KR20010083650A - Rubber material and method for preparing thereof - Google Patents

Abstract

PURPOSE: Provided is rubber materials to improve fire-retardancy and high temperature adaptability required to rubber products to be used in hot environment or combustible environment, such as automobile engine. CONSTITUTION: The rubber materials use chloropolyethylene (CPE) as a source rubber and contains aluminium hydroxide as a functional additive. The aluminium hydroxide is added in 20 to 100 weight parts based on 100 weight parts of source rubber and preferably 40 to 60 weight parts to provide effectively the fire-retardancy. Alternatively, synthetic phosphoric esters-based fire-retardants can be used. The phosphoric esters-based fire-retardants are, for example N,N-bis(diphenylphosphoro)diaminohexane (BDPDH) or diphenylbutylamidophosphate (DPBAP) The BDPDH is added in 50 to 30 weight parts based on 100 weight parts of the source rubber.

Description

Rubber material and its manufacturing method {RUBBER MATERIAL AND METHOD FOR PREPARING THEREOF}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber material having excellent flame retardancy and heat resistance, and a method of manufacturing the same, and more particularly, to a rubber product used around a high temperature or flammable environment, such as an automobile engine. The present invention relates to a rubber material having improved flame retardancy and heat resistance and a method of manufacturing the same.

In general, rubber material is a representative polymer material among the chemical materials used in our daily life and has a low production cost and many advantages in terms of the flexibility, processability and elasticity of rubber materials. It is a special function that inorganic materials do not have.

Therefore, rubber materials are used for most hoses, dust, oil, oil seals, etc. used in automobiles, and are not only the most important materials for the tires of transportation engines. It is also widely used as an insulation and coating material for electrical and electronic devices.

Flame retardant and heat resistance are not a requirement for rubber parts used in a room temperature environment, but rubber products used in a high temperature environment such as an engine room space of a car or an environment exposed to a fire risk have a high level. Flame retardant and heat resistance are required. That is, in the case of automobiles, the rubber hose, which occupies the most part of the rubber parts used in the automobile, connects various parts of the automobile, and plays a role of transporting various fluids and gases and maintaining internal pressure by the fluid. Heat resistance to resist radiant heat and cold resistance to maintain its appearance even in cold weather, physically stable pressure and durability against various oils, oil resistance to chemical corrosion resistance, weather resistance stable to ozone and sunlight and high burst pressure against fluid As required, the rubber material constituting each part must meet the unique material specifications applicable to the part. In particular, in the case of hoses and vibration isolators which are installed in close proximity to the engine, since the constituent material is basically a flammable rubber material, heat resistance and flame retardance against temperature are particularly required as important properties.

Therefore, the rubber materials constituting the various rubber products in the related art should be processed to impart functionality to have an appropriate level of flame resistance and heat resistance within a range in which the basic physical properties are not deteriorated.

In the case of a polymer material such as a rubber material, an additive is usually blended into the rubber material in order to give a special functionality to the material. At this time, the interaction between the additive or the compounding agent and the existing rubber material has a great influence on the properties of the rubber material. The conventional description of such interactions is as follows.

a. F. According to A. F. Blanchard's research, several types of binding energy are involved in the interaction between filler and elastomer. A. Casale, M. W. In addition to the simple dispersing effect, MW Ranney et al. Show that the filler particle surface is actually bridging or coupling to the elastomer network as a chemical interaction of the filler. It has been reported that the spatial arrangement is stabilized or immobilized to exhibit necessary characteristics in dynamic performance. As such, in the identification of reinforcing properties for fillers, many studies have been made in relation to elasticity in terms of physical interactions as well as in chemical aspects. As such, inorganic materials as additives are in increasing demand according to the necessity of functional rubber materials having special functions such as strength, rigidity, elasticity improvement, electrical function, biological function, optical function, and separation function such as metals. It is done.

On the other hand, the conventional theory of the flame retardant mechanism that suppresses combustion during the combustion of the combustible material is as follows. According to Lewin et al., The combustion of rubbers is a complex phenomenon involving heat flow and chemical reactions. The rubber is pyrolyzed by flame or heat to generate flammable gas, which is combined with oxygen to burn. Therefore, it has been reported that combustion diffusion can be prevented by first stopping the thermal decomposition of rubber, or completely suppressing the generation of flammable gas, or by interrupting the chain reaction of combustion by cutting off the oxygen supply.

