyl group, R1 and R2 is hydrogen or a C1-C6 alkyl group and n is an integer of 2-100.

Description

Composition of polyamide resin for band cable

The present invention relates to a polyamide resin composition for a band cable, and more specifically, to a polyamide resin, a specific phosphorus compound, a fluorine compound, a plasticizer and an impact agent are mixed in a certain component ratio, and the specific phosphorus compound and the fluorine compound The present invention relates to a polyamide resin composition which is particularly useful for automobile band cables because of its mixed use, which has improved physical properties and flexibility compared to conventional polyamide resin compositions and at the same time improves long-term heat resistance and flexibility without an additional secondary hydrothermal treatment process. .

In general, polyamide resin composition has better heat resistance and mechanical properties than general-purpose resins such as olefin resins, and has excellent electrical, friction and abrasion properties along with properties such as oil resistance and chemical resistance among chemical properties, and reinforces various additives. It is used in parts of the automotive industry, electrical, electronics, general industry, etc. to obtain a composition having a variety of functions through the provision of various properties,

However, polyamide resins require strength with moderate flexibility in order to be applied as a material for band cables. In more detail, in order to bundle the wires, physical properties such as flexibility are required for continuous operational efficiency, and a bending strength (Lance holding force) that can withstand the wire-bundling material without being released by external force is also required.

There are many ways to show flexibility, which is the basic characteristic of band cable materials. Typical flexibility is to add plasticizer only, impact agent only, and mix and add plasticizer and impact agent. And can have flexural strength and impact strength. However, the use of only such additive components results in poor long-term heat resistance, and also requires a hot water treatment process (Annealing, usually 60 to 80 ° C. × 20 to 30 minutes) in the production process, making it difficult to obtain productivity improvement. There is this.

In other words, the polyamide resin for band cable is used for the interior and exterior of automobiles, and thus is subject to environmentally sensitive changes.In particular, in order to bundle electric wires around the engine, physical properties are degraded due to temperature rise and decomposition of the resin by moisture in a high temperature and high humidity environment. Since the long-term heat, long-term heat and humidity characteristics with respect to heat is required, in particular to improve productivity, the annealing process should be omitted. However, the existing band cable used for interior and exterior of automobiles is generally made of nylon-66 or copolyamide, but lacks sufficient flexibility as necessary to absorb moisture by secondary annealing process with water. This method is time consuming even in the productivity of the product, especially the long-term heat resistance due to the moisture absorbed by moisture, and due to the initial heat deformation temperature, the major disadvantages such as deterioration of physical properties due to heat during long-term commercial use there was.

As mentioned above, the addition of moisture, a plasticizer, or an impact agent increases the flexibility of the resin, but causes disadvantages in long-term heat resistance and low productivity.

Looking at the related literature, first, in order to improve the flexibility of the polyamide resin by adding only a plasticizer, US Pat. Nos. 6,384,115 and 6,239,216 and 5,032,633 disclose techniques for adding plasticizers of sulfonamide and benzoate derivatives. The long-term heat resistance and initial heat deformation temperature drop, productivity and impact characteristics are inferior.

U.S. Patent No. 6,348,563 improves flexibility by using hydroxybenzoic ester plasticizers in polyamide 11 and polyamide 12 resins, but it is inferior to polyamide 6 in terms of long-term heat resistance, lower initial thermal deformation temperature, lower productivity, and higher rigidity. There are disadvantages.

Korean Patent Laid-Open Publication No. 1999-0029902 discloses a soft and brittle transition temperature by using plasticizers of sulfonamide derivatives in copolyamides of polyamide 11 and polyamide 12 resins for the use of flexible tubes for transporting fuel type liquids. Lower and improved technology is known, but there are disadvantages in that it is inferior to polyamide 6 in long-term heat resistance, lower initial heat deformation temperature, lower productivity and rigidity.

