CN100417690C - Flame retardant resin composition - Google Patents
Flame retardant resin composition Download PDFInfo
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- CN100417690C CN100417690C CNB2005800062007A CN200580006200A CN100417690C CN 100417690 C CN100417690 C CN 100417690C CN B2005800062007 A CNB2005800062007 A CN B2005800062007A CN 200580006200 A CN200580006200 A CN 200580006200A CN 100417690 C CN100417690 C CN 100417690C
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Abstract
Disclosed is a flame retardant resin composition which contains inorganic particles, preferably fly ash, containing a composite of silicon dioxide and aluminum oxide and having D50 of 1-10 mum as the inorganic particle component.
Description
Technical field
The present invention relates to the flame-retardant molded material or the moulded products of flame retardant resin composition and the described composition of use.
Background technology
The resin combination that is used for the Electrical and Electronic apparatus field considers to have good flame retardant resistance from the aspect of its security; Therefore, " flame retardant resin " carried out the extensive studies exploitation.Polycarbonate type resin has good thermotolerance, good electrical characteristic etc., so they are being developed the resin material as flame retardant resin composition energetically.
At present, the resin combination that is used for the Electrical and Electronic apparatus field need have higher flame retardant resistance, and is making great efforts further to improve the flame retardant resistance of polycarbonate type resin by adding various fire retardants.
Bromine-containing compound, phosphorus compound etc. are as conventional fire retardant.Yet, in recent years, need not use any halogen atom to obtain flame retardant resistance.Under such condition, making great efforts to improve its flame retardant resistance by in polycarbonate type resin, mixing the small amounts of inorganic particle.
For example, disclose a kind of flame retardant resin composition among the JP-A-2004-010825 (patent documentation 1), wherein in aromatic polycarbonate, cooperate the inorganic particulate of silicon-dioxide etc.Specifically, for improving the flame retardant resistance of described aromatic polycarbonate, the shape of the inorganic particulate that consideration is cooperated.
JP-A-2001-152030 (patent documentation 2) also discloses a kind of fire retardant material, and it contains by the inorganic porous material of load fire retardant being pulverized the particle of the granularity 10～100nm that obtains.Say exactly, it is by roasting sintered glass for example, silicon-dioxide, the inorganic materials of aluminum oxide etc. forms porous material, load thereon is selected from metal, the additive of metal-salt and mineral compound (fire retardant) makes the porous material (particle) of load-carrying additive and resin (for example polycarbonate or polypropylene) pass through twin screw extruder then, carries out micronization and mixing simultaneously.Patent documentation 2 records, in the described fire retardant material, thereby additive disperses to realize flame retardant resistance preferably.
Patent documentation 1:JP-A-2004-010825
Patent documentation 2:JP-A-2001-152030
Summary of the invention
The problem to be solved in the present invention
Yet above-mentioned routine techniques is difficult to stably realize high-caliber flame retardant resistance.That is to say, often be better than the flame retardant resistance of conventional polycarbonate type resin by the flame retardant resistance that cooperates inorganic particulate to realize at polycarbonate type resin; Yet described flame retardant resistance is the V-0 standard by stipulating as known UL 94 tests of the standard of high fire resistance (the equipment unit flammability test of plastic material) not, and can not be by the V-2 standard of above-mentioned test determination.
In addition, in the resin beyond the polycarbonate type resin, also the material that is used to improve flame retardant resistance various researchs have been carried out.Yet, in any combination research, be difficult to stably realize enough flame retardant resistances.
The present invention considers the problems referred to above and carries out that purpose is the poly carbonate resin composition that stably obtains good flame retardant resistance.
Solve the method for described problem
According to the present invention, a kind of flame retardant resin composition that contains polycarbonate type resin and inorganic particulate is provided, wherein inorganic particulate contains the particle of being made up of the mixture of silicon-dioxide and aluminum oxide, and 50% granularity (D50) is 1～10 micron.The present invention is above-mentioned flame retardant resin composition, and wherein inorganic particulate amount with 1～60 weight % in all compositions contains.
According to the present invention, also providing wherein, inorganic particulate is the above-mentioned flame retardant resin composition of flying dust.
Flame retardant resin composition of the present invention contains polycarbonate type resin and inorganic particulate, wherein (i) described inorganic particulate contain the mixture of silicon-dioxide and aluminum oxide at least and (ii) the granularity of described inorganic particulate be controlled at specified range.As described in the background section, there are some examples to study silicon dioxide granule or aluminium oxide particles are coupled to technology in the resin, yet for the also not research of use of the particle of the mixture that contains silicon-dioxide and aluminum oxide.Among the present invention, contain the inorganic particulate of this mixture, realize independent silicon dioxide granule, independent aluminium oxide particles or its mixture good flame retardant resistance that can not obtain only by use.
The reason of the flame retardant resistance that is improved by above-mentioned composition is not clear.Yet reason is considered to resin combination of the present invention when catching fire, and above-mentioned specific inorganic particulate acts on polycarbonate type resin and forms the opposing burning structures.
Preferably, inorganic particulate of the present invention also contains aluminium oxide particles and silicon dioxide granule except that comprising the particle that contains above-mentioned mixture.Aluminium oxide particles and silicon dioxide granule are respectively to contain aluminum oxide as the particle of main component with contain the particle of silicon-dioxide as main component as used herein, and can contain other component of minute quantity.By the complex particle of use by silicon-dioxide and aluminum oxide, the inorganic particulate that silicon dioxide granule and aluminium oxide particles are formed, resin combination of the present invention has improved flame retardant resistance.Reason is not clear, but thinks that inorganic particulate manifests more reliably to the effect of polycarbonate type resin.
The preferred example of inorganic particulate is a flying dust.Flying dust is a generic term, is used to be illustrated in the combustion ash that heat power plant produces, and especially is illustrated in the fine powdered coal that produces in the heat power plant by the fine coal combustion method coal combustion for example.In JP-A-2000-336254, for example disclose flying dust has been added in the thermoplastic polyester method with the physical strength of improving described thermoplastic polyester.The polyester and resin composition of being made up of the flying dust of the thermoplastic polyester of 30～99 weight parts and 70～1 weight parts is disclosed among the JP-A-2000-336254.Described flying dust has 1,000～8,000cm
2The specific surface area of/g.
Inorganic particulate comprises the commercially available flying dust that is disclosed among the JP-A-2000-336254, and its D50 is above 10 microns.Incidentally, D50 is that the accumulated value of the diameter particle that is no more than that diameter is the granularity of point of 50 weight % of described total particle.Among the present invention, the D50 of the inorganic particulate that uses is controlled at 10 microns or littler by stage treatment etc., and because the synergistic effect of these inorganic particulates and polycarbonate type resin stably realizes good flame retardant resistance first in the decline that suppresses formability.
The invention effect
Among the present invention, for the flame retardant resin composition that uses polycarbonate type resin and inorganic particulate, described inorganic particulate contains at least that silicon-dioxide and the mixture of aluminum oxide and the granularity of described inorganic particulate are controlled at specified range; Therefore can stably realize good flame retardant resistance.
Description of drawings
Fig. 1 shows the figure that concerns between the D50 of flying dust and the flame retardant resistance.
Fig. 2 shows the figure that concerns between the amount of flying dust and the flame retardant resistance.
