CN103304848A - Fire retardant, fire retardant composition, electric wire and cable - Google Patents
Fire retardant, fire retardant composition, electric wire and cable Download PDFInfo
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- CN103304848A CN103304848A CN2013100622325A CN201310062232A CN103304848A CN 103304848 A CN103304848 A CN 103304848A CN 2013100622325 A CN2013100622325 A CN 2013100622325A CN 201310062232 A CN201310062232 A CN 201310062232A CN 103304848 A CN103304848 A CN 103304848A
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- magnesium hydroxide
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Abstract
The present invention provides a fire retardant with improved acid resistance, a fire retardant composition containing the fire retardant, and an electric wire and a cable which have coating material formed by using the fire retardant composition. The fire retardant contains magnesium hydroxide on which surface treatment is performed with an epoxy silane coupling agent and an amino silane coupling agent.
Description
Technical field
The present invention relates to fire retardant, flame-retardant composition and electric wire, cable, in more detail, the electric wire, the cable that relate to fire retardant contained in the flame-retardant composition of the coating material that can be used as halogen-free flame-retardant wire, cable, contain the flame-retardant composition of this fire retardant and possess the coating material that forms with this flame-retardant composition.
Background technology
When electric wire, cable fire, for prevent from being fuming, the secondary disaster such as toxicity, corrosion, controlling the use of halogenated flame retardant.Therefore, for example, as giving one of coating material fire retardant with flame retardant resistance, use at present magnesium hydroxide.Yet magnesium hydroxide has apt to deteriorate, deteriorated shortcoming in itself.Particularly, under acid atmosphere, has following shortcoming:, and separate out or stripping etc. by generating magnesium salts with acid-respons.
As its countermeasure or in order to improve other function, following scheme is proposed repeatedly: with respect to magnesium hydroxide, utilize the organic materialss such as lipid acid or silane coupled material to implement surface treatment.In addition, after the inorganic materials enforcement surface treatment that utilizes take silicon oxide (silica (Silica)), aluminum oxide etc. as principal constituent, further implement (for example, with reference to patent documentation 1 and patent documentations 2 etc.) such as surface treatments with above-mentioned organic materials.
Yet, about acid resistance, solved fully, and required further improvement.
The prior art document
Patent documentation
Patent documentation 1: No. 2645086 communique of Japanese Patent
Patent documentation 2: No. 4106928 communique of Japanese Patent
Summary of the invention
The problem that invention will solve
The present invention carries out in view of the above-mentioned problems, and the fire retardant that provides acid resistance to be improved, electric wire, the cable that contains the flame-retardant composition of this fire retardant and possess the coating material that forms with this flame-retardant composition are provided its purpose.
Be used for solving the means of problem
To achieve these goals, by the invention provides following fire retardant, flame-retardant composition and electric wire, cable.
［ 1 ］ a kind of fire retardant, it contains by epoxy is that silane coupling agent and amino are that silane coupling agent has been implemented the surface-treated magnesium hydroxide.
［ 2 ］ according to above-mentioned ［ 1 ］ described fire retardant, wherein, described epoxy is that silane coupling agent and described amino are that silane coupling agent adds respectively 0.1～10 mass parts in surface treatment amount with respect to magnesium hydroxide 100 mass parts.
［ 3 ］ according to above-mentioned ［ 1 ］ or ［ 2 ］ described fire retardant, wherein, described magnesium hydroxide is being that silane coupling agent and described amino are before silane coupling agent is implemented surface treatment, to have implemented surface treatment by inorganic materials by described epoxy.
［ 4 ］ according to above-mentioned ［ 3 ］ described fire retardant, wherein, described inorganic materials is added 0.1～20 mass parts in surface treatment amount with respect to magnesium hydroxide 100 mass parts.
［ 5 ］ according to above-mentioned ［ 3 ］ or ［ 4 ］ described fire retardant, wherein, described inorganic materials is silicon oxide, aluminum oxide, titanium oxide, zirconium white, magnesium oxide, zinc oxide, stannic oxide, vanadium oxide, manganese oxide or their mixture.
［ 6 ］ a kind of flame-retardant composition, it contains each described fire retardant in plastics or rubber and above-mentioned ［ 1 ］～［ 5 ］.