In Korean Patent Laid-Open No. 1999-0031363, a polyamide having improved heat resistance was prepared by adding hexamethylene diamine, a phosphorus-based nucleating agent, to a copolyamide polymerized with a salt composed of hexamethylene diamine and dicarboxylic acid and a C6-C12 lactam. However, a technique for improving flexibility by adding butylbenzene sulfonamide as a softening agent is known, but it is insufficient in impact strength, high in price, and insufficient in productivity for applications requiring impact properties, which are basic properties required for band cable materials. There is this.

Next, by adding only an impact resistant agent, Korean Patent Laid-Open Publication No. 2002-0046389 added ethylene propylene rubber to a polypropylene resin to improve flexibility and to improve heat resistance, which is a disadvantage of general purpose resins by excessive talc filling, Compared with the amide resin, there are shortcomings such as long-term heat resistance and initial heat deformation temperature reduction, and the impact strength and elongation are deteriorated, and the density due to excessive talc is increased, thereby increasing the weight of the molded article.

Korean Patent Laid-Open Publication No. 1990-0018273 discloses a rubber in which a styrene-acrylonitrile copolymer is grafted onto ethylene propylene rubber to polyamide resin, or an ethylene propylene diene monomer rubber (grafted with maleic hydride) (EPDM-g). A technique of improving flexibility and impact properties by using an impact agent of -MA) is known, but there are disadvantages in that productivity is low due to a lack of long-term heat resistance, an initial heat deformation temperature decrease, and a low crystallization rate.

Thus, in order to improve the heat resistance of polyamide resin, Korean Patent Publication No. 2001-0011821 adds a thermoplastic rubber elastomer and a propionate copolymer of olefins grafted with unsaturated carboxylic acid to a polyamide resin to improve impact resistance and strength. However, lack of long-term heat resistance, initial thermal deformation temperature drop, flexibility and elongation are not applicable to the bend cable material.

Next, a plasticizer and an impact agent are mixed and used. In Korean Patent Laid-Open Publication No. 1998-0048236, a technique of improving flexibility by adding a benzenesulfonamide derivative and ethylene propylene diene rubber to a polyamide resin for use as a pipe or tube. Although it is known, there are disadvantages in long-term heat resistance and initial heat deformation temperature decrease, productivity is low.

Korean Patent Laid-Open Publication Nos. 2002-0058165 and 2002-0010356 describe the use of ethylene propylene diene monomer rubber (EPDM-g-MA) impactors and sulfones grafted with maleic anhydride to polyamide resins for automotive interior and exterior components. Techniques for improving flexibility using amide-based plasticizers are known, but there are disadvantages in that initial heat deformation temperature is lowered, long-term heat resistance and productivity are lowered. Korean Patent Publication No. 2002-0056468 discloses flexibility and flexibility by using ethylene propylene diene monomer rubber (EPDM-g-MA) and sulfonamide-based plasticizers grafted with maleic anhydride on polyamide resin as a fuel filter housing. Techniques for improving the flowability are known, but there is a shortage of long-term heat resistance, initial heat deformation temperature reduction production.

Korean Patent Publication No. 2001-0014337 discloses ethylene propylene diene monomer rubber (EPDM-g-) grafted with maleic anhydride to polyamide resin as a material for pipe or conduit for transporting fluids such as fuel in a flammable engine. Impact resistance and flexibility were added by adding the impact resistant material of MA) and butyl benzene sulfonamide (N-BBSA or N-butyl benzene sulfonamide) plasticizer, but there are short-term heat resistance and weak strength.

As described above, the conventionally known literature has a long-term heat resistance, which is an important function for use in automobile interior and exterior, although sufficient flexibility and impact strength that can be used as a band cable material are satisfied when a plasticizer and an impact agent are mixed. Since the hot water treatment process (Annealing) must be passed, the productivity improvement was not satisfied at the same time. In order to improve this, there is also a method of adding a long-term heat-resistant agent, but it is difficult to secure long-term heat resistance only with long-term heat-resistant and there is a disadvantage that productivity does not increase.

A method of securing long-term heat resistance and improving productivity at the same time is a method of injecting a nucleating agent. Nucleating agents are largely divided into organic nucleating agents and inorganic nucleating agents, and organic nucleating agents such as sorbitol can increase the rate of crystallization but are poor in heat resistance.

