CN102123947B - Magnesium hydrate composition and manufacturing method thereof, and resin composition and molded article thereof - Google Patents

Abstract

Provided is a magnesium hydrate composition comprising magnesium hydrate particles containing iron and/or manganese and sulfur. The content (M) of the iron and/or manganese as measured using an atomic absorption spectrophotometer is in the range of 10-1,000 ppm with respect to the magnesium hydrate particles, the content (S) of the sulfur as measured using an infrared absorption method is in the range of 10 to 1,800 ppm with respect to the magnesium hydrate particles, and the ratio (S/M) of the content (S) of the sulfur to the content (M) of the iron and/or manganese is in the range of 1.0 to 1.8. The magnesium hydrate composition has excellent flame retardancy and sustainability thereof when mixed with a resin, and excellent thermal deterioration resistance and a good hue can be imparted.

Description

Magnesium hydroxide composition, its manufacture method and resin combination and molding thereof

Technical field

The present invention relates to compare with magnesium hydroxide in the past, magnesium hydroxide composition and the manufacture method thereof of high flame retardant and good tone be can give resin, and the resin combination that the resistance to thermal deterioration, the flame retardant resistance that form in resin are good and the molding being formed by this resin combination are engaged in.In further detail, relate to a kind of magnesium hydroxide composition, its manufacture method and be engaged in the resin combination that the resistance to thermal deterioration, the flame retardant resistance that form in resin are good and the molding being formed by this resin combination, described magnesium hydroxide composition has the following advantages: while being engaged in resin, dispersed good magnesium hydroxide particles improves its flame retardant resistance owing to containing specific metallic element, and due to the cause that contains metallic element, can produce hardly tone and worsen.

Background technology

For synthetic resins, although because resin itself compares the reasons such as light high, the easy shaping of intensity, low price with metallographic phase, be widely used in each field.But resin, also far away than the easy burning of metal, has therefore proposed the requirement to the flame retardant resistance of resin forming product, it is high and strict that this requirement becomes.In order to reach the object that meets this fire-retardantization requirement, proposed in the past and used the fire retardant of halogen compounds and ANTIMONY TRIOXIDE SB 203 99.8 PCT, and extensively implemented gradually.

But, this halogen compounds adds and is exposed on man-hour under high temperature in shaping, because its temperature makes a part, decompose to produce halogen gas, thereby have, make processing machine and forming mill burn into produce detrimentally affect etc. to the thermotolerance of resin and rubber, weathering resistance to manufacture the problem in upper, physical property.In addition, because halogen gas is toxic to human body, the operating environment while therefore not only making to manufacture worsens, and is engaged in and while using in resin, rubber, has the situations such as the fire of causing, when molding is discarded, burning disposal, there is a large amount of problems such as cigarette that contain toxic gas that produce.Particularly the generation of toxic gas during fire is great problem, when occurring, fire postpones because fire-retardantization of resin forming product makes fire spreading, although for example take, strive for that the people's that live within doors evacuation time is that object is used, but due to its toxic gas, health is produced to detrimentally affect, sometimes even can make people lose one's life.The original application target of this situation and halogen compounds is put the cart before the horse, and is the thing that definitely avoid.

In addition, as the fire retardant beyond halogen flame retardant, can enumerate phosphorus flame retardant.But, because phosphorus flame retardant mostly is liquid, thereby there is following many problems that must solve: the physical strengths such as shock-resistance that are combined with the resin forming product of phosphorus flame retardant reduce; Due to easy hydrolysis, so long-term water tolerance, the weathering resistance of molding are poor; Possibility of the Environmental Hormone Pollution that existence causes due to dyeing of phosphorus compound etc., such as not only meeting the desired UL-94 specifications such as electric wire, cable, automobile electrical gas distribution, and there is long-term water tolerance and weathering resistance, on not impact of environment, this is very difficult to prior art.

Therefore,, to not existing the requirement of the non-halogen flame retardant of the problems referred to above to improve, metal hydroxidess such as aluminium hydroxide, magnesium hydroxide receives publicity.But, aluminium hydroxide starts to decompose at approximately 190 ℃, dehydration, therefore the temperature that being engaged to is shaped adds man-hour is in 190 ℃ of above resins time, adding aluminium hydroxide decomposition in man-hour, dewatering and foam, processing on not only the manufacturing difficulty that becomes, and the physical property such as the intensity of resin and rubber, weathering resistance reduces, and also damages the outward appearance of product etc., the problem that the resin that significantly infringement value of the product, so existence is used is restricted.

On the other hand, for magnesium hydroxide, because dehydration, decomposition starting temperature are 340 ℃, therefore have advantages of and may be fitted in nearly all resin.And magnesium hydroxide has following two kinds: the brucite powder as natural mineral is broken to fine, carries out as required classification and adjust being called as of granularity natural product or the magnesium hydroxide of heavy product; And the bittern that the magnesium chloride generating as by product when take magnesium chloride in seawater or salt manufacturing is main component carries out after purifying, the chemical combination product that obtain with alkali reaction.

In order not damaging, to coordinate the outward appearance, intensity, weather resistance of the resin forming product that magnesium hydroxide obtains etc., to wish that these magnesium hydroxide particles are with fine form homogeneous and dispersed good particle.While there is the macroparticle of single or firm aggegation in resin forming product, for example, while using in the molding of above-mentioned electric wire, cable, automobile electrical gas distribution, with used the molding with fine form homogeneous and dispersed good particle and compared, the pit on molding surface, convex portion become many, diminish outward appearance.In addition, in resin, rubber, coordinate and take magnesium hydroxide while being main inorganic particulate, shock-resistance, tensile strength improve well-known and are to commonly use, but it depends on the particle diameter of inorganic particulate, and when particle diameter is large, the reduction of intensity physical property is well-known too.Although its detailed mechanism is also indefinite at present, while there is the macroparticle irrelevant with particle single or aggegation in resin, the intensity of resin molded body can not meet required physical property.And easily in the surface of molding, expose, thereby the moisture and the carbon dioxide magnesium hydroxide that absorb in atmosphere become magnesiumcarbonate, due to its volume change or rotten, thereby generation is peeled off or departs from resin boundary surface, the weather resistance of infringement molding etc., because these are former thereby value of the product is reduced.

For natural product, because raw material is mineral, so the particle size adjusting method of particle is the easier methods such as pulverizing, classification, so have advantages of and can manufacture at an easy rate, adjust.But, in order to reach the object of removing oversize particle, while strengthening pulverizing or repeatedly pulverizing more than necessary degree, there is the problem as powder that can generate firm and thick agglomeration between fine particle due to its surface, even the method addressing this problem is pulverized, any method of classification, up to the present do not disclose yet.In addition, the shape of the particle heterogeneity that becomes during pulverizing, therefore performance, by decomposing, during flame retardant resistance that dehydration causes, can not obtain the flame retardant effect of homogeneous, is not preferred.Although also proposed, by add surface treatment agent when pulverizing, to carry out surface-treated method when pulverizing, from the viewpoint of cost and dispersed, still cannot solve the above problems.

And, therefore owing to take natural crystal as raw material, there is caused by contained impurity painted and contain the worries such as asbestos, with current technology, be difficult to remove at an easy rate these materials.Therefore, there is the problem of cost savings lost as using the maximum advantage of natural product.

On the other hand, for the magnesium hydroxide of chemical combination product, can select not containing the objectionable raw material such as asbestos or the raw material except natural crystal, or can remove by enforcement purifying less expensively.And by adjusting reaction conditions, can adjust to a certain extent granularity or the dispersion of the particle of generation, be therefore used in particular in recent years the purposes such as electric wire, cable, electronic unit.

For example, the magnesium hydroxide that the synthesis method of the magnesium hydroxide proposing in use patent documentation 1 obtains, its crystalline structure is compared with magnesium hydroxide in the past, structural distortion is little, therefore there is specific shape and granularity, there is the feature such as residual few of secondary aggegation few and dispersed good, water molecules or air, can be for above-mentioned purposes.

But, in order to meet the fire-retardant specification of UL-94 of one of index as the flame retardant resistance of electric wire, cable etc., must be in resin coordinate in a large number, there is thus the problem that physical property, particularly Emhorn (Izod) shock strength that makes molding original, elongation, tensile strength etc. reduce.

In addition, in patent documentation 2, proposed to make the crystallization of magnesium hydroxide contain in manganese, iron, cobalt, nickel, copper, zinc any and form complex metal hydroxide.By the part of the crystallization of magnesium hydroxide being formed to the oxyhydroxide of composite metal salt, thereby reduce its decomposition, dehydration temperaturre and improve flame retardant resistance, solved patent documentation 1 magnesium hydroxide particles a large amount of cooperations with problem.But, because the metallic element of bringing in the crystalline structure of magnesium hydroxide is present in crystallization as oxyhydroxide, therefore there is the painted significant problem of particle self.

