CN1163907A - Flame-retardant thermoplastic resin composition - Google Patents
Flame-retardant thermoplastic resin composition Download PDFInfo
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- CN1163907A CN1163907A CN 97104505 CN97104505A CN1163907A CN 1163907 A CN1163907 A CN 1163907A CN 97104505 CN97104505 CN 97104505 CN 97104505 A CN97104505 A CN 97104505A CN 1163907 A CN1163907 A CN 1163907A
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Abstract
The present invention provide a flame-retardant resin composition having an extremely low adhesion to metals and excellent thermal stability and light resistance and free from the formation of black extraneous matter. A frame-retardant thermoplastic resin composition characterized by being prepared by incorporating 1 to 1,000 ppm of a basic inorganic compound (D) soluble in a solvent into a resin composition (C) composed of 60 to 98% by weight of a thermoplastic styrene resin (A) and 40 to 2% by weight of a halogenated epoxy flame-retardant (B) having a terminal epoxy group.
Description
The present invention relates to a kind of flame resistance thermoplastic resin compositions, said composition has good thermostability, photostabilization, extremely low to the adhesion of metal, and can not form the black foreign matter.
Styrene resin with excellent mechanical properties, molding performance and outward appearance has been used to various purposes, especially is used as the material of household electrical appliance and business automation equipment shell.In these fields, require material to have flame retardant properties to reduce the scorching loss that is brought of fire, also require material to have good photostabilization to reduce because of long-term exposure caused variable color under indoor light.
On the other hand, because the development of new molding technology such as hot-runner mould molding technology requires resin material to have higher quality, and requires the molding defect of resin material few more good more.Especially in the hot-runner mould molding technology, molten resin rests on heat and annotates and makes the variable color of gained moulded parts in the mouth and form the tendency of burning defectives such as vestige, even more serious than with the product of traditional cold flowing mould channel molding technology manufacturing.In this case, require resin material to have high thermal stability.Especially existing flame-retarded resin material, people think that its thermostability is relatively poor.
Recently, the halogenation epoxy oligomer is used as fire retardant gradually, and this is the balance of utilizing between its flowability and shock-resistance, with and photostabilization, equally also be from point of view of environment protection.The halogenation epoxy oligomer roughly is divided into two kinds, promptly have a kind of (the not dead front type) of end epoxy group(ing) thus and be added with tribromophenol on its end epoxy group(ing) and encircle the another kind (dead front type) be opened.
Yet if use not case type halogenation epoxy oligomer, oligopolymer can stick on the metal parts such as screw rod and barrel of molding machinery in the moulding process, thereby causes defective, as the formation of foreign matter, though its photostabilization and thermostability are very excellent.
JP-A1-101350 has proposed a kind of technology that addresses the above problem: add 0.1 to 10 weight part alkaline inorganic compound such as hydrotalcite.JP-A6-93158 has proposed to improve the technology of thermostability by adding specific zeolite.Yet even adopt these technology to improve thermostability, the reduction of its shock-resistance but is inevitably, because the material that is added is a granulous, and these technology can not solve the problem with metal adhesion.
On the other hand, if use case type halogenation epoxy oligomer, the photostabilization of products obtained therefrom is on duty mutually, though almost not because of using dead front type not to bring the defective that metal adhesion or thermostability are reduced.
Therefore, at present with the halogenation epoxy oligomer as fire retardant to obtain having excellent heat stability and photostabilization, and fire retardant material that can not form black foreign matter low to the adhesion of metal be impossible.
Through further investigation, the inventor has solved the above-mentioned problems in the prior art, Here it is by sneaking into a kind of method that dissolves in the alkaline inorganic compound of solvent to containing the thermoplastic styrene resin and having in the flame-retarded resin of epoxy-terminated halogenation epoxy fire retardant, obtained having excellent heat stability and photostabilization, low and can not form the fire-proof resin composition of black foreign matter to the adhesion of metal.