Accordingly, the present inventors have tried to develop a material that can simultaneously express physical properties such as flexibility and long-term heat resistance of polyamide resin. As a result, a phosphorus compound and a fluorine compound are mixed in a polyamide resin composition containing a conventional plasticizer and an impact agent at a constant ratio, and radicals and unstable hydroperoxides (hydroperoxide, ROOH) generated during the thermal decomposition reaction due to the steric hindrance effect of the phosphorus compound The polyamide-based resin composition prepared by preventing the formation of the amide compound and giving the flexibility to the fluorine-based compound not only improves long-term heat resistance but also has the same or more flexibility as the conventional one without additional annealing. To complete.

Accordingly, an object of the present invention is to provide a polyamide resin composition having a long-term heat resistance and flexibility equal to or higher than that of the prior art without using an additional step by using a specific phosphorus compound and a fluorine compound.

The present invention (1) 100 parts by weight of polyamide resin,

(2) 0.2 to 0.8 parts by weight of a phosphorus compound represented by the following formula (1),

(3) 0.2 to 0.8 parts by weight of a fluorine compound represented by the following formula (2),

(4) 4 to 9 parts by weight of a sulfonamide plasticizer, and

(5) The polyamide resin composition comprising 8 to 15 parts by weight of an ethylene-propylene-diene terpolymer impact agent to which maleic anhydride is grafted is characterized.

[Formula 1]

In Formula 1, Ar ₁ And Ar ₂ is a substituted or unsubstituted aryl group having 6 to 7 carbon atoms, respectively, wherein the aryl substituent is selected from a hydrogen atom and an alkyl group having ₁ to ₆ carbon atoms, and R ₁ and R ₂ are each hydrogen or C ₁ to C ₆ It is an alkyl group.

[Formula 2]

(-CF ₂ -CF _2- ) _n

In Chemical Formula 2, n represents an integer of 2 to 100.

Referring to the present invention in more detail as follows.

In order to secure long-term heat resistance and flexibility in which the polyamide resin composition used for automobile interior and exterior is important, structural effects of steric hindrance are large so that radicals and unstable radicals generated when a pyrolysis reaction is performed in the polyamide resin A mixture of a phosphorus compound represented by Chemical Formula 1 and a fluorine compound represented by Chemical Formula 2 having flexible properties by preventing formation of hydroperoxide (ROOH), which is a structure, and exhibiting strong thermal or hydrolytic properties, By injection molding, the present invention relates to a polyamide resin composition for a band cable having an equivalent or longer term heat resistance and flexibility without additional heat treatment processes conventionally used.

Looking at the components used in the polyamide resin composition for a band cable of the present invention in more detail as follows.

First, polyamide resins are conventional resins commonly used in the art, and there are no particular restrictions on their selection. Preferably, the polyamide resin has a relative viscosity ranging from 2.5 to 3.5 (at 20 ° C., 1 g of a resin component in 100 ml of 96% sulfuric acid), and the relative viscosity is less than 2.5 and has rigidity, impact strength, and heat resistance. In case of exceeding 3.5, excessive frictional heat between the screw and the resin in the molding machine is generated, and the resin is decomposed or high pressure is required for molding, which causes excessive pressure on the molding machine and the mold, making injection molding difficult. It is desirable to maintain the above range.

However, in the polyamide resin constituting the resin component of the present invention, polyamide 6 and polyamide 66 may be used alone or in combination thereof. However, in the case of using these alone, it is more preferable to use polyamide 6 and polyamide 66 in the present invention because the flexibility may be slightly reduced due to the cost increase or the increase of excessive crystallization region.

In the case where the polyamides 6 and 66 are mixed and used, they are each used in a weight ratio of 30 to 70:30 to 70, and preferably in a 50:50 weight ratio, respectively. The use of the polyamide 6 is effective in improving the bonding force, the fastening force, etc. when the band cable is manufactured when properly used as a component involved in improving the flexibility properties of the band cable. If the amount of polyamide 6 is less than 30 weight ratio, the flexibility for the band cable is too high, and thus, the bonding strength and the fastening force are insufficient, and when the amount of the polyamide 6 exceeds 70 weight ratio, the flexibility for the band cable is improved. Is slightly lowered, it is preferable to use the appropriate amount as described above.