However, although inorganic materials have excellent heat resistance and high temperature properties compared to metals or polymer materials, they have not been widely used as high-temperature structural materials because of their weakness and the disadvantage of requiring a large amount of heat during manufacture. Most of rubber materials used in rubber products are produced without basic flame-retardant processing, but only when the basic compound is produced or when flame-retardant is used, inorganic flame retardants such as antimony oxide are used. There is a trend.

The raw rubbers which have been mainly used as a fluid transport hose material are chloroprene rubber, chloroprene-styrene copolymer, acrylonitrile butadiene rubber, and ethylene acrylate rubber. Flame retardant materials have mainly used inorganic flame retardants.

Therefore, a rubber material was needed to overcome these problems, and in particular, the rubber raw material and additives for the hose which are currently used in automobiles are replaced with other raw material rubbers and functional additives, and the rubber is more effective than the conventional rubber materials even though the production cost is low. Material is required.

Therefore, in order to satisfy the above requirements, aluminum hydroxide or phosphate ester flame retardant which is a new functional additive prepared according to the present invention using chloropolyethylene (CPE) as a raw material rubber and not the raw material rubber. It is an object to provide a rubber material excellent in heat resistance and flame retardancy by blending.

In addition, an object of the present invention is to provide a method for producing a rubber material excellent in heat resistance and flame retardancy by combining a new functional additive in chloropolyethylene raw material rubber and a method for producing the functional additive.

1 is a view showing the results of XRD analysis of the crystal phase before and after purification of aluminum etching by-products according to the present invention.

Figure 2 is a graph showing the results of PSA analysis of the crystalline phase after grinding of aluminum etching by-products according to the present invention.

Figure 3 is a reaction scheme of a functional additive according to the present invention, a flame retardant N, N'-bis (diphenyl phosphoro) diamino hexane (BDPDH) and diphenyl butyl amido phosphate (DPBAP).

4 is a flowchart showing a method for producing a rubber material incorporating a functional additive according to the present invention.

5 is a rheograph of vulcanized rubber in which a hydrate is mixed with aluminum hydroxide as a functional additive according to the present invention.

6 is a flow graph of the vulcanized rubber in which the phosphate ester flame retardant is mixed with a functional additive according to the present invention (Rheograph).

Figure 7 is a graph showing the thermal analysis results of the compounded rubber material not added functional additives according to the present invention.

8 is a graph showing the thermal analysis results of the rubber material prepared by adding the functional additive according to the present invention.

In order to achieve the object of the present invention, the present invention provides a rubber material characterized by using chloropolyethylene (CPE) as the raw material rubber, by adding aluminum hydroxide to the raw material rubber to improve the flame resistance and heat resistance.

The present invention also provides a rubber material, characterized in that the aluminum hydroxide is added 20 to 100 parts by weight based on 100 parts by weight of the chloropolyethylene (CPE) raw material rubber.

In addition, the present invention is that the aluminum hydroxide is added to 20 parts by weight or more based on 100 parts by weight of the chloropolyethylene (CPE) raw material rubber to act as an effective heat-resistant agent, 40-60 parts by weight to act as an effective flame retardant Provided is a rubber material characterized by the above-mentioned.

On the other hand, the present invention provides a rubber material characterized by using chloropolyethylene (CPE) as the raw material rubber, by adding a synthetic phosphate ester flame retardant to the raw material rubber.

The present invention also provides a rubber material, wherein the phosphate ester flame retardant is N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutyl amidophosphate (DPBAP).

The present invention also provides a rubber material, characterized in that the BDPDH or DPBAP is added 5-30 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber.

In another aspect, the present invention provides a rubber material characterized in that the BDPDH is added 25 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber, the DPBAP is added 15 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber. .

The present invention also relates to N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutyl amidophosphate obtained from aluminum hydroxide or flame retardant material synthesis process obtained from aluminum hydroxide manufacturing process in chloropolyethylene raw material rubber. Compounding each of (DPBAP); Mixing oil in the blend; Aging the oil mixture; And it provides a method for producing a rubber material comprising the step of mixing a curing agent, accelerator in the aging mixture.