The invention provides a kind of flame resistance thermoplastic resin compositions, said composition comprises a kind of alkaline inorganic compound (D) that dissolves in solvent that is had a kind of resin combination (C) and 1 to 1000ppm (is benchmark with (C)) that one (or several) epoxy-terminated a kind of halogenated epoxy resin (B) forms by a kind of thermoplastic resin (A) and 40 to 2wt.% of 60 to 98%wt.%.Described thermoplastic resin (A) is selected from the group of being made up of the mixture of a kind of rubber reinforced resin (A-1) and this rubber reinforced resin (A-1) and a kind of polymkeric substance (A-2).Described (A-1) is in the presence of rubber polymer, by aromatic ethenyl monomer or aromatic ethenyl monomer and another kind of can obtaining through polymerization with the monomeric mixture of this aromatic ethenyl monomer copolymerization.The polymkeric substance that described (A-2) is a kind of aromatic ethenyl monomer or this aromatic ethenyl monomer with another kind of can with the polymkeric substance of monomeric a kind of mixture of this monomer copolymerization.Described halogenated epoxy resin (B) is shown in following general formula (1):
Wherein X represents a halogen atom, and n represents to be at least 0 integer, and i represents an integer of 1 to 4, and R represents:
And/or Y ': hydrogen atom or
(R
1Be phenyl group, can be replaced that the amount of Y is that benchmark is 100 to 40mol% with R) by low-grade alkyl group and/or halogen atom.
Inorganic chemical combination compound (D) preferably can be water-soluble material.
Preferred compositions contains 70 to 98wt.% (A), 30 to 2wt.% (B) and 1 to 800ppm (D).Another kind of preferred compositions contains 75 to 97wt.% (A), 25 to 3wt.% (B) and 10 to 500ppm (D).
Alkaline inorganic compound (D) is preferably selected from the group of being made up of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and saleratus.
The present invention also provides a kind of method for compositions of making above-mentioned definition, comprises being dissolved in alkaline inorganic compound in the solvent and with gained solution and steps such as resin combination (C) mixes.Solvent is water preferably.
Below the present invention is specifically described.
The used thermoplastic resin composition of the present invention (A) is that rubber reinforced resin (A-1) (this resin is in the presence of rubber polymer (a), can be obtained through graft polymerization with the mixture of the monomer (c) of this monomer (b) copolymerization by monomer component aromatic ethenyl monomer (b) or this aromatic ethenyl monomer (b) and another kind) or this rubber reinforced resin (A-1) mix the mixture that obtains with the polymkeric substance (A-2) that this monomer component polymerization obtains.The ratio of rubber reinforced resin (A-1) and polymkeric substance (A-2), promptly (A-1)/(A-2) is preferably in 100/0 to 5/95 scope.
The used rubber polymer (a) of the present invention comprising: for example, and polyhutadiene, polyisoprene, styrene/butadiene copolymers, ethylene/alpha-olefin copolymer, ethylene/alpha-olefin/polyene copolymer, acrylic rubber, silicon rubber, styrene/butadiene block copolymer, hydrogenated styrene/butadiene block copolymer and hydrogenated butadiene multipolymer.These rubber polymers (a) use separately or use with their two or more the form of mixture.
The consumption of rubber polymer (a) is a benchmark with component (A-1), and preferably in 10 to 70wt.% scope, more preferably 10 to 65wt.%, and preferred especially 15 to 65wt.%.If the consumption of rubber polymer (a) is less than 10wt.%, impact strength is not enough, and on the contrary, if more than 70wt.%, rigidity is not enough.
Aromatic ethenyl monomer (b) comprising: for example, and vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene and Vinylstyrene.Wherein, optimization styrene and alpha-methyl styrene.These aromatic ethenyl monomers use separately or use with their two or more form of mixtures.
The amount of the aromatic ethenyl monomer (b) that is contained in the component (A-1) is preferably 30 to 90wt.%, and more preferably 35 to 80wt.%, and preferred especially 35 to 85wt.%.The amount of this monomer (b) is preferably 50 to 100wt.% in the component (A-2), and more preferably 60 to 100wt.%, and preferred especially 70 to 100wt.%.
