KR100605338B1 - Manufacturing method for high condensed and high dispersed incombustible master batch for olefin resin and product thereby - Google Patents

Abstract

The present invention relates to a highly concentrated high dispersion flame retardant master batch manufacturing method for olefin resins, and in particular, to minimize the change in the mechanical properties of the olefin resin intrinsic, which can occur when using a flame retardant master batch to impart flame retardancy to the olefin resin, It relates to a highly concentrated high dispersion flame retardant master batch manufacturing method for preventing the deflection of the flame retardant master batch according to.

To this end, according to the method for producing a highly concentrated high dispersion flame retardant masterbatch for olefinic resins according to the present invention, it is prepared by blending and blending 60 to 96 parts by weight of flame retardant to 4 to 40 parts by weight of polymer material, and is produced through a series of steps. In order to obtain flame retardancy by mixing the master batch with the olefin resin, the purpose is to prevent or delay the ignition of the olefin resin in the event of fire, and also to suppress or reduce the generation of toxic gas generated.

The present invention realizes a high concentration of a flame retardant content of 60 to 96 weight ratio compared to a 4 to 40 weight ratio polymer material that does not have a general flame retardant masterbatch, and realizes high dispersibility, maximizing the intrinsic properties and characteristics of the olefin resin by using a highly concentrated product It maximizes the flame retardant effect according to the selection and ratio of flame retardant suitable for the characteristics of high dispersibility and olefin resin, and it is easy to produce without being restricted by processing conditions (injection, extrusion) due to high dispersibility. It makes it easy to add flame retardancy to the final product, improves productivity by unifying the process and maximizing efficiency with ease of operation. Safety and environmental problems are minimized, and price competitiveness and import speed Obtained the effect of obtaining technical responsiveness

Olefin, High Concentration, High Dispersion, Flame Retardant, Master Batch, Composition

Description

 Manufacturing Method and High Condensed and High Dispersed Incombustible Master Batch for Olefin Resin and Product Thereby

1 is a block diagram showing a master batch manufacturing process according to the present invention.

* Description of the symbols for the main parts of the drawings *

10: Weighing 20: Mixing

30: kneading 40: extrusion

50: cutting (pellet) 60: blending

The present invention relates to a highly concentrated high dispersion flame retardant master batch manufacturing method for olefin resins, and in particular, to minimize the change in the mechanical properties of the olefin resin intrinsic, which can occur when using a flame retardant master batch to impart flame retardancy to the olefin resin, It relates to a highly concentrated high dispersion flame retardant master batch manufacturing method for preventing the deflection of the flame retardant master batch according to.

Recently, polymers used in household appliances, public transportation, electrical and electronic components, etc. are required to have various grades of flame retardance so that continuous combustion does not occur in a fire. Accordingly, the flame retardant technology of polymers is rapidly developing. For example, (a) a method that is resistant to oxidative degradation and has a high decomposition temperature by modification of a polymer itself, (b) a method of diluting a flammable material by addition of an inorganic filler, or (c) a halogen-based or phosphorus-based There is a method of adding an effective flame retardant to the polymer of.

However, the selection of the polymer by the method of (a) is very narrow and economically burdensome, and the method of (b) is constrained due to the significant decrease in physical properties due to the high flame retardancy of the resin. Subsequently, the method of said (c) is generally used abundantly. Therefore, many flame retardants by the addition of a flame retardant for the flame retardation of the polymer have been studied.

As the flame retardant, halogen-based flame retardants such as chlorine and bromine compounds, metal hydrates such as magnesium hydroxide and aluminum hydroxide, and non-halogen flame retardants of phosphorus and nitrogen compounds may be used alone or in combination.

The present invention is to describe a highly concentrated highly dispersed flame retardant master batch added to the olefin resins commonly used in many kinds of polymer materials to impart flame retardancy.