The present invention also provides an aluminum hydroxide manufacturing step of etching the aluminum surface (etching); Washing the aluminum hydroxide produced from the etching treatment step with water; Extracting the aluminum hydroxide washed in the washing step; Washing the aluminum hydroxide extracted in the extraction step with water; Drying the aluminum hydroxide washed in the washing step; And blending the aluminum hydroxide obtained from the aluminum hydroxide manufacturing process, which comprises grinding the aluminum hydroxide dried in the drying step into fine particles with a ball mill, into the chloropolyethylene raw material rubber. Provide a method.

In addition, the present invention uses a solvent extraction method using ethyl alcohol in the aluminum hydroxide extraction step, wherein the water / ethyl alcohol ratio is 70/30, the aluminum hydroxide drying step is dried at 150 ℃ for 2 hours or more, the aluminum hydroxide The fine particles pulverized in the crushing step provide a method for producing a rubber material, characterized in that 2㎛.

The present invention also provides a step of producing a BDPDH of the flame retardant material synthesis step of adding a little dropwise diphenylchlorophosphate to hexamethylenediamine; Reacting the mixture with heating and stirring to obtain a precipitate; Washing to remove hexamethylenediamine that has not reacted in the precipitation step; And dissolving the washed precipitate in ethyl alcohol to recrystallize in an aqueous solution.

In addition, the present invention is a process for producing DPBAP during the synthesis of flame retardant material is obtained by adding butylamine while stirring diphenylchlorophosphate to obtain a gel solid and neutralizing the obtained gel solid with sodium hydroxide to remove HCl It provides a rubber material manufacturing method comprising the step of.

In order to achieve the above technical configuration, the present invention uses chloropolyethylene as the raw material rubber, ethylene acrylate rubber as a typical raw material rubber used in rubber materials that require flame retardancy and heat resistance until now, such as rubber materials for automobile hoses However, since the flame retardancy is insufficient in the basic characteristics of the material as described above, in the present invention is to use chloropolyethylene as a raw material rubber that can be replaced.

The chloropolyethylene has excellent cold resistance in terms of basic physical properties, very low unit cost, excellent chemical corrosion resistance to alcohol, alkali and acid, and wear resistance, anti-flexibility and anti-cracking resistance. It is excellent and has good resistance to weather, ozone, sunlight, oxidation and the like, and has appropriately possessed the advantages of other raw material rubbers such as chloroprene rubber, chloroprene-styrene copolymer, acrylonitrile butadiene rubber and epichlorohydrin. In addition, depending on the content of chlorine, the optimum physical properties (heat resistance, compression set, low temperature, oil resistance, tear resistance and flame retardancy) can be obtained, and the blendability with additives is good.

In addition, the present invention manufactures and uses a new functional additive different from the conventional additives, among which aluminum hydroxide is processed to by-products generated during the aluminum surface treatment to make high purity and then ball-mill (ball-mill) to have a very small particle size It is used as a powder state.

In addition, it is used to synthesize a phosphate ester compound having excellent flame retardancy as another functional additive, the synthesized compound is N, N'-bis (diphenyl phosphoro) diamino hexane (BDPDH) and diphenyl butyl amido phosphate ( DPBAP).

The present invention relates to N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutyl amidophosphate (DPBAP) obtained from a process of synthesizing aluminum hydroxide or flame retardant material obtained from aluminum hydroxide manufacturing process in chloropolyethylene raw material rubber. Each compound); Mixing oil in the blend; Aging the oil mixture; And it provides a rubber material excellent in flame retardancy and heat resistance comprising the step of mixing a curing agent, accelerator in the aging mixture.

Hereinafter, the manufacturing method of the rubber material will be described in detail.

Preparation of Aluminum Hydroxide

Inorganic aluminum hydroxide was used after processing through the following process from the by-products generated after the surface etching treatment, a process necessary for increasing the chemical corrosion resistance of aluminum. First, it was washed with clean water only, and the purity was 90 ~ 95%. Solvent extraction using ethyl alcohol was performed to improve the purity, and the mixing ratio with water was about 70/30 of water / ethyl alcohol. In order to remove the foreign substances dissolved in the alcohol and alcohol in the sample was rewashed only with clean water, and the sample was dried at 150 ℃ for at least 2 hours to obtain the aluminum hydroxide to remove the water.

1 is an XRD analysis performed to determine the crystal phase before and after the etching of by-products. The aluminum hydroxide after the refining process was pulverized at a speed of 135 rpm using a ball mill, and then pulverized into fine particles of 2 μm or less (analysis of particle size by PSA) and blended in a rubber material. 2 is a PSA analysis result performed to determine the particle size distribution of the crystal phase after grinding of the etching by-product.