In the present invention, in order to reinforce long-term heat resistance which is resistant to heat of the band cable used for automobile interior and exterior, the phosphorus-based compound represented by Chemical Formula 1 having a characteristic of preventing decomposition by long-term heat is used. Preference is given to using, 2'-methylene bis- (4,6-di-tert-butyl phenyl) phosphate.

The phosphorus compound is used in an amount of 0.2 to 0.8 parts by weight, preferably 0.3 to 0.5 parts by weight, based on 100 parts by weight of a polyamide resin, and if less than 0.2 parts by weight, long-term heat resistance and initial heat deformation temperature improving effect cannot be obtained simultaneously. When the amount exceeds 0.8 parts by weight, the result is insignificant in terms of the same heat resistance effect as the case of using less than the above range.

In addition, the present invention uses a fluorine-based compound represented by the formula (2) having a flexible feature in order to reinforce the flexibility of the band cable, specifically the trade name A3800, (Mitsubishi Rayon: manufacturer) can be used. The fluorine-based compound is a hydrocarbon-based organic compound in which fluorine is present at each terminal, and they are excellent in compatibility, and are also highly reactive with polyamide so that they are well melted and kneaded well. There is.

The fluorine-based compound is used in an amount of 0.2 to 0.8 parts by weight, preferably 0.3 to 0.5 parts by weight, based on 100 parts by weight of polyamide resin. There is a disadvantage in that the bending strength and impact strength required for use as a band cable is sharply lowered.

In addition, the plasticizer and the impact resistant agent usually used in the polyamide resin composition for a band cable are additionally used.

The present invention adds a plasticizer generally used in the art in order to add flexibility, the plasticizer should be excellent in plasticization efficiency and low volatility at high temperature, sulfonamide excellent compatibility with the polyamide resin composition The plasticizer is specifically used under the trade name Uniplex 214 (manufactured by Unitex Chemical Corporation).

The present invention adds impact resistance as a flexible modifier in order to impart impact characteristics, and to enhance flexibility, which is a problem that the pyrolysates due to decomposition of gas volatilized at a high temperature in injection molding with the plasticizer alone adheres to the mold. Impact resistance is used as the softening modifier because it affects the release property and the surface defect of the injection molding. The shock-resistant agent is generally used in the art, and is not particularly limited, and specifically, using ethylene, propylene, and diene terpolymer terpolymers grafted with maleic anhydride, in the present invention, Exxelor VA1803 products (Exxon Company: Manufacturer) is recommended.

The plasticizer and the impact agent are 4 to 9 parts by weight and 8 to 15 parts by weight, preferably 5 to 8 parts by weight and 10 to 13 parts by weight, respectively, based on 100 parts by weight of the polyamide resin, and the two components are independent. In each case, since the flexibility and heat resistance characteristics do not meet the purpose of the present invention, must be used mixed.

In the case of the mixed use, the total amount of the plasticizer and the impact agent is preferably maintained in the range of 12 to 24 parts by weight based on 100 parts by weight of the polyamide resin. Is less than 10 kg · cm / cm, and higher than the flexural strength suitable for the band cable (more than 500 kg / cm 2), there is a problem that its use as an application is unsuitable.

In addition to the components described above, copper (Iganox 1010 (Shiba-Gaiji Co., Ltd.) as a heat-resistant agent, calcium stearate, zinc stearate, magnesium stearate, polyethylene wax, montan wax, etc., as a heat-resistant agent within the scope without departing from the object of the present invention, copper ( Cu) -based or potassium (K) -based compounds and, if necessary, conventional pigments and the like may further be used.

On the other hand, looking at the process for producing a polyamide resin composition for a band cable according to the present invention. The manufacturing process is not particularly limited to those generally used in the art, and the following describes an example of using a twin screw extruder, but is not limited thereto.