Fig. 3 is the figure (FA-A4) that shows the flying dust size-grade distribution.
Fig. 4 is the figure (FA-A5) that shows the flying dust size-grade distribution.
Fig. 5 is the figure (FA-A8) that shows the flying dust size-grade distribution.
Fig. 6 is the figure (FA-A9) that shows the flying dust size-grade distribution.
Fig. 7 is the figure (FA-A10) that shows the flying dust size-grade distribution.
Fig. 8 is the figure (FA-A11) that shows the flying dust size-grade distribution.
Preferred forms of the present invention
Below illustrate in greater detail embodiments of the present invention.
Flame retardant resin composition among the present invention is that the inorganic particulate of specified particle size scope and polycarbonate type resin are cooperated, and it is characterized in that described inorganic particulate contains the mixture of silicon-dioxide and aluminum oxide.By this composition, described polycarbonate type resin composition has improved flame retardant resistance and keeps the formability of described polycarbonate type resin.
Polycarbonate type resin among the present invention is the resin with repeating unit of following general formula (1).
[Chemical formula 1]
(wherein, R
1And R
2Respectively do for oneself the alkyl of 1～6 carbon atom or 6～12 carbon atoms aryl and each other can be identical or different; Each integer of 0～4 naturally of m and n; Z is a singly-bound, the alkylene of 1～6 carbon atom or alkylidene, and the cycloalkanes support of 5～20 carbon atoms or cycloalkanes fork, fluorenylidene, or-O-,-S-,-SO-,-S0
2-or-the CO-key).
Polycarbonate resin is for for example phosgenation by making dihydroxyl biaryl compound and phosgene reaction with the polymkeric substance of the ester exchange method manufacturing that makes the dihydroxyl biaryl compound and react with carbonic ether (for example diphenyl carbonate), representational example is by 2, the polycarbonate type resin that two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-are made.
As described dihydroxyl biaryl compound, except that dihydroxyphenyl propane, also can enumerate two (hydroxyaryl) alkane such as two (4-hydroxyphenyl) methane, 1, two (4-hydroxyphenyl) ethane of 1-, 2, two (4-hydroxyphenyl) butane of 2-, 2, two (4-hydroxyphenyl) octanes of 2-, two (4-hydroxyphenyl) phenylmethane, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxyl-3-trimethylphenylmethane base) propane of 2-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (the 4-hydroxyls-3 of 2-, the 5-dibromo phenyl) propane, 2, two (4-hydroxyl-3,5-dichlorophenyl) propane of 2-etc.; Two (hydroxyaryl) naphthenic hydrocarbon is as 1, two (4-hydroxy phenyl) pentamethylene and 1 of 1-, two (4-hydroxyphenyl) hexanaphthenes of 1-; The dihydroxyl diaryl ether is as 4,4 '-dihydroxydiphenyl ether and 4,4 '-dihydroxy-3,3 '-dimethyl diphenyl ether; The dihydroxyl diaryl sulfide is as 4,4 '-dihydroxyl diphenyl sulfide; The dihydroxyl diaryl sulphoxide is as 4,4 '-dihydroxyl diphenyl sulfoxide and 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide; Dihydroxyl diaryl sulfone is as 4,4 '-dihydroxy diphenylsulphone and 4,4 '-dihydroxy-3,3 '-diphenylsulfone dimethyl; Or the like.
These dihydroxyl biaryl compounds can use individually or use with two or more mixture.The preferred compound that does not have halogenic substituent that uses is not because halogen-containing gas can be dispersed in the environment when it burns.
Can use piperazine with described dihydroxyl biaryl compound, dipiperidino quinhydrones, Resorcinol, 4,4 '-dihydroxybiphenyl, quinhydrones etc.
Also can use ternary or the phenolic compound more than it with described dihydroxyl biaryl compound, Phloroglucinol for example, 4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptene, 2,4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptane, 1,3,5-three (4-hydroxyphenyl) benzene, 1,1,1-three (4-hydroxyphenyl) ethane and 2, two [4,4-two (4-hydroxyphenyl) cyclohexyl] propane of 2-.
The polycarbonate type resin preferred number average molecular weight is 10,000～100,000.
The number-average molecular weight of polycarbonate type resin is 10,000 or higher the time, can stably obtain superior resin combination aspect physical strength and flame retardant resistance.The number-average molecular weight of polycarbonate type resin is 100,000 or lower the time, the resin combination of gained has suitable range of viscosities, therefore has good formability.
Polycarbonate type resin among the present invention can be by above-mentioned starting material, use the molecular regulation agent in case of necessity, and catalyzer etc. are by known method manufacturing.
Among the present invention, have no particular limits, but for example water content is preferred 1 000ppm or littler for the water content of polycarbonate type resin.Water content is more stably made described resin combination in this scope.
The content of polycarbonate type resin is with respect to the total amount of described flame retardant resin composition, preferred 10 weight % or higher, more preferably 40 weight % or higher, further preferred 60 weight % or higher, and preferred 99 weight % or lower, more preferably 95 weight % or lower, further preferred 80 weight % or lower.By adopting this content,, provide good flame retardant resistance with the effect of described inorganic particulate.
Be used for inorganic particulate of the present invention and represent the main particle of forming by inorganic component, also comprise the inorganic particulate that contains a small amount of organic constituent.
Being used for inorganic particulate of the present invention is the particle that contains the mixture of silicon-dioxide and aluminum oxide.At this, the mixture of silicon-dioxide and aluminum oxide represent to have silicon-dioxide mutually with aluminum oxide particle mutually.As its concrete form, can enumerate the particle of the composite oxides that for example contain silicon and aluminium and silicon dioxide granule and aluminium oxide particles interfused particle each other wherein.
By using the inorganic particulate of this composition, can realize good flame retardant resistance, this good flame retardant resistance uses aluminium oxide particles or its simple mixtures not to realize separately by using silicon dioxide granule separately.
Preferably, inorganic particulate also contains aluminium oxide particles and silicon dioxide granule except that above-mentioned complex particle.By using this inorganic particulate that contains several different sorts particles, can stably obtain the flame retardant resin composition of excellent flame retardancy.
As inorganic particulate, can enumerate the particle of the combined oxidation compounds that for example contains silicon and aluminium and the inorganic particulate of forming by the mixture of silicon dioxide granule and aluminium oxide particles with this formation.
This inorganic particulate cheaply is restriction especially not, can enumerate for example flying dust.
The burning ash that derives from incinerator etc. is the combustion ash that obtains by the various waste materials that burn.Simultaneously, flying dust is the combustion ash of coal that produces in the coal incinerators of heat power plant; Because the composition of coal is known clearly, so described flying dust with the combustion ash that produces in the incinerator by comparison, and the content of the heavy metal outside silicon and the aluminium etc. is low.In the described flying dust, also be easy to control the content of heavy metal etc. relatively.Therefore, when flying dust adds resin combination as filler, have flying dust and can not dysgenic advantage be arranged environment.
Flame retardant resin composition among the present invention has sufficient flame retardant resistance not containing under the situation of the fire retardant of phosphorus compound, halogenated compound etc. for example.Consider from the viewpoint of environment protection, preferably do not use any phosphorus compound or any halogenated compound.
