CN104080889A - Halogen-free flame retardant, method for producing same, resin composition, molded article, and molded part - Google Patents

Halogen-free flame retardant, method for producing same, resin composition, molded article, and molded part Download PDF

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Publication number
CN104080889A
CN104080889A CN201380007773.6A CN201380007773A CN104080889A CN 104080889 A CN104080889 A CN 104080889A CN 201380007773 A CN201380007773 A CN 201380007773A CN 104080889 A CN104080889 A CN 104080889A
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quality
halogen
alkoxy
magnesium hydroxide
free flame
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CN104080889B (en
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松井诚二
村松克洋
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Konoshima Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Silicon Polymers (AREA)
  • Inorganic Insulating Materials (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

Provided are the following: a resin composition that comprises a magnesium hydroxide flame retardant and has excellent acid resistance, water resistance, and mechanical strength; a molded article; and a molded part. The present invention relates to the following: a halogen-free flame retardant having magnesium hydroxide particles and, formed on the surface of the particles, a coating layer containing SiO2 and an alkoxy-modified silicone compound and/or a hydrolysis product thereof; a method for producing a halogen-free flame retardant using an alkoxy-modified silicone compound; a resin composition containing the halogen-free flame retardant; and a molded article and a molded part molded from the composition.

Description

Halogen-free flame retardants, its manufacture method, resin combination, formed body and profiled part
Technical field
The present invention relates to halogen-free flame retardants and its manufacture method, resin combination, formed body and profiled part.Insulated line that resin combination of the present invention uses for the inside and outside distribution of electric/electronic device, insulated line, electric flexible cord cable automobile for, electric wire for communication, communication cable, electric wire for electric power, cable, optical fiber cord, Connectorized fiber optic cabling, electric wire for automobiles, cable, automobile, rail truck, boats and ships, aircraft, industrial machine material, electronics, electronic unit etc. for automobile for electric power.
Background technology
Insulated line cable flexible cord, optical fibre core, optical fiber cord automobile electrical cable wire, automobile, rail truck, boats and ships, aircraft, industrial machine material, electronics, electronic unit etc. are required the various characteristicses such as flame retardant resistance, thermotolerance, mechanical characteristics (for example, tensile properties, wearability) all the time.Therefore, the coating material using as these wiring materials, mainly uses polyvinyl chloride (PVC) compound, has coordinated the polyolefin compound of the halogenated flame retardant that contains bromine atoms, chlorine atom in molecule.
But, will burn them time, sometimes produce corrosive gases from the contained halogen compound of coating material, in recent years, this problem is in question, has carried out with not worrying to produce the research that halogen is the flame-retarded resin of the bittern-free flame-proof material coating of gas etc.Bittern-free flame-proof material embodies flame retardant resistance by the fire retardant of Halogen is not engaged in resin, use various resins, such as polyolefin-based resins, nylon are that resin, polyester based resin have coordinated the material of the metal hydroxides such as aluminium hydroxide, magnesium hydroxide as fire retardant.Such metal hydroxides, in order to embody high flame retardant, need to coordinate in large quantities compared with halogenated flame retardant.As metal hydroxides, the flame retardant effect of magnesium hydroxide is higher, as being widely used to the halogen-free flame retardants of the interpolations such as polyolefin-based resins.
But, the resin combination that has coordinated such magnesium hydroxide to acid a little less than, because the physical property such as oxynitride contained in such as acid rain, waste gas etc., various acid medicines significantly reduce.Therefore, proposed to utilize phosphoric acid ester etc. to carry out surface-treated method to the surface of magnesium hydroxide.But if use the magnesium hydroxide of processing through phosphoric acid ester, the physical strength of resin combination significantly reduces, in addition, its acid resistance is also insufficient.
In addition, patent documentation 1 (Japanese kokai publication hei 01-320219 communique) has proposed to carry out surface-treated method with soft silica, even if use the method acid resistance also insufficient, and to improve acid resistance, the dispersiveness of resin combination significantly reduces or water tolerance variation, and the remarkable reduction of volume specific resistance occurs.
In addition, patent documentation 2 (TOHKEMY 2003-253266 communique) has proposed that the two has carried out surface-treated magnesium hydroxide and resin combination with soft silica and various surface treatment agent.Also proposed with soft silica and the two magnesium hydroxide and resin combination thereof that has carried out processing of methylhydrogenpolysi,oxane.But the acid resistance of this resin combination is also insufficient, the reduction of the physical strength of resin combination is also very large, and has the problem of resin dispersion aspect.
As the patent documentation beyond above-mentioned, it is that tensio-active agent, phosphoric acid ester, silane coupling agent, aluminum coupling agent, titanate coupling agent, organosilane, methylhydrogenpolysi,oxane or organosilazanes carry out surface treatment to magnesium hydroxide that patent documentation 3 (TOHKEMY 2008-169397 communique) has proposed to utilize soft silica and higher fatty acid, higher fatty acid an alkali metal salt, polyvalent alcohol high-grade aliphatic ester, negatively charged ion.
Patent documentation 4 (Japanese kokai publication hei 10-338818 communique) has proposed to utilize the surface of aluminium hydroxide coating magnesium hydroxide particles.Patent documentation 5 (TOHKEMY 2002-285162 communique) has proposed, with soft silica and the silicoorganic compound with SiH base, magnesium hydroxide particles is carried out to surface treatment.But the acid resistance of the resin combination of the magnesium hydroxide of use patent documentation 3,4 is insufficient.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 01-320219 communique
Patent documentation 2: TOHKEMY 2003-253266 communique
Patent documentation 3: TOHKEMY 2008-169397 communique
Patent documentation 4: Japanese kokai publication hei 10-338818 communique
Summary of the invention
The object of this invention is to provide the resin combination that contains magnesium hydroxide flame retardant and acid resistance, water tolerance and physical strength excellence and formed body, formed body parts.