While using in the molding such as electric wire, cable, electronic unit, even the complex metal hydroxide particle of patent documentation 2, also need in resin, rubber, coordinate in a large number, while therefore for example using in automobile electrical gas distribution, the object original with electric wire coatings etc. is not directly related, but by each electric wire coloring the secondary object distinguished, there is the remarkable painted problem being restricted due to particle self.Also can in resin, rubber, add hue adjustment agent to adjust tone, but because the amount of the magnesium hydroxide coordinating in resin is large, therefore also must add a large amount of tone conditioning agents, if consider the impact on plasticity, weathering resistance, weather resistance like this, the use of hue adjustment agent is restricted.

In addition, metal hydroxides is because its hydroxyl decomposes and dewaters and bring into play fire retardation, but above-mentioned metallic element is because atomic molar ratio magnesium is large, while being therefore engaged in resin with the identical ratio of the magnesium hydroxide with in the past, the hydroxyl coordinating reduces relatively, the problem that exists flame retardant resistance to reduce.By increasing mixing ratio, can address the above problem, but along with mixing ratio increase produces again the new problem of the intensity physical property reduction of plasticity, resin forming product.

And; although can add the muriate of above-mentioned metallic element in when reaction, the muriate of nickel, chromium, cobalt is expensive, and using, when discarded, need to consider the strict protection of environment etc.; if want cheap and produce in large quantities, use, needing the more problems solving.

In addition, in patent documentation 3, impurity and the physical property of in magnesium hydroxide particles, as sosoloid or inclusion, sneaking into are studied, find contrary with patent documentation 2, when iron, manganese, cobalt, chromium, copper, vanadium, nickel exist with specified quantitative above as impurity, thermal degradation when to resin exerts an influence, and has proposed their content to be strictly limited in below specified quantitative.

But, the particle obtaining in patent documentation 3, the flame retardant resistance of having brought although realized the raising of the resistance to thermal deterioration while being engaged in resin, rubber improves, and resistance to thermal deterioration is necessarily abundant hardly, and the problems of tone and a large amount of cooperations in resin, rubber are not solved completely.

In addition, one of requirement that flame retardant resistance is improved in recent years, can enumerate the performance of lasting flame retardant resistance.Metal hydroxides as magnesium hydroxide, once decompose, after dehydration with flame retardant resistance without any relation, the problem that therefore exists persistence to be short of, but in above-mentioned patent documentation 1～3, the problem of lasting flame retardant resistance is not proposed to any countermeasure of improving.

Prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication sho 52-115799 communique

Patent documentation 2: Japanese kokai publication hei 6-41441 communique

Patent documentation 3: Japanese kokai publication hei 9-227784 communique

Summary of the invention

The problem that invention will solve

The present invention is in view of above-mentioned truth, the cooperation of small amount is provided, and can not cause that the reduction of physical property and flame retardant resistance and its persistence are good, can give to resin magnesium hydroxide composition and the manufacture method thereof of good resistance to thermal deterioration and tone simultaneously, and the resin combination and the molding thereof that coordinate said composition to form.

The means of dealing with problems

The inventor etc. be take to solve the above problems as object and are conducted in-depth research, found that a kind of magnesium hydroxide composition, its manufacture method and coordinate this magnesium hydroxide composition and the resin combination and the molding thereof that form, wherein, the iron that contains specified quantitative and/or manganese and sulphur composition and the composition of the magnesium hydroxide that forms, while being engaged in resin, flame retardant resistance and its persistence are good, and can suppress due to iron by containing sulphur composition, painted and the thermal degradation when of the former thereby generation of manganese, its result can obtain not damaging the intensity physical property of resin, flame retardant resistance and persistence thereof are good, the resin combination of resistance to thermal deterioration and excellent color tone, and electric wire, cable, the molding such as electronic unit, thereby completed the present invention.

; a first aspect of the present invention is to provide magnesium hydroxide composition; it is characterized in that; comprise the magnesium hydroxide particles that contains iron and/or manganese and sulphur; the scope that the iron of measuring with atomic absorption spectrophotometer and/or the content M of manganese are 10～1000ppm with respect to magnesium hydroxide particles, the scope that the content S of the sulphur of measuring by infrared absorption is 10～1800ppm with respect to magnesium hydroxide particles.

As preferred mode, be magnesium hydroxide composition, it is characterized in that, the scope that the content S of sulphur is 1.0～1.8 with respect to the ratio S/M of the content M of iron and/or manganese.

As preferred mode, be magnesium hydroxide composition, it is characterized in that, whiteness W is more than 98, and L value is more than 78, and b value is below 3.5.

In addition, as preferred mode, it is magnesium hydroxide composition, it is characterized in that, use and to be selected from lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, their metal-salt, their amine salt, at least one the surface treatment agent in their ester, tensio-active agent, coupling agent, phosphoric acid ester carries out surface treatment.

In addition, as preferred mode, be magnesium hydroxide composition, it is characterized in that, with 50% fixed median size Dp of laser diffraction and scattering formula size-grade distribution instrumentation ₅₀be 0.5～2.0 μ m, with the fixed maximum particle diameter D of laser diffraction and scattering formula size-grade distribution instrumentation _maxbeing below 6.5 μ m, is 1～10m with the BET specific surface area Sw of determination of nitrogen adsorption ²/ g.

A second aspect of the present invention is to provide the manufacture method of magnesium hydroxide composition, it is characterized in that, the magnesium chloride solution that makes to contain sulfate ion react with hydroxide solution and magnesium hydroxide particles or it is carried out to surface treatment and surface treatment magnesium hydroxide particles in, add ferric chloride Solution and/or manganese chloride solution.

A third aspect of the present invention is to provide the manufacture method of magnesium hydroxide composition, it is characterized in that, magnesium chloride solution is reacted with hydroxide solution magnesium hydroxide particles or it has been carried out in surface-treated surface treatment magnesium hydroxide particles, add the solution be mixed with ferric chloride Solution and/or manganese chloride solution and sulphur compound.

It as preferred mode, is the manufacture method of magnesium hydroxide composition, it is characterized in that, with respect to magnesium hydroxide particles or to it, carry out surface treatment and the surface treatment magnesium hydroxide particles that forms, the iron in ferric chloride Solution and/or manganese chloride solution and/or the amount of manganese are 10～1000ppm.

As preferred mode, be the manufacture method of magnesium hydroxide composition, it is characterized in that, the mole number Sm of the sulphur in sulphur compound is 1.9～3.3 with respect to the ratio Sm/Mm of the mole number Mm of the iron in ferric chloride Solution and/or manganese chloride solution and/or manganese.

As preferred mode, be the manufacture method of magnesium hydroxide composition, it is characterized in that, sulphur compound is for being selected from least one the reductive agent in thiosulfuric acid compound, De Gulin (デ Network ロ リ Application).

A fourth aspect of the present invention is to provide resin combination, it is characterized in that, it is engaged in above-mentioned magnesium hydroxide composition in resin and forms.

A fifth aspect of the present invention is to provide molding, it is characterized in that, it is shaped above-mentioned resin combination and forms.

Invention effect

Magnesium hydroxide composition of the present invention, because the iron that contains specified quantitative and/or manganese and sulphur composition form, while being therefore engaged in resin, flame retardant resistance and persistence thereof are good, utilize sulphur to become to assign to simultaneously and suppress due to the former of iron, manganese thereby painted, the thermal degradation when that produce, thus can provide a kind of obtain do not damage that intensity physical property, flame retardant resistance and the persistence thereof of resin is good, the magnesium hydroxide composition of the molding such as the resin combination of resistance to thermal deterioration and excellent color tone and electric wire, cable, electronic unit.

Embodiment

Magnesium hydroxide composition of the present invention is characterised in that, comprise the magnesium hydroxide particles that contains iron and/or manganese and sulphur, the scope that the content M of iron and/or manganese is 10～1000ppm with respect to magnesium hydroxide particles, the scope that the content S of sulphur is 10～1800ppm with respect to magnesium hydroxide particles.

Magnesium hydroxide composition of the present invention is by containing iron, the manganese in above-mentioned scope, be engaged in while bringing into play its function as fire retardant in resin, from the free iron of the particle surface of magnesium hydroxide particles, manganese, resin, as dehydrogenation catalyst, work, remove hydrogen atom in resin and residual carbon only.The uninflammability carbon that this residual carbon is called as charcoal (チ ヤ mono-) by generation improves flame retardant resistance, and then, thereby its decomposition, burning of continuing to hinder resin further improve the persistence as fire retardant.

When the content M of the iron of magnesium hydroxide composition and/or manganese surpasses 1000ppm, what from the viewpoint of the persistence of flame retardant resistance, improve is preferred, but painted becoming significantly, and the thermal degradation when of these metal pair resins generation detrimentally affect.It is agnogenio really, but inferring is due to the whole iron adding and/or manganese is very difficult, react with sulphur compound completely, along with addition increase is not reacted with sulphur compound and residual iron and/or manganese is oxidized and painted, or because they are produced detrimentally affect by free radical to the thermal degradation when of resin.In addition, along with the part by weight that in magnesium hydroxide composition, iron and/or manganese occupy increases, thereby bring the ratio of the magnesium hydroxide particles of fire retardation to reduce, cannot give sufficient flame retardant resistance to the resin coordinating.