Among the present invention, preferred 1 micron or bigger of the D50 of inorganic particulate, more preferably 3 microns or bigger.Preferred 10 microns or littler of D50, more preferably 7 microns or littler.
D50 is 1 micron or bigger the time, resin combination has improved flame retardant resistance and can suppress the reduction of described resin combination formability.In addition, dispersing of inorganic particulate be can suppress, and processibility and Treatment Stability in the described resin combination preparation process improved.
D50 is 3 microns or bigger the time, described resin combination has higher flame retardant resistance.In addition, further suppress dispersing of inorganic particulate, and further improve processibility and Treatment Stability in the described resin combination preparation process.
D50 is 10 microns or littler the time, resin combination has improved flame retardant resistance and can suppress the reduction of described resin combination formability.Described D50 is 7 microns or littler the time, the carbonization of polycarbonate type resin when further promoting burning, and this makes described resin combination have higher flame retardant resistance.
Among the present invention, inorganic particulate satisfies above-mentioned D50 granularity requirements, and needs further to satisfy following granularity requirements.
Wish inorganic particulate with preferred 70% or higher, more preferably 90% or higher accumulated value to contain particle diameter be 20 microns or littler particle.Ratio with particle of 20 microns or littler particle diameter is 70% or higher the time with respect to total inorganic particulate, the flame retardant resistance that is improved.In addition, suppress the reduction of resin combination formability.The ratio of described particle with 20 microns or littler particle diameter is 90% or higher the time with respect to total inorganic particulate, obtains further improved flame retardant resistance.In addition, further suppress the reduction of resin combination formability.
For example can measure the particle diameter of described inorganic particulate by the method for section of using electron microscope observation to derive from the moulding product of resin combination.
Specifically, use transmission electron microscope to observe the ultrathin section(ing) of resin combination, or use scanning electron microscope to observe the face that cuts out of resin combination matter sample; Take a picture; Use photo, measure 100 above particles particle diameter separately in the resin combination.Incidentally, by the area (S) of measurement particle and from (4S/p)
1/2Calculate the size of each particle.Also can pass through light scattering method (explanation after a while) and measure the size of described inorganic particulate, and obtain equal basically value.
Among the present invention, the total content of silicon-dioxide is 44～85 weight % with respect to the total amount of inorganic particulate in the preferred inorganic particulate, and the total content of aluminum oxide is 15～40 weight %.The total content of total silicon-dioxide and total aluminum oxide is 60 weight % or higher with respect to the total amount of inorganic particulate in the also preferred inorganic particulate.Preferred silicon-dioxide and aluminum oxide are contained in the inorganic particulate with composite form.For example, in the flying dust, the mullite (for the mixture of silicon-dioxide and aluminum oxide) [" Coal Ash Handbook " 2000, EnvironmentalTechnology Association and Japan Fly Ash Association] that contains 3～45 weight %.Therefore, consider preferred flying dust thus.
Among the present invention, have no particular limits for the content of inorganic particulate in the flame retardant resin composition.Yet the content of inorganic particulate is preferably 1 weight % or higher with respect to total resin combination, more preferably 5 weight % or higher, further preferred 20 weight % or higher.The content of inorganic particulate also is preferably 60 weight % or littler, more preferably 50 weight % or littler, further preferred 40 weight % or littler.
Inorganic particulate content is 1 weight % or higher the time, resin combination has stably improved flame retardant resistance and can stably suppress the reduction of resin combination formability.The content of inorganic particulate is 5 weight % or higher the time, resin combination can more stably have improved flame retardant resistance.The content of inorganic particulate is 10 weight % or higher the time, resin combination can have higher flame retardant resistance.
The content of inorganic particulate is 65 weight % or higher the time, difficulty is tended in injection molding.Yet, when content is 60 weight % or littler the time, described resin combination has the flame retardant resistance that good injection molding is become reconciled.The content of described inorganic particulate is 50 weight % or littler the time, the ratio of resin Composition and inorganic particulate is suitable in the resin combination, and the flame retardant resistance that is improved.The moulding of resin combination is also easier.The content of inorganic particulate is 40 weight % or littler the time, the flame retardant resistance of resin combination is higher and formability resin combination is better.
Among the present invention, preferably use flying dust (following suitably be abbreviated as " FA ") as inorganic particulate.
FA is the fine powder of combustion ash of coal, and it is collected by the particle collector with the heat power plant of fine coal combustion method coal combustion etc.
FA contains following component usually.
(a) silicon-dioxide: 44～80 weight %
(b) aluminum oxide: 15～40 weight %
(c) other component: ferric oxide (Fe
2O
3), titanium dioxide (TiO
2), magnesium oxide (MgO), calcium oxide (CaO) etc.
Be used for FA of the present invention, silicon-dioxide (silica: SiO
2) the preferred 44 weight % or higher of content, more preferably 50 weight % or higher.Content also is preferably 85 weight % or littler, more preferably 75 weight % or littler.Scope the time, because the synergistic effect between inorganic particulate and the polycarbonate type resin composition, resin combination can stably have improved flame retardant resistance to the content of silicon-dioxide for this reason.
Simultaneously, aluminum oxide (alumina: Al
2O
3) content be preferably 10 weight % or higher, more preferably 15 weight % or higher.Content also is preferably 40 weight % or littler, more preferably 30 weight % or littler.Scope the time, because the synergistic effect between inorganic particulate and the polycarbonate type resin composition, resin combination can stably have improved flame retardant resistance to the content of aluminum oxide for this reason.
Be used for FA of the present invention, the total content of silicon-dioxide and aluminum oxide is preferably 60 weight % or higher, more preferably 70 weight % or higher, further preferred 80 weight % or higher.The total content of silicon-dioxide and aluminum oxide also is preferably 99 weight % or littler, more preferably 95 weight % or littler.Scope the time, because the synergistic effect between inorganic particulate and the polycarbonate type resin composition, resin combination can stably have improved flame retardant resistance to the total content of silicon-dioxide and aluminum oxide for this reason.
Among the FA, a silicon-dioxide and an aluminum oxide part form composite oxides, and a part forms the particle that has by the heterogeneous structure of silicon-dioxide phase and aluminum oxide phase composite.
Among the FA, as long as the content of silicon-dioxide and aluminum oxide is in the above-mentioned scope of mentioning, ferric oxide (Fe then
2O
3), titanium dioxide (TiO
2), magnesium oxide (MgO) and calcium oxide (CaO) be the flame retardant resistance of deterioration resin combination not, formability etc.Except that these oxide compounds, FA contains a spot of heavy metal etc.; Yet the concentration of heavy metal etc. is low with the level of the burning ash that derives from incinerator etc. by comparison.Its reason is to burn the combustion ash of ash for obtaining by the various waste materials that burn, and FA is the combustion ash of coal that produces in heat power plant.
Because FA is produced by the known raw material formed, relatively easily control the content of heavy metal among the FA etc.By applying the measure etc. of a small amount of heavy metal stripping of prevention, can further reduce its detrimentally affect to resin combination or its moulding product.
Among the FA, in the time of by electron microscope observation, most particle has sphere.Therefore, by using FA, the decline of formability in the time of suppressing the resin combination moulding, and further improve the flame retardant resistance of resin combination.