The discoveries such as the inventor are arranged and are contained SiO by the surface at magnesium hydroxide particles 2with the coating of alkoxy-modified silicoorganic compound and/or its hydrolyzate, obtain the resin combination of acid resistance, water tolerance and physical strength excellence, complete the present invention.
That is, the present invention relates to halogen-free flame retardants, it has magnesium hydroxide particles and is formed at its surperficial coating, and this coating contains SiO 2with alkoxy-modified silicoorganic compound and/or its hydrolyzate.
In the present invention, alkoxy-modified silicoorganic compound refer to the silicoorganic compound at side chain and/or end with alkoxyl group.As alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-etc., can mix and have alkoxyl group of more than two kinds.
Silicoorganic compound are to have the compound of the siloxanes such as dimethyl siloxane, diphenyl siloxane, methylphenyl siloxane, methyl hydrogen siloxane as repeating unit, as alkoxy-modified silicoorganic compound, can illustrate the side chain of these compounds and/or part or all alkoxy of end replaces the compound forming.Wherein, consider preferably there are the silicoorganic compound of alkoxyl group at side chain from the reactive viewpoint with the surperficial hydroxyl that is present in inorganic materials.
In addition, the hydrolyzate of alkoxy-modified silicoorganic compound refer to alkoxyl group part or all be hydrolyzed and generate the compound of hydroxyl.
Particularly, as the hydrolyzate of above-mentioned alkoxy-modified silicoorganic compound, can enumerate (the Si-OCH by RO- 3oR) m (Si-OCH 3oH) n-R (1) or HO-(Si-OCH 3oR) m (Si-OCH 3oH) n-R (2) or HO-(Si-OCH 3oR) m (Si-OCH 3oH) n-H (3)
The alkoxy-modified methylsiloxane compound representing etc.
Wherein, R represents at least one in methyl, ethyl, sec.-propyl, and m, n are integer, m >=0, n >=1, m+n=2～100,000.Should illustrate, above-mentioned R needs not to be a kind of functional group, for example, can as methyl and ethyl, mix existence by alkyl of more than two kinds.(Si-OCH 3oR) m (Si-OCH 3oH) record of n is not to represent to exist respectively (Si-OCH 3oR) block of m and (Si-OCH 3oH) block of n, but represent to exist m (Si-OCH 3oR) part and n (Si-OCH 3oH) part.The difference of formula (1), (2), (3) with by starting raw material RO-(Si-OCH 3oR) degree that m+n-R etc. is hydrolyzed is relevant.And can be alkoxy-modified methylsiloxane compound arbitrarily in formula (1), (2), (3), in addition, can mix the compound that has formula (1), (2), (3).
M+n is preferably 3～100, most preferably is 3～15.Should illustrate, in this specification sheets, with～while representing scope, comprise upper and lower bound.In addition, the expression such as 1 quality % in fire retardant is 1 quality % etc. with respect to magnesium hydroxide 100 quality %.SiO 2content is not particularly limited, and is preferably 0.3～9 quality %, more preferably 1～7 quality %, more preferably 1.5～5 quality %.If SiO 2content is too much, and the dispersiveness of fire retardant in resin reduces and the outward appearance of resin combination etc. significantly reduces, or acid resistance significantly reduces.If SiO 2content is very few, and acid resistance reduces.Alkoxy-modified silicoorganic compound content is not particularly limited, and is preferably in the same manner 0.3～9 quality %, more preferably 1～7 quality %, more preferably 1.5～5 quality %.If the content of alkoxy-modified silicoorganic compound is too much, the dispersiveness of fire retardant in resin significantly reduces, and cause the outward appearance of resin combination etc. to be badly damaged by the caused foaming of organic volatilization in alkoxy-modified silicoorganic compound, and acid resistance reduction, and then cost rises.In addition, if the content of alkoxy-modified silicoorganic compound is very few, acid proof effect reduces.Preferably, with respect to magnesium hydroxide 100 quality %, contain SiO 20.3～9 quality %, alkoxy-modified silicoorganic compound 0.3～9 quality %, more preferably, with respect to magnesium hydroxide 100 quality %, contain SiO 21～7 quality %, alkoxy-modified silicoorganic compound 1～7 quality %, particularly preferably, with respect to magnesium hydroxide 100 quality %, contain SiO 21.5～5 quality %, alkoxy-modified silicoorganic compound 1.5～5 quality %.
Preferably with SiO 2be that the 1st layer, above-mentioned alkoxy-modified silicoorganic compound and/or its hydrolyzate are the 2nd layer of coating magnesium hydroxide particles surface, also can utilize SiO 2carry out coating with the mixture of above-mentioned alkoxy-modified silicoorganic compound.
In the manufacture method of halogen-free flame retardants of the present invention, can in magnesium hydroxide aqeous suspension, add water miscible silicon compound or colloid silica and form SiO 2coating, then, uses alkoxy-modified silicoorganic compound to form the coating that contains alkoxy-modified silicoorganic compound and/or its hydrolyzate.Utilize SiO 2while forming coating with the mixture of alkoxy-modified silicoorganic compound etc., can enumerate following method: be modulated in advance and in the aqueous dispersions of water miscible silicon compound or colloid silica, add alkoxy-modified silicoorganic compound and stir the mixing water forming and disperse liquid, added magnesium hydroxide aqeous suspension and form mixing coating.