At present, due to the advantages of low price, easy processing, and light weight of the final product at home and abroad, polymer materials are replacing metal materials in many parts. In particular, the ratio of olefin resin in general plastic is very high. However, these resins are not flame retardant, and when flame retardancy is required, flame retardancy is imparted by adding a reactor to polymerization of olefin resins to impart flame retardancy and processing by adding a flame retardant to compound processing. In order to manufacture a reactor by adding a double reactor, a separate manufacturing facility is necessary, and since the price of a product is high, generally, a method of adding a flame retardant in processing an olefin resin is used.

Currently, in Japan, Europe, the United States, etc., there is already a master batch of flame retardant and flame retardant supplements, so it is easy to apply flame retardant through blending. However, these products are expensive and they are expensive to use in Korea. There is a technical problem that is difficult to apply.

In Korea, compounding using powdered flame retardants is common in the manufacture of flame retardant polymers. In this case, the environmental health problems of workers due to the scattering of flame retardants and the product quality due to undispersion occur. To overcome this, the trend is to favor flame retardant master batches.

However, in the case of the flame retardant master batch for olefin resins, it is difficult to manufacture the flame retardant content in high concentration due to the manufacturing characteristics. Currently, the flame retardant master batch applied in Korea is generally applied to products having a flame retardant content of 50 weight ratio or less compared to the polymer material content of 50 weight ratio. In order to impart flame retardancy to the olefin resin when such a product is applied, a certain amount of flame retardant must be included, and a large amount of flame retardant master batch must be added to the polymer material. As a result, a large amount of other components other than the flame retardant are prescribed, affecting the inherent physical properties of the existing olefin resins, and causing processing defects (yellowing, bromination, deterioration of properties, poor fusion, etc.) when processing olefin resins. It has limitations. In addition, when processing an olefin resin using a highly concentrated product, there is a possibility of deviation between products due to the deflection of the master batch components in a part of the product.

Therefore, the method for producing highly concentrated highly dispersed flame retardant master batches to minimize the change in the mechanical properties of the olefin resin inherent in the use of the flame retardant master batch to impart flame retardancy to the olefin resin and to prevent the deflection of the flame retardant master batch due to the high concentration. This became necessary.

The present invention is to solve this problem; An object of the present invention is to use a minimum amount of polymer composite materials, to produce a master batch with the highest flame retardant content, and to minimize the mixing of heterogeneous resins and components when applied to olefin resins to minimize the change in mechanical properties, olefin resin processing To provide a flame-retardant master batch manufacturing method for highly concentrated olefin resin to minimize molding defects during

Another object of the present invention is to provide a method for producing a flame retardant master batch for a highly dispersible olefin resin which solves a problem of dispersibility which is likely to occur when using a highly concentrated master batch.

Another object of the present invention is a polymer material having a weight ratio of 4 to 40 by weight, which has a safe and easy pellet shape in terms of handling dispersion and health and safety of the working environment, and minimizes mechanical properties when imparting flame retardance to an olefin resin when preparing a compound. It is to provide a highly concentrated highly dispersed flame retardant master batch manufacturing method of the flame retardant content of 60 to 96 weight ratio.

The present invention for achieving this object is specifically,

In the highly concentrated highly dispersed flame retardant master batch manufacturing method,

A metering step of weighing the olefin resin, the lubricant and the dispersant, the flame retardant and the flame retardant aid;

A mixing step of mixing the weighed composition so that a classification phenomenon between the raw materials does not occur due to the difference in specific gravity between the heavy and light raw materials;

Kneading step of kneading to a condition that the discharge temperature is 110-170 degrees Celsius by inputting polypropylene during the process of using the motor speed of 800-1500 RPM and agitating with the speed reduced to the required speed by the transmission;

An extrusion step of extruding the working temperature of the cylinder, the die, and the conical so as to be 130-200 degrees Celsius;

A cutting step of forming the compressed master batch into pellets;

Characterized in that it comprises a blending step of blending in order to uniformly distribute a predetermined amount of pellets produced and produced continuously to equalize the quality of the master batch,

The metering step comprises 2 to 20 weight ratio of olefin resin, 2 to 20 weight ratio of lubricant and dispersant, 60 to 96 weight ratio of total amount of flame retardant and flame retardant, and flame retardant 1 to flame retardant at total amount of flame retardant and flame retardant. Characterized in that the weight ratio of 1 to 6 ratio,