At present, FA produces in heat power plant etc. in large quantities, and its major part is used as industrial waste.Therefore, the FA cost is low, makes low-costly to make flame retardant resin composition.
Fig. 3 represents the size-grade distribution of the FA shown in the following table 1.
Among this FA-A4, D50 is 3.9 microns, and the accumulated value of 20 microns of sizes or littler particle is 97%, and the accumulated value that is of a size of 0.5 micron or bigger particle is 96%.Described FA-A4 has two size-grade distribution peak values at about 1.5 microns and about 6.0 microns,, has unique bimodal distribution that is.
When having such two peak values in the FA size-grade distribution, the resin combination that contains described FA stably has good flame retardant resistance.In addition, in resin combination, stably suppress the reduction of formability.
Among the commercially available FA, D50 is usually above 10 microns; Therefore the present invention can not use commercially available FA itself.Therefore, the preferred use by stage treatment etc. carried out the FA that granularity control obtains to commercially available FA.Thereby, obtain significant synergistic effect between polycarbonate type resin and the inorganic particulate and can stably realize good flame retardant resistance.In addition, can keep the good formability of resin combination.
Incidentally,, have to make the stage treatment of using sieve, use the stage treatment of airflow classification device etc. with certain openings as the method for inorganic particulate granularity control.
When containing that for example the resin combination of the inorganic particulate of FA is used as the moulding product, according to the environment for use or the using method of these moulding product, can be from described moulding product a spot of heavy metal of stripping.Incidentally, among the present invention, " heavy metal etc. " are total heavy metal, and are such as chromium (VI), plumbous and silver-colored and such as the harmful element of selenium and arsenic.
In the flame retardant resin composition of the present invention, when FA is used as inorganic particulate, only otherwise the performance and the outward appearance of infringement flame retardant resin composition can be used the measure that prevents indivisible strippings such as heavy metal.
Measure as the stripping that prevents heavy metal etc., for example can use add in resin combination of the present invention that stripping prevents the method for agent and on resin combination moulding product of the present invention surface formation have the method that stripping prevents the film (for example apply from the teeth outwards and contain the coating that stripping prevents agent) of ability.
Prevent the measure of stripping by use, though at the content of heavy metal etc. with the kind of coal (it is the raw material of FA) with the combustion conditions when making FA etc. when changing a little, can suppress the stripping of heavy metal etc. reliably.In addition, use FA because can not consider the content of heavy metal etc., can be more effectively as utilization of resources FA (it be the byproduct of heat power plant).
As the measure that prevents strippings such as heavy metal, in resin combination of the present invention, add stripping prevent the method for agent be simple and life-time service effective.
Stripping as heavy metal etc. prevents agent, and that can mention has sorbent material or the reductive agent that all uses mineral compound, an ion exchange resin etc.
As sorbent material that all uses mineral compound or reductive agent, that can mention is for example ferrous sulfate or ferric sulfate, show severity special graceful stone, Sulfothiorine, hydrotalcite and hydroxylapatite.Ferrous and the special graceful stone of showing severity of preferably sulfuric acid especially.
As ion exchange resin, what can mention is resin, anionite-exchange resin, Zeo-karb etc.
Prevent the effect of agent as this stripping, what can mention is, sorbent material is by forming sorbent material (for example hydrate of the metal oxide of metal such as iron) absorption heavy metal etc. in resin, or reductive agent reduction and make heavy metal etc. insoluble.When reductive agent and sorbent material were used in combination, heavy metal etc. was reduced and makes more adsorbable sometimes.Therefore, sorbent material and reductive agent can be used as the mixture use.
Stripping prevents agent hydrate often, such as the ferrous sulfate monohydrate.Therefore, in the time of its excessive adding, water evaporates in the injection molding of resin combination, and moulding product surface the line of silver color may occur (hereinafter to be referred as " silver "), or because stripping prevents that agent from causing the variable color of moulding product, the outward appearance of these reduction moulding product.
Therefore, stripping prevents the add-on of agent preferably at the most less than 2 weight %, more preferably 1 weight % or littler.
When FA was used as inorganic particulate, stripping prevented agent counting 1/1000 or higher with respect to the weight ratio of FA, preferred especially 1/100 or higher the time, can prevent the stripping of heavy metal etc.For example, when resin combination of the present invention contained FA with the amount of 10 weight %, stripping prevented that the required addition of agent from being 0.01 weight % or higher, preferred 0.1 weight % or higher and less than 2 weight %.Thereby, can suppress the generation of bad outward appearance, and the stripping that can prevent heavy metal etc.
Have stripping when preventing the film of ability when on the surface of resin combination moulding product, forming, can use with water repellency film or water impermeable membrane and cover the surperficial method of moulding product.Have no particular limits for the water repellency film, still for example can use the film of fluorine type resin.Use this film and stripping to prevent that the combination of agent from being more effective for the stripping that prevents heavy metal etc.
Among the present invention, the resin combination that contains polycarbonate type resin and inorganic particulate preferably further contains fiber formation property fluorinated polymer that can form fibrous texture (filamentary structure) in resin combination.By using fiber formation property fluorinated polymer, when burning, can avoid the phenomenon of dripping.
Form the property fluorinated polymer as fiber, that can mention is tetrafluoroethylene, based on the multipolymer (for example tetrafluoroethylene/hexafluoropropylene copolymer) of tetrafluoroethylene, and partially fluorinated polymkeric substance, the polycarbonate of making by fluorinated biphenyl phenol etc.
As fiber formation property fluorinated polymer, also can use various forms of fluoropolymers, fluoropolymer such as fine powder form, the water dispersion of fluoropolymer, the fluoropolymer of powder type/acrylonitritrile-styrene resin mixture, the fluoropolymer of powder type/polymethylmethacrylate mixture etc.
Fiber forms the suitable addition of property fluorinated polymer based on the preferred 0.05 weight % or higher of total flame retardant resin composition, more preferably 0.1 weight % or higher.Suitable also preferably 5 weight % or littler, more preferably 1 weight % or littler, further preferred 0.8 weight % or littler of addition.
The add-on that forms the property fluorinated polymer when fiber is 0.05 weight % or higher the time, dripping when stably obtaining burning prevents effect.The add-on that fiber forms the property fluorinated polymer is 0.1 weight % or higher the time, resin combination has higher flame retardant resistance.
The add-on that fiber forms the property fluorinated polymer is 5 weight % or littler the time, polymkeric substance is dispersed in the resin easily; Polymkeric substance can be easily and the polycarbonate type resin uniform mixing as a result, makes stably to make flame retardant resin composition.The add-on that fiber forms the property fluorinated polymer is 1 weight % or littler the time, resin combination has higher flame retardant resistance.The add-on that fiber forms the property fluorinated polymer is 0.8 weight % or littler the time, described resin combination has further higher flame retardant resistance.
Contain the inorganic particulate (for example FA) of the particle that comprises silicon-dioxide and aluminum oxide by cooperation, the resin combination that contains polycarbonate type resin demonstrates the reason of flame retardant resistance, is considered to following.
Polycarbonate type resin has carbonic acid ester bond in its chemical structure; The hydroxyl on oxygen in these carbonic acid ester bonds and inorganic particulate surface forms hydrogen bond; Thereby described polycarbonate type resin is heat-staple.By having the inorganic particulate of specified particle size scope, the degree that forms hydrogen bond with polycarbonate type resin is higher, and easily form the mixture between inorganic particulate and the polycarbonate type resin when burning, it promotes carbonization and finally shockingly improves flame retardant resistance.
