Magnesium hydroxide flame retarder and production thereof

[Detailed Description of the Invention]

(Field of the Invention) The 0 present invention about the magnesium hydroxide series fire retardant which the present invention excelled in white-proof Fancy, and its process relates to the fire-resistant olefin system resin composition which blended this fire retardant further. (PRIOR ART) It is known for many years that magnesium hydroxide is the outstanding fire retardant to olefin system resin etc., and being comparatively large quantity and blending magnesium hydroxide with olefin system resin with metal soap as occasion demands is also performed widely. Magnesium hydroxide used for this fire retardant, A caustic alkali or slaked lime milk is made to add and react into sea water or bitterness of life, and output is washed, A small amount of sodium hydroxide is added to the method of drying, and magnesium hydroxide, How to carry out pressurization heat-treatment by the autoclave middle class (JP,50-23680,B), How to carry out pressurization heat-treatment of the basic magnesium salt in a water medium (JP,52-115799,A), The method (for example, JP,61-168522,A and 62 No. -123014 gazette) of making water-soluble magnesium salt and ammonia react, and manufacturing magnesium hydroxide salt, etc. are known. (Problem which an invention tends to solve) Although the above-mentioned magnesium hydroxide currently conventionally used for fire retardant has the comparatively well-organized particle shape, such as hexagon tabular, and comparatively regular and detailed particle diameter, for example and it has an advantage of making it filled up comparatively so much to olefin system resin etc., These compounded resin constituents have some problems which should still be solved. One of them is producing the phenomenon called what is called a white flower phenomenon that white Powder cloth produces to the cast surface, when the resin-molding article which blended magnesium hydroxide series fire retardant so much is placed into the atmosphere for a long period of time. This white flower phenomenon's analysis of that powder will accept it to be what is depended on the magnesium hydroxide blended into the cast reacting with carbon dioxide in the atmosphere from To which is magnesium carbonate. The two are that mechanical properties like fracture growth deteriorate considerably in the olefin system resin composition which blended publicly known magnesium hydroxide series fire retardant, especially the thing blended with comparatively large resin of the elastic modulus. Therefore, the above-mentioned problem in that of conventional magnesium hydroxide series fire retardant is canceled, and the object of the present invention is to provide magnesium hydroxide fire retardant excellent in white-proof Fancy and mechanical properties, such as growth, and its process. Other objects of the present invention are low costs comparatively, and providing easy magnesium hydroxide series fire retardant and its process also has manufacture. (Means for solving a problem) According to the present invention, the wet milling of the natural blue site is carried out so that the median size by the Coulter counter method may be set to 2 thru/or 6 micrometers, The surface treatment of this pulverization thing is carried out with the ammonium salt or amine salt of fatty acid, and the process of the magnesium hydroxide series fire retardant drying subsequently is provided. The magnesium hydroxide particles which according to the present invention have the developed blue site type crystal structure again, and have a 2 thru/or 6-micrometer median size and 1xten to three or less lattice distorted coefficient, The fatty acid layer which covers the surface of the particle and in which at least one copy forms magnesium salt is comprised, and I001 is the X diffraction peak intensity of the plane indices [001] of a sample among a formula type, and it is ■. the magnesium hydroxide series fire retardant which 1 excelled in white-proof Fancy, wherein the degree for Arrangement come out of and defined (D0) which is the X diffraction peak intensity of the plane indices [101] of a sample is two or more is provided. According to the present invention, the flame retardant resin composition which blends the magnesium hydroxide series fire retardant of further the above-mentioned specification with olefin system resin is provided. (OPERATION) It is one feature to use a natural blue site as materials of magnesium hydroxide in the present invention. At a natural blue site, the blue site type crystal structure is well developed, and, moreover, a lattice distorted coefficient also has especially the feature which is not accepted 1x10 to three or less in synthetic magnesium hydroxide that it is 8X10 to three or less. This artificer found out the fact which has the interest like the next in the research process in which it results in the present invention. That is, the sample of the