The olefin-based resin is characterized in that the specific gravity of 0.90 to 0.94 polyethylene and small polycrystalline atactic polypropylene or a mixture of 2 to 20 by weight,

The flame retardant adjuvant is characterized in that the antimony trioxide, antimony pentoxide or a mixture thereof,

The flame retardant is characterized in that the halogen-containing flame retardant organic material, characterized in that the halogen content combined with hydrocarbon is 60 to 85 weight ratio compared to 100 weight ratio of the total amount of the flame retardant,

The flame retardant is characterized in that the thermal decomposition temperature is 350 ℃ to 1300 ℃, the particle size is 2 to 50㎛,

The mixing step is characterized in that the mixing at 500 to 1000 RPM, which is an appropriate rotational speed for 5 to 20 minutes so that classification does not occur between the raw materials,

The kneading step is characterized in that the addition of the artificial polypropylene having a weight ratio of 2 to 20 during the stirring process,

The cutting step is a water-cooling method (Underwater cutting) to cool and cut by extrusion into the water, or air-cooling (Hot-Cuttung) to cool the air without contacting water and cut the ferret (optional), if necessary, the master batch It relates to a highly concentrated high dispersion flame retardant master batch production method characterized by forming a pellet.

It also relates to a product characterized in that it is produced by mixing with the master batch and the resin produced by the highly concentrated highly dispersed flame retardant master batch production method described above.

1 shows a block diagram showing a highly concentrated highly dispersed flame retardant master batch manufacturing process according to the present invention.

Hereinafter, one preferred embodiment according to the present invention will be described in detail with reference to the accompanying drawings.

Highly concentrated high dispersion flame retardant master batch manufacturing method, as shown in Figure 1, the weighing step (10) for accurately weighing the weight and the mixing step 20 and uniformly mixing the composition components in the metered composition in a super mixer A kneading step 30 for mixing and forming a molten state, an extrusion step 40 for extruding melted and melted resin using a continuous twin extruder and a kneader, and a uniformly extruded resin It consists of a blending step 60 to obtain a product in pellet form through a cutting step 50 that is cut to size and blend for uniform distribution of the master batch.

In more detail, the metering step 10 is composed of 2 to 20 weight ratio of olefin resin, 2 to 20 weight ratio of lubricant and dispersant, 60 to 96 weight ratio of total amount of flame retardant and flame retardant, and total amount of flame retardant and flame retardant aid. In the weight ratio of the flame retardant aid 1 to the flame retardant 1 to 6 ratio is to be weighed, each weight may vary within a given weight ratio, if necessary.
The flame retardant uses a flame retardant having a pyrolysis temperature of 200 ° C., but more preferably a flame retardant having a thermal decomposition temperature of 350 ° C. to 1300 ° C., and aluminum hydroxide or magnesium hydroxide has a thermal decomposition temperature of about 230 ° C. and 320 ° C., respectively. The melting temperature is about 120 ° C to 130 ° C, which is easy to mold, and is a commonly used material.However, in order to add flame retardancy, a flame retardant having a thermal decomposition temperature of 350 ° C to 1300 ° C is applied. It is more preferable that the particle size is 2 to 50 µm so as to be easy.

Mixing step 20 is a suitable rotation for 5 to 20 minutes in order to prevent the classification between the raw materials due to the difference in specific gravity between the composition of the heavy weight and the relatively light raw material in the weighed composition, such as olefin resin Mixing with 500 to 1000 RPM,

In the kneading step 30, the discharge temperature is 110-Centigrade by inputting an atactic polypropylene having a ratio of 2 to 20 by weight while the rotation speed of the motor is 800-1500 RPM and the stirring speed is reduced to the required speed with the transmission. Stirring so as to distribute the compositions uniformly at the conditions of 170 degrees and melting to facilitate extrusion.

The extrusion step 40 is to extrude the cylinder, the die, and the conical at a working temperature of 130-200 degrees Celsius, the temperature of each of the slightly different, but the difference between the melting temperature of the working polypropylene and polyethylene Therefore, the range of working temperature is determined.