On the other hand, during the not enough 10ppm of the content M of iron and/or manganese, from the viewpoint of tone, thermal degradation when be preferably, but from the viewpoint of flame retardant resistance, while using separately with magnesium hydroxide particles, difference is little, and the effect that flame retardant resistance and persistence thereof are improved diminishes.The total amount M of iron and manganese is preferably 100～1000ppm, more preferably 200～500ppm.

Should illustrate, the atomic absorption spectrophotometer AA6700F that the content of iron and manganese is used Shimadzu Corp's (strain) to manufacture measures.

In addition, magnesium hydroxide composition is by containing sulphur with above-mentioned scope, thereby although contain iron, manganese, is difficult to produce the thermal degradation when of resin, can give good tone to magnesium hydroxide composition of the present invention, resin combination and molding.By containing sulphur with above-mentioned scope, thereby prevent thermal degradation when, give the cause and mechanism of good tone indefinite, but infer it is due in magnesium hydroxide composition, sulphur becomes the form of the complex chemical compounds such as the double salt of the vitriol of iron or manganese or sulphite, sulfur-bearing or sulfur-bearing complex salt, thereby suppresses the activity of iron or manganese.

When the content S of sulphur surpasses 1800ppm, magnesium hydroxide composition self and coordinated the resin combination of this magnesium hydroxide composition and the tone of molding worsens.Tone worsens agnogenio really, but infer it is that compound due to sulphur not only react with iron or manganese, and generate magnesium or as vitriol, the sulphite of the calcium of other impurity etc., it is many that it contains quantitative change.On the other hand, during the content S of sulphur is not enough 10ppm, tone variation not only, and also its thermal degradation when worsens while becoming resin molded body.Its reason is also indefinite, but infers it is because the compound of sulphur is few, therefore can not fully act on the iron that contains magnesium hydroxide particles or manganese, therefore cannot suppress painted, the free radical by the oxyhydroxide generation of iron or manganese.The content S of sulphur is preferably 100～1800ppm, more preferably 200～800ppm.

Should illustrate, infrared absorption method, the carbon that uses particularly the manufacture of LECO company, the Sulfur Analysis device CS-444 for content of sulphur measure.

The content S of sulphur is preferably 1.0～1.8 with respect to the ratio S/M of the content M of iron and/or manganese, more preferably 1.2～1.5 scope.

Ratio S/M surpasses at 1.8 o'clock, has magnesium hydroxide composition self and has coordinated the resin combination of this magnesium hydroxide composition and the tendency of the tone of molding deterioration.Show the agnogenio of this tendency, but infer it is that compound due to sulphur not only react with iron, manganese, and generate magnesium or as vitriol, the sulphite of the calcium of other impurity etc., it is many that it contains quantitative change.

On the other hand, during ratio S/M less than 1.0, not only there is the tendency that tone worsens, and there is the tendency that while becoming molding, its thermal degradation when also worsens.Its reason is also indefinite, but infers it is because the compound of sulphur is few, therefore can not fully act on the iron that contains magnesium hydroxide particles or manganese, therefore cannot suppress painted, the free radical by the oxyhydroxide generation of iron or manganese.

The tone of magnesium hydroxide composition of the present invention is that the whiteness W as powder of the magnesium hydroxide composition of measuring with KETT (ケ Star ト) formula phototube blancometer, is preferably more than 98, more preferably more than 100, is particularly preferably more than 102.

During whiteness W less than 98, coordinate the resin combination of magnesium hydroxide composition formation of the present invention or the molding of being made by it, painted due to magnesium hydroxide composition, thereby can produce preferred cooperation tinting material etc. and adjust the situation of its tone, therefore there is the tendency of the weakened of such molding.

Should illustrate, the powder whiteness meter C-100-3 that whiteness W is used KETT company to manufacture measures.

In addition, make magnesium hydroxide composition be dispersed in butyric acid two-2-ethylhexyl with the ratio of 1: 2 (following, referred to as DOP) in, the tone that represents this mixture with HunterLab colour system (color specification system) is (following, referred to as the moistening look of DOP) time L value, be preferably more than 78, more preferably more than 80, more preferably more than 81.5.

And then the b value of the moistening look of DOP, is preferably below 3.5, more preferably below 2.8, more preferably below 2.0.

During L value less than 78 or b value over 3.5 o'clock, coordinate the resin combination of magnesium hydroxide composition formation or the molding of being made by it, because the impact of the tone of magnesium hydroxide composition is colored, painted and produce and to have to coordinate tinting material etc. to adjust the situation of its tone in order to make up this, therefore there is the tendency that the intensity etc. of molding dies down.

Should illustrate, the mensuration of the employing HunterLab colour system in the present invention is to measure with the colour examining colour-difference-metre ZE2000 that Japanese electric look industry (strain) is manufactured.

Magnesium hydroxide composition of the present invention, preferably meets specific particle property.That is, preferably use 50% median size Dp of the fixed magnesium hydroxide composition of laser diffraction and scattering formula size-grade distribution instrumentation ₅₀be 0.5～2.0 μ m, 0.5～1.5 μ m more preferably, more preferably the scope of 0.5～1.2 μ m, in addition, is used the maximum particle diameter D of the fixed magnesium hydroxide composition of laser diffraction and scattering formula size-grade distribution instrumentation _maxbe below 6.5 μ m, more preferably below 5.5 μ m, the scope below 4.5 μ m more preferably, and, use the BET specific surface area Sw of determination of nitrogen adsorption to be preferably 1～10m ²/ g, more preferably 2～7m ²the scope of/g is suitable.

Magnesium hydroxide composition of the present invention is by meeting 50% above-mentioned median size Dp ₅₀, maximum particle diameter D _maxand BET specific surface area Sw, while bringing into play its effect as fire retardant in being fitted to resin, can in resin, exist whole dispersion, and be fine, therefore during presence of fire and the contact area of particle many, because the decomposition of hydroxyl causes dehydration, become easily, pretend for fire retardant be effective.In addition, not only bring into play the function as fire retardant, and be preferably dull and stereotyped shape as the shape of particle.

50% median size Dp ₅₀during less than 0.5 μ m, particle is too fine, so the surface of particle can become greatly, aggegation occurs and attempts stabilization, easily generates agglomeration while being therefore coupled in resin or during shaping resin composition.In addition, while there is the macroparticle of firm aggegation in resin forming product, and compare with fine mode homogeneous and dispersed good particle, have that pit on molding surface, convex portion become many and the situation that diminishes outward appearance.And, to shock-resistance, tensile strength equal strength physical property, its detailed mechanism is also indefinite at present, but while there is macroparticle in resin, during to molding stress application, with resin equally can be crooked and do not absorb energy, be therefore created in the destruction of the peeling off of resin boundary surface, particle, the intensity with resin molded body can not meet the situation of required physical property.And in addition, particle easily exposes in the surface of molding, absorb moisture and carbon dioxide in atmosphere, magnesium hydroxide becomes magnesiumcarbonate, by the rotten of volume change or surface, produced by this and the peeling off or depart from of resin boundary surface, sometimes produce the problem as the weather resistance reduction of molding etc.In addition, the situation of the small-particle of less than 0.5 μ m, on the surface of all particles, load iron and/or manganese are difficult from current technology equably, in the time of therefore in being coupled to resin combination or molding, in the persistence of flame retardant resistance, have deteriorated tendency aspect giving.

On the other hand, median size Dp ₅₀while surpassing 2.0 μ m, because macroparticle is present in resin forming product, therefore with above-mentioned median size Dp ₅₀same during less than 0.5 μ m, sometimes produce be damaged to body outward appearance, reduce shock-resistance or tensile strength equal strength physical property, reduce the problems such as weather resistance.

Maximum particle diameter D _maxwhile surpassing 6.5 μ m, the oversize particle irrelevant with single particle, agglutination particle is present in resin in a large number, they is engaged in while making composition in resin, with above-mentioned median size Dp ₅₀same while surpassing 2.0 μ m, sometimes produce be damaged to body outward appearance, reduce shock-resistance or tensile strength equal strength physical property, reduce the problems such as weather resistance.

In addition 50% median size Dp, ₅₀, maximum particle diameter D _maxmensuration be the MicrotracFRA laser diffraction and scattering formula size-grade distribution meter that uses Leeds & Northrup company to manufacture, the methyl alcohol of take is measured as solvent.

BET specific surface area Sw deficiency 1m ²during/g, huge single particle is present in magnesium hydroxide composition in a large number, with above-mentioned median size Dp ₅₀same while surpassing 2.0 μ m, have produce be damaged to body outward appearance, reduce shock-resistance or tensile strength equal strength physical property, reduce the tendency of the problems such as weather resistance.

