KR100532735B1 - A Surface Treated Magnesium Hydroxide, Method of Preparation Thereof And A Polymeric Composite Material With Improved Flame Resistance - Google Patents

Abstract

The polymer compound having improved flame resistance is 25 to 75 parts by weight, preferably 35 to 60 parts by weight of a thermoplastic material (based on 100 parts by weight of the polymer compound) and 75 to 25 parts by weight, preferably 65 to 40 parts by weight of magnesium hydroxide ( 100 parts by weight of the polymer compound), and the magnesium hydroxide is surface treated with a surface active agent or a surface active agent is mixed uniformly. The magnesium hydroxide has a particle size of 4.0 μm or less, a particle size of 50 μm or less of 1.4 μm, and a crystal aggregate having a specific surface area of 25 m ² / g or less by the BET method. The magnesium hydroxide has a particle size of 150Å or more and 500Å or less by the X-ray powder diffraction method, the aspect ratio is within the range of 2 to 5, the strain in the <004> direction is 4.2 × 10 ⁻³ or less, and the strain in the <110> direction is 3.0. It ^consists of a powder crystal product of 10 × ³ . The method for preparing the surface-treated magnesium hydroxide includes the steps of adding a surface active agent or a portion thereof in the form of a solution or suspension to the aqueous suspension of magnesium hydroxide, mixing the mixture, and treating the surface by separating water. It is characterized by the steps of providing magnesium hydroxide. The mixture of magnesium hydroxide and the surfactant or part thereof is mixed in a mixer at a temperature at which the surfactant can be uniformly deposited on the surface of the magnesium hydroxide, and the product is cooled.

Description

A Surface Treated Magnesium Hydroxide, Method of Preparation Thereof And A Polymeric Composite Material With Improved Flame Resistance

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to magnesium hydroxide surface treated with a surface active agent that provides improved flame resistance to the polymer compound, and relates to a polymer compound having improved flame resistance used in cable manufacturing, the electric and automotive industries. Is composed of surface treated magnesium hydroxide powder and polymer material. The invention also relates to a process for the preparation of surface treated magnesium hydroxide powders.

In many applications in the cable manufacturing, electrical and automotive industries, there are polymer materials that are capable of working thermoplastically and at the same time requiring flame resistance. Most flame retardant polymers are composed of flame retardants based on organic halogen compounds and polymers having halogen molecules attached to the polymer structure as known to date. In addition to enhanced flame resistance, such polymers show some disadvantages. They have no self-extinguishing capacity, are harmful to smoke and the environment, and release corrosive byproducts during thermal oxidative decomposition processes.

If magnesium hydroxide powder is used as the flame retardant in the polymer material, the above technical and environmental (ecological) disadvantages are eliminated. Water that has been chemically bound by the thermal decomposition of magnesium hydroxide is liberated, thereby promoting self-extinguishing and releasing harmless and non-corrosive by-products produced in magnesium hydroxide during the process of thermal oxidative decomposition.

The disadvantage of using magnesium hydroxide as a flame retardant in a synthetic resin is that it is possible to substantially reduce the flammability of a polymer compound when a large amount of magnesium hydroxide is mixed in the synthetic resin. The amount is in most cases within the range of 40% to 65% in the polymer compound. It is quite difficult to evenly mix this much amount of magnesium hydroxide with a polymeric material. This is because the polymer is in most cases a non-polar linear structure composed of long chains, whereas the magnesium hydroxide molecule is polar and the form of the magnesium hydroxide powder particles by the preparation method is hexagonal or spherical. Furthermore, after mixing such a large amount of magnesium hydroxide into a polymeric material, some of its properties, in particular impact strength, strength, ductility, and relative elongation, are lowered. The degree of deterioration of the properties is also due to the ability of the polymer structure to accept magnesium hydroxide before the magnesium hydroxide is mixed with the polymer material and to increase the homogeneous dispersibility of magnesium hydroxide in the polymer structure as much as possible. Depends on the pretreatment method. Water separated from magnesium hydroxide has been found to self-extinguish when the nearest one is located, so the V-0 grade required for flammability can be obtained when there is a complete dispersion of the surface treated magnesium hydroxide. The physical properties of magnesium hydroxide crystals that form aggregates are disadvantageous from this point of view. There is generally no mutual affinity between the polymeric material and magnesium hydroxide. The phase boundary (J. Manson, L. Sperling: Polymer Blends and Composites, Heyden, London 1976), which exists between the polymer structure and the magnesium hydroxide particles, has a decisive influence on the physical properties of the compound. Its interface has properties that vary within a limited thickness and within the relative physical properties of the polymer and magnesium hydroxide [P. Theocaris: Adv. in Polymer Sci. 66 , 149 (1985). Proper surface treatment of the magnesium hydroxide particles results in the formation of an interface where the maximum adhesion between the magnesium hydroxide particles and the polymer and thus the pressure transfer to the filler is achieved. The bonding interface must dissipate energy and prevent pressure concentrations [P. Mardsen, L. Ziemiansky, Br. Polym. J. 11 , 199 (1977).

At present, the most frequently used method to have a positive effect on the properties of the compound, while having a positive effect on the mixing of magnesium hydroxide into the polymer material is a method of surface-treated powdered magnesium hydroxide particles before mixing. Surface treatment of suitable powdered magnesium hydroxide particles satisfies all of the complex requirements mentioned above, so that a given amount of magnesium hydroxide is added to a double-screw compounding extruder of Werner & Pfleiderer Co., KO-kneader of Buss Co., The kneading-granulating device Berstorff ZE 40 EA) should be used to mix the polymer material without any problems to give the material the required appearance, satisfactory flame resistance, workability and practical properties. Properly selected surfactants reduce the energy wall when mixing magnesium hydroxide into the polymer, remove the charge on the surface of the magnesium hydroxide, thereby mixing to the polymer on the one hand and homogeneity of the magnesium hydroxide particles in the polymer compound on the other hand. It promotes a dispersion, positively affects the interfacial properties, enhances the mutual bonding force between inorganic fillers and organic polymers, achieves uniform dispersion of magnesium hydroxide particles in the compound, and couples between the magnesium hydroxide and the polymer structure. It should act as a means to devise the affinity between the ring agent, the binder and the compound to enhance the workability and practicality of the compound.

Alkali salts based on higher fatty acids having the number of carbon molecules of aliphatic chains in Japanese Patent 60243155, US Patent 4 098 762, 5 143 965 and German Patent DT 26 24 065 AL and DE 26 59 933 B1 or their equivalents Surfactants based on alkali salts of alkylsulfates, alkylsulfonates, alkylarylsulfonates or sulforesinic acid esters have been used. Especially sodium stearate, sodium or potassium oleate, sodium or potassium palmitate, sodium or potassium laurate, potassium behenate, sodium laurylbenzenesulfonate, sodium octadecinate, sodium laurylsulfonate, and disodium 2- Surfactants such as sulfoethyl-α-sulfostearate were used

Czechoslovak Patent 241 640 recommends the use of hydrophobic substances, such as mixtures of higher fatty acids or silanes or titanates, as additives to magnesium hydroxide before they are incorporated into polymers. In particular, mixtures of higher fatty acids, aminopropyltriethoxysilane, ethylenediaminopropyl-trimethoxysilane, and triisostearoylisopropyl titanate were used.