［ 7 ］ according to above-mentioned ［ 6 ］ described flame-retardant composition, wherein, contain described fire retardant 40～300 mass parts with respect to described plastics or rubber 100 mass parts.
［ 8 ］ a kind of electric wire, it possesses the coating material that uses above-mentioned ［ 6 ］ or ［ 7 ］ described flame-retardant composition to form.
［ 9 ］ a kind of cable, it possesses the coating material that uses above-mentioned ［ 6 ］ or ［ 7 ］ described flame-retardant composition to form.
The invention effect
According to the present invention, provide the fire retardant that acid resistance is improved, electric wire, the cable that contains the flame-retardant composition of this fire retardant and possess the coating material that forms with this flame-retardant composition.Especially, the present invention effectively is applicable to halogen-free flame-retardant wire used in high humidity atmosphere, cable.
For the mode that carries out an invention
The embodiment summary
The fire retardant of present embodiment is for the fire retardant that contains magnesium hydroxide, and utilizing epoxy is that silane coupling agent and amino are that silane coupling agent has been implemented the surface-treated fire retardant.In addition, the flame-retardant composition of present embodiment is the flame-retardant composition that contains plastics or rubber and fire retardant, wherein, as fire retardant, contain that to comprise by epoxy be that silane coupling agent and amino are the fire retardant that silane coupling agent has been implemented the surface-treated magnesium hydroxide.And then, the electric wire of present embodiment, cable are electric wire, the cables that possesses the coating material that forms with flame-retardant composition, wherein, as coating material, possess the coating material of having used the flame-retardant composition that contains fire retardant to form, it is that silane coupling agent and amino are that silane coupling agent has been implemented the surface-treated magnesium hydroxide that described fire retardant contains by epoxy.
Embodiment
Below, the embodiment of fire retardant of the present invention, flame-retardant composition and electric wire, cable is carried out specific description.
1. fire retardant
It is that silane coupling agent and amino are that silane coupling agent has been implemented the surface-treated magnesium hydroxide that the fire retardant of present embodiment contains by epoxy.
As the magnesium hydroxide that can be used for present embodiment, can use synthetic magnesium hydroxide that the magnesium in the seawater synthesizes as raw material or with the brucite of natural brucite ore grinding.As its form, shape, be not particularly limited, but for example can enumerate powder footpath or particle diameter is powder or the particle shape of 0.1～50 μ m.
In the present embodiment; as the surface-treated surface treatment agent that is used for implementing magnesium hydroxide; only having epoxy is that silane coupling agent and amino are that unusual effect is just brought into play in the combination of silane coupling agent; be still not clear about its reason; but can think, carry out chemical reaction as epoxy group(ing) and the amino of the moiety of each silane coupling agent, its bonding force is higher; think consequently with respect to magnesium hydroxide, forming by epoxy is that silane coupling agent and amino are the duplicate protection layer that silane coupling agent consists of.
For the mechanism of action of common silane coupling agent, alkoxyl group in the silane coupled agent molecule partly be hydrolyzed and the silanol group that forms by the surface of adsorption by hydrogen bond in such inorganic materials such as magnesium hydroxide, and then carry out Chemical bond by dehydration condensation.Be positioned at the outside as functional groups such as the epoxy group(ing) of the part in the silane coupled agent molecule, amino, vinyl, acryl, methacryloyl with respect to magnesium hydroxide particles.Think at this, even adsorbed the silane coupling agent of identical silane coupling agent or other combinations different from present embodiment, its absorption, bonding force are also little, therefore the protection effect of magnesium hydroxide are diminished.
On the other hand, epoxy group(ing) is reactive high with amino, its bonding force is larger, therefore, part in a kind of silane coupled agent molecule is adsorbed in the surface of magnesium hydroxide, form the 1st layer of silane coupled layer, the functional group that is arranged in its outside and the functional group of a part that consists of another kind of silane coupling agent carry out Chemical bond.Consequently, the functional group in the 2nd layer of silane coupling agent is positioned at the magnesium hydroxide side, and alkoxyl group or silanol group are positioned at the outside.Can think, by such reaction, form the protective layer that firmly carries out chemically combined 2 layers of silane coupling agent, so acid resistance improve.