In addition, it is believed that the silicon-dioxide that is present in the inorganic particulate and the mixture of aluminum oxide play a role as fire-retardant catalyzer specifically to polycarbonate type resin.Especially, when using FA, in the incendiary initial period, the lip-deep organic constituent vaporization of moulding product, and the surface is contained high density F A or is become polycarbonate-FA matrix material; These also are believed to be helpful in high flame retardant resistance.
Among the present invention, can in flame retardant resin composition, add various additives (thermo-stabilizer for example, antioxidant, tinting material, white dyes, filler, releasing agent, tenderizer, static inhibitor, softening agent and dispersion agent), impact modifier, other polymkeric substance etc., only otherwise the effect of infringement flame retardant resin composition gets final product.In addition, inorganic particulate (for example FA) can be used surface treatments such as silane type coupler, titanate type coupler.
As having that thermo-stabilizer can be mentioned, for example: metal bisulfite salt, such as sodium pyrosulfate, sal enixum and lithium hydrogen sulfate; And metal sulfate, such as Tai-Ace S 150.They can use with the amount of 0～0.5 weight % usually.
As filler, that can mention has, for example: glass fibre, granulated glass sphere, sheet glass, carbon fiber, talcum powder, clay powders, mica, potassium titanate crystal whisker, wollastonite powder etc.
As impact modifier, that can mention has, for example: glass fibre, organic fibre, acrylic elastomer, polyester elastomer, the MBS of nucleocapsid form, methyl methacrylate-acrylonitritrile-styrene resin is based on the rubber of ethylene-propylene, based on rubber of ethylene-propylene-diene etc.Especially, glass fibre is as the excellent performance of impact modifier.
As softening agent, that can mention has, trimellitate for example, pyromellitic ester, polycarbonate diol, trimethylolpropane tris benzoic ether, two Dipentaerythritols that contract, polycaprolactone, p-hydroxy-benzoic acid alkyl ester etc.
As dispersion agent, that can mention has for example alkene-maleic acid, styrene-maleic anhydride copolymer, a sodium naphthalene sulfonate etc.
The fire retardant that can add other in case of necessity.As such fire retardant, that can mention has a phosphorus compound, heat absorbent (for example metal hydroxides or borate), and nitrogen compound (for example trimeric cyanamide), based on the fire retardant of siloxanes, carbonization promotor (for example metal-salt), halogenated compound, etc.
Among the present invention, have no particular limits for the method for making resin combination of the present invention.As described method, having of can mentioning uses known mixing tank such as rotating cylinder, the belt stirrer, and Banbury mixing tank or kneading machine mix, or use known forcing machine to carry out fusion such as simple helix forcing machine or twin screw extruder and knead.
Can illustration for example: comprise preparing respectively starting material premix of forming by ball shape component (for example resin Composition) and the starting material premix of forming by powdered component (inorganic particulate that for example comprises FA etc.), described premix is dosed to forcing machine independently and carries out the method that fusion is kneaded; Independently of one another starting material are dosed to forcing machine and carry out the method that fusion is kneaded with comprising.
Also can be dispersed in masterbatch in organic solvent, the molten resin etc., and in the moulding resin composition, mix these masterbatch and obtain this resin combination by using mixing tank to make inorganic particulate wherein.
Because the preparation masterbatch can suppress dispersing and can improving processibility and Treatment Stability of inorganic particulate, so these methods are effective especially when the granularity of inorganic particulate is little.
During fusion was kneaded, the barrel temperature of forcing machine can be set in 200～400 ℃, and preferred 220～350 ℃, more preferably 230～300 ℃.The revolution speed of screw of forcing machine can be set in 30～700rpm, preferred 80～500rpm, more preferably 100～300rpm.
During fusion was kneaded, the average residence time in the forcing machine can be set at 10～150 seconds, and preferred 20～100 seconds, more preferably 30～60 seconds.The temperature of molten resin composition preferably sets at 250～300 ℃, and is carrying out being noticed when described fusion is kneaded that making does not have excessive heat to put on described resin combination when kneading.The resin combination that fusion is kneaded is extruded from the die head that is assemblied in the forcing machine front end as the line material, and makes the ball shape, thereby can obtain the resin combination ball.
In the manufacturing of this flame retardant resin composition, can when kneading, fusion outgas.The degassing is illustrated in barometric point under or decompression time, by being assemblied in the ventilating pit of described forcing machine, removes the volatile constituent that fusion is kneaded and produced in the step.
The flame retardant resin composition ball that so obtains has high flame retardant resistance, therefore can be used as flame-retardant molded material, is used to form in Electrical and Electronic equipment purposes, building materials purposes, the trolley part purposes, daily necessities purposes, medical treatment and nursing purposes, agricultural use, toy, the moulding product of amusement article etc.
Among the present invention, also provide the flame-retardant molded material that contains above-mentioned flame retardant resin composition.
Incidentally, even the resin molding material that flame-retardant-resin formed material represents also to have this inhibition resin combination incendiary performance among the present invention in high temperature oxidation stability atmosphere.The resin combination ball that its representative instance is made up of flame retardant resin composition.
Flame retardant resin composition of the present invention can be as the composition that can improve flame retardant resistance.By suitably this flame retardant resin composition being matched with in thermoplastic resin etc., can obtain flame-retardant molded material.Therefore, flame-retardant molded material of the present invention can be the material of only being made up of above-mentioned flame retardant resin composition, perhaps contains the thermoplastic resin beyond the polycarbonate type resin in order further to improve formability (for example melt fluidity) and mechanical property (for example shock-resistance).
As this thermoplastic resin, can use for example to be selected from: polystyrene type resin is such as polystyrene, high-impact polystyrene, styrene-butadiene copolymer rubber etc.; Polyphenylene ether type resin; The polyolefin-type resin; The polyvinyl chloride-type resin; The polyamides amine type resin; Polyester resin; Polypropylene type resin; Polyphenylene sulfide type resin; Polymethacrylate type resin; The polymkeric substance of modified rubber; The polyacrylate resin; Acrylonitrile-butadiene copolymer rubber; Acrylonitritrile-styrene resin and its acrylic rubber modifier; With the polymkeric substance of styrene-based such as acrylonitrile-butadiene-styrene copolymer, based on one or both or more kinds of combinations of rubber (EPDM)/styrol copolymer of vinyl cyanide/ethylene-propylene-diene etc.
In these thermoplastic resins, preferred polyhutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, butyl polyacrylate etc.
Among the present invention, have no particular limits for the ratio of flame retardant resin composition in flame-retardant molded material; Yet the preferred 10 weight % or higher of described ratio, more preferably 30 weight % or higher, further preferred 60 weight % or higher, and preferred 99 weight % or littler, more preferably 85 weight % or littler, further preferred 70 weight % or littler.
The ratio of flame retardant resin composition is 10 weight % or higher the time, the flame-retardant molded material that contains this resin combination shows that little formability reduces, and still stably has the flame retardant resistance of raising.The ratio of flame retardant resin composition is 30 weight % or higher the time, flame-retardant shaped material has good balance between flame retardant resistance and formability.The ratio of flame retardant resin composition is 60 weight % or bigger the time, flame-retardant molded material has better balance between flame retardant resistance and formability.