The use of alkoxysilanes for the surface treatment of magnesium hydroxide is disclosed in PCT WO 90/13516 but is not given a particular alkoxysilane.

Surface treatment of magnesium hydroxide in US Pat. No. 4,769,179 is carried out using phosphorus containing titanate. Organophosphite titanates and organophosphate titanates are particularly relevant. The following titanates are recommended: tetraisopropyl di (dioctylphosphite) titanate, tetraisopropyl bis (dilaurylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butoxy ) Di- (di-tri-decyl) phosphite titanate, isopropyl tri (dioctylpyrophosphate) titanate, and bis (dioctylpyrophosphate) oxyacetate-titanate.

In EP 0 356 139 Al, other phosphorus containing composite compounds are recommended for the surface treatment of magnesium hydroxide. Diaalcoholamino salts of alcohol phosphate esters or alcohol phosphate esters or metal salts thereof are related. Diethanol amino salts of dioleyl alcohol phosphate esters, sodium salts of lauryl alcohol phosphate esters, diethanolamino salts of stearyl alcohol phosphate esters, sodium salts of erukyl alcohol phosphate esters, and diethanols of arachyl alcohol phosphate esters Amino salts were used. In the comparative example, the surface treatment was performed using sodium oleate.

According to US Patent 4 698 379 and European Patent 0 189 098 A2, it is preferable to use saturated or unsaturated fatty acids, metal salts of fatty acids, fatty acid esters, surfactants, silanes or titanates for the surface treatment of spherical particles of magnesium hydroxide. Among them, titanate is preferred. In particular stearic acid, sodium stearate, monostearylglycerol ester, glycidylsilane, and tetrastearyl titanate were used.

 These methods of surface treatment of powdered magnesium hydroxide have in common that the surfactant consists of only one substance. In view of the variety of requirements related to the mixing of magnesium hydroxide into polymers and the consequent mechanical, electrical and process properties of the compounds produced, it is very difficult for one type of surfactant to satisfy such diverse actions. . Therefore, it is more advantageous to use two or more surface active agents for the surface treatment of magnesium hydroxide.

From the published patent publications (PCT WO 95/19935, PCT WO 96/16902) stearic acid, oleic acid, lauric acid, palmitic acid, sodium or potassium stearate, potassium behenate, sodium montanate, sodium or potassium oleate, sodium or Potassium palmitate, sodium or potassium laurate, sodium dilaurylbenzenesulfonate, potassium octadecylsulfonate, sodium lauryl sulfonate, disodium-2-sulfoethyl-α-sulfostearate, ammonia salts of fatty acids It can be seen that their mixture was also used.

According to US Pat. No. 4,396,730, a good effect is obtained when magnesium hydroxide surface-treated with alkali oleate (eg sodium oleate) is mixed with a treatment agent such as magnesium oleate or aluminum oleate. The enhanced effect of such mixed use has been compared to the case of mixing untreated magnesium hydroxide or magnesium stearate.

Czechoslovak Patent 261 162 discloses mixing untreated magnesium hydroxide into polyolefins with partial esters of fatty acids having 12 to 22 carbons, polybasic alcohols having 3 to 10 carbons, or mixtures of the aforementioned fatty acids or salts thereof. The method of making it is recommended.

German patent DE 39 27 861 AL includes a mixture of calcium, magnesium, zinc salts and fatty acid amides, preferably stearate amides, oleate amides and behenate amides of C ₁₂ -C ₁₈ fatty acids, preferably palmitic or stearic acid. It is said to improve when mixed with the resin.

A disadvantage of this method is that the mixture of surfactants mentioned above consists of chemically similar substances with similar functions, with only one minor component being added to one component. In most cases higher fatty acids or salts or derivatives thereof are used which act as slippers and lubricants and in limited cases as coupling agents.

On the other hand, EP 0 426 196 Al recommends silanes, titanates, aluminates, zirconates, zircon aluminates or mixtures thereof. Also in this case, in most cases, a treatment agent which acts as a coupling agent and has similar properties and functions is involved, and the mixture cannot meet the above-mentioned various requirements for the surface-treated magnesium hydroxide mentioned above. .

Improvements can be expected in US Pat. No. 4,913,965. However, in this case, 25 to 60 parts by weight of vinyl based on 100 parts by weight of crystallographically defined magnesium hydroxide and copolymer having a crystal size larger than 800 mm in the <101> direction and a strain in the <101> direction less than 3.0 × 10 ^−3. It relates to the case where it is limited to ethylenevinyl acetate copolymer comprising acetate. In such a system, magnesium hydroxide is recommended to surface magnesium hydroxide with at least one carboxylic acid (C ₈ -C ₂₄ ) or a metal salt thereof. The amount of the treating agent is 0.1 to 5 parts by weight based on 100 parts by weight of magnesium hydroxide. One of the additives used in the mixing of surface treated magnesium hydroxide is organosilanes which act as coupling agents at very low concentrations (0.017 to 0.277 parts by weight based on 100 parts by weight magnesium hydroxide). However, only two variables were used to evaluate the action of the surfactant, namely limited oxygen and melt flow index, which were not sufficient in terms of workability for cable production, and mechanical properties such as strength, ductility, hardness and elasticity. There is a decrease.

The main disadvantage of the above-mentioned solution is that the requirements for surface treatment of magnesium hydroxide and the requirements for flame resistance and workability cannot be combined in terms of mixing magnesium hydroxide into thermoplastic materials. This is because in most cases, surface treatment is performed using a one-component treatment agent, and even when a mixed treatment agent is used, it is composed of chemically and functionally similar components that cannot bring a high effect. It is further evidence that the sufficient effect of the proposed surface treatment method is not described in the above-mentioned patent specification. In evaluating the overall process, it is necessary to mention the performance of the mixing machine (magnesium hydroxide demand per unit time), the external surface of the mold compound, variables characterizing flammability, and the required physical properties of the compound. The molten polymer material filled with the required amount of magnesium hydroxide is avoided because the filler powder floats on the molten surface and the working rate of the mixing machine is lowered. These variables characterize the shortcomings in terms of adhesion and mutual bonding of organic and inorganic materials. The appearance of the mold compound has an inhomogeneous structure such as "spots" which, when undesirable, exhibits a heterogeneous distribution of magnesium hydroxide in the polymer. This relates to insufficient nonpolarization of the magnesium hydroxide surface (insufficient charge removal from the surface) and reduced functionality of the interface.

In addition to the surface treatment of magnesium hydroxide particles, the mixing, workability, and flame retardancy to the polymer material are greatly influenced by the physical properties of the magnesium hydroxide crystal particles. The interaction between the particles and the polymer structure depends on many factors, among which the porosity, particle size, particle size distribution, and the aggregation tendency of magnesium hydroxide crystals indirectly characterized by S _BET [GR Cotten: Rubber Chem. Technol. 58 , 744 (1985)]. Magnesium hydroxide crystals (primary particles) have a tendency to agglomerate inherently and usually form secondary particles of a size of about one to several tens of micrometers. These secondary particles are powder crystal products that are mixed in the polymer material. If the degree of aggregation of the primary particles is high, the mixing of magnesium hydroxide becomes difficult and it is difficult to achieve uniform dispersion in the compound. So far, the solution to this problem has been to grind large aggregated magnesium hydroxide particles (for example, in Czechoslovakia Patent 241 640, agglomerates larger than 50 μm are pulverized), or large-sized crystals (primary particles) by precipitation and crystallization processes. Operation by precipitation and crystallization processes to produce minimal cohesion affinity (for example according to US Pat. No. 4,098,762, 4 913 965 and German Patent DE 26 59 933 B1, DT 26 24 065 Al. Crystal size should be larger than 800Å).