As concrete manufacture method, by with Mg (OH) 2in the magnesium hydroxide aqeous suspension that the meter concentration that converts is 1～50g/dL, under the condition of 20～95 DEG C of temperature, add water miscible silicon compound, add mineral acid etc., carry out pH regulator (neutralization) and formation SiO 2coating, then, under the condition of 20～95 DEG C of temperature, pH6～12, adds alkoxy-modified silicoorganic compound, forms the coating that contains alkoxy-modified silicoorganic compound and/or its hydrolyzate.Or, the colloid silica aqueous dispersions of pH6～12 can be added to magnesium hydroxide aqeous suspension, keep certain hour 20～95 DEG C of temperature, form thus SiO 2coating, then, can add alkoxy-modified silicoorganic compound.
At this moment,, as alkoxy-modified silicoorganic compound, preferably use by RO-(Si-OCH 3oR) the alkoxy-modified methylsiloxane compound that m+n-R represents.Wherein, R represents at least one in methyl, ethyl, sec.-propyl, and m, n are integer, m >=0, n >=1, m+n=2～100,000.SiO 2can be with interpolations such as the forms of water glass, also can add with the form of colloid silica etc.The ratio of Si:Na during for water glass is arbitrarily.
Alkoxy-modified silicoorganic compound, for example, have initial (Si-OCH 3oR) skeleton of m+n, the OR in skeleton reacts with water and is hydrolyzed, and becomes (Si-OCH 3oR) m (Si-OCH 3oH) skeleton of n.Temperature of reaction is that 20～95 DEG C, pH are 6～12nd, suitable, during lower than 20 DEG C, and the SiO of alkoxy-modified silicoorganic compound and the 1st layer 2, substrate the reaction on magnesium hydroxide surface insufficient, while exceeding 95 DEG C, be difficult to carry out uniform surface treatment, acid resistance reduces.PH was lower than 6 o'clock, and when surface treatment, magnesium hydroxide dissolves disappearance completely.In addition, pH exceedes at 12 o'clock, as the SiO of surface treatment agent 2, alkoxy-modified silicoorganic compound not with magnesium hydroxide bonding, therefore acid resistance is poor.
As used silicon compound, can enumerate the silicate such as water glass, potassium silicate.In addition, as the mineral acid for regulating pH, can use sulfuric acid, hydrochloric acid etc., as the pH after pH regulator, preferably 6～10, more preferably 6～9.
In addition, the invention reside in the resin combination that contains halogen-free flame retardants 10～300 quality % as described above with respect to resinous principle 100 quality %.Resinous principle is the ratio below 30 quality % with respect to resinous principle 100 quality %, and can contain the composition beyond the synthetic resins such as tenderizer, antioxidant.For having used resin combination, formed body, the profiled part of halogen-free flame retardants of the present invention, acid resistance and water tolerance and physical strength excellence.Preferably, with respect to above-mentioned resinous principle 100 quality %, contain above-mentioned halogen-free flame retardants 120～300 quality %.Preferred above-mentioned resinous principle is taking polyolefin-based resins as principal constituent in addition.
The present invention is also to use the formed body that above-mentioned resin combination moulding obtains or the profiled part being formed by the electric wire, cable, optical fiber cord or the Connectorized fiber optic cabling that use above-mentioned resin combination to carry out coating.
SiO 2there is the key very strong with magnesium hydroxide, can suppress magnesium hydroxide caused by acid deteriorated, particularly high to organic acid effects such as acetic acid.On the other hand, if use SiO 2the surface of coating magnesium hydroxide completely, the dispersiveness of magnesium hydroxide in resin significantly reduces, the resin combination that cannot be disperseed equably.On the other hand, the alkoxy-modified silicoorganic compound shown in formula (1) etc. have hydrophobicity, have the effect that does not allow acid substance approach magnesium hydroxide surface.In addition, by the alkoxy-modified silicoorganic compound of the expressions such as formula (1) compared with other organosilicone compounds such as methyl hydrogen silicone, more strongly with magnesium hydroxide bonding, so significantly improve acid resistance.This is because the alkoxy-modified silicoorganic compound of formula (1) etc. and magnesium hydroxide generation hydrolysis reaction and bonding.In addition, all can improve acid resistance by the alkoxy-modified silicoorganic compound of the expressions such as formula (1) to organic acid and mineral acid, especially larger to the effect of mineral acid.
SiO 2have to contact with water and just water is contained in to inner character, therefore use SiO 2carry out the non-constant of water tolerance of surface-treated magnesium hydroxide, when composition is immersed in water, the problem that has volume specific resistance significantly to reduce.But due to alkoxy-modified silicoorganic compound and the magnesium hydroxide bonding strongly of formula (1) etc., there is hydrophobicity, so that the water tolerance of resin combination etc. improve.
Halogen-free flame retardants is appended to the surface treatment of carrying out with the 3rd composition.These are processed material and are defined as the thing quality and quantity that does not depart from effect of the present invention.The material of processing as appending can be that coupling agent, titanic acid ester are that coupling agent, fatty acid series material, phosphoric acid ester or aluminum oxide, titanium oxide, zirconium white etc. are processed with modified organic silicon compound, various silane coupling agent, aluminium beyond above-mentioned.The amount of these treatment agents is not particularly limited, and is generally 0.05～7 quality % left and right with respect to magnesium hydroxide 100 quality %.