Can comprise vinyl cyanide base monomer with the monomer (c) of another kind of aromatic ethenyl monomer (b) copolymerization, as vinyl cyanide and methacrylonitrile; Acrylate such as methyl acrylate, ethyl propenoate and butyl acrylate; Methacrylic ester such as methyl methacrylate, Jia Jibingxisuanyizhi and butyl methacrylate; Unsaturated acid anhydride such as maleic anhydride; Unsaturated acid such as vinylformic acid and methacrylic acid; And unsaturated dicarboxyl imide such as maleimide, N-phenylmaleimide and N-methyl maleimide.These monomers use separately or use with their two or more the form of mixture.Component (A-1) but in the preferred no more than 50wt.% of monomeric amount of copolymerization, more preferably no more than 40wt.%, preferred especially no more than 30wt.%; The preferred no more than 50wt.% of amount of copolymerisable monomer in the component (A-2), more preferably no more than 40wt.%, preferred especially no more than 30wt.%.
Component (A) can have no particular limits with known polymerization process such as letex polymerization, suspension polymerization, solution polymerization or bulk polymerization production.Wherein, from the operability of blend and the operability aspect of extruding, floating liquid polymer is preferred.The emulsion polymerisation process that is cured with sour agglomerative method is preferred.
Halogenated epoxy resin (B) used among the present invention is shown in above-mentioned general formula (1).Halogen atom X in the component (B) is bromine atoms, chlorine atom or similar atom.For obtaining high flame retardant effect, preferred bromine.I is the integer in 1 to 4 scope, preferred 2.
End group R in the component (B) is following Y and/or Y ':
And/or Y ': hydrogen atom or
(R
1Be the phenyl group that can be replaced by low alkyl group and/or halogen atom).
As for Y and Y
1Ratio, suppose R=Y+Y '=100mol%, the relative quantity of Y is 100 to 40mol%, preferred 100 to 45mol%, more preferably 100 to 50mol%.Be lower than 40mol% if the amount of Y is benchmark with R, the photostabilization of final composition seriously reduces.
The molecular weight of component (B) is preferably 1300 to 50,000.If be lower than 1300, the thermotolerance of final composition is not enough.On the contrary, be higher than 50,000, the mobile reduction if be increased to.
Relative content as for styrene resin (A) in the fire-proof resin composition of the present invention and fire-retardant component (B), suppose that component (A)+component (B) is 100wt.%, then the content of component (A) is 60 to 90wt.%, and preferred 70 to 98wt.%, and more preferably 75 to 97wt.%; The content of component (B) is 40 to 2wt.%, and preferred 30 to 2wt.%, and more preferably 25 to 2wt.%.If the relative content of component (B) is lower than 2wt.%, can not realize effectively fire-retardant.On the contrary, if the relative content of component (B) is higher than 40wt.%, the impact resistance of fire-proof resin composition reduces.
The used alkaline inorganic compound (D) of the present invention is the material that can be dissolved in the solvent.The available solvent is the neat solvent that can buy on the market usually herein, as water; Alcohols is as methyl alcohol and ethanol; Ketone is as acetone and methylethylketone; And halohydrocarbon, as chloroform and methylene dichloride.The mixture of solution not to be covered such as aqueous sulphuric acid soln, sodium chloride solution or two or more solvents.Phrase " can be dissolved in the material in the solvent " and be meant and can dissolve this material of 1g in the 100g solvent at least.Though dissolve in the material of above-mentioned any solvent and all be can be used for of the present invention, from being easy to the dissolving aspect, preferably water-soluble material.If the solubleness of alkaline inorganic compound (D) in the 100g solvent is less than 1g, the shock-resistant and poor heat stability of the composition that finally obtains, and unavoidably can form the black foreign matter.