The disadvantage of this method is the increased energy and cost. The grinding process requires the installation of expensive equipment on the technical line, and also requires energy for its operation. The preparation of large scale single crystals on an industrial scale requires a lot of energy due to the low concentration of solvent, long crystallization time, and consequently many reaction solutions.

It is an object of the present invention to surface-treatment by mixing the required amount of magnesium hydroxide in a thermoplastic material and its homogeneous dispersion, affinity with the thermoplastic material and thereby improved flame resistance, the required workability and practicality. To provide magnesium hydroxide.

It is still another object of the present invention to provide a polymer compound having improved flame resistance and necessary work characteristics by using the surface-treated magnesium hydroxide of the present invention as an flame retardant.

Another object of the present invention is to provide a method for preparing magnesium hydroxide surface-treated with a surfactant.

Further important features of the present invention will become apparent from the following description.

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According to this object of the present invention, magnesium hydroxide must satisfy the general state of the inorganic powder filler. The specific surface area of magnesium hydroxide is 25 m ² / g or less as measured by the BET method, and it is preferable that 50% or more of particles have a diameter of 1.4 µm or less and no particles having a diameter of 4 µm or more. Small sized particles with these characteristics show minimal cohesion of crystals (primary particles). If magnesium hydroxide is provided in the form of a powder crystal product consisting of hexagonal crystals, the agglomeration effect can be minimized by preparing magnesium hydroxide crystals having defined shapes and geometrical properties and energy states on their surfaces. have. In particular, the crystal size in the <004> direction by the X-ray diffraction method is 150 Pa or more and 500 Pa or less, the aspect ratio is within the range of 2 to 5, the strain in the <004> direction is 4.2 x 10 ^-3 or less, and <110 If the strain in the> direction is 3.0 × 10 ⁻³ or less, the agglomeration of the crystals is minimized to produce secondary particles having the desired size and specific surface area as mentioned above. Aspect ratio is defined as the ratio of the crystal size in the <110> direction to the crystal size in the <004> direction. The aspect ratio is an important form variable because it represents the ratio of width to thickness in hexagonal plates. Strain characterizes the energy state for the phase of the crystal. This is described in detail in HP Klug, LE Alexander: X-RAY DIFFRACTION PROCEDURES, Second Edition, John Wiley & Sons, New York 1974. The formulas for crystal size and strain calculations can also be found in the Philips X-Ray diffractometer's manual: PC-APD SOFTWARE OPERATION MANUAL, Edition Notice, Forth Edition, April 1992. More energy is not required than to prepare a large decision not to make such a decision, for example, prepared according to US Patents 4 098 762, 4 913 965, and German Patent DE 26 59 933 B1, DT 26 24 065 A1. Lose.

An important finding of the present invention is a formulation in which various requirements for the surfactant can be satisfied. If a mixture of two or more substances is used as the surfactant, the mixing property of magnesium hydroxide with the polymer will be improved and the heat resistance and workability of the polymer can be improved. And practical properties will be improved. Such surfactants consist of titanates, metal salts of fatty acids, and / or mixtures of fatty acid amides or mixtures of titanates and higher fatty acids or mixtures of silanes and higher fatty acids. The use of such mixtures in certain amounts and in certain concentration ratios has a better effect than using the components of such mixtures alone.

A more important finding of the present invention is that aromatic organic compounds having at least three or more conjugated double bonds are added as surfactants by the above-mentioned mixtures, thereby improving the appearance and physical properties of the polymer compound, which is usually magnesium hydroxide particles. Is to effectively remove the charge on the surface. This effect is important even when the concentration of aromatic polymer compound is low. This improvement is observed when an aromatic compound having at least three conjugated bonds is added to each of titanate, silane, metal salts of fatty acids and / or fatty acid amides, or higher fatty acids, as compared to the case where these substances are used alone. lost.

When a mixture of titanate and a metal salt of fatty acid and / or fatty acid amide or a mixture of higher fatty acids and titanate is used as the surfactant mixture, the amount of the recommended mixed surfactant is 0.5 to 4.0 parts by weight based on 100 parts by weight of magnesium hydroxide. Preferably 1.5 to 3.0 parts by weight.

The amount of titanate in the surfactant is 0.05 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of metal salts of fatty acids and / or fatty acid amides as well as higher fatty acids in the surface active agent is 0.05 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

A mixture of a titanate, fatty acid and / or fatty acid amide metal salt, and an aromatic organic compound having at least three or more conjugated bonds or a mixture of higher fatty acids, titanate, and an aromatic organic compound having at least three or more conjugated bonds If a mixture is used the recommended amount of mixed surfactant is from 0.5 to 4.0 parts by weight, preferably from 1.5 to 3.0 parts by weight, based on 100 parts by weight of magnesium hydroxide.

The amount of titanate in the surface active agent is 0.01 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of metal salts of fatty acids and / or fatty acid amides as well as higher fatty acids in the surface active agent is 0.01 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of the aromatic organic compound having at least three or more conjugated bonds among the surface active agents is 0.002 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight based on 100 parts by weight of magnesium hydroxide.

When a mixture of higher fatty acids and silanes is used as the surfactant mixture, the amount of the recommended mixed surfactant is 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of silane in the surface active agent is 0.3 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of the higher fatty acid in the surface active agent is 0.05 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

When a mixture of higher fatty acids, silanes and aromatic organic compounds having three or more conjugated double bonds is used as the surfactant mixture, the recommended amount of the mixed surfactant is 0.5 to 4.0 parts by weight, preferably 100 parts by weight of magnesium hydroxide. 1.0 to 3.0 parts by weight.

The amount of silane in the surface active agent is 0.01 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of the higher fatty acid in the surface active agent is 0.01 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide.

The amount of the aromatic organic compound having at least three or more conjugated double bonds among the surface active agents is 0.002 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight based on 100 parts by weight of magnesium hydroxide. Polymeric compounds having (a) powdered magnesium hydroxide surface-treated with the surfactant; And (b) a polymer material. Furthermore, the polymer compound having improved flame resistance is 75 to 25 parts by weight, preferably 65 to 40 parts by weight, surface-treated by a surfactant or uniformly mixed with the surfactant. Magnesium hydroxide (based on 100 parts by weight of the polymer compound) and 25 to 75 parts by weight, preferably 35 to 60 parts by weight of the polymer material (based on 100 parts by weight of the polymer compound). Other additives generally used for this purpose are required. It is possible to form part of the polymer compound as needed and depending on the polymer material selected.