Resin combination of the present invention is by disperseing above-mentioned halogen-free flame retardants to obtain in resin, and formed body obtains by resin combination being utilized forming machine carry out moulding.Such halogen-free flame retardants adds 10～400 quality % with respect to resinous principle 100 quality % conventionally in resin.As can be very large realize the scope of acid proof effect, be not particularly limited, in resinous principle 100 quality %, be preferably 50～350 quality %, more preferably 120～300 quality %.If the amount of halogen-free flame retardants is too much, resin characteristics produce deteriorated, or become be difficult to dispersed, acid resistance variation.
Add halogen-free flame retardants and can form the resin of resin combination, having thermoplastic resin, thermosetting resin etc., particularly preferably thermoplastic resin.As thermoplastic resin, can enumerate polyethylene, polypropylene, ethylene-alpha-olefin copolymer, vinyl-vinyl acetate copolymer, styrene series elastomer, polyhutadiene, isoprene, ethylene-propylene and be rubber, ethylene-propylene and be the polyolefin-based resins such as rubber, polyester, polymeric amide with and elastomerics, urethane, MODIFIED PP O, MODIFIED PP E, polystyrene, ABS resin, polycarbonate, polyvinyl chloride, neoprene, chlorosulphonation rubber etc.Wherein, the elastomerics of preferred polyolefm, polyester, polymeric amide, the kind of thermoplastic resin is arbitrarily.
In the present invention, can and use other halogen-free flame retardantss in the resin combination that is dispersed with halogen-free flame retardants resin.Also the amount of use, taking quality as unit, for example, is overall below 2/3 of halogen-free flame retardants, is preferably below 1/2.In the present invention, can in the resin combination that is dispersed with halogen-free flame retardants resin, coordinate as required respectively various additives.As these additives, can enumerate the various additives such as such as fire retardant, antiaging agent, weather resisting agent, copper(greening)inhibitor, thermo-stabilizer, softening agent, lubricant, lubrication prescription, weighting agent, tinting material, compatilizer, static inhibitor, whipping agent, linking agent, crosslinking coagent.In addition, these additives can coordinate a kind and two or more.
As making this such halogen-free flame retardants be dispersed in the method in thermoplastic resin.For example utilize roller mixing roll, Banbury mixer, kneader, single shaft mixing roll, twin shaft mixing roll to mix.In addition, formed body disperses this halogen-free flame retardants or limit dispersion moulding by stacked moulding etc. such as extrusion shaping machine, injection moulding machine, blow molding machine, pressure forming machine, calendering formation machine for limit.In addition, the resin combination of gained, formed body can be implemented crosslinking reaction by the whole bag of tricks such as heat treated or electron beam, UV treatment.As cross-linking method, can enumerate chemical crosslink technique, electron beam crosslinking, silane cross-linking method etc.
Embodiment
Most preferred embodiment of the present invention is below shown, embodiment does not limit the claimed scope of patent application.
Embodiment
(the manufacture embodiment of fire retardant a)
In the polyethylene container made of 100L capacity, add the 3.8N-HCl solution of 67L, under agitation gradation marginally adds the general magnesium hydroxide of total amount 7.4kg (below, to be also designated as " Mg (OH) 2") powder dissolution filter.Should illustrate, make HCl and Mg (OH) 2dissolve with equivalent, to filtering the artificial MgCl obtaining 2solution carries out quantitative analysis, result, MgCl by EDTA volumetry 2concentration is 170g/L.By this artificial MgCl 2solution divides gets 44L, adds lentamente wherein the 8.3N-NaOH solution (Mg of 17L under stirring 2+with OH -mole ratio be 1:1.8), separate out the Mg (OH) of 4.1kg 2.Add again pure water, the suspension of preparation 67L.Hastelloy (Hastelloy) the C-276 system that has that this suspension is flowed into 100L capacity connects in the autoclave of liquid portion, under stirring, carries out the hydrothermal treatment consists of 5 hours at 190 DEG C.
After slurries after hydrothermal treatment consists are filtered, solids component is fully cleaned with 20 times of pure water more than capacity.Thereafter, again refund in pure water, modulation is with Mg (OH) 2solid component concentration is counted the emulsification slurries of 100g/L.These emulsification slurries 33L is taked in the SUS316 container made of 70L capacity (with Mg (OH) 2solids component quality meter, is equivalent to 100g), heat slurries while stirring until 80 DEG C.Slurry temperature is maintained to 80 DEG C, under agitation, add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions (three-wheel chemical industry Co., Ltd. system, the SiO in solution of 3 quality % counted in conversion 2concentration is 29 quality %), then, dripped and be adjusted to the aqueous sulfuric acid of 10 quality % concentration until reach pH9.0 with approximately 1 hour, then carry out the slaking of 30 minutes and make soft silica be created on particle surface at 80 DEG C.Then, add with respect to Mg (OH) 2solids component quality is the methoxyl group modified methyl silicone (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: AFP-1) of 3 quality %, then, carries out the surface treatment of 1 hour at 80 DEG C.
Methoxyl group modified methyl silicone when interpolation is by chemical formula RO-(Si-OCH 3oR) m+n – R (4) represents, is hydrolyzed in surface-treated process, becomes the compound of formula (1), (2) or (3).