Be not particularly limited can be used for alkaline inorganic compound of the present invention, as long as they have alkalescence to HCl.These compounds comprise, for example, and oxyhydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, strontium hydroxide and hydrated barta; Oxide compound such as potassium oxide, Cs2O, rubidium oxide, magnesium oxide, calcium oxide, barium oxide and strontium oxide; Carbonate such as yellow soda ash, salt of wormwood, cesium carbonate and magnesiumcarbonate; Supercarbonate such as lithium bicarbonate, sodium bicarbonate and saleratus; Tetraborate such as sodium tetraborate (sodium tetraborate decahydrate; Borax) and potassium tetraborate; Metaborate such as sodium metaborate and potassium metaborate; Metaphosphate such as sodium-metaphosphate and potassium metaphosphate; Monothio phosphoric acid salt such as Trisodium thiophosphate and monothio potassiumphosphate; Imidodiphosphate such as imidodiphosphoric acid sodium and potassium imino diphosphate; Inorganic base such as metallic element are as the oxyhydroxide and the oxide compound of basic metal (comprising lithium, sodium, potassium, rubidium and caesium), alkaline-earth metal (as magnesium, calcium, strontium and barium) and the 3rd family's element (comprising aluminium); The carbonate of these metallic elements and ammonium, supercarbonate, borate (as tetraborate and metaborate), phosphoric acid salt (as monothio phosphoric acid salt and imidodiphosphate); And contain weak acid and weakly alkaline mineral alkali or salt.
In these compounds, the oxyhydroxide of preferred as alkali and alkaline-earth metal, oxide compound, carbonate and supercarbonate.
The consumption of used alkaline inorganic compound (D) is a benchmark with resin combination (C), is 1 to 1000ppm, and preferred 1 to 800ppm, and more preferably 10 to 500ppm.If the amount of component (D) with resin combination (C) be benchmark greater than 1000ppm, then the adhesion of metal is increased, on the contrary,, then unavoidably form the black foreign matter and can't obtain thermostability if be lower than 1ppm.
The used alkaline inorganic compound (D) of the present invention is preferably sneaked in the composition as follows; The solution of preparation alkaline inorganic compound is sneaked into the additive solution of gained in the composition then earlier.The available solvent comprises water herein; Alcohols such as methyl alcohol and ethanol; Ketone such as acetone and methylethylketone; With halogenated hydrocarbons such as chloroform and methylene dichloride.Basic cpd solvent is not particularly limited, as long as can dissolve therein.
The used alkaline inorganic compound of the present invention (D) is preferably sneaked in the composition as follows; The aqueous solution of preparation alkaline inorganic compound in solvent is sneaked into the additive aqueous solution of gained in the composition then earlier.
Compare with directly sneaking into of alkaline inorganic compound, more wish the mode mixed-alkali compound with the preparation additive solution, because basic cpd can disperse fully like this, and the latter has reduced the possibility that shock-resistance reduces.
To the method for sneaking into of basic cpd also without limits.This compound can sneak into also with the form of the mixture of itself and other component and can extrude/sneaks in the kneading process.
If desired, flame resistance thermoplastic resin compositions of the present invention also can contain other fire retardant and additive, only otherwise damage purpose of the present invention.
The example of other fire retardant comprises halogen containing flame-retardant such as tetrabromo-bisphenol and derivative, tetrabromophthalic anhydride, PBDE, bromination carbonic ether oligopolymer and terminal groups modification product thereof, bromination (dibromo or tribromo) polystyrene, brominated polyphenylether and tricresyl phosphate dibromo phenyl ester; Organophosphorous fire retardant such as triphenylphosphate and triphenyl phosphite; With the piperazine fire retardant.These fire retardants can use separately also and can use with their two or more the form of mixture.The consumption of these fire retardants, for per 100 parts by weight resin compositions (c), best no more than 40 weight parts.
Can use auxiliary flame retardant to improve the flame retardant effect of fire retardant component.The example of auxiliary flame retardant comprises antimony containing compounds such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony tetroxide, (colloidal state) antimony peroxide, sodium antimoniate and phosphoric acid antimony; With metal oxide such as zinc.In these compounds, preferred antimony fire retardant, preferred especially ANTIMONY TRIOXIDE SB 203 99.8 PCT.The consumption of auxiliary flame retardant, for per 100 parts by weight resin compositions (c), best no more than 15 weight parts.
Flame resistance thermoplastic resin compositions also can contain another kind of additive so that it has antidrip dropping down property.This additive comprises halogenated polyolefin such as chlorinatedpolyethylene, polyvinyl chloride and tetrafluoroethylene; Silicon compound such as polydimethylsiloxane, silicon rubber and this silicon rubber carry out the graftomer that graft polymerization obtains with the resin component; Polyphenylene oxides; And phenol resins.The consumption of this additive, per 100 parts by weight resin compositions (c), preferably no more than 10 weight parts.