First, it is produced at a constant cylinder barrel temperature in the temperature range of 265 to 275 ℃ using a twin screw extruder. At this time, when the barrel temperature is less than 265 ° C., the melting point of polyamide 66 is almost similar, so that sufficient melt-kneading occurs in the extruder, and the plasticizer is pyrolyzed or volatilized in a range exceeding 275 ° C., thereby causing the desired physical properties. Since it cannot be obtained, the physical properties of the resin composition are maximized in the above temperature range. Next, using an extruder with three inlets, a polyamide resin, a heat-resistant agent and a pigment in the first inlet, an impact agent in the second inlet, and a plasticizer in the third inlet are added to the screw share in the extruder. It is preferable because it can bring about the effect of uniform kneading. In addition, it is desirable to minimize residence time in order to reduce volatilization of the plasticizer and maximize the physical properties of the composition during melt kneading. As described above in the range that does not violate the object of the present invention, a thermal stabilizer, a releasing agent, a weathering agent, or a pigment may be added through the third inlet.

The polyamide resin composition prepared as described above has a heat deformation temperature of 50 to 60 ° C., an initial tensile strength of 420 to 480 kg / cm 2, and a long-term heat resistance (120 ° C., Aging test at 300 hours UL OVEN) for 100 to 100 ° C. 130%, flexural strength of 400 to 500 kg / cm 2, impact strength of 10 to 17 kg · cm / cm, and suitable for band cables.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1

As shown in Table 1, based on 100 parts by weight of polyamide resin in which 50: 50% by weight of polyamide 6 and 66 were mixed in the primary raw material inlet using a heated twin screw extruder maintained at about 267 ° C. , 0.5 parts by weight of sodium 2,2'-methylene bis- (4,6-di-tert-butyl phenyl) phosphate as a heat-resisting agent, 12 parts by weight of impact-resistant VA-1803 (manufactured by Exxon), plasticizer U214 ( Unitex Chemical Corporation: 7 parts by weight of the manufacturer, 0.4 parts by weight of A3800 (Mitsubishi Rayon Co., Ltd.), a fluorine compound, 0.5 parts by weight of IRGANOX 1010 (manufactured by Ciba Specialty Chemical, Inc.) as a heat-resistant agent, and 0.7 parts by weight of calcium stearate as a release agent. The hot melt kneading process was performed to prepare a polyamide resin composition.

The polyamide resin composition was melt kneaded in a heated twin screw extruder, and then made into a chip state and dried using a dehumidifying dryer for 85 hours for 3 hours.

Examples 2-4 and Comparative Examples 1-7

The same procedure as in Example 1 was performed, but the polyamide resin composition was prepared by changing the contents of the phosphorus-based compound, the fluorine-based compound, the impact agent and the plasticizer, as shown in Table 1 below.

The polyamide resin composition was melt kneaded in a heated twin screw extruder, and then made into a chip state and dried using a dehumidifying dryer for 85 hours for 3 hours.

division Composition (parts by weight) ^* Phosphorus Compound Shock-resistant Plasticizer Fluorine compound Example One 0.5 12 7 0.4 2 0.5 12 7 0.5 3 0.4 13 8 0.5 4 0.4 10 7 0.4 Comparative example One 0.1 12 7 0.3 2 0.5 - 8 0.5 3 0.5 12 - 0.4 4 0.5 7 3 0.4 5 0.5 16 10 0.4 6 0.4 11 7 0.1 7 0.4 11 7 1.0 Phosphorus compound: Sodium 2,2'-methylene bis- (4,6-di-tert-butyl phenyl) phosphate impact agent: VA-1803, Exxon plasticizer: U-214, Unitex Chemical Corporation Fluorine compound: A3800 Rayon *: The content ratio of each component based on 100 parts by weight of polyamide resin

The polyamide resin composition obtained above was evaluated for physical properties based on the following evaluation criteria, and the results are shown in Table 2 below.

(1) long-term heat resistance

Long-term heat resistance evaluation method according to ASTM D638 after making a 1/8 inch dumbbell specimen for measuring the tensile strength, and then measured the initial physical properties, and put the same tensile strength specimen in a UL oven and set the temperature to 120 ℃ and left for 300 hours Dumbbell specimens were measured at a measuring speed of 50 mm / min, and the tensile strength value at that time was used as a criterion for evaluation of long-term heat resistance.