Synthesis of Flame Retardant Materials

N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) was added dropwise to hexamethylenediamine in a three-necked flask, and diphenylchlorophosphate was added dropwise, and the temperature was raised to 120 ° C. After complete completion, unreacted hexamethylenediamine was removed by washing with water, and then dissolved in ethyl alcohol and recrystallized from an aqueous solution.

Diphenylbutyl amido phosphate (DPBAP) is a dilute chloro phosphate in a three-necked flask, slowly adding butylamine while stirring and when the reaction is completed, a gel-like solid is produced, which is present in the form of HCl salt, The solution was neutralized with dilute sodium hydroxide solution to remove HCl, and a white powdery solid, diphenylbutyl amidophosphate (DPBAP) was obtained. This is advantageous in that synthesis at room temperature is much easier than conventional methods. Figure 3 shows the synthesis of the flame retardant carried out in the present invention.

Compounding and Kneading

It was blended and kneaded according to FIG. 4, which is a flowchart for preparing a rubber specimen incorporating a functional additive. First, a rubber roll mill with a diameter of 20cm and a length of 51cm was used to mix various additives in the raw material rubber.The order of input of the materials was chloropolyethylene (CPE) and aluminum hydroxide or N, N as a functional additive. '-Bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutyl amidophosphate (DPBAP), and mixed with oil, and aged with other additives [carbon black, MgO-D (product of DAISO Japan) ), OF-100 (manufactured by DAISO, Japan), and M-181 (manufactured by DAISO, Japan)] were kneaded so as to be dispersed well.

Herein, the curing agent that can be used in the present invention includes organic compounds such as bendidine, paraamino phenol, paraphenylene diamine, naphthyl amines, quinones, dihydradine oxalate, and hydrazine sulfate in addition to MgO-D. It is also effective to mix the recycled rubber, rubber powder and the like. In addition to the above-mentioned M-181, other mercaptans such as aromatic thiol compounds may be used as the accelerator.

Hereinafter will be described an embodiment according to the present invention. However, the present invention is not limited to the examples.

Example 1-5

Aluminum hydroxide is used as a functional additive, and the rubber material mixture ratio is shown in Table 1a.

(Unit: parts by weight) Example Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 CPE 100 100 100 100 100 100 C / B 20 20 20 20 20 20 MgO-D 5 5 5 5 5 5 Oil 10 10 10 10 10 10 1) Al (OH) ₃ 0 20 40 60 80 100 OF-100 One One One One One One M-181 3 3 3 3 3 3

Example 6-11

BDPDH is used as a functional additive, and the mixing ratio of rubber materials is shown in Table 1b.

(Unit: parts by weight) Example Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 CPE 100 100 100 100 100 100 100 C / B 20 20 20 20 20 20 20 MgO-D 5 5 5 5 5 5 5 Oil 10 10 10 10 10 10 10 2) BDPDH 0 5 10 15 20 25 30 OF-100 One One One One One One One M-181 3 3 3 3 3 3 3

Example 12-17

DPBAP is used as a functional additive, and the mixing ratio of rubber materials is shown in Table 1c.

(Unit: parts by weight) Example Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 CPE 100 100 100 100 100 100 100 C / B 20 20 20 20 20 20 20 MgO-D 5 5 5 5 5 5 5 Oil 10 10 10 10 10 10 10 3) DPBAP 0 5 10 15 20 25 30 OF-100 One One One One One One One M-181 3 3 3 3 3 3 3

Characteristic test method of manufactured rubber material

Vulcanization Characteristics of Test Specimen

The vulcanization temperature was set to 190 ° C. and the maximum torque, minimum torque, Ts2, Tc90 were measured using a rheometer. Here, Ts2 is an initial time (Scorch time) when the rubber starts to vulcanize, and represents a time when the torque value is two points higher than the minimum value, and Tc90 represents a time when the rubber is vulcanized 90%.

Physical properties

The hardness test was measured with a spring hardness tester, and the tensile test measured tensile strength, 100% tensile stress and elongation rate according to KS 6518 (Physical test method of vulcanized rubber).

Heat resistance

After vulcanized rubber was set at a heat resistance temperature of 160 ° C. in a rubber aging tester and left for 70 hours, hardness, tensile strength, tensile stress, and elongation rate were measured. Thermogravimetric Analysis (TGA) of Seiko Instruments Inc. It was investigated in an N ₂ atmosphere. The temperature increase rate was 10 degreeC / min, and measured to 33 degreeC-700 degreeC.