M >=0, n >=1, characteristic that m+n is about 7, m+n while being 3～15 scope is equal, can make m+n in wider 3～100 range, and m+n is the widest is 2～100,000.R is methyl, can be also ethyl or sec.-propyl, forms methoxyl group during for methyl, forms oxyethyl group during for ethyl, forms isopropoxy during for sec.-propyl.M=0, n=1, m+n are 1 o'clock, are methyltrimethoxy silane, and this is the material different from methoxyl group modified methyl silicone, and characteristic when coating magnesium hydroxide particles surface is also different from this invention.OH base in methoxyl group modified methyl silicone is born and the SiO of the 1st layer 2or the bonding on the magnesium hydroxide particles surface of substrate, while replacing OH base with hydrogen atom, the acid resistance of halogen-free flame retardants reduces.Should illustrate, Si atom is with methyl but large-scale when alkyl linked with propyl group, decyl etc., the acid resistance deficiency during as halogen-free flameproof agent.
After surface treatment, carry out vacuum filtration, use with respect to Mg (OH) 2solids component quality is that 5 times of pure water more than capacity clean.Dry after cleaning, pulverizing, obtain Mg (OH) 2powder (fire retardant of the present invention a).In surface-treated process, generate SiO by dripping sulfuric acid (pH regulator) 2.The soft silica generating is all attached to magnesium hydroxide surface and becomes the coating of the 1st layer, and the tunicle of alkoxy-modified methylsiloxane is as the 2nd layer of generation.
(the manufacture embodiment of fire retardant b)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 5 quality % and the methoxyl group modified methyl silicone of 5 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant b.
(the manufacture embodiment of fire retardant c)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 0.3 quality % and the methoxyl group modified methyl silicone of 3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant c.
(the manufacture embodiment of fire retardant d)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 3 quality % and the methoxyl group modified methyl silicone of 0.3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant d.
(the manufacture embodiment of fire retardant e)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 1 quality % and the methoxyl group modified methyl silicone of 7 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant e.
(the manufacture embodiment of fire retardant f)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 7 quality % and the methoxyl group modified methyl silicone of 1.5 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant f.
(the manufacture embodiment of fire retardant g)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 1.5 quality % and the methoxyl group modified methyl silicone of 7 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant g.
(the manufacture embodiment of fire retardant h)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 1 quality % and the methoxyl group modified methyl silicone of 0.3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant h.
(the manufacture embodiment of fire retardant i)
Will be with Mg (OH) 2the emulsification slurries 33L that solid component concentration is counted 100g/L takes in the SUS316 container made of 70L capacity (with Mg (OH) 2solids component quality meter, is equivalent to 100g), heat slurries while stirring until 80 DEG C.Slurry temperature is maintained to 80 DEG C, under stirring, add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions (three-wheel chemical industry Co., Ltd. system, the SiO in solution of 2 quality % counted in conversion 2concentration is 29 quality %), then, dripped and be adjusted into the aqueous sulfuric acid of 10 quality % concentration until reach pH9.0 with approximately 1 hour, then, carry out the slaking of 30 minutes and make soft silica be created on particle surface at 80 DEG C.Then, add with respect to Mg (OH) 2solids component quality is the above-mentioned methoxyl group modified methyl silicoorganic compound (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: AFP-1) of 2 quality %, then, stirs 1 hour at 80 DEG C.And then, with vinyltrimethoxy silane with respect to Mg (OH) 2solids component quality is that the mode of 0.6 quality % is added vinyltrimethoxy silane (the Shin-Etsu Chemial Co., Ltd's system that is adjusted to the 0.5wt% of pH3.0 with acetic acid, trade(brand)name: KBM-1003) aqueous solution, then, carry out surface treatment 80 DEG C of stirrings 8 hours, in addition, similarly carry out with fire retardant a, manufacture fire retardant i.
(the manufacture embodiment of fire retardant j)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 2 quality %, the methoxyl group modified methyl silicone of 2 quality %, γ-methacryloxypropyl trimethoxy silane (Shin-Etsu Chemial Co., Ltd's system of 0.6 quality % are counted in conversion, trade(brand)name: KBM-503), in addition, similarly carry out with fire retardant i, manufacture fire retardant j.
(the manufacture embodiment of fire retardant k)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 9 quality % and the methoxyl group modified methyl silicone of 9 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant k.
(the manufacture comparative example of fire retardant l)
Only add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant l.
(the manufacture comparative example of fire retardant m)
Only add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 0.3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant m.
(the manufacture comparative example of fire retardant o)
Only add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 9 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant o.
(the manufacture comparative example of fire retardant p)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 3 quality % and the methyl hydrogen silicone (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KF-99) of 1 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant p.
(the manufacture comparative example of fire retardant q)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 3 quality % and the methyl hydrogen silicone (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KF-99) of 5 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant q.
(the manufacture comparative example of fire retardant r)
Add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions of 3 quality % and the methyl hydrogen silicone (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KF-99) of 3 quality % are counted in conversion, in addition, similarly carry out with fire retardant a, manufacture fire retardant q.