Titanates mainly used for the purposes of the present invention are monoalkoxy titanates, chelated titanates, a quaternized titanate, coordination type titanates, cycloheteroatom titanates, or neoalkoxy titanates. The following are examples of monoalkoxy titanates: titanium (IV) 2-propanolate, tri isooctadecanoate-O; Titanium (IV) bis 2-methyl-2-propenoato-O, isooctadecanoate-O 2-propaneolato; Titanium- (IV) 2-propanoleito, tri (dodecyl) benzenesulfonato-O; titanium (IV) 2-propanoleito, tri (dioctyl) phosphato-O; Titanium (IV) (4-amino) benzene sulfonato-O, bis (dodecyl) benzene sulfonato-O, 2-propanolato; Titanium (IV), tri (2-methyl) -2-propenoato-O, methoxydiglycolylato; Titanium (IV) 2-propanoleito, tri (dioctyl) pyrophosphate-O; Titanium (IV), tri (2-propenoato-O), methoxydiglycolylato; Titanium (IV) 2-propanoleito, tri (3,6-diaza) hexanoleito. The following are examples of chelate titanates: titanium (IV) bis [4- (2-phenyl) -2-propyl-2] phenollacto, oxoethylenediolato; Titanium (IV) bis (dioctyl) pyrophosphate-O, oxoethylenediolato, (adduct), (dioctyl) (hydrogen) phosphite-O; Titanium (IV) oxoethylenediolato, tri (2-methyl) -2-propenoato-O; Titanium (IV) bis (butyl, methyl) pyrophosphato-O, oxoethylene-dioleito, (addition), bis (dioctyl) hydrogen phosphite; Titanium (IV) bis (dioctyl) phosphato-O, ethylenediolato; Titanium (IV) bis (dioctyl) pyrophosphato-O, ethylenediolato, (adduct), bis (dioctyl) hydrogen phosphite. Examples of quaternized titanates are given as follows: titanium (IV) bis (dioctyl) pyrophosphato-O, oxoethylenediolato, (additive), 2 moles of 2-N, N-dimethylamino -2-methylpropanol; Titanium (IV) bis (butyl methyl) -pyrophosphato-O, (adduct), 2 moles of 2-N, N-dimethylamino-2-methylpropanol; Titanium (IV) ethylenediolato, bis (dioctyl) pyrophosphate-O, bis (triethyl) amine salt; Titanium (IV) ethylenediolato bis (dioctyl) pyrophosphate-O, bis (dialkyl) amino alkyl-2-methyl propenoate; Titanium (IV) bis (dioctyl) pyrophosphate-O, ethylenediolato, (adduct), 2 moles of acrylato-O active amine; Titanium (IV) bis (dioctyl) pyrophosphato-O, ethylenediolato, (adduct), 2 moles of 2-methylpropenoamido-N active amine; Titanium (IV) bis (butyl, methyl) pyrophosphato, ethylenediolato, bis (dialkyl) amino alkyl acrylate salts; Titanium (IV) (bis-2-propeneolato-methyl) -1-butanolato, bis (dioctyl) pyrophosphato-O, (additive), 3 moles of N, N-dimethylamino- Alkyl propenamides; Titanium (IV) 2,2 (bis-2-propeneolato-methyl) -1-butanoleito, tri (dialkyl) pyrophosphato-O, (additive), n mol of N, N- Dimethylamino-propyl methacrylamide and the alkyl group is octyl or isooctyl and n = 1-3. The following are examples of coordination type titanates: titanium (IV) tetrakis 2-propanoleito, (adduct), 2 moles of (dioctyl) hydrogen phosphate; Titanium (IV) tetrakis octanoleito, (adduct), 2 moles of (di-tridecyl) hydrogen phosphite; Titanium (IV) tetrakis (bis 2-propenolate methyl) -1-butanolato, (adduct), 2 moles of (di-tridecyl) hydrogen phosphite. The following is an example of cycloheteroatom titanate: titanium (IV) bis octanoolato, sclo (dioctyl) pyrophosphato-O, O; Titanium (IV) biscyclo (dioctyl) pyrophosphato-O, O. The following is an example of neoalkoxy titanate: titanium (IV) 2,2 (bis 2-propenolatomethyl) butanolato, tri (dioctyl) phosphate-O; Titanium (IV) 2,2 (bis 2-propenolatetomethyl) butanolato, trineodecanoeto-O; Titanium (IV) 2,2 (bis 2-propenolatomethyl) butanolato, tri (dioctyl) pyrophosphate-O; Titanium (IV) 2,2 (bis 2-propenolatomethyl) butanolato, tri (dodecyl) benzenesulfonato-O; Titanium (IV) 2,2 (bis 2-propenolatomethyl) butanolato, tri (2-ethylenediamino) ethylrayto; Titanium (IV) 2,2 (bis 2-propenolatomethyl) butanolato, tri (3-amino) phenylrayto; Titanium (IV) 2,2 (bis-2-propenolatetomethyl) butanolate; Tri (6-hydroxy) hexanoato-O. Preferably quaternized titanate is used, in particular the alkyl group is octyl or isooctyl, n is 1-3, titanium (IV) 2,2- (bis 2-propenolato-methyl) butanoleito, tri (Dialkyl) pyrophosphato-O, (addition), n mol of N, N-dimethylaminopropylmethacrylamide is used. Instead of one kind of titanate, a number of titanate mixtures suitably selected may equally be used. The choice of suitable titanate is not limited by the titanate list above.

For the purposes of the present invention it is possible to use metal salts of fatty acids and / or fatty acid amides containing a metal cation selected from alkali metals or alkaline earth metals and a carbon chain consisting of 8 to 24 carbon atoms. As examples of such salts, sodium or potassium oleate, sodium or potassium palmitate, zinc or magnesium stearate, palmitate amide, stearic acid amide, oleic acid amide, or mixtures thereof are shown. Preferably a technical mixture of fatty acids and metal salts of fatty acid amides can be used.

It is possible to use fatty acids containing a carbon chain of 8 to 24 carbon atoms for the purposes of the present invention. As examples of such fatty acids, technical mixtures of oleic acid, palmitic acid, stearic acid, and preferably higher fatty acids are given, in particular palmitic acid, stearic acid may be used.

Various types of organofunctional silanes may be used for the purposes of the present invention. Examples of such organofunctional silanes include octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyl-tri (2-methoxyethoxysilane ), Gamma-methacryl-oxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxy Silane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane or other amino Functional groups, triamino functional groups, or isocyanato functional silanes or polysulfidosilanes or vinyl-modified polydimethylsiloxanes or organosilane esters are shown, preferably gamma-aminopropyltriethoxysilane or This compound is used.

Examples of aromatic organic compounds having at least three or more conjugated double bonds include 4-dimethylaminoazobenzene, 1,4-diaminoanthraquinone, or preferably 2,2 '-(1,2-ethenedyldi-4,1- Phenylene) bisbenzochazole is shown.

Examples of polymeric materials that can be used according to the invention include polyolefins, polyamides, PVC, ethylene-propylene copolymers (EPM), ethylene-propylene-diene copolymers (EPDM), ethylene-vinylacetate copolymers (EVA), And their block copolymers, polystyrenes, styrene-based elastomers (eg SBS, SIS, SEBS), ether-ester-block copolymers (EEBC), thermoplastic PUR-elastomers (TPU), polyether-polyamide- Block copolymer (PEBA), thermoplastic silicone rubber (TPQ), styrene-acrylonitrile copolymer (SAN), ethylene-ethylacrylate copolymer (EEA), isobutylene-isoprene copolymer (IIR), rubber ABS, AAS, AS, MBS, chlorinated polyolefin (PE chloride, PP chloride), vinyl chloride-propylene copolymer, polyvinylacetate, polyacetal, polyimide, polycarbonate, polysulfone, polyphenylene oxide, polybutylene tere The de-rate, methacrylic polymers, and mixture of them technically by appropriate mixing ratio are presented.