On the other hand, Sw surpasses 10m ²during/g, in magnesium hydroxide composition, fine particle becomes many, while preserving as powder or while being coupled in resin, easily generates agglomeration, with above-mentioned median size Dp during shaping resin composition ₅₀same while surpassing 2.0 μ m, have produce be damaged to body outward appearance, reduce shock-resistance or tensile strength equal strength physical property, reduce the tendency of the problems such as weather resistance.

In addition, nitrogen adsorption type BET specific surface area is that the NOVA2000 that uses ユ ア サ ア イ オ ニ Network ス (strain) to manufacture measures.

Magnesium hydroxide composition of the present invention, while being engaged in resin combination, according to all physical property such as its weather resistance, intensity, improve, and the stability of particle, dispersiveness, with the object that the affinity of resin improves, gives water repellency, preferably with surface treatment agent, carry out surface treatment (coating).As this surface treatment agent, can enumerate: lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, their salt, their ester, tensio-active agent, coupling agent and the phosphoric acid ester etc. such as metal-salt, amine salt, they can be used in combination two or more separately or as required.

About above-mentioned surface treatment agent, from above-mentioned all physical property, purposes, the viewpoint of the impact of environment, operability, cost is considered to carry out suitably selecting, for example, in the EEA or EVA resin purposes using with resin in the coating as environment-friendly electric wire (エ コ Electricity Line), from the viewpoint of tone, preferably by lipid acid or its metal-salt, silane coupling agent, carry out surface treatment, and then, for tone and recent flame retardant resistance and the strict demand of intensity physical property, more preferably silane coupling agent.

As the lipid acid using in the present invention, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, such as enumerating: the saturated fatty acid such as acetic acid, butyric acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic, lignoceric acid; The unsaturated fatty acidss such as Sorbic Acid, elaidic acid, Zoomeric acid, oleic acid, linolic acid, linolenic acid, cetoleic acid, sinapinic acid, ricinolic acid; The alicyclic carboxylic acids such as naphthenic acid with ring penta ring or hexamethylene ring; Take the benzene carboxylic acid that phenylformic acid, phthalic acid etc. are representative; The aromatic carboxylic acids such as carboxylic acid of the naphthalene such as naphthoic acid, naphthalic acid; The resinous acids such as sylvic acid, pimaric acid, palustric acid, neoabietic acid, wherein from the viewpoint of the stability of the reactivity with magnesium hydroxide, particle, dispersiveness, cost, the preferred mixing acid of stearic acid and palmitinic acid.

As metal-salt, the amine salt of lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, such as enumerating: Salt of saturated fatty acids such as potassium laurate, potassium myristate, potassium palmitate, Sodium pentadecanecarboxylate, barium stearate, calcium stearate, Zinic stearas, potassium stearate, cobalt stearate (II), stearic acid tin (IV), sodium stearate, lead stearates (II); The unsaturated fatty acid salts such as zinc oleate, potassium oleate, cobalt oleate (II), sodium oleate, potassium diethanolamine salt; The alicyclic carboxylic acid salt such as lead naphthenate, cyclohexyl lead butyrate; The aromatic carboxylic acid salt such as Sodium Benzoate, sodium salicylate; The resinates such as sodium abietate, potassium rosinate, pimaric acid sodium, pimaric acid potassium, palustric acid sodium, palustric acid potassium, neoabietic acid sodium, neoabietic acid potassium.

In addition; also can be when the surface treatment of magnesium hydroxide particles of the present invention or before surface treatment; in described lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, mix in advance the compound with lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, strontium, barium, zinc, aluminium, lead, cobalt, tin, acyl group; react, to make metal-salt, the amine salt of suitable lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid.

In the metal-salt of above lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, from the viewpoint of the stability of the reactivity with magnesium hydroxide, particle, dispersiveness, cost, also preferably use and take the mixing soap that stearic acid or palmitinic acid be main component.

As lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, the ester of resinous acid, for example can enumerate: ethyl hexanoate, caproic acid vinyl ester, Wickenol 116, ethyl octylate, capric acid allyl ester, ethyl decylate, capric acid vinyl ester, ethyl sebacate, Wickenol 117, isooctanoic acid hexadecyl ester, misery base ten diester of dimethyl-octa, Laurate methyl, butyl laurate, lauric acid lauryl, Myristicin acid methylester, Isopropyl myristate, cetyl myristate, tetradecanoic acid myristyl ester, the different cetyl of tetradecanoic acid, tetradecanoic acid octyl group ten diester, different 13 esters of tetradecanoic acid, Uniphat A60, Wickenol 111, Wickenol 155, cetin, the different stearyl ester of palmitinic acid, methyl stearate, butyl stearate, octyl stearate, stearic acid stearyl, stearic acid cholesteryl ester, the different cetyl of Unimac 5680, methyl behenate, the polyunsaturated fatty acid esters such as docosyl ester (ベ ヘ ニ Le), the unsaturated fatty acid esters such as Witconol 2301, ethyl linoleate, isopropyl ester, sweet oil acetoacetic ester (オ リ mono-Block オ レ イ Application acid エ チ Le), sinapinic acid methyl esters, other, the thermotolerance special fatty acid esters such as fatty acid ester of longer chain fatty acid high alcohol ester, amyl-based polyol (containing long-chain, medium chain) fatty acid series ester and meta-ester compound, Dipentaerythritol long chain fatty acid ester, compound (complex) medium chain fatty acid ester, 12-stearyl-Standamul 7061,12-stearyl-stearic acid iso stearyl ester, 12-stearyl-stearic acid stearyl, tallow fatty acid monooctyl ester, polyhydric alcohol fatty acid ester/alkyl glycerylether, the aromatic ester that the benzoates of take is representative, wherein, from the viewpoint of the stability of the reactivity with magnesium hydroxide, particle, dispersiveness, cost, is preferably used the polyvalent alcohol stearate of polyhydric alcohol fatty acid ester or palmitinic acid, stearic acid stearyl.

As tensio-active agent, comprising polymkeric substance and an alkali metal salt thereof of the monomer with vinyl, in the group of the partially or completely corrective being formed by ammonium and amine, for example, as monomer, can enumerate: α, β-mono-ethene (モ ノ エ チ レ Application) unsaturated monocarboxylic, α, β-mono-ethene unsaturated dicarboxylic acid, alkyl methacrylate, (methyl) propenyl ether ((メ タ) ア Network リ Le エ mono-テ Le) with alkoxyl group, (methyl) acrylate with epoxy group(ing), α, the unsaturated hydroxy ester of β-mono-ethene, polyalkylene glycol mono (methyl) acrylate, vinyl acetate, vinyl aromatic, unsaturated nitrile, unsaturated dicarboxylic acid ester, Vinyl Ether, conjugated diolefine, chain alkene, cyclic olefin, the monomer that contains sulfo group etc.In addition, tensio-active agent as other types, can enumerate: alkyl oxide sulfuric acid, alkyl oxide phosphoric acid, alkyl aryl ether sulfuric acid, alkylaryl ether phosphoric acid, alkyl sulfuric ester, alkyl phosphate, alkylaryl sulfuric acid, alkylaryl phosphoric acid, alkylamide sulfate, alkylsulphonic acid, alkyl benzene sulphonate (ABS), alkyl naphthalene sulfonic acid, sulfo-succinic acid, sulfosuccinic ester, alpha-olefin sulfonic acid, N-acyl group sulfonic acid, N-acylamino acid, alkyl ether carboxylic acid, acylated peptide, fatty amine, aliphatics quaternary amine, aromatic series quaternary ammonium, trimethyl-glycine, aminocarboxylic acid, imidazolidine derivatives, alkyl oxide, alkyl allyl ethers, alkyl ester, alkylamine, dehydrated sorbitol derivative, many ring phenyl ethers, aliphatic ester, fluoroalkyl carbonic acid, perfluoroalkyl carbonic acid, perfluoro alkyl sulfonic acid, acetylene alcohol, acetylenediol etc.Wherein, from the viewpoint of the dispersiveness of magnesium hydroxide particles self and stability, improve with the affinity of resin, cost, preferably use vitriol, sulfuric acid ether, the sulfuric esters such as alkyl oxide sulfuric acid, alkyl aryl ether sulfuric acid, alkyl sulfuric ester.

Example as silane coupling agent, can enumerate: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl, three ('beta '-methoxy oxyethyl group) silane, γ-r-chloropropyl trimethoxyl silane, γ-methacryloxypropyl trimethoxy silane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ mercaptopropyitrimethoxy silane, γ aminopropyltriethoxy silane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ-urea groups (ユ レ イ De) propyl-triethoxysilicane etc., dispersiveness and stability from magnesium hydroxide particles self, improve with the affinity of resin, the aspect of cost is considered, preferably use vinyltrimethoxy silane, and β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane.