Be silane coupling agent as the epoxy that can be used for present embodiment, for example can enumerate 2-(3,4 epoxycyclohexyls) ethyl trimethoxy silane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.In addition, in embodiment described later, use the 3-glycidoxypropyltrime,hoxysilane.
Be silane coupling agent about the amino that can be used for present embodiment, for example can enumerate the N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330 etc.Need to prove, in embodiment described later, used the 3-TSL 8330.
Epoxy is that silane coupling agent and amino are that silane coupling agent preferably adds respectively 0.1～10 mass parts in surface treatment amount with respect to magnesium hydroxide 100 mass parts, more preferably adds 0.1～3 mass parts.If less than 0.1 mass parts, then sometimes do not expect sufficient additive effect; If surpass 10 mass parts, then magnesium hydroxide particles condenses each other and forms bulk, causes product appearance, mechanical properties variation.
As the interpolation of silane coupling agent order, can be method successively: with a kind of silane coupling agent magnesium hydroxide is carried out surface treatment, then, carry out surface treatment with another kind of silane coupling agent; Perhaps also can be for carrying out the so-called simultaneously method of surface-treated with 2 kinds of silane coupling agents simultaneously.
Be not particularly limited as the surface-treated method of utilizing silane coupling agent, damp process is for example arranged, in magnesium hydroxide slurry, add silane coupling agent; Drying process is while use the stirring magnesium hydroxide particles such as Henschel stirrer to add silane coupling agent; So-called simultaneously mixing method is added magnesium hydroxide in resin when other Synergist S-421 95 is mixing; Deng, can use any method.
By utilizing 2 kinds of silane coupling agents to carry out surface treatment, at the 2 layer protective layer of the surface of magnesium hydroxide formation based on silane coupling agent.This is with the surface treatment method such as method, while method is irrelevant, all identical successively.At the same time in the situation of method; at first; wherein a kind of silane coupling agent is adsorbed in the surface of magnesium hydroxide; the functional group reactions on the surface of another kind of silane coupling agent and the silane coupling agent of initial absorption (be the outside with respect to magnesium hydroxide) therefore similarly forms 2 layers of protective layer with the situation of method successively.
Magnesium hydroxide was implemented surface treatment by inorganic materials before implementing surface treatment by silane coupling agent, acid resistance is further improved thus, thereby preferred.
In this situation, inorganic materials with respect to magnesium hydroxide 100 mass parts, is preferably added 0.1～20 mass parts in surface treatment amount, more preferably adds 0.1～3 mass parts.
Be not particularly limited as inorganic materials, but for example can enumerate silicon oxide, aluminum oxide, acidifying titanium, zirconium white, magnesium oxide, zinc oxide, stannic oxide, vanadium oxide, manganese oxide or their mixture.
2. flame-retardant composition
The flame-retardant composition of present embodiment contains plastics or rubber and above-mentioned fire retardant.
Be not particularly limited as the plastics that can be used for present embodiment or rubber (base polymer), but for example can enumerate plastics or rubber take following material as principal constituent: ethylene vinyl acetate copolymer (EVA), Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE), ultra-low density polyethylene (VLDPE), high density polyethylene(HDPE) (HDPE), ethylene-ethyl acrylate copolymer (EEA), the ethylene-methyl methacrylate glycidyl ester copolymer, ethene-1-Butylene copolymer, ethene-butylene-hexene terpolymer, ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOR), the ethylene copolymer polypropylene, ethylene-propylene copolymer (EPR), poly--4-methyl-amylene-1, toxilic acid grafting Low Density Polyethylene, hydrogenated styrene-butadienecopolymer (H-SBR), toxilic acid grafting straight chain shape Low Density Polyethylene, ethene and carbonatoms are the multipolymer of 4～20 alpha-olefin, ethylene-styrene copolymer, toxilic acid grafted ethene-methyl acrylate copolymer, toxilic acid grafted ethene-vinyl acetate copolymer, ethene-copolymer-maleic anhydride, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-propylene-butene-1 terpolymers take butene-1 as principal constituent etc.They can use separately a kind maybe can be mixed with two or more.