Additives such as antioxidants, UV stabilizers, antistatic agents, pigments, dyes, plasticizers, fillers, viscosity modifiers, metal deactivators, crosslinking agents, fibrous reinforcing fillers, etc. may be composed of a portion of the polymer compound as required by the choice of polymer material. Can be.

As examples of the additives mentioned above a) oxidizing agents are: mono-cumyl diphenylamine, 4,4-dicumyl diphenylamine and their technical mixtures, phenyl-α-naphthylamine, 2,6-di-tert -Butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, thiobis (β-naphthol), styrenated phenol, distearyl thiodipropionate, dilauryl thiodipropionate , [Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenol) propiotate] methane, 2,2-thio [diethyl-bis-3- (3,5-di-tert -Butyl-4-hydroxyphenol) propionate], N, N'-diphenyl-p-phenylenedi-amine, N, N'-di-β-naphthyl-p-phenylenediamine, N-iso Propyl-N'-phenyl-p-phenylenediamine, trinonylphenylphosphite, 4,4'-isopropylidene bis-phenol, phenol, 1,1-bis- (4-oxyphenyl) cyclohexane, dialkyl Ethylene trialkylphenol, 2-mercaptomethylbenzimidazole; b) UV stabilizers include: carboxyphenyl salicylate, p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, benzophenone, 4-dodecyloxy-2-hydroxybenzophenone , 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate; c) antistatic agents include sulfonated oleic acid, pentaerythritol monostearate, phosphate esters, lauryltrimethylammonium chloride, alifetic amines, alkylphenols; d) As dyes: rhodamine, methyl violet, prussian blue, yellow cadmium, red cadmium, titanium white, red iron oxide, barium sulfate, zinc sulfate, ultramarine, eosin, cobalt blue, benzidine yellow, carmine 6B, carbon black ; e) Plasticizers include: dimethylphthalate, diethylphthalate, n-octylphthalate, di-n-butylphthalate, di-2-ethylhexyl adipate, di-n-decyl adipate, tributyl phosphate, tri-2- Ethylhexyl phosphate, dioctyl sebacate, bearing oil, epoxidized soybean oil; f) Fillers include: calcium carbonate, asbestos, glass fibers, aluminum powder, copper powder, iron powder, alumina, talc, gypsum, graphite, carbon black, barium sulfate, dolomite, silica gel, titanium oxide, iron oxide, silica carbide; g) binders include: dicumyl peroxide, tert-butylcumyl peroxide, α, α'-bis (tert-butylperoxy-m-isopropylbenzene), tetramethylthiuram disulfide, tetraethylthiuram disulfide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide; h) Fibrous reinforcing fillers include: asbestos, fiberglass, potassium titanate, fibrous magnesium hydroxide, fibrous magnesium oxide, carbon fiber; And the like, and the scope of the additives used by the examples given is not limited.

The amount of the additive is determined, for example, about 0.01 to 5% by weight of antioxidants, about 0.01 to 1.0% by weight of UV stabilizers, about 0.1 to 2.0% by weight of antistatic agents, and dyes based on the weight of the polymer material. Is about 0.1 to 5% by weight, about 10 to 60% by weight of the softener, about 5 to 60% by weight of the filler, about 1.0 to 10% by weight of the crosslinking agent, and 5 to 50% by weight of the fibrous reinforcement filler. .

All components of the surfactant according to the invention must be brought into contact with magnesium hydroxide simultaneously. This is because only this state allows the components to be uniformly diffused on the surface of the magnesium hydroxide. The surface of the magnesium hydroxide particles in this case is said to have been treated with a complete surfactant. After only some of the components of the surfactant are contacted with magnesium hydroxide, the surface treated magnesium hydroxide can be mixed with the polymeric material together with the remaining components of the surfactant according to the invention. Magnesium hydroxide particles in this case are said to have been treated with an incomplete surfactant. In the latter case, the effect is reduced because some of the surfactant is added to the surface-treated magnesium hydroxide prior to mixing with the polymer, and the surface is covered by an incomplete surfactant compared to the case where it is placed directly on the surface of the magnesium hydroxide. The effect is reduced.

According to the present invention, a surface-treated magnesium hydroxide is prepared by adding a complete or incomplete surfactant in the form of a solution or emulsion to an aqueous suspension of magnesium hydroxide, stirring the mixture, and then separating the water. Can be. When dissolving higher fatty acid, its metal salt or amide in water, solubility can be improved by adding a small amount of ammonia. Surface treatment is usually performed at room temperature of 20-30 degreeC. The process can be carried out by a continuous mixer with a stirrer or by a batch method. In the case of a batch method, the contact and stirring time should not normally exceed 45 minutes, usually about 30 minutes. After filtration the filter cake is dried at 110 to 130 ° C. until constant weight.

According to another method of preparing surface-treated magnesium hydroxide, a mixture of magnesium hydroxide and a complete or incomplete surfactant is mixed at an elevated temperature such that the surfactant can be uniformly dispersed on the surface of the magnesium hydroxide particles. The product is then cooled. This method uses a high speed flow mixer that obtains the heat required to increase the flowability of the surfactant and adhesion to the magnesium hydroxide particle surface from the kinetic energy during the particle collision process.

According to another method of preparing surface treated magnesium hydroxide, a complete or incomplete surface active agent is added to the aqueous suspension of magnesium hydroxide so that the aqueous suspension has a temperature of 110-200 ° C. and 0.2-1.6 MPa. Hydrothermally treated and then cooled and the water is dried and separated.

The following examples illustrate the invention in more detail, and the scope of the invention is not limited to the following examples.

Example 1

The crystal size in the direction of magnesium hydroxide measured by X-ray powder diffraction (powder X-ray diffractormeter Philips PW 1820 using detector PW 1710) was 458 Å and a laser diffractometer measuring particle size and particle size distribution ( Aspect ratio measured by SK Laser Micron Sizer PRO-7000, SEISHIN) is 2.2: 1, the strain in the <004> direction is 1.92 × 10 ^-3 , the strain in the <110> direction is 2.85 × 10 ^-3 , d ₅₀ Is 1.01 μm, and S _BET measured from adsorption isotherm (ACUSORB 2100 E, MICROMERITICS) of nitrogen adsorption is 9120 kg, 2258 kg of magnesium hydroxide in the form of filter cake containing 8.6 m ² / g, 35.2 wt% of dry matter. The demineralized water at 30 ° C. is washed and filtered in a reactor equipped with a stirrer. 7.95 kg of titanium (IV) 2,2- (bis-2-propenolatomethyl) butanoleito, tri (diisooctyl) pyrophosphato-O and as an additive N, N-dimethylamino-propyl methacryl Separately prepared 2500 kg aqueous solution containing a mixture of amide and 11.92 kg of fatty acid and metal salt of fatty acid amide (Struktol Polydis TR 016). Suspension of magnesium hydroxide and an aqueous solution of the treating agent are continuously supplied to a through-flow blender, and dried to 110 to 130 ℃ after filtration to obtain a surface-treated magnesium hydroxide.