As phosphoric acid ester, for example, can enumerate: tricresyl phosphate methyl ester, tricresyl phosphate ethyl ester, tricresyl phosphate butyl ester, phosphoric acid 2-(ethyl hexyl) ester, phosphoric acid butoxy ethyl ester, Triphenyl phosphate, tritolyl phosphate, tricresyl phosphate (xylyl) ester, phosphoric acid cresols diphenyl, phosphoric acid 2-ethylhexyl diphenyl, phosphoric acid cresols diphenyl, phosphoric acid 2-ethylhexyl diphenyl, phosphoric acid cresols two-2,6-xylyl ester, phosphoric acid Resorcinol diphenyl, various aromatic condensation phosphoric acid ester, phosphoric acid 2-chloroethyl-chloropropyl ester, di(2-ethylhexyl)phosphate chloropropyl ester, phosphoric acid tribromo neo-pentyl ester, halogen-containing condensed phosphoric acid, phosphoric acid is two-2-(ethyl hexyl) ester, di(2-ethylhexyl)phosphate isodecyl ester, acid phosphoric acid 2-methacryloyl oxygen base ethyl ester, di(2-ethylhexyl)phosphate phenyl-2-methacryloyl oxygen base ethyl ester, acid methyl-phosphate, acid phosphoric acid ethyl ester, acid phosphoric acid butyl ester, di(2-ethylhexyl)phosphate butyl ester, phosphoric acid monobutyl ester, acid phosphoric acid 2-butyl polyhexamethylene, acid phosphoric acid isodecyl ester, phosphoric acid one isodecyl ester, tricresyl phosphite phenylester, hydrogen phosphorous acid dibutyl ester (ジ Block チ Le Ha イ De ロ ジ エ Application ホ ス Off ア イ ト), hydrogen phosphorous acid dibutyl ester, diphenyl phosphate chloride (ジ Off エ ニ Le ホ ス ホ ロ Network ロ リ デ mono-ト), dichloro-phenyl phosphate, polyoxyethylene lauryl ether phosphoric acid, alkyl is 12～26 polyoxy alkyl oxide phosphoric acid, with polyoxyethylene alkyl phenyl ether phosphoric acid, with polyoxyethylene dialkyl phenyl organic ether phosphoric acid etc., from dispersiveness and the stability of magnesium hydroxide particles self, improve with the affinity of resin, the aspect of cost is considered, is preferably used tricresyl phosphate ethyl ester or tricresyl phosphate butyl ester.

The treatment capacity of above-mentioned surface treatment agent, in the resin combination obtaining in can be according to the present invention, the kind of resin used, purposes etc. are suitably selected, for example, while being coupled in synthetic resins, with respect to particle 100 weight parts, be generally 0.01～10 weight part, be preferably 0.05～8 weight part.

During treatment capacity less than 0.01 weight part of surface treatment agent, do not observe the improved effect of the operability while manufacturing resin combination or molding, in addition, the magnesium hydroxide particles adsorption moisture of surface treatment not in resin, thereby form magnesiumcarbonate with carbon dioxide gas precursor reactant in the atmosphere being dissolved in wherein and cause whiting etc., without any change, cannot bring into play the usefulness of surface treatment agent with the magnesium hydroxide particles of non-processor.On the other hand, when surface treatment amount surpasses 10 weight part, for example, be coupled to while making molding in resin, the intensity of resin significantly reduces, and the shape that according to circumstances continuous cropping is molding also cannot keep, therefore not preferred.

Should illustrate, magnesium hydroxide composition of the present invention, can be according to its application target and suitably selective action, effect.For example, compare while more focusing on flame retardant resistance with tone, take and significantly improve flame retardant resistance as object, can select the many magnesium hydroxide compositions of content of iron and/or manganese and sulphur, or, to compare the object of more focusing on tone with flame retardant resistance, can select the poor magnesium hydroxide composition of iron and/or manganese and sulphur.In addition, also can select both magnesium hydroxide compositions middle, that color harmony flame retardant resistance all improves.

As the preferred method for the manufacture of magnesium hydroxide composition of the present invention, such as enumerating following methods: after magnesium chloride solution is mixed with certain proportion with the hydroxide solution of sodium hydroxide, calcium hydroxide, ammonium hydroxide etc., in autoclave, under the condition more than 120 ℃, more than 2 hours, carry out hydro-thermal reaction, the method for suitably dewatering, washing; In seawater, drop into slaked lime and obtain magnesium hydroxide particles, it is burnt till and reacts the method that obtains magnesium hydroxide particles with water after making magnesium oxide.Can use the method arbitrarily in these methods, but consider from the viewpoint of granularity, dispersiveness, foreign matter content, tone, cost, preferably the former method.Should illustrate, the upper limit of temperature, time has no particular limits, but considers from cost of energy, productive viewpoint, is preferably 300 ℃ of left and right, about 8 hours, and more preferably temperature is lower, the time is shorter.

According to raising iron and/or manganese, be present in the object of the probability on magnesium hydroxide particles surface, preferably after generating magnesium hydroxide particles, add iron and/or manganese.For sulphur composition, may reside in the magnesium chloride as raw material, also can be same with iron and/or manganese, after generating magnesium hydroxide particles, add again.

For magnesium chloride, the bittern generating as by product in the time of can obtaining easy and at an easy rate from preparing salt by working up seawater, but need to be by its desulfurization, and then remove the trace impurities such as Repone K.But magnesium hydroxide composition of the present invention, can be used sulfate ion contained in bittern, therefore can reduce it removes desired cost, labour, is therefore favourable.

But, from the viewpoint of the magnesium hydroxide composition on gained or coordinate this magnesium hydroxide composition and the resin combination that forms, with and the impact of the tone of molding, resistance to thermal deterioration, preferably sulphur composition also adds after generating magnesium hydroxide particles.Can select method arbitrarily, as long as the physical property of their desired costs of consideration, operability, gained particle is selected.

While adding sulphur composition after generating magnesium hydroxide particles, preferably carry out with the interpolation of iron and/or manganese simultaneously, particularly be more preferably the solution that contains ferric chloride Solution and sulphur composition is pre-mixed, add in magnesium hydroxide particles or surface treated magnesium hydroxide particles, make to load on its surface.

Add iron in magnesium hydroxide particles or surface-treated magnesium hydroxide particles, in ferric chloride Solution and/or manganese chloride solution and/or the content of manganese to, with respect to magnesium hydroxide particles preferably in the scope of 10～1000ppm, more preferably in the scope of 100～1000ppm, further preferably in the scope of 200～500ppm.Above-mentioned iron and/or manganese when the quantity not sufficient 10ppm, flame retardant resistance is insufficient, on the other hand, while surpassing 1000ppm, magnesium hydroxide composition self, has coordinated the resin combination of this magnesium hydroxide composition or the tone of molding to have the tendency of deterioration.

For with iron(ic) chloride and/or manganese chloride solution simultaneously or the sulphur compound adding in advance, the mole number Sm of the sulphur in sulphur compound is with respect to the ratio Sm/Mm of the mole number Mm of the iron in ferric chloride Solution and/or manganese chloride solution and/or manganese, preferably in 1.9～3.3 scope, more preferably in 2.1～2.8 scope.During above-mentioned mol ratio Sm/Mm less than 1.9, magnesium hydroxide composition self, coordinated the resin combination of this magnesium hydroxide composition or the tone of molding, thermal degradation when to worsen, on the other hand, surpassed at 3.3 o'clock, aforesaid tone has the tendency of deterioration.

Sulphur compound is more preferably selected from any the above reductive agent in thiosulfuric acid class or De Gulin.

Reductive agent as thiosulfuric acid class, can enumerate: vat powder (Ha イ De ロ サ Le Off ア イ ト) (V-Brite B (inferior Ami sulfuric acid Na ト リ ウ system)), rongalite C (formolation sodium hydrosulfite), rongalite Z (formolation bisulphite zinc), hypo (Sulfothiorine), S-WAT (Ami sulphur Cao) (S-WAT), a sulfuration sulphur, sulfuric acid oxyamine etc., but from the viewpoint of environment and cost, operability, preferred hypo and vat powder, particularly vat powder is can bring into play effect on a small quantity, therefore from the viewpoint of cost, preferably use.

Should illustrate, in the manufacture method of magnesium hydroxide composition of the present invention, be pre-mixed the solution of ferric chloride Solution and/or manganese chloride solution and sulphur compound, can add in any of magnesium hydroxide particles or surface treatment magnesium hydroxide particles, in addition, also can be when surface treatment and surface treatment agent add simultaneously.

And, even add during the state in dry powder or suspension liquid at magnesium hydroxide particles or surface treatment magnesium hydroxide particles, demonstrate effect aspect the tone in the time of also in the color harmony of particle is engaged in resin and flame retardant resistance raising.

But, with wet type, magnesium hydroxide particles is carried out after surface treatment, be added on when being pre-mixed the solution of sulphur compound in ferric chloride Solution and/or manganese chloride solution and being dried, be favourable aspect operability, while being engaged in resin, aspect flame retardant resistance, tone, be good.