Thermoplastic resin composition of the present invention can also be contained filler, as glass fibre, carbon fiber, granulated glass sphere, talcum, mica and kaolin with contain well-known additive such as the consumption of coupling agent, oxidation inhibitor, softening agent, tinting material, lubricant, static inhibitor and antiseptic-germicide, this additive, per 100 parts by weight resin compositions (c) are no more than 100 weight parts preferably.
According to required performance, flame resistance thermoplastic resin compositions of the present invention can with another kind of polymer blending.This polymkeric substance comprises polyethylene, polypropylene, polyphenylene oxide, polymeric amide, polyester, polycarbonate, polysulfones, polyvinylidene difluoride (PVDF), polyester elastomer or polyamide elastomer.The consumption of this polymkeric substance, per 100 parts by weight resin compositions (c) are no more than 100 weight parts preferably.
Flame resistance thermoplastic resin compositions of the present invention is to use various forcing machines, Banbury mixing roll, kneader or rolling press to mediate above-mentioned component and obtains.These components can adopt once to mediate and also can adopt the multistage to add the method for mediating.
Resulting flame resistance thermoplastic resin compositions of the present invention can be used, and for example, injection moulding, sheet material extrusion molding, vacuum moulding or frothing mold method are molded as various moulded partss.
The advantage of flame resistance thermoplastic resin compositions of the present invention is extremely low to the adhesion of metal, has good thermostability and photostabilization and can not form the black foreign matter.Flame resistance thermoplastic resin compositions of the present invention has high industrial value, thereby industrial very useful, (comprise fading in the formation of black foreign matter and the molding step) because can reduction in the numbers of seconds, and said composition is to be suitable for use as the product that requirement tone behind life-time service has only slight change, as the resin material of household electrical appliance and business automation equipment.
The following examples be used for further specifying of the present invention, be anything but be used for limiting of the present invention.Among the embodiment, umber, per-cent and ppm all are by weight calculation.
The component of used fire-proof resin composition in embodiment and the Comparative Examples:
[method for preparing rubber reinforced resin (A-1)]
Polymerization single polymerization monomer component in the presence of rubber polymer shown in the table 1.The content of rubber polymer and to constitute the ratio of each component of this base material as shown in table 1 in the gained rubber reinforced resin.Condense with sulfuric acid then by well-known letex polymerization and to obtain rubber reinforced resin (A-1)-1.Obtain rubber reinforced resin (A-1)-2 by well-known mass polymerization.
Table 1
Rubber reinforced resin (A-1)
[method for preparing polymkeric substance (A-2)]
| Code name | Rubber polymer | Matrix | ||
| Kind | Content (%) | The monomer component | Polymerization ratio | |
| ?(A-1)-l ?(A-1)-2 | The polyhutadiene polyhutadiene | ????40 ????20 | Styrene/acrylonitrile vinylbenzene | ????75/25 ????100 |
Prepare polymkeric substance (A-2) by the ratio that provides in the table 2 by the monomer component.Prepare polymkeric substance (A-2)-1 by known solution polymerization process, prepare polymkeric substance (A-2)-2 by known bulk polymerization.
Table 2
Polymkeric substance (A-2)
The commodity fire retardant that provides in [preparation of halogenated epoxy fire retardant] use table 3.
| Code name | The monomer component | Polymerization ratio |
| ????(A-2)-1 ????(A-2)-2 | Styrene/acrylonitrile vinylbenzene | ????75/25 ????100 |
Table 3
Halogenated epoxy resin (B)
| Code name | Kind | Epoxy-terminated enclosed *(％) | Molecular weight | Rank ** |
| ??B-1 ??B-2 ??B-3 | End group does not seal end group and does not seal end-block | ?????0 ?????0 ????100 | ????1600 ????3000 ????2000 | ??EP-16 ??EP-30 ??EC-20 |
* use the tribromophenol end-blocking
* Dainippon Ink ﹠amp; Chemicals, the product of Inc [preparation of ANTIMONY TRIOXIDE SB 203 99.8 PCT]
Use The Nippon Mining ﹠amp; The product A TOX-S that Concentrating Co.Ltd. produces.[preparation of basic cpd]
The basic cpd aqueous solution that provides in the use table 4 or basic cpd itself.