Dough-granulation extruder comprising a polymer compound consisting of 65 parts by weight of surface-treated magnesium hydroxide and 35 parts by weight of polypropylene (homogeneous polymer, melt flow index is specified at 230 ° C. and 2.16 kg at 5 g / 10 min). Prepared by (Werner & Pfleiderer ZSK 30). Test specimens are prepared by injection at 230 ° C. Physical properties are given in Table 1.

Example 2

Example using a technical mixture of 10.33 kg of higher fatty acids, in particular a mixture containing palmitic acid and stearic acid dissolved by addition of a small amount of ammonia, instead of a mixture of 11.92 kg of fatty acids and metal salts of fatty acid amides used in Example 1 The same process as in 1 is carried out. The physical properties of the materials are given in Table 1.

Example 3

The procedure according to Example 1, except that the aqueous solution of the surfactant further contains 0.08 kg of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole. The same process is carried out. The physical properties of the materials are given in Table 1.

Example 4

The process according to Example 2, except that the aqueous solution of the surfactant further contains 0.08 kg of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole. The same process is carried out. The physical properties of the materials are given in Table 1.

Example 5

The crystal size of magnesium hydroxide measured by X-ray powder diffraction in the <004> direction is 358, the aspect ratio is 3.2: 1, the strain in the <004> direction is 2.92 × 10 ^-3 , and the <110> direction. Has a strain of 2.25 × 10 ^-3 , d ₅₀ of 1.03μm, S _BET of 9.4 m ² / g, 2273 kg of magnesium hydroxide in the form of filter cake containing 35.1 wt% of dry matter, 9120 kg of demineralized water at 30 ° C. It is washed and filtered in a reactor equipped with a stirrer. 23.9 kg of titanium (IV) 2,2- (bis-2-propenolatomethyl) butanolito, tri (diisooctyl) pyrophosphato-O and as an additive N, N-dimethylamino-propyl methacryl Separately 2500 kg of an aqueous solution containing a mixture of amide and 0.160 kg of 2,2 '-(1,2-ethenyldi-4,1-phenylene) bisbenzochazole are prepared separately. Suspension of magnesium hydroxide and an aqueous solution of the treatment agent are continuously supplied to a through-flow blender, and filtered and dried to 110 to 130 ℃ to obtain a surface-treated magnesium hydroxide.

The polymer compound is prepared in the same manner as in Example 1. The physical properties of the materials are given in Table 1.

Example 6

The same procedure as in Example 5 was carried out using a mixture of 23.85 kg of fatty acid and metal salt of fatty acid amide (Struktol Polydis TR 016) instead of the titanate used in Example 5. The physical properties of the materials are given in Table 1.

Comparative Example 1

The procedure according to Example 5, wherein 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole was not added to the aqueous solution used in Example 5, and the aqueous solution contained only titanate. The same process as is carried out. The physical properties of the materials are given in Table 1.

Comparative Example 2

2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole was not added to the aqueous solution used in Example 6, and the aqueous solution contained only a mixture of fatty acids and metal salts of fatty acid amides. The same process as that in Example 6 is carried out. The physical properties of the materials are given in Table 1.

Example 7

The crystal size of magnesium hydroxide in the <004> direction measured by X-ray powder diffraction was 182 Å, the aspect ratio was 4.65: 1, the strain in the <004> direction was 3.96 × 10 ^-3 , and the <110> direction. Has a strain of 1.92 × 10 ⁻³ , d ₅₀ of 0.98 μm, S _BET of 9.6 m ² / g, and 30 kg of magnesium hydroxide aqueous suspension containing 7.5% by weight of dry matter. 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzoin containing 4 kg of aqueous ammonia solution containing 0.0225 kg of stearic acid and 2.25 x 10 ^-4 kg of surfactant 0.5 kg of an aqueous solution of azole is mixed at room temperature. The mixture is stirred for 30 minutes, filtered and dried at 110 ° C. until constant temperature.

The compound is prepared by the kneading machine Brabender according to the following mixing ratio: 100 parts by weight of Levapren 400 (EVA-copolymer, 40% VAC, Bayer AG), 150 parts by weight of surface-treated magnesium hydroxide, 20 parts by weight of carbon black FEF , 6 parts by weight of dioctyl sebacate (plasticizer), 8 parts by weight of Perkadox BC 40K (peroxide), 1.5 parts by weight of Duasantox 86 (antioxidant), and 2 parts by weight of TAIC. The results are given in Table 2.

Comparative Example 3

The same procedure as in Example 7 was carried out except that an aqueous solution of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole was not added. The physical properties of the materials are given in Table 2.

Example 8

30 kg of an aqueous suspension of magnesium hydroxide having the same physical properties as those given in Example 7 and 7.5% by weight of dry matter contained 0.68 kg of an aqueous solution containing 0.034 kg of gamma-aminopropyltriethoxysilane and 4.5 × 10 ⁻ 0.5 kg of an aqueous solution containing ⁴ kg of 2,2 '-(1,2-ethenyldi-4,1-phenylene) bisbenzochazole is mixed at room temperature. The mixture is stirred for 30 minutes, filtered and dried at 110 ° C. until constant weight.

The polymer compound is prepared by the kneading machine Brabender at a temperature of 160 ° C. according to the following mixing ratio: 9.66 parts by weight of Escorene LL 1004 YB (LLDPE), 29.00 parts by weight of Escorene Ultra 00226 (EVA-copolymer containing 26% VAC) , 61.10 parts by weight of surface-treated magnesium hydroxide, 0.04 part by weight of Triganox (peroxide), 0.20 part by weight of Irganox 1010 (antioxidant). The physical properties of the materials are given in Table 2.

Comparative Example 4

The same procedure as in Example 8 was carried out except that an aqueous solution of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole was not added. The physical properties of the materials are given in Table 2.

Example 9

30 kg of an aqueous suspension of magnesium hydroxide having the same physical properties and 7.5% by weight of dry matter as those given in Example 7 are 0.0225 kg of a technical mixture of higher fatty acids, specifically 4 kg of an aqueous ammonia solution containing palmitic acid and stearic acid. And 0.68 kg of an aqueous solution containing 0.034 kg of vinyl-tri (2-methoxyethoxysilane) at room temperature. The mixture is stirred for 30 minutes, filtered and dried at 110 ° C. until constant weight.

Preparation of the polymer compound is carried out in the same manner as in Example 8. The physical properties of the materials are given in Table 2.

Example 10

0.5 kg of an aqueous solution containing 1.05 × 10 ⁻⁴ kg of 2,2 ′-(1,2-ethenyldi-4,1-phenylene) -bisbenzochazole was added to the aqueous suspension of magnesium hydroxide The same process as in Example 9 was carried out except for mixing. The physical properties of the materials are given in Table 2.

Example 11

4.8 kg of titanium (IV) bis (butylmethyl) -pyrophosphato-O, 4.8 kg of zinc stearate, and 1.6 × 10 additionally comprising 2-N, N-dimethylamino-2-methylpropanol 8000 kg of magnesium hydroxide aqueous solution containing 800 kg of aqueous solution containing ^-2 kg of 2,2 '-(1,2-ethenyldi-4,1-phenylene) bisbenzochazole, containing 320 kg of magnesium hydroxide Is added to the suspension. The mixture is hydrothermally treated at 140 ° C. and 0.7 MPa for 15 minutes. After cooling to 60 ° C., filtered, the product is washed with water and dried at 110-130 ° C. The process of preparing the polymer compound is the same as in Example 1. The physical properties of the materials are given in Table 1.