In the present embodiment, with respect to plastics or rubber 100 mass parts, preferably contain above-mentioned fire retardant 40～300 mass parts.If less than 40 mass parts, the flame retardant resistance step-down of composition sometimes then; If surpass 300 mass parts, then sometimes the detrimentally affect of forming process, the mechanical characteristicies etc. such as mixing property, cable be extrudability is increased.
In the present embodiment, in flame-retardant composition, can add as required antioxidant, UV light absorber, flame retardant, lubricant (processing aid), other weighting agent, stablizer (carbon black, metal oxide etc.), various functional organic material, tinting material etc.
3. electric wire, cable
The electric wire of present embodiment, cable possess the coating material that forms with above-mentioned flame-retardant composition.For example, the formation of electric wire comprises: copper conductor and use above-mentioned flame-retardant composition coated copper conductor after carry out crosslinked and coating material that form.In addition, the formation of cable comprises: electric wire and come the outside of covered electric cable and the sheath that forms with above-mentioned flame-retardant composition.And then specifically, the formation of the cable of present embodiment comprises: 3 wires, and it possesses copper conductor and uses on the above-mentioned flame-retardant composition coated copper conductor and the coating material that forms; Jie is at thing, the paper that becomes with the electric wire twisted etc.; The writing that surpasses all the others band, it is wound in periphery; And as outermost sheath, it is that above-mentioned flame-retardant composition is extruded coating and formation.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not subjected to any restriction of these embodiment.
(embodiment 1)
With ethylene-ethyl acrylate copolymer (EEA) (EA content 10 quality %, MI=0.4g/10 minute, JPE company system: trade(brand)name: A1100) 100 mass parts, magnesium hydroxide G(is with respect to not utilizing inorganic materials to carry out surface-treated magnesium hydroxide (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, epoxy with 2 mass parts is that silane coupling agent carries out surface treatment, then, amino with 2 mass parts is that silane coupling agent carries out the surface-treated magnesium hydroxide) 120 mass parts, carbon black (tokai carbon system as flame retardant, trade(brand)name: SEAST G116) 5 mass parts, antioxidant (Japanese BASF(strain) system, trade(brand)name: Irganox1010) 0.5 mass parts, and processing aid (Zinic stearas) 0.5 mass parts, utilize 6 feet open roll mills (Open roll), at approximately 140 ℃ after lower mixing 10 minutes, about 180 ℃ of lower extrusion formings 5 minutes, made approximately 1mm thick * 50mm is wide * the long sheet material of 60mm.In addition, as the surface preparation of silane coupling agent, damp process, method have successively been used.In addition, the making specific as follows of above-mentioned magnesium hydroxide: in 1 liter of aqeous suspension that concentration 200g/ rises, add each silane coupling agent of 4.0g, this suspension is at room temperature stirred 20 hours after, dry, pulverize.
Use resulting sheet material, estimate acid resistance.Show the result in table 1.In addition, acid resistance is estimated according to anti-nitric acid shown below.In this situation, as changes in weight≤3mg/cm
2The time think to have the effect (zero) that improves anti-nitric acid.When the changes in weight of sheet material greater than 3mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.The following mensuration of anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h, and then in pure water, behind normal temperature dipping 24h, behind 80 ℃ of lower dry 6h, measure the changes in weight (mg/cm of every surface-area
2).
[table 1]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
(embodiment 2, comparative example 1～6)
As shown in table 1 such, changed mix proportion, in addition, similarly to Example 1 operation.In addition, the magnesium hydroxide A～H in the table 1 is as follows.Use resulting sheet material, estimate acid resistance.In this situation, as changes in weight≤3mg/cm
2The time think to have the effect (zero) that improves anti-nitric acid.When the changes in weight of sheet material greater than 3mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.Show the result in table 1.