magnesium hydroxide which has various lattice distorted coefficients was prepared, this magnesium hydroxide was immersed into carbonated water, the relation between a lattice distorted coefficient and the amount of magnesium carbonate generation was investigated, and the result shown in the diagram of Drawing 1 was obtained. From the result of Drawing 1, the amount of generation of magnesium carbonate in a magnesium hydroxide particle surface has the more obvious fact that the amount of generation of magnesium carbonate increases, as there is a close relation to the lattice distorted coefficient of magnesium hydroxide and a lattice distorted coefficient becomes large. In the present invention, based on this knowledge, the crystal is well developed and, moreover, uses a natural blue site as materials as a comparatively small thing of lattice distortion. By the way, if a natural blue site has big and rough particles and they remain as it is, it cannot be blended into resin. It is the second feature that carry out the wet milling of this blue site, and 2 thru/or 6 micrometers of median sizes by the Coulter counter method moreover carry out particle size adjustment in the present invention so that it may be set especially to 2 thru/or 4 micrometers. If a blue site is ground in the air, the glabella of a blue site being easily divided by pickpocket stress, and becoming a formless substance in X-rays by exfoliation and the re-crystal of [001] sides is known (the second board of a "clay handbook"). If this is ground for particle size adjustment though a natural blue site will have the developed crystal structure in the Clay Science of Japan line, Gihodo Shuppan, and (1967), considering this publicly known fact, it will be predicted that a special crystal structure is destroyed. However, it is without it will change the degree of crystallinity and lattice distorted coefficient of this blue site on substance if the wet milling of the natural blue site is carried out according to the present invention, In the 0 present invention which can carry out particle size adjustment to the particle size mentioned above, It is also important that a particle size is in a mentioned range, if the tendency for the mechanical strength of the constituent blended with resin to fall becomes remarkable if particle diameter becomes large across a mentioned range and particle diameter becomes smaller than a mentioned range on the other hand, there is a tendency for the fusion flow characteristic and fabrication nature of a combination constituent to fall, and neither is preferred. Subsequently, the surface treatment of the obtained pulverization thing is carried out with the ammonium salt or amine salt of fatty acid, and drying is the third feature. That is, the active field of magnesium hydroxide still exists in the blue site pulverization thing. If the surface treatment of this pulverization thing is carried out with the ammonium salt or amine salt of fatty acid and this thing is dried, this salt will decompose, ammonia and amine will Devaluation and active fatty acid will remain on the surface. It reacts to the magnesium hydroxide site of this fatty acid where at least one copy is active, and blocking of an active side is performed. In this way, according to the present invention, it will be understood that the magnesium hydroxide series fire retardant by which reactivity with carbon dioxide was controlled notably is provided, And the fatty acid magnesium which exists in a magnesium hydroxide particle surface, and fatty acid show the operation which promotes the dispersibility to the inside of resin as a dispersing agent which covers magnesium hydroxide particles. In blue site type magnesium hydroxide particles, There is little activity in respect of being parallel to the direction of C axis [001], in the magnesium hydroxide series fire retardant of the 0 present invention with large activity in respect of a transverse direction to this, also in the state where particle diameter was made detailed, the crystal to the direction of C axis is developed, and it will also be understood that the activity is small. The X diffraction image of magnesium hydroxide (blue site) according [ the Ath table of the following ] to an ASTM card on the other hand Drawing 2 indicates the X diffraction image of the magnesium hydroxide series fire retardant of the present invention to be is shown. The Ath table As for contrast with Drawing 2 and the Ath table, the magnesium hydroxide series fire retardant of the present invention shows that the [0013 page crystal is developed. The degree for Arrangement (00) of the above-mentioned formula (1) can prescribe this feature. Especially in the thing of the present invention, the degree for Arrangement of conventional synthetic magnesium hydroxide series fire retardant (D0) is three or more two or more to this degree for Arrangement (D0) being 1.7 or less. According to this feature, when the fire retardant of the present invention is excellent in white-proof Fancy and it blends with resin, it has the feature that the maintenance rate of growth is large. (Suitable mode of an invention) The natural blue site (bruclte) used for the present invention, Having the developed blue site type crystal structure, generally especially 85 thru/or 95% of purity and the example of representation of the composition in which what has 8xten to four or less lattice distorted coefficient especially is [ 1x10 to three or less ] preferred are as follows 80 thru/or 96%. 