(the manufacture comparative example of fire retardant s)
Will be with Mg (OH) 2the emulsification slurries 33L that solid component concentration is counted 100g/L takes in the SUS316 container made of 70L capacity (with Mg (OH) 2solids component quality meter, is equivalent to 100g), heating slurry is until 80 DEG C of liquid while stirring.Maintain slurry temperature at 80 DEG C, under stirring, add with respect to Mg (OH) 2solids component quality is with SiO 2no. 3 sodium silicate solutions (three-wheel chemical industry Co., Ltd. system, the SiO in solution of 1 quality % counted in conversion 2concentration is 29 quality %), then, drip the aqueous sulfuric acid that is adjusted into 10 quality % concentration until pH9.0 with approximately 1 hour, then, carry out the slaking of 30 minutes and make soft silica be created on particle surface at 80 DEG C.Then, with octadecyl phosphoric acid ester with respect to Mg (OH) 2solids component quality is the octadecyl phosphoric acid ester sodium water solution that the mode of 3 quality % is added the 3wt% that is adjusted into 80 DEG C, then, carries out surface treatment 80 DEG C of stirrings 1 hour, in addition, similarly carries out with fire retardant a, manufactures fire retardant s.
(the manufacture comparative example of fire retardant t)
Will be with Mg (OH) 2the emulsification slurries 33L that solid component concentration is counted 100g/L takes in the SUS316 container made of 70L capacity (with Mg (OH) 2solids component quality meter, is equivalent to 100g), heat slurries while stirring until 80 DEG C.Slurry temperature is maintained to 80 DEG C, under stirring, with octadecyl phosphoric acid ester with respect to Mg (OH) 2solids component quality is the octadecyl phosphoric acid ester sodium water solution that the mode of 2.3 quality % is added the 3wt% that is adjusted into 80 DEG C, then, stirs hour and carries out surface treatment at 80 DEG C 1, in addition, similarly carries out with fire retardant a, manufactures fire retardant t.
(the manufacture comparative example of fire retardant u)
With respect to Mg (OH) 2solids component quality, adds octadecyl phosphoric acid ester sodium water solution in the mode of only counting 3 quality % with octadecyl phosphoric acid ester, in addition, similarly carries out with fire retardant t, manufactures fire retardant u.
(the manufacture comparative example of fire retardant v)
With respect to Mg (OH) 2solids component quality, adds the sodium stearate aqueous solution in the mode of only counting 3 quality % with stearic acid, in addition, similarly carries out with fire retardant t, manufactures fire retardant v.
(the manufacture comparative example of fire retardant w)
With respect to Mg (OH) 2solids component quality, adds aqueous solution sodium oleate in the mode of only counting 2.5 quality % with oleic acid, in addition, similarly carries out with fire retardant t, manufactures fire retardant w.
(the manufacture comparative example of fire retardant x)
Add with respect to Mg (OH) 2solids component quality is with SiO 2conversion is counted No. 3 sodium silicate solutions of 3 quality % and is counted the sodium stearate aqueous solution of 3 quality % with stearic acid, in addition, similarly carries out with fire retardant t, manufactures fire retardant x.
(the manufacture comparative example of fire retardant y)
Will be with Mg (OH) 2the emulsification slurries 33L that solid component concentration is counted 100g/L takes in the SUS316 container made of 70L capacity (with Mg (OH) 2solids component quality meter, is equivalent to 100g), heat slurries while stirring until 80 DEG C.Slurry temperature is maintained to 80 DEG C, under stirring, at 80 DEG C, add with respect to Mg (OH) 2solids component quality is with SiO 2the colloid soft silica solution (Nissan Chemical Ind Ltd's system, trade(brand)name: SNOWTEX O) of the 20 quality % concentration of 3 quality % is counted in conversion., add the decyl Trimethoxy silane (Shin-Etsu Chemial Co., Ltd system, trade(brand)name: KBM-3103C) of 3 quality %s and stir 1 hour and carry out surface treatment, in addition, similarly carrying out with fire retardant a, manufacturing fire retardant y thereafter.
(the manufacture comparative example of fire retardant z)
Add with respect to Mg (OH) 2solids component quality is with SiO 2the colloid soft silica solution of 20 quality % concentration and methyltrimethoxy silane (the Shin-Etsu Chemial Co., Ltd's system of 3 quality % of 3 quality % counted in conversion, trade(brand)name: KBM-13), in addition, similarly carry out with fire retardant y, manufacture fire retardant z.By embodiment, ((composition of fire retardant l～z) is shown in table 1～table 3, and % represents the quality % taking magnesium hydroxide as 100 quality % for fire retardant a～k) and comparative example.
[table 1]
[table 2]
[table 3]
Use the magnesium hydroxide of processing through like this, with the Banbury mixer title complex of mixture table 1～table 3 according to the specified ratio, carry out at 220 DEG C mixing, with FEEDER RUDER granulation.In addition, use this material, make 1mm sheet by roller, press.Be 220 DEG C in pressed temperature and carry out moulding.In addition, the resin material obtaining by the external diameter coating of 2.4mm in the outside of conductor diameter 1/0.8TA with the forcing machine of 25mm, obtains electric wire.Extruder head temperature is recorded in table 1.Sheet, electric wire to gained carry out following test.
1. tension test
Sheet is shaped to (2004) No. 3 dumbbells of JIS K7256, tests based on JIS K7113.Tensile strength is that 10MPa is above, elongation is more than 100% for qualified.
2. acid resisting test 1
Sheet is shaped to No. 3 dumbbells of JIS, after gravimetry, in 10% hydrochloric acid, floods 24 hours at 40 DEG C.After dipping, take out sheet, with after the abundant cleaning sheet of distilled water, dry under normal temperature, gravimetry.Based on JIS K7113 carry out tension test thereafter.The residual rate of tensile strength, the residual rate of elongation are more than 80% as qualified.In addition, if changes in weight is-15% taking next as qualified.