Flame retardant properties

The flame retardant properties were based on the UL (Underwriters Laboratory) standard, widely known as the flame retardant standard, and the flame retardancy of rubber specimens was measured by the UL94V method. In this method, five specimens (125 × 12 mm) are placed vertically in each weight range and a flame is placed on the bottom of the specimen for 10 seconds to remove and burn time is measured. It is to measure the sum of the combustion time of all the specimens, and the grade varies according to the combustion time and the result of burning the lower cotton with the flame debris or lump while burning. Table 2 shows the UL94V flame retardancy specification.

Assessment Methods V-0 V-1 V-2 Flame or Glowing ascending to the end of the specimen No No No Spark fragments fall and burn the cotton under the specimen No No Irrelevant Sum of combustion time of all specimens (sec) 50 seconds or less 250 seconds or less 250 seconds or less Burning time of the specimen (sec) 10 seconds or less 30 seconds or less 30 seconds or less Sum of second burning time and glowing time of specimen 30 seconds or less 60 seconds or less 60 seconds or less

Characteristics test result of manufactured rubber material

Vulcanization Characteristics

Variation of the vulcanization characteristics with the addition of aluminum hydroxide used as a functional additive in the present invention was tested. Crosslinking of an elastomer refers to a bond in which two or more chains are bonded to each other, and the interaction between the chain and the junction is generally a covalent bond. Ionic interactions, dipole-dipole interactions, reversible and physical interactions such as van del Waals force, etc. make the crosslinking effect more apparent, and the crosslinked polymer contains at least two crosslinks per chain, This is done by forming a two-dimensional or three-dimensional network with other chains. ODR test results carried out in the present invention shows a time-torque relationship and the vulcanization temperature was set to 190 ℃ was tested.

5 and Table 3 test the vulcanization characteristics according to the addition of aluminum hydroxide, the overall torque value was increased as the amount of addition of aluminum hydroxide.

Material classification Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Tmax 25.41 30.03 41.58 44.35 46.98 45.13 Tmin 4.46 7.23 11.31 11.60 11.23 11.20 Ts2 3.98 1.13 1.05 0.98 0.93 1.01 Tc90 1.20 3.93 4.05 4.03 4.00 4.35

This means that the crosslinking density of rubber increases during the vulcanization process, leading to an increase in hardness, tensile strength and tensile stress. The more the amount of aluminum hydroxide added, the longer the crosslinking time was. Therefore, it was found that aluminum hydroxide affects the formation of crosslinking of rubber material. do. In addition, as the amount of aluminum hydroxide increases, the scorch time tends to be faster, and it is considered that aluminum hydroxide affects the scorch time, which is because the reaction effect appears depending on the functional group. The Tmax value appeared to increase as the amount added increased. According to Jana et al report that the vulcanization rate is also affected by the amount of filler incorporation, it can be seen that as shown in Figure 5 shows an increasing curve gradually as the amount of filler is increased. Small amounts of fillers have the effect of promoting vulcanization, but the addition of large amounts of fillers shows that they have an effect of inhibiting vulcanization. This shows that there is a critical concentration to see the effect of vulcanization promotion. Excessive addition causes a lot of fillers between the rubbers, so that the crosslinking agents interfere with the formation of the three-dimensional network between the rubbers. The upward curve is shown.

6 and Table 4 show changes in the vulcanization characteristics of the phosphate ester flame retardant.

Material classification Comparative example Example 6/12 Example 7/13 Example 8/14 Example 9/15 Tmax 25.41 22.32 33.74 31.99 29.79 Tmin 4.46 3.09 7.17 8.62 5.43 Ts2 3.98 4.01 4.05 3.71 3.70 Tc90 1.20 1.25 1.20 1.00 1.11

This test result showed a slight irregularity in the flowability of the rubber material, because it is difficult to uniformly distribute the filler during the manufacture of the rubber material. In the vulcanization process, the unevenness of product performance is usually caused by the unevenness of temperature. For this specimen, the Tmin and Ts2 test values were found to be appropriate.