Table 4
Alkaline inorganic compound (D)
Embodiment 1 to 6 and Comparative Examples 1 to 5
| Code name | Kind | Addition means |
| ????D-1 ????D-2 ????D-3 ????D-4 | Sodium hydroxide sodium bicarbonate yellow soda ash A type synthetic zeolite (Ca-type) | Add with the interpolation of 4% aqueous solution form with directly interpolation of 4% aqueous solution form interpolation with 4% aqueous solution form |
Each component was mixed 3 minutes by the amount weighing that provides in table 5 and the table 6 and with the Henschel mixing roll.With mixture with the 50mm twin screw extruder under 180 to 210 ℃ of barrel zone temperatures, dissolve extrude and granulation to obtain testing pellet.This pellet was descended dry 3 hours at 80 ℃, and then 210 ℃ of barrel temperatures, 50 ℃ of following injection mouldings of mould temperature are to obtain test block.The measuring result of test block is shown in table 5 and 6.Measuring method is as described below:＜heat-resisting painted and gel test 〉
The 70g pellet is refined machine at 270 ℃ with the laboratory plastic roller, and 100rpm mediates down.Mediate the form and aspect of product and measure the variation of torque on the turning moment diagram with microscopic examination.
Heat-resisting color standard:
Zero: light colored
△: significantly painted
*: seriously painted
The gel standard:
Zero; Torque raises very little, does not almost observe gel.
△: can observe torque degree of liter and gel.
*: torque rising and gel are serious.＜to the adhesion of metal 〉
Pellet is layered on the 50 μ m stainless steel substrates.Cover the 50mm Kapton thereon, then with them 230 ℃ of hot pressing 30 minutes.Product is placed 180 ℃ temperature bath, stainless steel substrates is fixed on the anchor clamps of stretching testing machine in the temperature bath, Kapton is fixed on and carries out tension test on another anchor clamps.In this test, Kapton is dug and is split by distension from adhesive surface at 180 ℃.Add the adhesion of state of resin judgement from stainless steel substrates to metal.
Adherent standard:
Zero: Kapton sticks on the stainless steel substrates.
*: do not adhere to.＜falling-ball impact test 〉
Prepare thick 2.4mm, the flat board of 55 * 80mm is tested with falling ball impact test machine then.Falling sphere speed is 2.4m/sec.Unit is kg * cm.＜photostabilization 〉
Prepare thick 2.4mm, the flat board of 55 * 80mm carries out 300 hours photostabilization test then with xenon arc weather resistance test device.Measure fading extent to determine aberration (Δ E) with color difference meter.
Standard:
○：ΔE＜5
△：5≤ΔE≤10
×：ΔE＞10
Table 5
| Project | Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 2 | Comparative Examples 3 | Embodiment 4 | |
| Component | Rubber reinforced resin (A-1)-1 | ????35 | ????35 | ????35 | ????35 | ????35 | ????35 | ????35 |
| Polymkeric substance (A-2)-1 | ????50 | ????50 | ????50 | ????50 | ????50 | ????50 | ????50 | |
| Epoxy halogenide B-1 | ????15 | ????15 | ????15 | ????15 | ????15 | ????15 | ????15 | |
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | ????5 | ?????5 | ?????5 | ?????5 | ?????5 | ????- | ????- | |
| Alkaline inorganic compound (amount of solid matter) D-1 | ????- | ?100ppm | ?20ppm | ?500ppm | ?2000ppm | ????- | ?100ppm | |
| Performance | Heat-resisting painted | ????× | ????○ | ????○ | ????○ | ????○ | ????× | ????○ |
| Gel | ????× | ????○ | ????○ | ????○ | ????○ | ????× | ????○ | |
| Adhesion to metal | ????× | ????○ | ????○ | ????○ | ????× | ????× | ????○ | |
| Falling-ball impact test | ????150 | ????150 | ????150 | ????150 | ????130 | ????200 | ????200 | |
| Photostabilization (Δ E) | ?????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
Table 6