8th Table General range Optimum range Mg0 55.0~66.0% 59.0~65.0%51(h 8.0~1.0 7.0~2.0Ca0 4.0~1.0 3.O~1.5 red-heat loss in quantity 32.0~25.0 30.0~26.0 -- although this blue site is produced by the Kyoto Oe-yama Eyama mine and Fukuoka Bikidomade etc. also in our country Abundant production is carried out in the Democratic People's Republic of Korea, the People's Republic of China old Manchuria territory, etc. The wet milling of a natural blue site prepares the aqueous slurry of a blue site, This slurry is supplied to a ball mill, tower mill, circular vibrating mill, and spiral rotating vibrating mill, a planet Morphology machine, a Sand grat interchange, an atomizer, Barbe riser, super Miquelon Mill, a colloid mill, etc., and is ground. Generally 10 thru/or 25% of the weight of the range is suitable for especially the concentration of slurry 5 thru/or 30% of the weight. Although the particle size of a pulverization thing, suitably and generally, does not need to be in the range mentioned above, by request, it can perform part class operation to a liquid cyclone through pulverization slurry, and can also take out the thing of a desired particle size. As the fatty acid which adds the ammonium salt or amine salt of fatty acid to this pulverization slurry in the form of emulsified liquid, agitates this system to it, and performs a surface treatment to it, The saturation of carbon numbers 8 thru/or 20 thru/or unsaturated fatty acid, for example, lauric acid, Barh Myzin acid, Stearic acid, oleic acid, linoleic acid, arachin acid, tridecyl acid, Mixed fatty acid, such as myristic acid, pentadecyl acid, heptadecyl acid, nona decanoic acid, behenic acid, Liln acid, arachidonic acid, palm oil fatty acid, beef tallow fatty acid, soybean oil fatty acid, palm oil fatty acid, and hydrogenated oil fatty acid, etc. can be mentioned. Oleic acid is preferred also among these. Although it is preferred to use these fatty acid in the form of ammonium salt, it is also using amine salt and can use 1000 no, G or tree ethanol amine, morpholine, pyrrolidine, piperidine, etc. as amine in Can and this case. 0 both mixed churning with sufficient using such ammonium salt or especially amine salt in 2.0 thru/or 5.0% of the weight of quantity 1.5 thru/or 6.0% of the weight per blue site and as fatty acid, Although not restricted in particular, generally, it is good 20 thru/or 90degreeC, and to carry out at the temperature of 40 thru/or 80 degreeC especially, and it good after addition mixture to make it ripe under loose churning time to change. By means, such as filtration, centrifugal separation, and sedimentation, the surface treatment slurry obtained carries out solid-liquid separation, dries and cracks from a water medium, and is taken as a product. The magnesium hydroxide series fire retardant of the present invention is useful as fire retardant of various thermoplastics, especially olefin system resin. As olefin system resin, they are inside - of low -1, or high-density polyethylene, Polypropylene, an ethylene propylene copolymer, an ethylene butene-1 copolymer, An ethylene-vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, An ion bridge construction olefin copolymer (eye Onomer) etc. can be mentioned, and especially the magnesium hydroxide series fire retardant of the present invention can be blended in 100 thru/or 200% of the weight of quantity 90 thru/or 230% of the weight per resin. (EFFECT OF THE INVENTION) In the present invention, a crystal structure progresses, and a natural blue site where a lattice distorted coefficient is small is chosen as materials, and the wet milling of this is carried out, and the surface treatment of this is carried out with ammonium salt or amine salt of fatty acid. Therefore, also a point of particle structure, or in respect of surface activity, reactivity with carbon dioxide was controlled and magnesium hydroxide series fire retardant excellent in white-proof Fancy was provided. In this way, the resin-molding article which blended this fire retardant has the advantage of excelling in the appearance characteristic by temporality. This fire retardant is excellent in dispersibility to inside of resin in relation to that particle structure and surface structure. There is an advantage of a combination cast having large growth at the time of a fracture, and excelling also in mechanical strength. (EXAMPLE) Example 1 In this example, magnesium hydroxide series fire retardant excellent in white-proof