The ratio of flame retardant resin composition is 99 weight % or littler the time, the flame-retardant molded material that contains this resin combination tends to have excellent physical strength and formability.The ratio of flame retardant resin composition is 85 weight % or littler the time, flame-retardant molded material has good balance between flame retardant resistance and formability.The ratio of flame retardant resin composition is 75 weight % or bigger the time, flame-retardant molded material has better balance between flame retardant resistance and formability.
Among the present invention, can provide the moulding that contains above-mentioned flame retardant resin composition product.According to this formation, described moulding product superior performance aspect flame retardant resistance, and show that little formability reduces.
Forming method about above-mentioned flame-retardant molded material has no particular limits, and can use known method, such as injection molding, and gas assistant formation, extrusion moulding, blowing, injection compression molding etc.
The moulding product that obtain by such method have good flame retardant resistance; Therefore, it can be used to Electrical and Electronic equipment purposes, building materials purposes, trolley part purposes, daily necessities purposes, medical treatment and nursing purposes, agricultural use, toy, amusement article etc.Especially, described moulding product are suitable for the shell of the Electrical and Electronic equipment of flame retardant resistance that need be good.
More than put down in writing formation of the present invention.Any combination of these formations also can be used as embodiments of the present invention.
Embodiment
Further specify the present invention by embodiment.But, the invention is not restricted to this.
(1) method of measurement size-grade distribution
Use " D.H.S9200PRO Type FRA " size-grade distribution tester of producing by MICRO TRAC CO. by light scattering method, under the following conditions, measure the size-grade distribution of inorganic particulate.
Dispersion medium: 2 weight % sodium hexametaphosphate solution (specific refractory poweres: 1.33)
Measuring Time: 20 seconds, 3 times
Pre-treatment: about 20mg sample places the 30mL dispersion medium, and (20kHz 300kW) carried out dispersion treatment 3 minutes, and the dispersion that obtains places measuring cell, and used the pure water adjustment to obtain the concentration that 0.1g/ rises to use ultrasonic wave.
(2) starting material of Shi Yonging
(2-1) thermoplastic resin
PC: polycarbonate type resin [product of Sumitomo Dow Ltd., trade name: Calibre301-22 (weight-average molecular weight: 47,000, number-average molecular weight: 27,000)]
PET: polyethylene terephthalate (TOYOBO Co., the product of Ltd., trade name: PETMAX RE554)
PBT: polybutylene terephthalate (product of Mitsubishi Engineering Plastics K.K., trade name NOVADURAN 5010 R5)
PP: polypropylene (Sumitomo Chemical Co., the product of Ltd., trade(brand)name AH561) Ny: nylon-6 (Toray Industries, Ltd., product, trade name: (2-2) inorganic particulate Amilan CM1017)
FA: flying dust.Use product as shown in table 1 below
Table 1
The size-grade distribution of some FA shown in the meter 1, the result is shown in table 3～8.
Incidentally, the FA of A4～A7 is equivalent to the I type flying dust of JIS A 6201 (1999) regulations, and is suitable for realizing flame retardant resistance, and the II type flying dust (standard) that the FA of A8～A12 is equivalent to wherein stipulate also has bigger particle diameter.
FA-A8 is an II type flying dust; Yet because it has 9.9 microns little D50, the flame retardant resistance that is improved.
FA of the present invention confirms through ultimate analysis, comprises the particle as the mixture of silicon-dioxide and aluminum oxide, mainly particle and the main particle of being made up of silicon-dioxide of being made up of aluminum oxide.Although difference per sample and difference, the content of mullite among the FA (mixture of silicon-dioxide and aluminum oxide) is 3～44 weight %.
S: spheric silicon-dioxide (product of Denki Kagaku Kogyo K.K., trade name: FB3SCC, average particle size: 3.2 microns)
HS: the silicon-dioxide of pulverizing (product of Denki Kagaku Kogyo K.K., trade name: FS3CC, average particle size: 3.2 microns)
Al: spheric aluminum oxide (product of Showa Denko K.K., trade name: CB-A05S, average particle size: 2.9 microns)
(2-3) fiber formation property fluorinated polymer
PTFE: tetrafluoroethylene (Daikin Industries, the product of Ltd., trade name: PolyflonFA-500, fiber formation property fluorinated polymer)
(2-4) stripping prevents agent
FD-1:FeSO
4H
2O (ferrous sulfate monohydrate) (Fuji Titanium Industry Co., the product of Ltd., trade name: FD-1)
SW: the special graceful stone of showing severity (Sophia Co., the product brand name: Asre-S, chemical formula: Fe
8O
8(OH)
8-2x(SO
4)
xNH
20 (1≤x≤1.75))
(3) preparation of resin combination and synthetic resin
Polycarbonate type resin (Calibre 301-22) and FA are fed in the forcing machine of kneading continuously (product of KCK, KCK 0X2-35WEX (7)) that barrel temperature has been set in 280 ℃, knead in fusion with under shearing and extrude; In water, cool off then and the curing extrudate; The solidified extrudate is cut into ball.
Each the resin combination ball that obtains was 120 ℃ of dryings 4 hours, use 20 tons of injection moulding machine (Toshiba Machine Co., Ltd. product, EC20P-0.4A), in barrel temperature=280 ℃ with the condition compacted under of die head temperature=80 ℃, thereby (125mm * 13mm * 1.6mm) is used for the test piece that oxygen index estimates (125mm * 6.5mm * 3.0mm) and be used for the test piece that pliability test estimates (125mm * 12.7mm * 3.2mm) to make the test piece that flame retardant resistance estimates that is used for of all above-mentioned resin combinations.
Exceptionally, for containing poly-para Toluic Acid's glycol ester (PET), polybutylene terephthalate (PBT), the resin combination of polypropylene (PP) or nylon-6 (Ny) is kneaded and the barrel temperature injected is respectively 260 ℃.
(4) various evaluations
(4-1) evaluation of flame retardant resistance
Oxygen index, it is for estimating the index of flame retardant resistance, according to JIS K 7201 (ISO 4589), to the test piece (125mm * 6.5mm * 3.0mm) measure that oxygen index is estimated that is used for that obtains by injection molding.
Carry out the evaluation of flame retardant resistance by UL 94 tests, described UL 94 tests are that (125mm * 13mm * 1.6mm) placed 48 hours at the thermostatic chamber of 23 ℃ (temperature) and 50% (humidity) carries out testing (combustion test that is used for the plastic material of device feature) by UL 94 of Underwriters Laboratories regulation to it then by making the test piece that is used for the flame retardant resistance evaluation that obtains by injection molding.
UL 94 tests are the method for the evaluation of flame retardant resistance, and it comprises makes the test piece of the vertical specified dimension of maintenance contact 10 seconds with the flame of burner, checks the residual flame time of sample and the performance of dripping then.Flame retardant resistance is divided into level as shown in table 2 below.