Physical properties

The chloropolyethylene (CPE) material used in the present invention is blended while varying 20 to 100 parts by weight (phr) of aluminum hydroxide as shown in Table 1a, or 5 to 30 weights of two kinds of phosphate ester flame retardants, respectively as shown in Table 1b or Table 1c. The physical properties of the rubber compounded by varying the amount in the sub range were tested. Chloropolyethylene (CPE) is a crystalline rubber. When elongated, a crystal nucleus is formed in the rubber, and this nucleus acts as a reinforcing agent to improve the strength of the rubber.

Table 5 shows the results of measuring the hardness, tensile strength, elongation, and 100% Modulus of the vulcanized rubber in which 20 to 100 parts by weight of aluminum hydroxide was mixed.

Material classification Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Hs (kg / cm ² ) 70 80 82 84 85 85 Ts (kg / cm ² ) 143 121 116 111 105 98 Eb (%) 310 168 161 155 149 145 M100 (kgf / cm ² ) 63 56 52 47 43 39 ΔHs +9 +2 +3 +2 +1 +1 ΔTs +4 +2 +3 +1 -One -One ΔEb -68 -44 -42 -43 -42 -42 ΔM100 +2 -One +1 +1 +1 ± 0

The basic properties of the aluminum hydroxide were measured by varying the amount of aluminum hydroxide. The increase in hardness as the amount added increases the crosslinking density of the rubber during vulcanization as aluminum hydroxide is added to the formulation. In addition, the tensile test is a data for evaluating the physical properties of vulcanized rubber, which may be used to determine the optimum vulcanization condition of unvulcanized compound, and has a significant meaning as a test for chemical resistance or oil resistance. Tensile strength was the maximum value in the comparative example, and the tensile strength gradually decreased with the addition amount, which was lower than that of chloropolyethylene (CPE). The elongation rate of the vulcanizate is excellent in elongation rate in chloropolyethylene (CPE) as it is, and the elongation rate decreases as the amount added increases. It was also found that the 100% Modulus measurement result decreased as the amount of aluminum hydroxide added increased.

As a result of the above test, it can be seen that the aluminum hydroxide applied in the present invention has a property of curing the compound, so that it acts as a reinforcing agent, and the hardness is increased, and the amount of aluminum hydroxide added is 20 parts by weight. In the above it can be seen that the role of the filler rather than the reinforcing role. In general, the range of 20 to 100 parts by weight does not appear to show a large change in the basic physical properties, and considering the hardenability, the amount in Example 1 shows the most appropriate and ideal physical properties, and the results are shown in Table 5. It was confirmed from the results.

The heat resistance was tested for 70 hours at 160 ° C for the same rubber material, and it was found that the change of physical properties in the hardness, tensile strength and elongation with respect to heat was very small as the amount of addition increased than that without addition of aluminum hydroxide. Therefore, the addition of aluminum hydroxide can confirm the marked synergistic effect of the reinforcing agent and heat resistance. At 20 parts by weight, a significant decrease in physical property was confirmed, and above that, almost no change was observed according to the increase of the added amount. Therefore, it can be said that the addition amount of aluminum hydroxide as the heat resistant material is most suitable 20 parts by weight.

Table 6 shows the results of measuring tensile strength and elongation of vulcanized rubber in which BDPDH is mixed in a variable amount.

Table 7 shows the results obtained by measuring tensile strength and elongation of vulcanized rubber in which DPBAP is mixed with a variable amount.

phr. Comparative example Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Ts (㎏f / ㎠) +33 +50 +42 +55 +77 +58 +58 △ Eb (%) 428 364 412 408 453 451 503 ΔTs (kgf / ㎠) +33 +50 +42 +55 +77 +58 +58 △ Eb (%) -74 -62 -71 -75 -77 -74 -76

phr. Comparative example Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Ts (㎏f / ㎠) +33 +50 +42 +55 +77 +58 +58 △ Eb (%) 428 364 412 408 453 451 503 ΔTs (kgf / ㎠) +33 +50 +42 +55 +77 +58 +58 △ Eb (%) -74 -62 -71 -75 -77 -74 -76

Basic properties were measured by varying the amount of BDPDH and DPBAP, and when BDPDH was added, the hardness increased from the initial value when the amount was 5 parts by weight, and the amount was slightly decreased in the range of 10 to 20 parts by weight. In parts by weight, the hardness was greatly reduced. When DPBAP was added, the hardness decreased slightly from the initial value when the added amount was 5 parts by weight, and increased when the amount was 10 parts by weight. The decrease in tensile strength as the amount added increases the crosslinking density of rubber during vulcanization as BDPDH and DPBAP are added to the formulation.In the range of BDPDH, DPBAP is more than 25 parts by weight. In the case of 15 parts by weight or more shows a decrease in the basic physical properties, it can be seen that the appropriate blending amount is below the above range. Also, considering only the basic physical properties, DPBAP was found to have a more stable compounding property for rubber materials than BDPDH.