Fancy is manufactured by using natural blue site (Brucite) as materials, and the constituent blended with olefin system resin is explained. As a natural blue site, three kinds (A-1*B-1, C-1), the product from the Korean Cattle island, the product from a loth mine of Lancaster, Texas, U.S., and the product from Astestus of the Canada Quebec state, were chosen. The composition (analytical value), blue Cyto purity, and a median size were measured, and it was shown in the 1st table of the following. For comparison, it measured similarly about the synthetic-compounds magnesium hydroxide (made by A company) compounded from sea water magnesium, and it combined and displayed on the 1st table. The measuring method used for below by the present invention for physical-properties specification or identification is indicated. ■ Measuring method Knee of a powder X diffraction According to the procedure of the powder X-ray diffraction method of a usual state method, it measured on the measurement conditions shown below using Physical science Electricity fellows X diffraction device (goniometer PMG-52, rate meter ECP-D2). (Measurement conditions) Target Cu filter nickel Detector SC voltage 40 kV Current 20 mA Count scale 8000 C/s Damping Time Constant 1 Sec Scan Speed 178 Degrees / Win Chart Speed 2 Cod/win Recei Bing Slit 0.3 Amm Sinta Ring Slit 1Degree 2 * Granthing Angle 6 * ■ On the foundation [ figure / which was measured under the conditions of the powder X-ray diffraction method of a statement by the 0th paragraph of the measuring method Knee above of the lattice distorted coefficient of plane indices (101) / diffraction ], The method procedure (refer to "X ray technical-analysis method" Ohm-Sha bookstore (1965)) which Jones (Jorns) etc. have proposed is followed, Plane indices (101) and (202) an angle were asked for beta (true half-value width) after amendment using high purity silicon (99.99% of purity), and it asked for eta (lattice distorted coefficient) using the formula (1) of following Hol l. theta -- nib -- a rack angle beta: True half-value width (Radians) epsilon; crystal Child diameter (person) eta: Lattice distorted coefficient ■ Measuring method Knee of the degree for Arrangement (D0) On the basis of the diffraction figure measured under the measurement conditions shown below with the powder X-ray diffraction method of the above-mentioned statement, plane indices (001) and the intensity of the diffraction peak of (101) were substituted for the following combination degree (D0) type (2), and it asked for the degree for Arrangement (D0). Degree for Arrangement (D0) =I(001)/I (101) - (2) 1 (001) Peak intensity of nibble side plane indices (001) (c.p.s.) Peak intensity (c.p.s.) (measurement conditions) of I (101) nibble side plane indices (101) Target Cu Filter nickel Detector SC voltage 30 kV Current 15 a+A Count full scale 8000 c/s damping time constant 1 Sec Scan Speed 2-Degree[/L. ] 1Lin Chart Speed 1 Cm/minm/m-Jens Slit 1 * Recei Bing Slit 0.15 Amm Sinta Ring Slit 1 * Granthing Angle 6@ ■ On the basis of the diffraction figure which measured and carried out the measuring method Knee sample of blue site purity (%) under the measurement conditions shown below with the powder X-ray diffraction method of the above-mentioned statement, the diffraction peak of plane indices (101) was used and a fixed quantity was measured with the internal reference method. As an internal reference method, it is Ahead silica gel powder (product made from Slag Chemical industry) to a sample by a usual state method (refer to "X ray technical-analysis method" Ohm-Sha bookstore (1965)). It is calcium fluoride (CaF) to the amount % of Jill Tong LP gas-105 501i. The Wako Pure Chem make and a reagent best are added 10% of the weight by outside Deleting, and it is after mixture homogeneously enough, In the case of the blue site of a powder X diffraction figure measured under the following measurement conditions, in the case of plane indices (101) and calcium fluoride, it calculated from the surface ratio of the diffraction peak of plane indices (111), and it calculated the content of the blue side at percent. (Measurement conditions) Target Cu filter nickel Detector SC voltage 40 kV Current 20 mA Count full scale 8000 c/s damping time constant 2 Sec Scan Speed 174 Degrees / Min Chart Speed 1 Cm/+in Diver Jens Slit 1 * Recei Bing Slit 0.3 Amm Sinta Ring Slit 1 * Granthing Angle 6@ ■ CO2 -- after adding and carrying out homogeneous distribution of the sample powder 20g into Co2 gas saturated solution 60OIIIIL in measuring method Knee 25 degreeC of which reactant test, by 25 degreeC, it was neglected for three days, it ranked next, the solid part was dried by 110 degreeC after filtering a liquid part, and it was considered as the reactant measurement sample with CO. On the basis of the diffraction figure which measured the sample made to contact CO2 with a described method according to a powder X-ray diffraction method and measurement conditions given [ above-mentioned ] in 0 paragraphs, reactant measurement used the diffraction peak of plane indices (101), and measured it in fixed quantity with the standard addition method. As a standard addition method, it is silica gel (the same product made from Slag Chemical industry as the above) after 50-% of the weight addition first to a sample by a usual state method, In outside Deleting, blue site standard goods are respectively added with 5 % of the weight and 10 % of the weight, it calculates from the increase ratio in area of the diffraction peak of plane indices (101), the quantity of magnesium hydroxide reacted to CO2 is calculated, and it is a reaction with CO□ from this value, It was estimated that reactivity was low, so that the figure made into the amount of generation of the generated magnesium carbonate (%) was small. ■ Measure and take 1 g of samples to the measuring method Knee 200mA beaker of a mean particle size (median size), add deionized water 150mIl to this, and make it distribute for 2 minutes by an ultrasonic wave under churning. Subsequently, the Coulter counter TA If type by a Coulter counter company is used, and these dispersion liquid are measured using aperture tube 100micrometer. It asked for the mean particle size (median size (micro!l)) from the cumulative distribution figure obtained at this time. 150 g of natural blue sites (sample number A-1 and B-1) and water 750g (20% of slurry concentration) used as these materials were taken to the pot mill made from Magnetic of capacity 71, respectively, the Flint ball was used as grinding media, and was rotated for 8 hours, and wet milling was performed. It is begun in a container to take two kinds (sample number A-2, B-2) of after-pulverization pulverization slurry. It heats to the temperature of about 80 degreeC, and it pours under churning of emulsion solution of the oleic acid ammonium Ahead prepared, and receives this slurry liquid at blue site solid content, The quantity of oleic acid ammonium applied the quantity which corresponds to 2.5% of the weight, and also it agitated for 2 hours, holding to about 80 degreeC, and the surface treatment was carried out, making some oleic acid ammonium react to each blue site particle surface. Two kinds (sample number A-4 and B-4) of blue site type magnesium hydroxide series fire retardant powder by which filtered, washed, dried by 110 degreeC after this surface treatment, and the surface treatment was carried out with oleic acid ammonium were manufactured. It filters from the blue site slurry before [ which is depended on oleic acid ammonium among two kinds of blue site samples manufactured here ] carrying out a blue site surface treatment, It dried, and about two kinds (sample A-3, B-3) of prepared unsettled blue site particle powder, physical-properties measurement shown below was performed and the result was shown in the 2nd table of the following. Physical-properties measurement same as a comparative example was performed for the above-mentioned synthetic compounds, and the result was combined with the 2nd table and displayed. Subsequently, using the two kinds of samples, it blended with olefin system resin, and the evaluation as a resin product was pulled, it carried out by the growth remaining rate test and the carbon dioxide-proof test (white-proof Fancy), and the test of the limiting oxygen index estimated the fire-resistant effect common. The above-mentioned synthetic compounds were similarly evaluated as a comparative example. Resin selected in this example chose two kinds, E V A by east A (Ethylene Vinyl Acetate: Ultra Sen 630) marketed for industry, and Nippon Unicar EEA (Ethylene Ethyl Acrylate : DPDJ 6169). To 100 weight sections of resin, the loadings to resin add 130 weight sections of sample powder, and a 3.5-inch kneading roll is used for them, Roll kneading is carried out for 10 minutes by 100 degreeC, and the surface inserts into the press board made from stainless steel by which Teflon processing was carried out, It pressed for 7 minutes by 130 degreeC, and prepared each piece for an examination of a sheet (as for a dumbbell type (it is -7113 to JIS), and the object for a carbon dioxide-proof test, in the object for a growth remaining rate test, 60mmX 120 mmX 1 am and the object for a limiting-oxygen-index measurement test are 8 wax 80 am x 1 am at 1 mm in thickness). Using the above piece for an examination of a sheet, each physical-properties test was done and the result was displayed on the 3rd table. The test measuring method which performed physical-properties evaluation of the resin product in which fire retardant was blended with below is indicated. ■ The sheet for an examination which was pulled and was prepared with the measuring method Knee described method of the growth remaining rate test, It hung in the desiccator saturated with 90% of related humidity by CO□ gas, settled on the homoiothermal room of 30 degreeC for two weeks, and measured to JIS- the sheet for an examination