The cooling method that can be selected in the gating step (50) is an underwater cutting method in which the extruded master batch is extruded into water, cooled, cooled, and the master batch is cut. An additional process that needs to go through the drying process is required, and it is possible to selectively adopt a hot-cutting method that cools the air without contact with water and cuts the pellets.

The blending step 60 is to produce a uniform flame retardant in the master batch produced, but to be able to compensate for this non-uniformity even if not uniformly distributed for the case is produced continuously for quality equalization It is to have a separate storage container in series with the container to interpolate the formed pellets and to continuously distribute the pellets of the master batch produced by blending. This is to ensure that the master batch injected at a constant weight ratio contains a flame retardant uniformly.

Performance Example

  Now, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples. In the present and comparative examples, several performances will be evaluated by the following method.

    (1) Flame retardancy is evaluated in accordance with UL Subject 94 (Underwriters Laboratories Inc.) 5 V class vertical combustion test, where the specimen thickness is 1/8 in.

  (2) Flexural strength and flexural modulus are evaluated according to ASTM D 790.

      (ASTM: Ameican Society of Testing Materials)

  (3) Tensile strength and elongation are evaluated according to ASTM D 638.

  (4) Izod impact strength is evaluated according to ASTM D 256.

  (5) The dispersibility test was applied to the flame retardant tarpaulin coating and randomized sampling, followed by CPAI-84 (Section 5: Flooring material) method of IFAI (Industrial Fabircs Association International), which is the most common tarpaulin flame retardant test standard for domestic authorized agency. Evaluate as a result deviation by analysis.

  Example 1

  Extruded and injected by mixing the PE and the flame retardant masterbatch having a flame retardant content of 80% by weight in the total amount of 100% by weight of the present invention as shown in Table 1, the injection temperature is 170 to 190 ℃, mold temperature is 60 ℃ And flame retardancy and physical properties measured after injecting into ASTM specimen mold at room temperature for 24 hours. The division in Table 1 represents the weight ratio of the master batch with respect to the polyethylene weight ratio, and the residual length represents the residual length limiting the burned length at a given specimen length (120 mm).

Flame retardancy is a vertical combustion test condition for UL 94-5V class. The specimen thickness is 1/8 in. And the length of burning per minute after the specimen is lit should be less than 76.2mm. In Table 1, the combustion time was natural digestion and combustion did not proceed any longer, and the combustion length satisfies the given conditions except for pure PE.

  As a result of Tables 1 and 2, even when the flame retardant masterbatch 5 weight ratio is used, it can be seen that excellent flame retardancy and mechanical properties as a whole are excellent.

  Table 3 shows the results of requesting a sample prepared by using a flame retardant content of 80 weight ratio flame retardant masterbatch for flame retardant coating at the time of preparing tarpaulin to CPAI-84 (Section 5: Flooring material) method to a certified institution. .

Master batch usage refers to the dosage of master batch mixed with 100 weight of resin.

If the thickness of the film is not good when the coating is not good dispersibility, the flame retardancy is not provided, the deviation of the measurement results are generated a lot, was used as an indirect method of measuring the dispersibility.

   original: Original specimen without pretreatment

   * leached: Experiment after drying for 72 hours in water

   * Acceptance criteria: 25mm or more for Original and Leached

  As a result of Table 3, the flame retardant within the total weight 100 shows excellent flame retardancy even when the amount of the highly concentrated master batch of 80 weight ratio is used, and the measurement variation of the specimen is very small despite the high concentration. In addition, it can be seen that there is almost no change from the original state in the leak test assuming washing. The smaller the deviation of the measured value, it can be seen that the dispersion was well made, and the adhesion was excellent, so that the deviation was little before the pretreatment and after the washing. These results were produced by flame retardant master batch of 80 weight ratio flame retardant and tested by various tarpaulin manufacturers in Korea, and as a result, excellent results in dispersibility and flame retardancy.

As described above, the method for producing a highly concentrated high dispersion flame retardant master batch for olefin resins according to the present invention has been described, but the scope of the present invention is not limited thereto, and all technical matters within the scope equivalent to those described in the claims are provided. I will say crazy.