Magnesium hydroxide A: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, epoxy with 2 mass parts is that silane coupling agent carries out surface treatment, then, the ethene base system silane coupling agent with 2 mass parts carries out the surface-treated magnesium hydroxide
Magnesium hydroxide B: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, epoxy with 2 mass parts is that silane coupling agent carries out surface treatment, then, the epoxy with 2 mass parts is that silane coupling agent carries out the surface-treated magnesium hydroxide
Magnesium hydroxide C: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, epoxy with 2 mass parts is that silane coupling agent carries out surface treatment, then, the methacrylate ester silane coupling agent with 2 mass parts carries out the surface-treated magnesium hydroxide
Magnesium hydroxide D: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, amino with 2 mass parts is that silane coupling agent carries out surface treatment, then, the ethene base system silane coupling agent with 2 mass parts carries out the surface-treated magnesium hydroxide
Magnesium hydroxide E: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, amino with 2 mass parts is that silane coupling agent carries out surface treatment, then, the amino with 2 mass parts is that silane coupling agent carries out the surface-treated magnesium hydroxide
Magnesium hydroxide F: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, amino with 2 mass parts is that silane coupling agent carries out surface treatment, then, the methacrylate ester silane coupling agent with 2 mass parts carries out the surface-treated magnesium hydroxide
Magnesium hydroxide G: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, epoxy with 2 mass parts is that silane coupling agent carries out surface treatment, then, the amino with 2 mass parts is that silane coupling agent carries out the surface-treated magnesium hydroxide
Magnesium hydroxide H: for the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) 100 mass parts, amino with 2 mass parts is that silane coupling agent carries out surface treatment, then, the epoxy with 2 mass parts is that silane coupling agent carries out the surface-treated magnesium hydroxide
(embodiment 3～4, comparative example 7～12)
As shown in table 2 such, changed mix proportion (as magnesium hydroxide, used before carrying out surface treatment with silane coupling agent and utilized inorganic materials to carry out the surface-treated magnesium hydroxide), in addition, similarly to Example 1 operation.In addition, the magnesium hydroxide I～P in the table 2 is as follows.Use resulting sheet material, estimate acid resistance.In this situation, as changes in weight≤2mg/cm
2The time think to have the effect (zero) that improves anti-nitric acid.When the changes in weight of sheet material greater than 2mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.Show the result in table 2.
Specifically, in this embodiment and comparative example, as the inorganic materials of clad magnesium hydroxide, used silicon oxide.As the silicon source, used water glass.2 liters of aqeous suspensioies that the concentration 150g/ of magnesium hydroxide is risen are heated to 80 ℃ temperature, add with SiO
2Behind the water glass of the predetermined amount that converts, add sulfuric acid with 1 hour, until the pH of aqeous suspension reaches preset value, and then, with this aqeous suspension 80 ℃ of lower slakings 1 hour, and at the highdensity coating layer that is consisted of by silicon oxide of the surface of magnesium hydroxide particles formation.From such aqeous suspension, magnesium hydroxide particles is filtered, washing, dry, pulverize.As described above, utilize silane coupling agent implement surface treatment thereafter.
[table 2]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
Magnesium hydroxide I: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the epoxy of 2 mass parts, then, carry out the surface-treated magnesium hydroxide with the ethene base system silane coupling agent of 2 mass parts
Magnesium hydroxide J: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the epoxy of 2 mass parts, then, be that silane coupling agent carries out the surface-treated magnesium hydroxide with the epoxy of 2 mass parts
Magnesium hydroxide K: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the epoxy of 2 mass parts, then, carry out the surface-treated magnesium hydroxide with the methacrylate ester silane coupling agent of 2 mass parts
Magnesium hydroxide L: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the amino of 2 mass parts, then, carry out the surface-treated magnesium hydroxide with the ethene base system silane coupling agent of 2 mass parts
Magnesium hydroxide M: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the amino of 2 mass parts, then, be that silane coupling agent carries out the surface-treated magnesium hydroxide with the amino of 2 mass parts
Magnesium hydroxide N: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the amino of 2 mass parts, then, carry out the surface-treated magnesium hydroxide with the methacrylate ester silane coupling agent of 2 mass parts
Magnesium hydroxide O: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the epoxy of 2 mass parts, then, be that silane coupling agent carries out the surface-treated magnesium hydroxide with the amino of 2 mass parts
Magnesium hydroxide P: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, be that silane coupling agent carries out surface treatment with the amino of 2 mass parts, then, be that silane coupling agent carries out the surface-treated magnesium hydroxide with the epoxy of 2 mass parts