Table 2
| Standard conditions | V-0 | V-1 | V-2 |
| The residual flame time after the flame contact (contact for the first time contacted separately with the second time) | ≤ 10 seconds | ≤ 30 seconds | ≤ 30 seconds |
| The total residual flame time of 10 contacts of 5 samples | ≤ 50 seconds | ≤ 250 seconds | ≤ 250 seconds |
| Flame contacts residual flame afterwards and reddens the time for the second time | ≤ 30 seconds | ≤ 30 seconds | ≤ 60 seconds |
| After-flame is to the sample of retaining clip position | Not | Not | Be |
| Light cotton by dripping | Not | Not | Not |
Incidentally, when combustion mode is not those minutes time-like shown in the table 2, flame retardant resistance is categorized as level " not V-2 ".Flame retardant resistance is V-0 in proper order, V-1 and (V-2 and not V-2), and V-0 is best.
Above-mentioned " residual flame time " for remove test piece continuation flaming combustion after the ignition source time span; " light cotton by dripping " and represent that being positioned at the cotton that is lower than the about 300mm in test piece lower end serves as a mark, by lighting from the dropping of test piece drippage.
(4-2) evaluation of physical strength
Measure the test piece that is used to estimate pliability test that obtains by injection molding (bending strength and the Young's modulus of 125mm * 12.7mm * 3.2mm) according to ASTM C-256.
(4-3) evaluation of formability
For estimating formability, the melt fluidity of the resin combination that measures.Resin combination was 120 ℃ of dryings 4 hours; Use 20 tons of injection moulding machines (Toshiba Machine Co., the product E C20P-0.4A of Ltd), in barrel temperature=280 ℃, die head temperature=80 ℃, injection pressure=1,600kg/cm
2With measure the helical flow of exsiccant composition under the condition of thickness=1 millimeter, and based on following standard evaluation melt flow property.
Zero: melt flow property is good
△: melt flow property deficiency
*: melt flow property is poor
Test example 1 (estimating flame retardant resistance) by oxygen index and formability
With the ratio that shows in the table 3 FA-A5 (D50=5.0 micron) is mixed into PC, makes various flame retardant resin compositions.Be used to estimate the test piece of oxygen index by each composition manufacturing, and measure oxygen index.And check the formability of each composition.The results are shown in table 3.As a reference, oxygen index and the formability of PC itself have been listed.
Table 3
Test example 2 (D50 of FA-A5 and the research of flame retardant resistance)
With the ratio that shows in the table 4 PTFE and FA are mixed into PC, make flame retardant resin composition.Estimate the flame retardant resistance and the average residual flame time of each composition and the formability of inspection group's compound by UL94.The results are shown in table 4.D50 and average residual flame time relation are as shown in Figure 1.As a reference, listed the result of PC itself.
Table 4
Knowing clearly from the result of table 4 and Fig. 1, is that 1～10 micron FA goes into the resin combination (test No.12 to 17) that polycarbonate type resin obtains and has good flame retardant resistance and formability by mixing D50.Therefore, it is believed that when mixing D50 was 1～10 micron FA, the dispersive ability of FA was good, and improve the flame retardant resistance that obtains resin combination.By mixing D50 is that the flame retardant resistance that 3～7 microns FA goes into the moulding product (test No.13 to 15) of the resin combination that polycarbonate type resin obtains has shockingly improvement.Therefore, it is believed that when mixing D50 and be 1～10 micron FA and go into polycarbonate type resin, the dispersive ability of FA is better, and further improves the flame retardant resistance that obtains resin combination.
Simultaneously, mix (test No.10 to 11 and 18 to 21) in the FA of D50 outside 1～micrometer range, the flame retardant resistance of gained is lower than the flame retardant resistance of used polycarbonate type resin itself, as table 4 and Fig. 1 shown in clearly.
Test example 3 (usage quantity of FA and flame retardant resistance and bending property)
With the ratio shown in the table 5 PTFE and FA-A5 are mixed into PC, make flame retardant resin composition.Estimate the flame retardant resistance and the average residual flame time of composition by UL 94.The also bending property of inspection group's compound and formability.The result is as shown in table 5.The consumption of FA and the relation between the average residual flame time are as shown in Figure 2.
Table 5
As can be known clear and definite from the result of table 5 and Fig. 2, the FA that will have a given particle diameter by the ratio with 5～50 weight % is mixed into the flame retardant resistance of the resin combination (test No.23～28) that polycarbonate type resin obtains and is shockingly improved.Therefore, think that when with the ratio of 5～50 weight % FA being mixed into polycarbonate type resin, the flame retardant resistance of the resin combination that obtains is improved, this is because the ratio of the FA in resin Composition and the resin combination is suitable.
Test example 4 evaluation of flame retardant resistance (when the using different types of inorganic particulate to)
The flame retardant resin composition that manufacturing is made up of PTFE and the inorganic particulate 30 weight % as shown in table 6 of PC, the 0.5 weight % of 69.5 weight %.Estimate the flame retardant resistance of described composition.The result is as shown in table 6.
Table 6
Clearly known by table 6, use the situation of FA (test No.30), compare with the situation of using silicon-dioxide (S or HS) or aluminum oxide (A1), flame retardant resistance has shockingly to be improved.Its reason is: FA is for comprising the inorganic particulate of the mixture that contains silicon-dioxide and aluminum oxide, does not comprise this mixture in particle of only being made up of silicon-dioxide (S or HS) or the particle (A1) only be made up of aluminum oxide.
Test example 5 (comparison of flame retardant resistance when using different resins)
With the amount shown in the table 7 PTFE (0.5 weight %) and FA-A5 are mixed in the thermoplastic resin shown in the table 7, make flame retardant resin composition.Estimate the flame retardant resistance of described composition.The result is as shown in table 7.
Table 7
By table 7 clearly as can be known, using polyethylene terephthalate (PET) (test No.37 and 38), polybutylene terephthalate (PBT) (test No.39 and 40), in polypropylene (PP) (test No.41 and 42) or the resin combination of 6-nylon (Ny) (test No.43 and 44), do not improve flame retardant resistance by utilizing FA as other thermoplastic resin.
Therefore, the improvement of knowing very much flame retardant resistance is by being used in combination polycarbonate type resin and comprising that the synergistic effect of the uniqueness that the inorganic particulate (FA that comprises specified particle size) of the particle of the mixture that contains silicon-dioxide and aluminum oxide causes obtains.
Therefore, use contains polycarbonate resin and comprises the resin combination of the inorganic particulate (FA that comprises specified particle size) of the particle of the mixture that contains silicon-dioxide and aluminum oxide, can provide flame retardant resistance height, melt fluidity and to the adaptability aspect of environment also excellent flame polycarbonate type resin composition and contain the flame-retardant molded material or the moulding product of described composition very with low cost.
Like this, can provide the flame retardant resin composition that has higher flame retardant resistance and suppress the formability reduction among the present invention.Especially, when the D50 of the inorganic particulate that uses was 3～7 microns, the flame retardant resistance of flame retardant resin composition and formability had good balance between the mechanical property etc.