As described in detail above, the present invention realizes a high concentration of a flame retardant content of 60 to 96 weight ratio compared to a 4 to 40 weight ratio polymer material that a general flame retardant masterbatch does not have, and realizes high dispersibility, thereby using a highly concentrated product. It maximizes the intrinsic properties and properties of the resin, maximizes the flame retardant effect according to the selection and proportion of flame retardant suitable for the properties of high dispersion and olefin resin, and restricts the processing conditions (injection, extrusion) of olefin resin due to the high dispersion. It is easy to give the end product a flame retardancy because it can be easily made without receiving it, and the productivity is improved by unifying the process and maximizing the efficiency by the simplicity of operation, and reducing the process of directly applying the flame retardant in the final product producer. Safety and environmental problems such as scattering, body contact and leakage accidents It has the effect of obtaining price competitiveness and rapid technological response compared to imported goods.

Claims (10)

In the highly concentrated highly dispersed flame retardant master batch manufacturing method, A metering step of weighing the olefin resin, the lubricant and the dispersant, the flame retardant and the flame retardant aid; A mixing step of mixing the weighed composition so that a classification phenomenon between the raw materials does not occur due to the difference in specific gravity between the heavy and light raw materials; Kneading step of kneading to a condition that the discharge temperature is 110-170 degrees Celsius by inputting polypropylene during the process of using the motor speed of 800-1500 RPM and agitating with the speed reduced to the required speed by the transmission; An extrusion step of extruding the working temperature of the cylinder, the die, and the conical so as to be 130-200 degrees Celsius; A ketting step of forming the compressed master batch into pellets; A method for producing a highly concentrated flame retardant masterbatch, comprising a blending step of blending in order to uniformly distribute a predetermined amount of pellets that are continuously produced and formed for quality equalization of the masterbatch. The method of claim 1, The metering step comprises 2 to 20 weight ratio of olefin resin, 2 to 20 weight ratio of lubricant and dispersant, 60 to 96 weight ratio of total amount of flame retardant and flame retardant, and flame retardant 1 to flame retardant at total amount of flame retardant and flame retardant. Method for producing a highly concentrated high dispersion flame retardant master batch, characterized in that the weight ratio of 1 to 6 ratio. The method of claim 2, The olefin resin is a highly concentrated high dispersion flame retardant master batch production method characterized in that the specific gravity of 0.90 to 0.94 polyethylene and small crystalline atactic polypropylene or a mixture of 2 to 20% by weight. The method of claim 3, wherein The flame retardant adjuvant is antimony trioxide, antimony pentoxide or a highly concentrated flame retardant master batch manufacturing method characterized in that a mixture thereof. The method of claim 4, wherein The flame retardant is characterized in that the halogen-containing flame-retardant organic material, and the halogen content combined with hydrocarbon is 60 to 85 weight ratio compared to 100 weight ratio of the total amount of the flame retardant, characterized in that highly concentrated high dispersion flame retardant master batch production method. The method of claim 5, The flame retardant is a pyrolytic temperature of 350 ℃ to 1300 ℃, the particle size is 2 to 50 ㎛ high concentrated highly dispersed flame retardant master batch manufacturing method. The method of claim 6, The mixing step is a highly concentrated high-dispersion flame retardant master batch manufacturing method characterized in that the mixing at 500 to 1000 RPM, the appropriate rotational speed for 5 to 20 minutes so that classification does not occur between the raw materials. The method of claim 7, wherein The kneading step is a high concentration of highly dispersed flame retardant master batch manufacturing method characterized in that the separate input of atactic polypropylene having a weight ratio of 2 to 20 during the stirring process. The method according to any one of claims 1 to 8, The cutting step is a water cooling method (Underwater cutting) to cool and cut by extrusion into the water, or air-cooling (Hot-Cuttung) to cool the air without contacting water and cut the ferret (optional), if necessary, the master batch Method for producing a highly concentrated high dispersion flame retardant masterbatch, characterized in that to form a pellet. delete

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