Mechanism for them is also indefinite, but infer it is due to by add iron and/or manganese after carrying out surface treatment with wet type, the homogeneity of their loads on magnesium hydroxide particles or surface treatment magnesium hydroxide particles is further enhanced and causes.

For the total amount M of the contained iron of magnesium hydroxide composition and manganese is adjusted into respect to magnesium hydroxide particles, is 10～1000ppm, the iron of iron(ic) chloride (II) or iron(ic) chloride (III) or Manganous chloride tetrahydrate or manganese are dissolved in water and are adjusted to above-mentioned scope.

In addition, for the content S of the contained sulphur of magnesium hydroxide composition is adjusted into respect to magnesium hydroxide particles, be 10～1800ppm, while utilizing the sulfate ion in bittern, add calcium chloride or bariumchloride to make the sulfate ion that exceeds requirement separate out and remove as calcium sulfate or barium sulfate after obtaining the sulfate ion amount in bittern.In addition, while using sulphur compound, in being dissolved with the water of iron(ic) chloride or Manganous chloride tetrahydrate, the sulphur composition of sulphur compound used is dissolved and adjusted according to above-mentioned scope.

For by the median size Dp of magnesium hydroxide composition ₅₀be adjusted into the scope of 0.5～2.0 μ m, preferably, magnesium in the magnesium chloride solution that makes to mix and the mol ratio of the hydroxyl in hydroxide solution are that 1: 2～2: 3, the fluid temperature of two liquid are 20 ℃ ± 10 ℃, at 1～15 minute, with interior, in magnesium chloride solution, drip hydroxide solution while stirring, and then at 4 hours, with interior, be warming up to more than 120 ℃ in autoclave, in this temperature, keep more than 1 hour.Distinguished that these conditions influence each other, for example, the mol ratio of magnesium and hydroxyl approaches 1: 2 or at 2: 3 o'clock, Dp ₅₀become large, there is the tendency that approaches 2.0 μ m.When the fluid temperature of two liquid approaches 10 ℃ or 30 ℃, Dp ₅₀become large, there is the tendency that approaches 2.0 μ m.Stirring should suitably be selected according to amount of liquid, but no matter whipping force is a little less than crossing by force still excessively, Dp ₅₀all become large, there is the tendency that approaches 2.0 μ m.About the intensification in autoclave, to reaching more than 120 ℃ time in short-term, Dp ₅₀diminish, there is the tendency that approaches 0.5 μ m, while approaching 4 hours, Dp ₅₀become large, there is the tendency that approaches 2.0 μ m.In autoclave in the more than 120 ℃ hold-times in short-term, there is Dp ₅₀become large tendency, less than is in the time of 1 hour, Dp ₅₀surpass 2.0 μ m, the hold-time, when elongated, has the tendency that particle diameter diminishes, even if but keep also not finding above for 8 hours Dp ₅₀there is large change.

For by the maximum particle diameter D of magnesium hydroxide composition _maxbe adjusted into below 6.5 μ m, with above-mentioned median size Dp ₅₀situation identical, preferably, magnesium in the magnesium chloride solution that makes to mix and the mol ratio of the hydroxyl in hydroxide solution are that 1: 2～2: 3, the fluid temperature of two liquid are 20 ℃ ± 10 ℃, at 1～15 minute, with interior, in magnesium chloride solution, drip hydroxide solution while stirring, and then at 4 hours, with interior, be warming up to more than 120 ℃ in autoclave, in this temperature, keep more than 1 hour.Distinguished that these conditions influence each other, for example, the mol ratio of magnesium and hydroxyl approaches 1: 2 or at 2: 3 o'clock, D _maxbecome large, there is the tendency that approaches 6.5 μ m.When the fluid temperature of two liquid approaches 10 ℃ or 30 ℃, D _maxbecome large, there is the tendency that approaches 6.5 μ m.Stirring should suitably be selected according to amount of liquid, but no matter whipping force is a little less than crossing by force still excessively, D _maxall become large, there is the tendency that approaches 6.5 μ m.About the intensification in autoclave, to reaching more than 120 ℃ time D in short-term _maxdiminish, D while approaching 4 hours _maxbecome large, there is the tendency that approaches 6.5 μ m.In autoclave in the more than 120 ℃ hold-times in short-term, there is D _maxbecome large tendency, less than is in the time of 1 hour, D _maxsurpass 6.5 μ m, the hold-time, when elongated, has D _maxthe tendency diminishing.

For the BET specific surface area Sw of magnesium hydroxide particles is adjusted into 1.0～10m ²/ g, with above-mentioned median size Dp ₅₀, maximum particle diameter D _maxequally, preferably, magnesium in the magnesium chloride solution that makes to mix and the mol ratio of the hydroxyl in hydroxide solution are that 1: 2～2: 3, the fluid temperature of two liquid are 20 ℃ ± 10 ℃, at 1～15 minute, with interior, in magnesium chloride solution, drip hydroxide solution while stirring, and then at 4 hours, with interior, be warming up to more than 120 ℃ in autoclave, in this temperature, keep more than 1 hour.Distinguished that these conditions influence each other, for example, the mol ratio of magnesium and hydroxyl approaches at 1: 2 o'clock, and it is large that Sw becomes, and has the 10m of approaching ²the tendency of/g, approaches at 2: 3 o'clock, and Sw diminishes, and has the 1m of approaching ²the tendency of/g.When the fluid temperature of two liquid approaches 10 ℃, it is large that Sw becomes, and has the 10m of approaching ²the tendency of/g, more approaches 30 ℃ of Sw and more diminishes, and has the 1m of approaching ²the tendency of/g.Stirring should suitably be selected according to amount of liquid, but whipping force is no matter a little less than crossing by force still excessively, Sw all becomes greatly, has the 10m of approaching ²the tendency of/g.For the intensification in autoclave, to arriving more than 120 ℃ time in short-term, Sw diminishes, and while approaching 4 hours, Sw has the 10m of approaching ²the tendency of/g.In autoclave in the more than 120 ℃ hold-times in short-term, there is Sw and become large tendency, less than is in the time of 1 hour, Sw surpasses 10m ²/ g, the hold-time, when elongated, has the tendency that Sw diminishes, even if but keep also not finding that Sw has large variation above in 8 hours.

Surface treatment or suspension liquid untreated, that added the magnesium hydroxide composition of iron(ic) chloride and/or Manganous chloride tetrahydrate and sulphur compound, as required, for example, by means such as suitable selection washing, dehydration, granulation, dry, pulverizing, classifications, can be made into the finished product form as magnesium hydroxide composition.

The magnesium hydroxide composition of the present invention obtaining is as mentioned above engaged in various resins and makes resin combination.Magnesium hydroxide composition of the present invention, with the total weight with respect to resin, is preferably 15～80wt%, the more preferably ratio cooperation of 20～70wt%.

The resin using in resin combination of the present invention is so long as the resin using usually used as molding, such as enumerating: thermoplastic resin, heat-curing resin or synthetic rubber etc.

As thermoplastic resin, can enumerate: as polyethylene, polypropylene, ethylene/propene copolymer, polybutene, the polyolefin resin of the polymkeric substance of the alkene (alhpa olefin) of poly--4-methylpentene-1 C2～C8 such as grade or multipolymer and so on, the multipolymer of alkene and diene, ethylene-acrylate copolymer, polystyrene, ABS resin, AAS resin, AS resin, MBS resin, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride-acetate ethylene copolymer, polyvinylidene dichloride, polyvinyl chloride, chlorinatedpolyethylene, Chlorinated Polypropylene III, VCP, Vinyl Acetate Copolymer, phenoxy resin, polyacetal, polymeric amide, polyimide, polycarbonate, polysulfones, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, the resin of polybutylene terephthalate and methacrylic etc.

In these thermoplastic resins, as preferred example in resin combination of the present invention, can enumerate polyolefin resin or its multipolymer, while wherein using in resin used in various conventional electric wires, the cables such as EEA resin, EVA resin, not only tone, good flame resistance and can give physical strength, be suitable.

As heat-curing resin, can enumerate: epoxy resin, resol, melamine resin, unsaturated polyester resin, Synolac and urea resin etc.In addition, as synthetic rubber, can enumerate: EPDM, isoprene-isobutylene rubber, synthetic polyisoprene, SBR, NBR, chlorosulfonated polyethylene, NIR, urethanes, divinyl rubber, acrylic rubber, silicone rubber and viton etc.

Resin combination of the present invention has good flame retardant resistance, but while further coordinating flame retardant, can reduce the mixing ratio of magnesium hydroxide composition particle of the present invention, and can further improve flame retardant effect.

As flame retardant, preferred red phosphorus, carbon dust or their mixture.As red phosphorus, except the common red phosphorus of using as fire retardant, such as using with surface-coated red phosphorus such as heat-curing resin, polyolefine, carboxylic acid polyalcohol, titanium oxide or titanium aluminium condensess.As carbon dust, can enumerate carbon black, gac or graphite, carbon black can be also the carbon black that uses any method adjustment of Audit For Process, channel process, Re Fa or acetylene method.