Flame Retardant Properties

All rubber polymers contain carbon as a main component, and carbon black, which is formulated for the role of reinforcing agent, also contains carbon as a main component. However, if the rubber chain contains components such as chlorine, nitrogen, halogens and phosphorus, which play a role in extinguishing, the flame retardancy may be increased to some extent.

In the present invention, two kinds of phosphate ester flame retardants of aluminum hydroxide or N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) and diphenylbutylamidophosphate (DPBAP) Compounds were each blended with chloropolyethylene (CPE) rubber material and flame retardance was measured at 160 ° C. for 1 hour. The test results when aluminum hydroxide was blended are shown in Table 8 and the test results when BDPDH or DPBAP were blended. Table 9 or Table 10, respectively.

(Unit: parts by weight) Assessment Methods Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Flame or glowing ascends to the end of the specimen none none none none none none Spark fragments fall and burn the cotton under the specimen none none none none none none Sum of combustion time of all specimens (sec) 226 170 86 72 74 71 Burning time of the specimen (sec) 45 38 17 14 15 14 Sum of second burning time and glowing time of specimen 51 42 20 16 19 17

(Unit: parts by weight) Assessment Methods Comparative example Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Flame or glowing ascends to the end of the specimen none none none none none none none Spark fragments fall and burn the cotton under the specimen none none none none none none none Sum of combustion time of all specimens (sec) 310 315 305 290 275 255 240 Burning time of the specimen (sec) 62 63 61 58 55 51 48 Sum of second burning time and glowing time of specimen 82 80 81 75 71 72 69

(Unit: weight part) Assessment Methods Comparative example Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Flame or glowing ascends to the end of the specimen none none none none none none none Spark fragments fall and burn the cotton under the specimen none none none none none none none Sum of combustion time of all specimens (sec) 348 320 309 298 280 265 255 Burning time of the specimen (sec) 67 65 62 60 56 53 51 Sum of second burning time and glowing time of specimen 84 86 85 79 79 77 75

According to the test results, chloropolyethylene (CPE) itself has some flame retardant and self-extinguishing properties, because chlorine, which is a flame retardant, is added to chloropolyethylene (CPE) used as raw material rubber. Significant flame-retardant effects were measured, respectively, by adding aluminum hydroxide or N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutylamidophosphate (DPBAP) as functional additives. Could know.

First, in the case of aluminum hydroxide, as shown in Table 8, when the addition amount was 40 parts by weight, it showed a sharp increase in flame retardancy, and showed an increase in flame retardancy up to 60 parts by weight, but there was little change. In addition, when BDPDH or DPBAP was added, the combustion time was decreased constantly as the amount of flame retardant was increased.Burning time was reduced up to 70 seconds for BDPDH and 93 seconds for DPBAP. Since the decrease was observed as a synergistic effect, it was confirmed that the rubber material produced in the present invention was very excellent in flame retardancy than the general rubber material.

Thermal analysis

FIG. 7 is a thermal analysis result of a rubber specimen made of chloropolyethylene (CPE) raw material rubber not added with a functional additive, and FIG. 8 is a thermal analysis result of a rubber specimen prepared by adding a functional additive.

Gradually increasing the temperature of the raw rubber, the rubber is vulcanized or softened, then carbonized and finally ashed. The temperature at which the temperature rises suddenly increases pyrolysis and the weight decreases is called the pyrolysis temperature. The pyrolysis temperature varies depending on the rubber but is usually completely ashed at 300 to 450 ° C. TGA is widely used to investigate the pyrolysis characteristics of rubber. It is a method of continuously measuring the weight loss of a sample while increasing the temperature of the sample at a constant rate. Stability can be investigated. The residual amount after the end of the thermal analysis is also used to estimate the amount of filler in the rubber composition.