(2) Heat deflection temperature: measured by making 1/4 inch specimen under the load of 18.6 kgf / ㎠ according to ASTM D648.

(3) Flexural strength: measured by making 1/8 inch specimens in accordance with ASTM D790.

(4) Impact Strength: Izod Notched impact strength was measured at room temperature by making 1/4 inch specimen according to ASTM D256.

division Properties The tensile strength Heat Deflection Temperature (℃) Flexural Strength (㎏ / ㎠) Impact Strength (㎏㎝ / ㎝) Initial (㎏ / ㎠) 120 ℃ × 300 hours (kg / ㎠) Retention rate (%) Example One 450 495 110 53 480 15 2 440 505 115 54 470 16 3 425 480 113 52 430 17 4 470 520 111 55 490 12 Comparative example One 440 295 67 45 465 14 2 650 780 120 58 960 8 3 660 772 117 48 700 10 4 580 667 115 54 600 8 5 390 273 70 42 350 20 6 500 520 104 50 520 11 7 465 530 114 55 370 8

As shown in Table 2, Examples 1 to 4 according to the present invention have a tensile strength retention of 110 to 115%, a heat deformation temperature of 53 to 55 ° C, a flexural strength of 430 to 490 kg / cm 2, and an impact strength. Was in the range of 12 to 17 kg · cm / cm, and it was confirmed that it had physical properties equal to or higher than those of the conventional Comparative Examples 1 to 7.

Comparative Examples 1 to 7 are examples of a case in which the components used in the present invention are excluded or the amount of the components used is different, and the physical properties corresponding to each of the comparative examples may be lower or significantly higher than those of the present invention. It was confirmed that it was difficult to maintain suitable physical properties for the band cable.

As described above, the polyamide resin composition for a band cable in which a specific phosphorus compound, a fluorine compound, a plasticizer, and an impact agent is added to the polyamide resin according to the present invention has a higher flexural strength, impact strength and elongation than in the prior art. The physical properties are maintained at equal or higher, and the long-term heat resistance and initial heat deformation temperature are improved than the materials applied to the parts showing the flexibility of the conventional automotive interior and exterior, so that the band cable, tie band and When applied as an extrusion material, its usefulness is expected.

Claims (3)

(1) 100 parts by weight of polyamide resin, (2) 0.2 to 0.8 parts by weight of a phosphorus compound represented by the following formula (1), (3) 0.2 to 0.8 parts by weight of a fluorine compound represented by the following formula (2), (4) 4 to 9 parts by weight of a sulfonamide plasticizer, and (5) 8 to 15 parts by weight of an impact agent for ethylene-propylene-diene terpolymer copolymer grafted with maleic anhydride Polyamide resin composition comprising a; [Formula 1]

In Formula 1, Ar ₁ And Ar ₂ is a substituted or unsubstituted aryl group having 6 to 7 carbon atoms, respectively, wherein the aryl substituent is selected from a hydrogen atom and an alkyl group having ₁ to ₆ carbon atoms, and R ₁ and R ₂ are each hydrogen or C ₁ to C ₆ An alkyl group; [Formula 2] (-CF ₂ -CF _2- ) _n In Chemical Formula 2, n represents an integer of 2 to 100. The polyamide resin composition according to claim 1, wherein the total amount of the plasticizer (4) and the impact resistant agent (5) is in the range of 12 to 24 parts by weight based on 100 parts by weight of the polyamide resin. The polyamide resin composition of claim 1, wherein the polyamide resin composition has a heat deformation temperature of 50 to 60 ° C., an initial tensile strength of 420 to 480 kg / cm 2, and a long-term heat resistance (Aging test at 120 ° C. for 300 hours UL OVEN). It is 100-130%, flexural strength is 400-500 kg / cm <2>, and impact strength is 10-17 kg * cm / cm, The polyamide resin composition characterized by the above-mentioned.