While coordinating flame retardant, with respect to all resins composition, be preferably 0.5～20wt%, more preferably the scope of 1～15wt%.

In not damaging the scope of effect of the present invention, can in resin combination of the present invention, coordinate other the additive except mentioned component.As this additive, such as enumerating: antioxidant, anti-static electricity interference agent, pigment, whipping agent, softening agent, weighting agent, strengthening agent, linking agent, photostabilizer, UV light absorber, lubricant etc.In addition, according to object, take and further improve flame retardant resistance as object, also can be used together the fire retardant of inorganic metal class beyond bromine class, Phosphorus, nitrogen class, magnesium hydroxide particles etc.

Can use various manufacturing process that resin combination of the present invention is made to molding.

Molding of the present invention can obtain as follows: adopt known methods such as extrusion molding, injection molded, calendaring molding that the resin combination obtaining is as mentioned above shaped.

According to molding of the present invention, owing to having coordinated magnesium hydroxide composition of the present invention, so flame retardant resistance and persistence good, and the outward appearance of molding is also excellent.As the purposes of this molding, can enumerate: the wallpaper that aforesaid electric wire, the coating of cable isoelectric line are used with, material of construction with the shell of, family's electrical article, foaminess thermal insulation material, mattress, electric, the junctor succeeding component of electronic component-use, semi-conductive sealing material, preforming material, Mulitilayer circuit board or circuit board use laminated plate etc.

Embodiment

Below, based on embodiment and comparative example, describe the present invention in detail.But the present invention is not subject to any restriction of these examples.

Should illustrate, in embodiments of the invention and comparative example, the MicrotracFRA laser diffraction and scattering formula size-grade distribution meter that the median size of magnesium hydroxide composition and maximum particle diameter are used Leeds & Northrup company to manufacture is measured.The NOVA2000 that BET specific surface area is used ユ ア サ ア イ オ ニ Network ス (strain) to manufacture measures, the content of iron and manganese, the atomic absorption spectrophotometer AA6700F that uses Shimadzu Seisakusho Ltd.'s (strain) to manufacture measures, sulphur is that the carbon, the Sulfur Analysis device CS-444 that use LECO company to manufacture measure, the powder whiteness meter C-100-3 that whiteness is used KETT company to manufacture measures, and the moistening look of DOP is used Japanese electric look industry (strain) colour examining colour-difference-metre ZE2000 processed to measure.

First, for the magnesium chloride solution that is used as the raw material of the magnesium hydroxide particles in embodiments of the invention and comparative example, by the following method of recording, adjust.

The adjustment > of < magnesium chloride solution 1

By take buck after salt in salt pan, with sand filtration and the absorption undertaken by gac, remove foreign matter and soil ulmin to carry out thick purifying, then in buck, add with thick purifying after the contained equimolar calcium chloride of sulfate ion of buck, sulfate ion in buck is precipitated as calcium sulfate, filter to remove calcium sulfate, make and take the purifying aqueous salt brine that magnesium chloride is principal constituent.

The purifying aqueous salt brine of gained is the magnesium chloride solution of Baumé gravity 1.33, the sulphur that to contain with respect to magnesium chloride be 2360ppm.

The adjustment > of < magnesium chloride solution 2

By take buck after salt in salt pan, with sand filtration and the absorption undertaken by gac, remove foreign matter and soil ulmin to carry out thick purifying, then in buck, add with thick purifying after the contained equimolar bariumchloride of sulfate ion of buck, sulfate ion in buck is precipitated as barium sulfate, filter to remove barium sulfate, make and take the purifying aqueous salt brine that magnesium chloride is principal constituent.

The purifying aqueous salt brine of gained is the magnesium chloride solution of Baumé gravity 1.33, the sulphur that to contain with respect to magnesium chloride be 0.8ppm.

The adjustment > of < hydroxide solution

Wingdale is carried out to lam-oil and burn till to make unslaked lime, the industrial milk of lime that it is digested and obtain is waited and removes pollutent with sieve, its concentration is adjusted to 12wt%.Gained milk of lime is the solution that contains calcium hydroxide, owing to take industrial application as object, therefore low price not only, and owing to burning till with lam-oil, therefore burn till with hard coal or coke and milk of lime compare, impurity much less.

Embodiment 1

90% the bariumchloride that is equivalent to the mole number of sulphur remaining in magnesium chloride solution 1 is added in aqueous salt brine, filter after barium sulfate is separated out, and then concentrate or dilute, be adjusted to the magnesium chloride solution of Baumé gravity 1.3.

The solution 5L of gained is joined in the autoclave of 10L, adjust fluid temperature to 20 ℃, under agitation condition, through 5 minutes, add the milk of lime 5L that fluid temperature is adjusted to the concentration 12wt% of 20 ℃, make magnesium chloride and calcium hydroxide reaction and generate magnesium hydroxide particles, and then add after finishing and keep whipped state heating high-pressure still from milk of lime, after within 2 and a half hours, making fluid temperature in autoclave rise to 160 ℃, maintain again 4 hours.

Afterwards, by natural heat release, undertaken cooling, with centrifuge, the reaction suspension liquid of the magnesium hydroxide particles of gained is dewatered, with tap water, clean, the specific conductivity of Cleaning Wastewater drops to than electrical conductivity of water from the beginning and only finishes to clean during the level of high 20 μ S/cm.

The vinyltriethoxysilane that magnesium hydroxide particles with respect in this magnesium hydroxide particles suspension liquid is equivalent to 0.5wt% mixes and dissolves in 1wt% acetum, and this vinyltriethoxysilane-acetic acid mixing solutions is added to and in magnesium hydroxide particles suspension liquid, carries out surface treatment.

And then, by the magnesium hydroxide particles in the suspension liquid with respect to this magnesium hydroxide particles, the iron(ic) chloride (III) that ferrous components is equivalent to 210ppm adds in magnesium hydroxide particles suspension liquid, after fully stirring, with spraying, is dried this suspension liquid is dried and obtains magnesium hydroxide composition.

The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 1.

Embodiment 2～7

The condition of recording, according to the method identical with embodiment 1, make magnesium hydroxide composition in becoming table 1.The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 1.

Should illustrate, in embodiment 2, add iron amount and be equivalent to the iron(ic) chloride (III) of 450ppm and the Manganous chloride tetrahydrate that manganese amount is equivalent to 45ppm.

Embodiment 8

Except the making time of the milk of lime in the magnesium chloride solution of putting in autoclave is become 12 minutes, according to method similarly to Example 1, make magnesium hydroxide composition.The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 1.

[table 1]

Embodiment 9

Dilution magnesium chloride solution 2 is adjusted the magnesium chloride solution of Baumé gravity 1.3, gained solution 5L is joined in the autoclave of 10L, adjust fluid temperature to 20 ℃, under agitation condition, through 5 minutes, add the milk of lime 5L that fluid temperature is adjusted to the concentration 12wt% of 20 ℃, make magnesium chloride and calcium hydroxide reaction and generate magnesium hydroxide, and then add after finishing and keep whipped state heating high-pressure still from milk of lime, after within 2 and a half hours, making fluid temperature in autoclave rise to 160 ℃, maintain again 4 hours.

Afterwards, by natural heat release, undertaken cooling, with centrifuge, the reaction suspension liquid of the magnesium hydroxide particles of gained is dewatered, after dehydration, with tap water, clean, when the specific conductivity of Cleaning Wastewater drops to the level than high 20 μ S/cm of electrical conductivity of water from the beginning, finish to clean.

The vinyltrimethoxy silane that magnesium hydroxide particles with respect in this magnesium hydroxide particles suspension liquid is equivalent to 0.5wt% mixes and dissolves in 1wt% acetum, and this vinyltriethoxysilane-acetic acid mixing solutions is added to and in magnesium hydroxide particles suspension liquid, carries out surface treatment.

And then, by the magnesium hydroxide particles with respect in surface treated magnesium hydroxide particles suspension liquid and ferrous components is equivalent to the iron(ic) chloride (III) of 210ppm and contain in the water that the vat powder of sulphur that is equivalent to the mole number of 2.2 times with respect to iron(ic) chloride (III) is dissolved in 100g after, add in magnesium hydroxide particles suspension liquid, after fully stirring, with spraying is dry, this suspension liquid is dried, obtains magnesium hydroxide composition.

The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 2.

Embodiment 10～15

The condition of recording, according to the method identical with embodiment 9, make magnesium hydroxide composition in becoming table 2.The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 2.

Embodiment 16

Except the making time of the milk of lime in the magnesium chloride solution of putting in autoclave is become 12 minutes, according to method similarly to Example 9, make magnesium hydroxide composition.

The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are illustrated in table 2.