Magnesium hydroxide Q: in the untreated magnesium hydroxide in surface (consonance chemical industrial company system, trade(brand)name: KISMA5) in particle water-soluble serous, in 80 ℃ temperature, add with respect to magnesium hydroxide 100 mass parts with SiO
2Be scaled the metso of 5 mass parts, and add in the resulting mixture in the sulfuric acid and above-mentioned slurries until pH6～9.5 form the coating layer that is made of silicic acid (silica) on the surface of magnesium hydroxide particles thus.Then, the methacrylate ester silane coupling agent with 2 mass parts carries out surface-treated magnesium hydroxide (protective layer that is produced by silane coupling agent is 1 layer)
(embodiment 5～8, comparative example 13～24)
Shown in table 3 and table 4, like that, changed mix proportion (being reduced to the use level of magnesium hydroxide with respect to base polymer 100 weight parts is 60 weight parts), in addition, operation similarly to Example 1.In addition, table 3 is identical with above-mentioned material with magnesium hydroxide A～P in the table 4.Use resulting sheet material, estimate acid resistance.At this moment, in the situation of the surface-treated magnesium hydroxide A～H that implements in advance to utilize inorganic materials, as the changes in weight≤0.4mg/cm of sheet material
2The time think to have the effect (zero) that improves anti-nitric acid, when the changes in weight of sheet material greater than 0.4mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.In addition, in the situation of the surface-treated magnesium hydroxide I～P that has implemented in advance to utilize inorganic materials, as the changes in weight≤0.2mg/cm of sheet material
2The time think to have the effect (zero) that improves anti-nitric acid, when the changes in weight of sheet material greater than 0.2mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.Show the result in table 3 and table 4.
It is the situation of 60 weight parts that table 3 and table 4 specifically demonstrate utilizing the use level of having implemented the surface-treated magnesium hydroxide as the silane coupling agent of fire retardant to be reduced to respect to base polymer 100 weight parts, in this situation, magnesium hydroxide in acid a little less than, polymkeric substance is excellent aspect acid resistance, therefore, in the situation of the use level that reduces magnesium hydroxide, acid resistance is improved comprehensively.Need to prove, even in the situation that use level is less than prior art, the present invention still has superiority.
[table 3]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
[table 4]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
(embodiment 9～12, comparative example 25～37)
Shown in table 5 and table 6, like that, changed mix proportion (increasing to the use level of magnesium hydroxide with respect to base polymer 100 weight parts is 180 weight parts), in addition, operation similarly to Example 1.In addition, table 5 is identical with above-mentioned material with magnesium hydroxide A～Q in the table 6.Use resulting sheet material, estimate acid resistance.At this moment, in the situation of the surface-treated magnesium hydroxide A～H that implements in advance to utilize inorganic materials, as the changes in weight≤12mg/cm of sheet material
2The time think to have the effect (zero) that improves anti-nitric acid, when the changes in weight of sheet material greater than 12mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.In addition, in the situation of the surface-treated magnesium hydroxide I～Q that has implemented in advance to utilize inorganic materials, as the changes in weight≤8mg/cm of sheet material
2The time think to have the effect (zero) that improves anti-nitric acid, when the changes in weight of sheet material greater than 8mg/cm
2The time think the effect (*) that does not improve anti-nitric acid.Show the result in table 5 and table 6.
It is the situation of 180 weight parts that table 5 and table 6 specifically demonstrate utilizing the use level of having implemented the surface-treated magnesium hydroxide as the silane coupling agent of fire retardant to increase to respect to base polymer 100 weight parts, in the situation of the use level that increases magnesium hydroxide, the amount of the magnesium hydroxide of contact acid also must increase, so acid resistance also descends comprehensively.Need to prove, even in the situation that use level more than prior art, the present invention still has superiority.
[table 5]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
[table 6]
Annotate) use level: mass parts
Zero: have the effect that improves anti-nitric acid, *: the effect that does not improve anti-nitric acid
EEA:EA content 10 quality %, MI=0.4g/10 minute, the A1100 processed of JPE company
Flame retardant: carbon black: SEAST G116
Antioxidant: Irganox1010
Processing aid: Zinic stearas
Anti-nitric acid: in 30% aqueous nitric acid, in normal temperature dipping 3h+ in pure water, in normal temperature dipping 24h+ in 80 ℃ of dry 6h
Use EEA as the situation of base mateiral although more than illustrate, but with ethylene propylene copolymer, acrylic rubber, ultra-low density polyethylene, straight chain shape Low Density Polyethylene, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, in the plastics such as ethylene methacrylic acid methyl terpolymer or the situation of rubber as base polymer, perhaps for these mixtures, contain and comprise that to utilize epoxy be that silane coupling agent and amino are the also excellence aspect acid resistance of flame-retardant composition of the silane coupling agent fire retardant of having implemented the surface-treated magnesium hydroxide.