put into this two-week CO2 gas after cutting to the Dan Bella type based on the tensile test method of a plastic given in -7113. It is shown that the tolerance which receives that a sheet pulls is strong, so that a growth remaining rate is large. ■ The sheet for an examination prepared with measuring method 2 described method of the carbon dioxide-proof test (white-proof Fancy), It hung in the desiccator saturated with 90% of related humidity by CO2 gas, and settled on the homoiothermal room of 30 degreeC for two weeks, the amount of weight increments of the sheet for an examination for these two weeks was calculated, and it expressed as the rate of a weight increment (%), and it was estimated that it excelled in carbon dioxide-proof nature (white-proof Fancy), so that the rate of increase was small. ■ Using the product candle method combustion tester made from measuring method Knee Oriental energy machine manufacture new of a limiting-oxygen-index (%) test, based on the A method given in -7201, it examined to JIS-, and asked for the limiting oxygen index (%), and it was estimated that a fire-resistant effect was large, so that this index was large. ■ It is based on a method given in measuring method Knee JIS- of an electrical-insulation-properties (VR, omega-cm) test -1723, After holding the piece of a resin sheet (thickness 1 m+a) which contains the sample of the specified quantity in the desiccator maintained at relation humidity 60% for 24 hours (20degreeC), pure vaseline is used for the piece of an examination sheet, and tin foil is stuck on it, and it is the Direct bias method, The electrical resistance value of the sheet was measured and volume resistivity value rho (ohm-c+a) was calculated with the following formula from this measured value. rho: Volume resistivity value (ohm-cm) A: Area (cm2) D of tin foil (the smaller one) : the result more than the thickness (cm) of a sheet, Two kinds of blue site [ each ] manufactured by the method of the present invention is prepared by the suitable diameter of a particle, moreover, a lattice distorted coefficient is small, and the crystal is well developed, and the degree for Arrangement is high, and it is effective for the Orientation distribution at the time of combination to resin. A blue site by which the surface treatment was carried out with oleic acid salt in this example is magnesium hydroxide which CO2 saturation underwater reactivity is pressed down low and cannot carbonic-acid-ize easily. And since reactivity with carbon dioxide is controlled, a sheet blended with resin does not have white Fancy, and I am understood with a sufficient time of comparing with a case where excelling in fire retardancy moreover is synthetic compounds. Example 2 This example explains the magnesium hydroxide series fire retardant by which the surface treatment was carried out with the ammonium salt or amine salt of fatty acid. The method same in the Example 1 using the slurry of sample number A= 2 prepared by the method of the statement in Example 1 as wet-milling slurry of a natural blue site as a statement, Two kinds of fatty acid salt was chosen from the 1st class of second impression reagent, and it carries out a surface treatment and dried [ filtered, washed and ] at a quantity rate shown in the 4th table of the following, and manufactured two kinds (reagent number 2-1 and 2-2) of blue site type magnesium hydroxide series fire retardant by which the surface treatment was carried out, respectively. Using oleic acid soda as a finishing agent, the surface treatment was carried out similarly, and after filtration, with ion exchange water, it washed enough and prepared. The comparative example sample was also prepared. About the fire retardant sample by which the white Fancy of a blue site system by which the surface treatment was carried out with the oleic acid salt prepared here was prevented, 130 copies of samples are blended with 100 copies of resin like the case of Example 1 at olefin system resin 2 My (EVA, EEA), respectively, that each measurement of physical properties is performed, and the result is combined with the 4th table and displayed. When the above result carries out the surface treatment of ammonium salt and amine salt of fatty acid, compared with a time of carrying out a surface treatment with oleic acid soda, the reactivity of COZ is low and excellent in white-proof Fancy. And it is understood that it is combination fire retardant to olefin system resin excellent also in electrical insulation properties.

[Brief Description of the Drawings]

Drawing 1 shows the related figure of the lattice distorted coefficient which the magnesium hydroxide series fire retardant of the present invention has, and the amount of generation of magnesium carbonate (%). Drawing 2 shows the X diffraction figure of magnesium hydroxide of the present invention, and composite magnesium hydroxide (comparative example). Applicant for a patent Drawing 1 of Mizusawa Industrial Chemicals, Ltd.