[table 2]

Comparative example 1～7

The condition of recording, according to the method identical with embodiment 1, make magnesium hydroxide composition in becoming table 3.The manufacturing conditions of the magnesium hydroxide composition of gained and all physical property are shown in to table 3.

[table 3]

Embodiment 17～32, comparative example 8～14

The magnesium hydroxide composition obtaining in coordinating 125 parts of embodiment 1～16 and comparative example 1～7 in ethylene-propylene acetoacetic ester resin (trade(brand)name エ バ Off レ Star Network ス-EEA) 100 weight parts of manufacturing at Mitsui, デ ユ Port Application Port リ ケ ミ カ ス (strain), 2 parts of ア デ カ ス タ Block AO-60 that the calcium stearate as lubricant, 0.2 weight part are manufactured as the rising sun electrochemical industry (strain) of stablizer, the ラ ボ Block ラ ス ト ミ Le 4C150-01 and twin shaft fan-shaped (segment) the forcing machine 2D25W that use (strain) Japan essence mechanism to do manufacturing mix and obtain resin combination.

The resin combination of gained is carried out to pressing mold at 150 ℃, make the sheet material that 3mm is thick.

The tone of < resin molded body is evaluated >

Making the sheet forming obtaining is the flat board of length and width 40mm, measures whiteness W, with L value and the b value representation of HunterLab colour system.

The flame retardant resistance of < resin molded body is evaluated >

The molding of using as the combustion test of utilizing oxygen index method, makes the test film of long 150mm * wide 6.5mm, based on JISK7201, measures oxygen index.In addition, in the limiting oxygen index determination of molding, the generation degree of the charcoal by visual observation.And then, for the persistence of flame retardant resistance, based on ASTM E1354, use cone calorimetry to obtain heat production speed, obtain from igniting and start to reaching golf calorific value (kw/m ²) till time T 1, with the ratio (T2/T1) of the time T 2 that to be reduced to thermal value after demonstrating golf calorific value be golf calorific value till 30%.

The resistance to thermal deterioration of < resin molded body is evaluated >

Resistance to thermal deterioration to molding, in being set as the Geer(-Evans)-oven of 150 ℃ of throttle openings 50% (ギ ア オ mono-Block Application) (the タ バ イ エスペツ Network Geer(-Evans)-oven GPHH-100 processed of company), made sheet material is cut into the wide 25mm of long 50mm and is suspended on swiveling ring, obtain on test film surface because particle is separated out time of causing till whiting and to the time till weight decrement 10%.

The intensity evaluation > of < resin molded body

For the sheet material of making, the rubber tensile properties based on JISK6251 carries out tension test, while obtaining its yield-point, the maximum tensile strength and fracture, extends.Should illustrate, be No. 1 shape of dumbbell shaped according to JISK6251 for the dumb bell (dumbbell) of this test.

The evaluation result of the resin molded body of embodiment 17～32 and comparative example 8～14 is shown in to table 4～6.

[table 4]

[table 5]

[table 6]

As known in above-mentioned table 1～6, the magnesium hydroxide composition of the present invention that the embodiment of take is representative can provide balance and possess resin combination and the molding of good tone, flame retardant resistance and persistence thereof, resistance to thermal deterioration and intensity.

On the other hand, as take comparative example as representative, the magnesium hydroxide composition of discontented unabridged version invention important document cannot provide balance and possess resin combination and the molding of good tone, flame retardant resistance and persistence thereof, intensity.

Particularly, the magnesium hydroxide composition of comparative example 1 is because the content of iron and manganese is few, therefore use the resin combination of the comparative example 8 of said composition to have no the generation of charcoal, and persistence is also bad.

In addition, the magnesium hydroxide composition of comparative example 2, because the content of iron and manganese is many, is therefore used the resin combination of the comparative example 9 of said composition, and L value, the b value of tone are bad, and resistance to thermal deterioration (to the time of decrement 10%) is also slightly poor.

In addition, the magnesium hydroxide composition of comparative example 3, because the content of sulphur is few, is therefore used the resin combination of the comparative example 10 of said composition, and resistance to thermal deterioration (to the time of decrement 10%) is poor.

In addition, the magnesium hydroxide composition of comparative example 4, because the content of sulphur is many, is therefore used the resin combination of the comparative example 11 of said composition, and resistance to thermal deterioration (to the time of decrement 10%) is poor, and the b value of tone is also slightly poor.

In addition, the magnesium hydroxide composition of comparative example 5, because ratio S/M is little, is therefore used the resin combination of the comparative example 12 of said composition, and the b value of tone and resistance to thermal deterioration (to the time of decrement 10%) are poor.

In addition, the magnesium hydroxide composition of comparative example 6, because ratio S/M is large, is therefore used the resin combination of the comparative example 13 of said composition, the L value difference of tone.

In addition, the magnesium hydroxide composition of comparative example 7, because the content of iron and manganese is few, is therefore used the resin combination of the comparative example 14 of said composition, have no the generation of charcoal, and persistence is also poor.

Utilizability in industry

Magnesium hydroxide composition of the present invention, due to the metallic element that contains iron and/or manganese and sulphur, thereby the cooperation with small amount, neither can cause the reduction of physical property, flame retardant resistance and persistence thereof are also good, can also give good resistance to thermal deterioration and tone to resin simultaneously, rather useful in the field of the resin combination that the molding therefore particularly using under the stringent condition of electric wire, cable, electronic unit etc. is used.

Claims (1)

1. magnesium hydroxide composition, it is characterized in that, comprise the magnesium hydroxide particles that contains iron and/or manganese and sulphur, the scope that the iron of measuring with atomic absorption spectrophotometer and/or the content M of manganese are 10 ~ 1000ppm with respect to magnesium hydroxide particles, the scope that the content S of the sulphur of measuring by infrared absorption is 10 ~ 1800ppm with respect to magnesium hydroxide particles, the scope that the content S of sulphur is 1.0 ~ 1.8 with respect to the ratio S/M of the content M of iron and/or manganese.

2. magnesium hydroxide composition claimed in claim 1, is characterized in that, whiteness W is more than 98, and L value is more than 78, and b value is below 3.5,

Wherein, whiteness W is used the powder whiteness meter C-100-3 that KETT company manufactures to measure,

L value is, magnesium hydroxide composition is dispersed in butyric acid two-2-ethylhexyl with the ratio of 1:2, the L value while representing the tone of this mixture with HunterLab colour system,

B value is the tone of said mixture.

3. the magnesium hydroxide composition described in claim 1 or 2, it is characterized in that, with being selected from lipid acid, alicyclic carboxylic acid, aromatic carboxylic acid, resinous acid, their metal-salt, their amine salt, at least one the surface treatment agent in their ester, tensio-active agent, coupling agent, phosphoric acid ester carries out surface treatment.

4. the magnesium hydroxide composition described in claim 1 or 2, is characterized in that, with 50% fixed median size Dp of laser diffraction and scattering formula size-grade distribution instrumentation ₅₀be 0.5 ~ 2.0 μ m, with the fixed maximum particle diameter D of laser diffraction and scattering formula size-grade distribution instrumentation _maxbeing below 6.5 μ m, is 1 ~ 10m with the BET specific surface area Sw of determination of nitrogen adsorption ²/ g.

5. the manufacture method of magnesium hydroxide composition claimed in claim 1, it is characterized in that, the magnesium chloride solution that makes to contain sulfate ion react with hydroxide solution and magnesium hydroxide particles or this magnesium hydroxide particles is carried out to surface treatment and surface treatment magnesium hydroxide particles in, add ferric chloride Solution and/or manganese chloride solution.

6. the manufacture method of magnesium hydroxide composition claimed in claim 1, it is characterized in that, magnesium chloride solution is reacted with hydroxide solution magnesium hydroxide particles or this magnesium hydroxide particles has been carried out in surface-treated surface treatment magnesium hydroxide particles, add the solution be mixed with ferric chloride Solution and/or manganese chloride solution and sulphur compound.

7. the manufacture method of the magnesium hydroxide composition described in claim 5 or 6, it is characterized in that, with respect to magnesium hydroxide particles or to this magnesium hydroxide particles, carry out surface treatment and the surface treatment magnesium hydroxide particles that forms, the iron in ferric chloride Solution and/or manganese chloride solution and/or the amount of manganese are 10 ~ 1000ppm.

8. the manufacture method of magnesium hydroxide composition claimed in claim 6, is characterized in that, the mole number Sm of the sulphur in sulphur compound is 1.9 ~ 3.3 with respect to the ratio Sm/Mm of the mole number Mm of the iron in ferric chloride Solution and/or manganese chloride solution and/or manganese.

9. the manufacture method of the magnesium hydroxide composition described in claim 6 or 8, is characterized in that, sulphur compound is at least one the reductive agent being selected from thiosulfuric acid compound, De Gulin.

10. resin combination, is characterized in that, it is the magnesium hydroxide composition described in any one in claim 1 ~ 4 is engaged in resin and forms.

11. molding, is characterized in that, it is shaped resin combination claimed in claim 10 and form.