Test example 6 (preventing the evaluation of agent) for the preventing property of strippings such as heavy metal by utilizing stripping
Use PC with the amount that table 8 shows, PTFE, FA-A5 and stripping prevent agent (the ferrous sulfate monohydrate or the special graceful stone of showing severity), make flame retardant resin composition.The flame retardant resistance of evaluating resin composition.In addition, when manufacturing was used for test piece that flame retardant resistance estimates, the outward appearance of also observing them was with the generation of checking silver (outward appearance) and the degree of generation.The result is as shown in table 8.In addition, according to Environmental Agency Notification No.46 (dissolution test that relates to the ambient quality standard of soil pollution), determine to carry out the stripping amount of metal of resin combination of the dissolution test of heavy metal etc. quantitatively.The test-results of stripping heavy metal etc. is as shown in table 9.As reference, the content of the heavy metal of FA-A5 etc. is as shown in table 10.
The evaluation of outward appearance
Based on following standard evaluation outward appearance.
Zero: do not observe silver basically
△: observe silver a little
*: observe silver
The test method of strippings such as heavy metal (dissolution test (Environmental Agency Notification No.46) that relates to according to the soil pollution ambient quality standard)
Sample: draw quantitative ball, and use stone mortar shape forcing machine (product of KCK, the velocity of discharge: 8kg/h) make kneading material at 280 ℃.The freezing and pulverizing kneading material obtains sample by nonmetal sieve (opening: 2 millimeters) then.Incidentally, 2 millimeters of diameters or littler ball itself use as sample.
Dissolution test is with the preparation of solution: to have hydrogen ion exponent be 5.8 to 6.3 by hydrochloric acid being added to the solution that obtains in the pure water, make the volume of whole solution become 500mL or more, weightmeasurement ratio becomes 10%, biased sample (unit: g) and solvent (unit: mL).
The method of stripping: at normal temperatures and pressures, use vibrational frequency to be adjusted to about 200 per minutes, vibration width and be adjusted to 4～5 centimetres the dissolution test of vibrator continuous shaking preparation with solution 6 hours.
The measurement of stripping quantity: will leave standstill by the sample solution that aforesaid operations obtains 10～30 minutes, then about 3, centrifugal 20 minutes of 000rpm; Supernatant liquor filters the membrane filter of 0.45 micron of pore size, collects filtrate; By ICP emmission spectrometric analysis or atomic absorption light spectrometry chromium (VI), arsenic, selenium, the amount of plumbous and mercury, with them as stripping quantity.
Table 8
Table 9
Table 10
Clearly know by table 9, containing under the situation of polycarbonate type resin and the resin combination (test No.45) of the inorganic particulate of the FA that contains specified particle size, in dissolution test, chromium (VI), arsenic and selenium that stripping is indivisible as heavy metal etc.Yet, by with 1/1,000 or the amount of higher (with respect to FA) will prevent the ferrous sulfate monohydrate of agent or the special graceful stone of showing severity is mixed into described resin combination as stripping, can suppress the stripping of heavy metal etc., keep high flame retardant simultaneously.As shown in table 8, stripping prevents that amount that agent is mixed into resin combination from less than 2.0 weight %, in the time of preferably less than 1.5 weight %, also producing silver when moulding, and therefore the moulding product that obtain have the outward appearance of raising.
As mentioned above, the present invention has been described by embodiment.These embodiment only are exemplary, and any those skilled in the art easily understand and have various changes, and these changes are also included within the scope of the present invention.
Among these embodiment, use FA as the inorganic particulate that contains the mixture of silicon-dioxide and aluminum oxide.Yet, also can use the ash that obtains by timber etc., silica-alumina complex particles etc. are as long as they have the composition of the present invention's regulation, particle diameter etc.
Industrial applicibility
Fire retardant resin composition of the present invention has good anti-flammability, therefore needing can be used for purposes, the especially shell of Electrical and Electronic equipment of anti-flammability.
Claims (13)
1. flame retardant resin composition comprises polycarbonate type resin and inorganic particulate that following general formula 1 is represented,
Wherein, R
1And R
2Respectively do for oneself the alkyl of 1～6 carbon atom or 6～12 carbon atoms aryl and each other can be identical or different; Each integer of 0～4 naturally of m and n; Z is a singly-bound, the alkylene of 1～6 carbon atom or alkylidene, and the cycloalkanes support of 5～20 carbon atoms or cycloalkanes fork, fluorenylidene, or-O-,-S-,-SO-,-SO
2-or-the CO-key,
Wherein inorganic particulate contains the particle of being made up of the mixture of silicon-dioxide and aluminum oxide, and 50% particle diameter (D50) is 1～10 micron.
2. flame retardant resin composition as claimed in claim 1, the amount of the inorganic particulate that contains in wherein whole compositions is 1～60 weight %.
3. flame retardant resin composition as claimed in claim 1, wherein inorganic particulate also contains aluminium oxide particles and silicon dioxide granule except that the particle of being made up of the mixture of silicon-dioxide and aluminum oxide.
4. flame retardant resin composition as claimed in claim 1, wherein inorganic particulate is a flying dust.
5. flame retardant resin composition as claimed in claim 1, it contains the stripping that is useful on the component stripping that prevents to be present in the inorganic particulate and prevents agent.
6. flame retardant resin composition as claimed in claim 5, wherein stripping prevents that agent from being to adsorb sorbent material or the ion exchange resin that is present in the component in the inorganic particulate.
7. flame retardant resin composition as claimed in claim 5 is used to wherein to prevent that the stripping that is present in the component stripping of inorganic particulate from preventing that agent is selected from the ferrous sulfate monohydrate and the special graceful stone of showing severity.
8. flame retardant resin composition as claimed in claim 1, wherein to contain particle diameter with 70 weight % or higher amount be 20 microns or littler particle to inorganic particulate.
9. flame retardant resin composition as claimed in claim 1, wherein based on the total amount of inorganic particulate, described inorganic particulate contains the silicon-dioxide of 44～85 weight % and the aluminum oxide of 15～40 weight %.
10. flame retardant resin composition as claimed in claim 9, wherein based on the total amount of inorganic particulate, the content sum of silicon-dioxide and aluminum oxide is 60 weight % or higher in the described inorganic particulate.
11. flame retardant resin composition as claimed in claim 1, it further contains based on total flame retardant resin composition is fiber formation property fluorinated polymer of 0.05～5 weight %.
12. contain just like each the flame-retardant molded material of flame retardant resin composition of claim 1～11.
13. the moulding product that obtain by each flame retardant resin composition of moulding such as claim 1～11.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280597A (en) * | 1997-11-28 | 2001-01-17 | 住友道株式会社 | Flame retardant polycarbonate resin composition |
| US6379797B1 (en) * | 1999-02-04 | 2002-04-30 | Tohoku Munekata Co Ltd | Resin additive |
| CN1367807A (en) * | 1999-08-09 | 2002-09-04 | 美国拜尔公司 | Flame retardant polycarbonate composition |
| JP2004043641A (en) * | 2002-07-11 | 2004-02-12 | Sekisui Chem Co Ltd | Fire-resistant resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280597A (en) * | 1997-11-28 | 2001-01-17 | 住友道株式会社 | Flame retardant polycarbonate resin composition |
| US6379797B1 (en) * | 1999-02-04 | 2002-04-30 | Tohoku Munekata Co Ltd | Resin additive |
| CN1367807A (en) * | 1999-08-09 | 2002-09-04 | 美国拜尔公司 | Flame retardant polycarbonate composition |
| JP2004043641A (en) * | 2002-07-11 | 2004-02-12 | Sekisui Chem Co Ltd | Fire-resistant resin composition |
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