3. acid resisting test 2
Sheet is shaped to No. 3 dumbbells of JIS, after gravimetry, in 10% sulfuric acid, floods 24 hours at 40 DEG C.After dipping, take out sheet, with after the abundant cleaning sheet of distilled water, dry under normal temperature, gravimetry.,, carry out tension test based on JIS K7113 thereafter.The residual rate of tensile strength, the residual rate of elongation are more than 80% as qualified.In addition, if changes in weight is-15% taking next as qualified.
4. acid resisting test 3
Sheet is shaped to No. 3 dumbbells of JIS, after gravimetry, in 10% acetic acid, floods 24 hours at 40 DEG C.After dipping, take out sheet, with after the abundant cleaning sheet of distilled water, dry under normal temperature, gravimetry.Based on JIS K7113 carry out tension test thereafter.The residual rate of tensile strength, the residual rate of elongation are more than 80% as qualified.In addition, if changes in weight is-15% taking next as qualified.
5. tension test (electric wire)
Extract conductor out and make tubular piece from electric wire, carrying out tension test by the condition of JIS C3005.Minute carry out taking draw speed as 200mm/.Tensile strength is that 10MPa is above, elongation is more than 100% for qualified.
6. acid resisting test 4
Sheet is shaped to No. 3 dumbbells of JIS, after gravimetry, in 10% hydrochloric acid, floods 24 hours at 40 DEG C.After dipping, take out sheet, with after the abundant cleaning sheet of distilled water, dry under normal temperature, gravimetry.By the condition of JIS C3005 carry out tension test thereafter.Minute carry out taking draw speed as 200mm/.The residual rate of tensile strength, the residual rate of elongation are more than 80% as qualified.In addition, if changes in weight is-15% taking next as qualified.
7. acid resisting test 5
Sheet is shaped to No. 3 dumbbells of JIS, after gravimetry, in 10% acetic acid, floods 24 hours at 40 DEG C.After dipping, take out sheet, with after the abundant cleaning sheet of distilled water, dry under normal temperature, gravimetry.By the condition of JIS C3005 carry out tension test thereafter.Minute carry out taking draw speed as 200mm/.The residual rate of tensile strength, the residual rate of elongation are more than 80% as qualified.In addition, if changes in weight is-15% taking next as qualified.
8. volume specific resistance
In the tank of 20 DEG C, flood 20m with the state that exposes electric wire two ends, according to JIS C3005, immersion was measured insulation resistance after 1 hour.Be to measure under 500V at voltage.Then directly soak 24 hours, measure the insulation resistance after immersion.Insulation resistance is converted into volume specific resistance by calculating.Criterion of acceptability is according to base mateiral and difference, for being 10 in immersion after 1 hour in the situation of ethylene vinyl acetate 13more than Ω cm, after 24 hours, be 10 in immersion 13more than Ω cm, in ethylene-alpha-olefin copolymer, polyacrylic situation, after 1 hour, be 10 in immersion 15more than Ω cm, soaking after 24 hours is 10 15more than Ω cm, for being 10 in immersion after 1 hour in the situation of polyester elastomer 13more than Ω cm, after 24 hours, be 10 in immersion 12more than Ω cm.
9. dispersion state test
Observe the surface of electric wire, confirm white magnesium hydroxide cohesion.That can't see the cohesion of white magnesium hydroxide with visual observation is designated as zero, sees the △ that is designated as of condensation product 2 below in the length of electric wire 10mm, see being designated as of its cohesion above ×.
The test-results of embodiment is shown in to table 4, table 5, the test-results of comparative example is shown in to table 6, table 7.In table, KS204T is that the metallocene of Japan Polyethylene Corp.'s system is plastomer, SP0540 is the Low Density Polyethylene of Prime Polymer Co., Ltd. system, PB222A is the Atactic Polypropelene of SunAllomer Co., Ltd. system, and EV180 is the ethylene vinyl acetate copolymer of DU PONT-MITSUI POLYCHEMICALS company system.NUC6510 is the ethylene vinyl acetate copolymer of Nippon Unicar Co., Ltd. system, SEPS4077 is the hydrogenated styrene based thermoplastic elastomerics of Kuraray company system, Diana Process Oil PW90 is the mineral oil softener of Idemitsu Kosen Co., Ltd.'s system, Hytrel 4477 is the polyetherester block copolymer of DU PONT-TORAY system, and Irganox is that the hindered phenol of Ciba company system is antioxidant.
In embodiment, acid resistance and water tolerance (volume specific resistance), tensile strength, elongation and outward appearance excellence.If particularly the alkoxy-modified methylsiloxane compound of formula (1) is changed to decyl Trimethoxy silane (fire retardant y) or methyltrimethoxy silane (fire retardant z), acid resistance reduces.The part of drawing grid in the table 6 of comparative example, table 7 represents the part of performance deficiency, table 6, the table 7 of table 4, table 5 and the comparative example of comparing embodiment, initial performance, acid resistance, volume specific resistance and outward appearance whole that meet tensile strength and elongation in known embodiment, cannot all meet these performances in comparative example.In addition, in embodiment, fire retardant a, b, i, j (the methoxyl group modified methyl silicone of soft silica and formula (1) is all 2～5 quality %) obtain excellent especially result, fire retardant e, f, g (the methoxyl group modified methyl silicone of soft silica and formula (1) is 1～7 quality %) obtain secondly excellent result, and fire retardant c, d, h, k (the methoxyl group modified methyl silicone of soft silica and formula (1) is 0.3～9 quality %) obtain result poor compared with other embodiment.