Pyrolysis initiation temperature of chloropolyethylene (CPE) starts around 239.0 ° C, but chloropolyethylene (CPE) with heat-resisting agent and filler is increased to 245.3 ° C according to the amount of heat-resisting agent and filler. The addition of aluminum hydroxide, a heat-resistant agent, can be seen as a result of the increase in heat resistance by 6.3 ° C. Secondary pyrolysis temperatures were approximately the same at 408.1 and 408.2, respectively. The residual amount of chloropolyethylene (CPE) at 700 ° C is about 28%, and the residual material at 700 ° C is carbon black, magnesium oxide, and oil used as additives based on 139 parts by weight of the total amount of chloropolyethylene (CPE). , OF-100 and M-181 appear to be oxidized and remain, which is consistent with the theoretical value [39/139 × 100 = 28.1]. In addition, similar values were obtained for the addition of heat-resistant and flame retardants.

Since the rubber material manufactured according to the present invention is excellent in flame retardancy and heat resistance compared to the conventional rubber material, for example, when the material of parts such as rubber hoses constituting an automobile, etc., the rubber hose can perform various functions in a space such as an engine room. Even if the fluid and gas are carried, it can withstand the radiant heat of the engine, and in particular, the hoses and dustproof devices installed in close proximity to the engine can have the characteristics of the material required to make a safer vehicle.

Claims (12)

In a rubber material, chloropolyethylene (CPE) is used as the raw material rubber, and aluminum hydroxide is added to the raw material rubber to improve flame resistance and heat resistance. The rubber material according to claim 1, wherein the aluminum hydroxide is added in an amount of 20 to 100 parts by weight based on 100 parts by weight of the chloropolyethylene (CPE) raw material rubber. According to claim 1, wherein the aluminum hydroxide is added to 20 parts by weight or more based on 100 parts by weight of the chloropolyethylene (CPE) raw material rubber to act as an effective heat-resistant agent, 40-60 parts by weight to add an effective flame retardant Rubber material, characterized in that. In a rubber material, chloropolyethylene (CPE) is used as the raw material rubber, and a synthetic phosphate ester flame retardant is added to the raw material rubber to improve the flame resistance. The rubber material according to claim 4, wherein the phosphate ester flame retardant is N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenylbutyl amidophosphate (DPBAP). The rubber material according to claim 5, wherein the BDPDH or DPBAP is added in an amount of 5-30 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber. The rubber material according to claim 5, wherein the BDPDH is added in an amount of 25 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber, and the DPBAP is added in an amount of 15 parts by weight based on 100 parts by weight of the chloropolyethylene raw material rubber. In the method for producing a rubber material, N, N'-bis (diphenylphosphoro) diaminohexane (BDPDH) or diphenyl obtained from a chloropolyethylene raw material rubber obtained from a process of producing aluminum hydroxide or a flame retardant material. Compounding butylamidophosphate (DPBAP), respectively; Mixing oil in the blend; Aging the oil mixture; And mixing a curing agent and an accelerator with the aging mixture. The method of claim 8, wherein the aluminum hydroxide manufacturing process comprises the steps of etching the aluminum surface (etching); Washing the aluminum hydroxide produced from the etching treatment step with water; Extracting the aluminum hydroxide washed in the washing step; Washing the aluminum hydroxide extracted in the extraction step with water; Drying the aluminum hydroxide washed in the washing step; And blending the aluminum hydroxide obtained from the aluminum hydroxide manufacturing process, comprising grinding the aluminum hydroxide dried in the drying step into fine particles with a ball mill, into a chloropolyethylene raw material rubber. . 10. The method of claim 9, wherein the aluminum hydroxide extraction step using a solvent extraction method using ethyl alcohol, wherein the water / ethyl alcohol ratio is 70/30, the aluminum hydroxide drying step is dried at 150 ℃ for 2 hours or more, The method of producing a rubber material, characterized in that the fine particles pulverized in the aluminum hydroxide crushing step is 2㎛. The method of claim 8, wherein the manufacturing of BDPDH during the flame retardant material synthesis process comprises the steps of dropwise addition of diphenylchlorophosphate to hexamethylenediamine little by little; Reacting the mixture with heating and stirring to obtain a precipitate; Washing to remove hexamethylenediamine that has not reacted in the precipitation step; And dissolving the washed precipitate in ethyl alcohol to recrystallize in an aqueous solution. The method of claim 8, wherein the step of preparing DPBAP during the flame retardant material synthesis step comprises adding butylamine while stirring diphenylchlorophosphate to obtain a gel solid and neutralizing the obtained gel solid with sodium hydroxide to obtain HCl. Rubber material manufacturing method comprising the step of removing.