Example 12

Titanium (IV) 2,2- (bis-2-propenolatomethyl deposited on 149.2 g of finely ground inert substrate after 30 kg of dry magnesium hydroxide powder having the same physical properties as in Example 1 was added to a high speed fluid mixer. A mixture of butanolato, tri (diisooctyl) pyrophosphate-O and a metal salt of fatty acid and fatty acid amide of 750 g (Struktol Polydis TR 016) and 30 g of 2,2 '-(1,2-ethenedyldi-) With 4,1-phenylene) bisbenzoacsol at 130 ° C. After cooling, the product is used to prepare a polymer compound in the same process as in Example 1. Properties of the properties are given in Table 1.

Example 13

19.1 kg of titanium (IV) 2-propanoleito, tri (dioctyl) phosphate-O as titanate, only 2.4 kg of Struktol instead of 11.92 kg of Struktol, aromatic compound with conjugated double bond Is carried out in the same manner as in Example 1, except that 20 g of 1,4-diaminoanthraquinone is used. The physical properties of the materials are given in Table 1.

Example 14

The same procedure as in Example 3 was carried out except that an aqueous solution of the compound to be added and an aqueous solution of only the bisbenzokazole derivative were added to the aqueous suspension of magnesium hydroxide. The product obtained after drying is homogeneously mixed with 10.3 kg of a mixture of fatty acids and metal salts of fatty acid amides (Struktol Polydis TR 016). The polymer compound is prepared in the same manner as in Example 1. The physical properties of the materials are given in Table 1.

Example 15

2.35 kg of titanium (IV) bis (dioctyl) pyrophosphato-O and oxoethylenediolato, 2.35 kg, wherein 2500 kg of aqueous solution additionally contains 2-N, N-dimethylamino-2-methylpropanol Same procedure as in Example 3, except that it contains stearic acid, and 0.08 kg of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) -bisbenzochazole Is carried out. The polymer compound is prepared in the same manner as in Example 1. The physical properties of the materials are given in Table 2.

Example 16

The procedure was carried out in the same manner as in Example 8, except that 4.5 g of the technical mixture of higher fatty acids and 6.7 g of gamma-aminopropyltriethoxysilane were used. The polymer compound is prepared in the same manner as in Example 8. The physical properties of the materials are given in Table 2.

Example 17

Except that 0.5 kg of an aqueous solution of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole containing 2.25 x 10 ^-4 kg of active agent is additionally added. The same procedure as in Example 16 is carried out. The physical properties of the materials are given in Table 2.

Example 18

The same procedure as in Example 7 was carried out except that 67.5 g of higher fatty acid was used.

The polymer compound is prepared in the following compounding ratio: 100 parts by weight of Buna AP 437 (EPDM-terpolymer), 200 parts by weight of surface-treated magnesium hydroxide, 1 part by weight of gamma-aminopropyltriethoxysilane, bearing oil (plasticizer) 40 Parts by weight, 40 parts by weight of carbon black FEF, 10 parts by weight of Perkadox BC 40K (peroxide), 10 parts by weight, 1.5 parts by weight of Dusantox 86 (antioxidant), and 1.8 parts by weight of TAIC. The physical properties of the materials are given in Table 2.

Example 19

Example except that 0.5 kg of an aqueous solution of 2,2 '-(1,2-ethenyldi-4,1-phenylene) bisbenzochazole containing 2.25 × 10 ⁻⁴ kg of active agent was added and used. The same procedure as in 18 is carried out. A high molecular compound is prepared in the same manner as in Example 18. The physical properties of the materials are given in Table 2.

Example 20

The same procedure as in Example 18 was carried out except that only 9.0 g of higher fatty acids were used.

The polymer compound is prepared in the same blending ratio as in Example 18 except that 6 parts by weight of gamma-aminopropyltriethoxysilane is used. The physical properties of the materials are given in Table 2.

Example 21

Example 20 except for further adding 0.5 kg of an aqueous solution of 2,2 '-(1,2-ethenedyldi-4,1-phenylene) bisbenzochazole containing 2.25 × 10 ⁻⁴ kg of active agent It is carried out in the same process as the process by. The polymer compound is prepared in the same manner as in Example 20. The physical properties of the materials are given in Table 2.

Example 22

The crystal size in the <004> direction is 522Å, the aspect ratio is 1.85: 1, the strain in the <004> direction is 1.96 × 10 ^-3 , the strain in the <110> direction is 3.12 × 10 ^-3 , and the d ₅₀ is 1.35 S _BET is carried out by the same procedure as in Example 3, except that magnesium hydroxide of 20.6 m ² / g is used. The physical properties of the materials are given in Table 1.

Example 23

4 kg of an aqueous ammonia solution containing 67.5 g of a mixture of higher fatty acids, 0.68 kg of an aqueous solution containing 11.25 g of gamma-aminopropyltriethoxysilane, and 2,2 '-(1,2) containing 2.25 x 10 ^-4 kg of an active agent. Magnesium hydroxide surface-treated in the same manner as in Example 7 was prepared except that 0.5 kg of an aqueous solution of ethenedyldi-4,1-phenylene) bisbenzokazole was used. A high molecular compound is prepared in the same manner as in Example 18 except that gamma-aminopropyltriethoxysilane is further added. The physical properties of the materials are given in Table 2.

Polymer material Magnesium Hydroxide Amount Appearance Flowability g / 10min 1) Flammability 2) Impact resistance 3) Refractive temperature under load C) Strength MPa 5) Hardness MPa 6) Magnesium hydroxide mixing rate kg / h 7) Example 1 PP 64.9 Very low 8.2 V-0 24 119.1 25.9 87 12 Example 2 PP 65.2 Very low 10.8 V-0 22 117.2 23.8 85 10 Example 3 PP 65 none 9.9 V-0 26 123.1 26.2 95 12 or more Example 4 PP 65.1 none 9.3 V-0 24 120 25.6 88 12 or more Example 5 PP 64.2 none 8.8 V-0 25 119.8 25.5 80 12 Example 6 PP 64.3 none 10.6 V-0 19 115 22.6 78 12 Comparative Example 1 PP 65 has exist 3.5 V-1 16 114.2 19.8 70 6 Comparative Example 2 PP 65 has exist 12.2 V-1 6 105.1 13.5 65 5 Example 11 PP 64.8 none 10.1 V-0 23 119.2 25.2 85 12 or more Example 12 PP 65.1 none 9.9 V-0 19 118.3 24.9 80 12 Example 13 PP 65 none 8.1 V-0 25 120.7 24.8 88 12 Example 14 PP 65 none 9.5 V-0 25 121.8 24.5 80 12 or more Example 15 PP 65.2 none 6.8 V-0 26 119.6 27 82 10 Example 22 PP 64.8 none 6.7 V-0 20 121.3 21.3 79 10 8) PP 100 none 5.2 Combustion 37 51