Claims (9)
1. fire retardant, it contains by epoxy is that silane coupling agent and amino are that silane coupling agent has been implemented the surface-treated magnesium hydroxide.
2. fire retardant according to claim 1, wherein, described epoxy is that silane coupling agent and described amino are that silane coupling agent adds respectively 0.1～10 mass parts in surface treatment amount with respect to magnesium hydroxide 100 mass parts.
3. fire retardant according to claim 1 and 2, wherein, described magnesium hydroxide is being that silane coupling agent and described amino are before silane coupling agent is implemented surface treatment, to have implemented surface treatment by inorganic materials by described epoxy.
4. fire retardant according to claim 3, wherein, described inorganic materials is added 0.1～20 mass parts in surface treatment amount with respect to magnesium hydroxide 100 mass parts.
5. according to claim 3 or 4 described fire retardants, wherein, described inorganic materials is silicon oxide, aluminum oxide, titanium oxide, zirconium white, magnesium oxide, zinc oxide, stannic oxide, vanadium oxide, manganese oxide or their mixture.
6. flame-retardant composition, it contains each described fire retardant in plastics or rubber and the claim 1～5.
7. flame-retardant composition according to claim 6 wherein, contains described fire retardant 40～300 mass parts with respect to described plastics or rubber 100 mass parts.
8. electric wire, it possesses the coating material that right to use requires 6 or 7 described flame-retardant compositions to form.
9. cable, it possesses the coating material that right to use requires 6 or 7 described flame-retardant compositions to form.
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| JP2012055676A JP5609906B2 (en) | 2012-03-13 | 2012-03-13 | Flame retardants, flame retardant compositions, wires and cables |
| JP2012-055676 | 2012-03-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384057A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of flame retardant of magnesium hydroxide, flame-retardant composition and its cable |
| CN109835927A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high temperature resistant, Gao Shushui fused magnesium oxide powder and preparation method thereof |
| CN110993210A (en) * | 2020-01-09 | 2020-04-10 | 甘肃永升线缆有限公司 | Anti-damage cable production method |
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| CN104530584B (en) * | 2014-11-07 | 2016-03-30 | 安徽省三乐门窗幕墙工程有限公司 | Shock-resistant plastic-steel door window section bar of a kind of good flame resistance and preparation method thereof |
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| JP6778320B2 (en) | 2017-04-25 | 2020-10-28 | 神島化学工業株式会社 | Alumina hydrate particles, flame retardants, resin compositions and electric wires / cables |
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| JP3984873B2 (en) * | 2002-06-19 | 2007-10-03 | 日本ユニカー株式会社 | Flame retardant resin composition containing metal hydrate |
| JP2004206890A (en) * | 2002-12-20 | 2004-07-22 | Furukawa Electric Co Ltd:The | Fire-resistant cable |
| JP5148648B2 (en) * | 2010-03-19 | 2013-02-20 | 富士フイルム株式会社 | Flame-retardant resin composition, method for producing the same, and molded product |
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| CN1948430A (en) * | 2005-10-12 | 2007-04-18 | 中国矿业大学（北京校区） | Preparation method of surface cladding type composite inorganic fire retardant |
| CN101880408A (en) * | 2010-06-25 | 2010-11-10 | 北京盛大华源科技有限公司 | Flame retardant and preparation method thereof |
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| CN109835927A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high temperature resistant, Gao Shushui fused magnesium oxide powder and preparation method thereof |
| CN108384057A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of flame retardant of magnesium hydroxide, flame-retardant composition and its cable |
| CN110993210A (en) * | 2020-01-09 | 2020-04-10 | 甘肃永升线缆有限公司 | Anti-damage cable production method |
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| JP5609906B2 (en) | 2014-10-22 |
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