[table 4]
[table 5]
[table 6]
[table 7]
Claims (according to the amendment of the 19th article of treaty)
1. (after amendment) a kind of halogen-free flame retardants, has magnesium hydroxide particles and the coating that is formed at this magnesium hydroxide particles surface, and described coating contains SiO 2and alkoxy-modified silicoorganic compound and/or its hydrolyzate, described alkoxy-modified silicoorganic compound have siloxanes and have alkoxyl group as repeating unit and at side chain.
2. halogen-free flame retardants according to claim 1, the hydrolyzate of described alkoxy-modified silicoorganic compound is the alkoxy-modified methylsiloxane compound by following formula (1) or formula (2) or formula (3) expression,
RO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-R (1)
HO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-R (2)
HO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-H (3)
Wherein, R represents at least one in methyl, ethyl, sec.-propyl, and m, n are integer, m >=0, n >=1, m+n=2～100,000.
3. halogen-free flame retardants according to claim 1 and 2, is characterized in that, by described SiO 2be that the 1st layer, described alkoxy-modified silicoorganic compound and/or its hydrolyzate are the mode coating magnesium hydroxide particles surface of the 2nd layer.
4. according to the halogen-free flame retardants described in any one in claim 1～3, it is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 0.3～9 quality % 2, 0.3～9 quality % described alkoxy-modified silicoorganic compound.
5. halogen-free flame retardants according to claim 4, is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 1～7 quality % 2, 1～7 quality % described alkoxy-modified silicoorganic compound.
6. halogen-free flame retardants according to claim 5, is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 1.5～5 quality % 2, 1.5～5 quality % described alkoxy-modified silicoorganic compound.
7. the manufacture method of (amendment after) a kind of halogen-free flame retardants adds water miscible silicon compound or colloid silica and forms SiO in magnesium hydroxide aqeous suspension 2coating, then, use alkoxy-modified silicoorganic compound to form coating, described coating contains alkoxy-modified silicoorganic compound and/or its hydrolyzate, and described alkoxy-modified silicoorganic compound have siloxanes and have alkoxyl group as repeating unit and at side chain.
8. a resin combination, with respect to resinous principle 100 quality %, the halogen-free flame retardants in the claim 1～6 that contains 10～300 quality % described in any one.
9. resin combination according to claim 8, is characterized in that, with respect to described resinous principle 100 quality %, contain 120～300 quality % described in carried out surface-treated magnesium hydroxide.
10. a formed body is that the resin combination moulding of right to use requirement 8 or 9 obtains.
11. 1 kinds of profiled parts are that electric wire, cable, optical fiber cord or the Connectorized fiber optic cabling that requires 8 or 9 resin combination to carry out coating by right to use forms.

Claims (11)

1. a halogen-free flame retardants, has magnesium hydroxide particles and the coating that is formed at this magnesium hydroxide particles surface, and described coating contains SiO 2and alkoxy-modified silicoorganic compound and/or its hydrolyzate.
2. halogen-free flame retardants according to claim 1, the hydrolyzate of described alkoxy-modified silicoorganic compound is the alkoxy-modified methylsiloxane compound by following formula (1) or formula (2) or formula (3) expression,
RO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-R (1)
HO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-R (2)
HO-(Si-O·CH 3·OR)m(Si-O·CH 3·OH)n-H (3)
Wherein, R represents at least one in methyl, ethyl, sec.-propyl, and m, n are integer, m >=0, n >=1, m+n=2～100,000.
3. halogen-free flame retardants according to claim 1 and 2, is characterized in that, by described SiO 2be that the 1st layer, described alkoxy-modified silicoorganic compound and/or its hydrolyzate are the mode coating magnesium hydroxide particles surface of the 2nd layer.
4. according to the halogen-free flame retardants described in any one in claim 1～3, it is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 0.3～9 quality % 2, 0.3～9 quality % described alkoxy-modified silicoorganic compound.
5. halogen-free flame retardants according to claim 4, is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 1～7 quality % 2, 1～7 quality % described alkoxy-modified silicoorganic compound.
6. halogen-free flame retardants according to claim 5, is characterized in that, with respect to magnesium hydroxide 100 quality %, the SiO that contains 1.5～5 quality % 2, 1.5～5 quality % described alkoxy-modified silicoorganic compound.
7. a manufacture method for halogen-free flame retardants adds water miscible silicon compound or colloid silica and forms SiO in magnesium hydroxide aqeous suspension 2coating, then, uses alkoxy-modified silicoorganic compound to form coating, and described coating contains alkoxy-modified silicoorganic compound and/or its hydrolyzate.
8. a resin combination, with respect to resinous principle 100 quality %, the halogen-free flame retardants in the claim 1～6 that contains 10～300 quality % described in any one.
9. resin combination according to claim 8, is characterized in that, with respect to described resinous principle 100 quality %, contain 120～300 quality % described in carried out surface-treated magnesium hydroxide.
10. a formed body is that the resin combination moulding of right to use requirement 8 or 9 obtains.
11. 1 kinds of profiled parts are that electric wire, cable, optical fiber cord or the Connectorized fiber optic cabling that requires 8 or 9 resin combination to carry out coating by right to use forms.
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CN104715848A (en) * 2015-03-17 2015-06-17 安徽太平洋电缆股份有限公司 Pre-branching fire protection insulation cable and machining method thereof

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