1) Measured at 230 ° C, 2.16 kg according to STN 64 0861

2) UL 94 (the thickness of the specimen is 3.2mm)

3) Impact strength according to STN 64 0612, Charpy method 23 ℃, kj / m ²

4) ISO 75, ART.B

5) Tensile strength according to STN 64 0605

6) Brinell hardness according to STN 64 0128, 60 s

7) Maximum mixing speed; instrument measuring range is 12kg / h or less, maximum mixing amount is 12 or more

8) Basic Polymers-Slovnaft, Bratislava Propylene ME 311

Polymer material Magnesium Hydroxide Amount Strength MPa 1) Ductility% 2) HardnessSh A 5) Shout% Flammability6) Example 7 EVA 52,2 Measure 7.46 485 83 24 V-0 3) after aging 7.41 435 85 24 V-0 Comparative Example 3 EVA 52.2 Measure 7.06 439 80 20 V-0 3) after aging 6.37 385 81 20 V-1 Example 8 PE + EVA 61.1 Measure 8.09 425 86 20 V-0 3) after aging 7.98 405 86 20 V-0 Comparative Example 4 PE + EVA 61.1 Measure 7.54 401 81 18 V-0 3) after aging 6.82 350 82 18 V-1 Example 9 PE + EVA 61.1 Measure 8.05 454 87 22 V-0 3) after aging 7.89 420 86 22 V-0 Example 10 PE + EVA 61.1 Measure 8.34 465 92 23 V-0 3) after aging 8.08 450 90 23 V-0 Example 16 PE + EVA 61.1 Measure 7.86 416 84 21 V-0 3) after aging 7.55 400 84 21 V-0 Example 17 PE + EVA 61.1 Measure 7.95 422 86 21 V-0 3) after aging 7.88 412 85 21 V-0

Polymer material Magnesium Hydroxide Amount Strength MPa 1) Ductility% 2) HardnessSh A 5) Shout% Flammability6) Example 18 EPDM 50.9 Measure 6.87 560 76 32 V-0 4) after aging 6.7 520 76 32 V-0 Example 19 EPDM 50.9 Measure 6.65 637 76 34 V-0 4) after aging 6.6 611 76 34 V-0 Example 20 EPDM 50.9 Measure 7.05 527 76 30 V-0 4) after aging 6.98 517 76 30 V-0 Example 21 EPDM 50.9 Measure 7.21 545 77 33 V-0 4) after aging 7.14 545 77 33 V-0 Example 23 EPDM 50.9 Measure 6.9 640 77 34 V-0 4) after aging 6.9 638 77 34 V-0

1) Tensile strength at burst point in accordance with STN 62 1436. According to STN 34 7470, a minimum strength of 6.5 MPa is required for EVA copolymer cables, and the rate of change after aging is within +/- 30%; A minimum strength of 5 MPa is required for EPDM rubber cables and a minimum strength of 4.2 MPa with a rate of change within +/- 25% after aging.

2) Ductility according to STN 62 1436. At least 200% ductility is required in accordance with STN 34 7470 for EVA copolymer cables, and the required rate of change after aging is within +/- 30%; At least 200% ductility is required for EPDM rubber cables, and the required rate of change after aging is within +/- 25%.

3) 10 days / 150 ℃

4) 7 days / 100 ℃

5) Hardness in accordance with STN 62 1431

6) UL 94 (3mm)

Claims (34)

(A) a titanate, a mixture of metal salts of fatty acids and fatty acid amides, and aromatic organic compounds having at least three conjugated double bonds, or (B) titanates and / or aromatic organic compounds having at least one higher fatty acid metal salt and at least three conjugated double bonds, or (C) aromatic organic compounds having a silane and / or at least one higher fatty acid and at least three conjugated double bonds, Magnesium hydroxide surface-treated with a surface active agent consisting of a mixture of Mn, wherein the amount of the surface active agent is 0.5 to 4.0 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of the surfactant is 1.5 to 3.0 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of titanate in the surfactant is 0.01 to 3.0 parts by weight based on 100 parts by weight of magnesium hydroxide. 4. The surface-treated magnesium hydroxide according to claim 3, wherein the amount of titanate in the surfactant is 0.4 to 1.5 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of metal salts of fatty acids and fatty acid amides in the surface active agent is 0.01 to 3.5 parts by weight based on 100 parts by weight of magnesium hydroxide. 6. The surface-treated magnesium hydroxide according to claim 5, wherein the amount of metal salts of fatty acids and fatty acid amides in the surface active agent is 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of at least one higher fatty acid metal salt in the surface active agent is 0.01 to 3.5 parts by weight based on 100 parts by weight of magnesium hydroxide. 8. The surface-treated magnesium hydroxide according to claim 7, wherein the amount of at least one higher fatty acid metal salt in the surface active agent is 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of silane in the surfactant is 0.01 to 3.0 parts by weight based on 100 parts by weight of magnesium hydroxide. 10. The surface-treated magnesium hydroxide according to claim 9, wherein the amount of silane in the surfactant is 0.4 to 1.5 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of at least one higher fatty acid in the surfactant is 0.01 to 3.5 parts by weight based on 100 parts by weight of magnesium hydroxide. 12. The surface-treated magnesium hydroxide according to claim 11, wherein the amount of at least one higher fatty acid in the surfactant is 1.0 to 2.5 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 1, wherein the amount of the aromatic organic compound having at least three conjugated double bonds is 0.002 to 0.1 parts by weight based on 100 parts by weight of magnesium hydroxide. The surface-treated magnesium hydroxide according to claim 13, wherein the amount of the aromatic organic compound having at least three conjugated double bonds is 0.005 to 0.05 parts by weight based on 100 parts by weight of magnesium hydroxide. A polymer compound having improved flame resistance, characterized in that it is composed of any one of the magnesium hydroxide and a polymer material selected from the group consisting of the surface-treated magnesium hydroxide of claim 1-14. The improved flame resistance according to claim 15, comprising 75 to 25 parts by weight of the surface-treated magnesium hydroxide based on 100 parts by weight of the polymer compound and 25 to 75 parts by weight of the polymer material based on 100 parts by weight of the polymer compound. Having a high molecular compound. 17. The improved flame resistance according to claim 16, comprising 65 to 40 parts by weight of the surface-treated magnesium hydroxide and 35 to 60 parts by weight of the polymer material based on 100 parts by weight of the polymer compound. Having a high molecular compound. A method for producing any one of the magnesium hydroxide selected from the group consisting of the surface-treated magnesium hydroxide of claim 1, wherein the surfactant or a portion of the surface active agent in the form of a solution or suspension is magnesium hydroxide Adding to the aqueous suspension of, mixing the mixture, and separating the water to provide surface-treated magnesium hydroxide, the method of producing surface-treated magnesium hydroxide. delete 15. A method for producing any one of the magnesium hydroxides selected from the group consisting of the surface-treated magnesium hydroxides of claim 1, wherein the surfactant or a portion of the surfactant is added to the aqueous suspension of magnesium hydroxide. The surface is characterized in that the suspension is subjected to hydrothermal treatment at a temperature of 100 to 200 ℃, pressure conditions of 0.2 to 1.6 MPa, cooling and then separating the water to provide a surface-treated magnesium hydroxide Process for producing treated magnesium hydroxide. delete delete delete delete delete delete delete delete delete delete delete delete delete delete