| Project | Embodiment 5 | Embodiment 6 | Comparative Examples 4 | Comparative Examples 5 | |
| Component | Rubber reinforced resin (A-1)-1 | ????35 | ????35 | ????35 | ????35 |
| Polymkeric substance (A-2)-1 | ????50 | ????50 | ????50 | ????50 | |
| Epoxy halogenide B-1 | ????15 | ????15 | ????15 | ????15 | |
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | ?????5 | ?????5 | ?????5 | ?????5 | |
| Alkaline inorganic compound (amount of solid matter) D-2 | ?200ppm | ||||
| ??????????D-3 | ?100ppm | ||||
| ??????????D-4 | ?200ppm | ?1.0part | |||
| Performance | Heat-resisting painted | ????○ | ????○ | ????× | ????○ |
| Gel | ????○ | ????○ | ????× | ????○ | |
| Adhesion to metal | ????○ | ????○ | ????× | ????○ | |
| Ball falling impact intensity | ????150 | ????150 | ????130 | ????40 | |
| Photostabilization (Δ E) | ????○ | ????○ | ????○ | ????○ | |
In the Comparative Examples 1 and 3 that does not add alkaline matter, low to the adhesion height and the thermostability of metal.
In the embodiment 1 to 6 that is added with alkaline matter, resulting composition has good thermostability, and shock-resistance and photostabilization are also low to the adhesion of metal.
In being added with the NaOH comparative example 2 of 2000ppm, very high to the adhesion of metal.
In the comparative example 4 and 5 who uses synthetic zeolite, some improvement of zeolite properties that adds 200ppm does not all have.Even add 1.0 parts of synthetic zeolites, these performances (except the thermostability) are not significantly improved yet, and shock-resistance has reduced on the contrary.
Embodiment 7 and 8 and Comparative Examples 6
Repeat the step identical with embodiment 1, just used among the embodiment 7 styrene resin (A-1)-2 with (A-2)-2, used epoxy halogenide B-2 among the embodiment 8, used the epoxy halogenide B-3 of end-sealed type in the Comparative Examples 6.Provided the result in the table 7.
Table 7
| Project | Embodiment 7 | Embodiment 8 | Comparative Examples 6 | |
| Composition | Rubber strengthens polymkeric substance (A-1)-1 | ????35 | ?????35 | |
| ??????(A-1)-2 | ????50 | |||
| Polymkeric substance (A-2)-1 | ????50 | ????50 | ||
| ??????(A-2)-2 | ????35 | |||
| Epoxy halogenide B-1 | ????15 | |||
| ??????B-2 | ????15 | |||
| ??????B-3 | ????15 | |||
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | ????5 | ????5 | ????5 | |
| Alkaline inorganic compound (amount of solid matter) D-1 | ?100ppm | ?100ppm | ??100ppm | |
| Performance | Heat-resisting painted | ????○ | ????○ | ????○ |
| Gel | ????○ | ????○ | ????○ | |
| Adhesion to metal | ????○ | ????○ | ????○ | |
| Ball falling impact intensity | ????100 | ???130 | ????150 | |
| Photostabilization (Δ E) | ????○ | ????○ | ????× | |
If use B-3 (end-sealed type), photostabilization low (Comparative Examples 6).
Claims (8)
1. flame resistance thermoplastic resin compositions, comprise having a kind of resin combination (C) that one or several epoxy-terminated a kind of halogenated epoxy resin (B) forms and be a kind of alkaline inorganic compound (D) that dissolves in solvent of 1 to 1000ppm of benchmark by a kind of thermoplastic resin (A) of 60 to 98wt.% and 40 to 2wt.% with (C), wherein
Resin (A) is selected from the group of being made up of following material:
In the presence of rubber, by aromatic ethenyl monomer component or this aromatic ethenyl monomer and another kind of a kind of rubber reinforced resin (A-1) that can obtain through polymerization with the monomeric mixture of this aromatic ethenyl monomer copolymerization and
A kind of mixture of this rubber reinforced resin (A-1) and polymkeric substance (A-2), this polymkeric substance (A-2) be a kind of polymkeric substance of aromatic ethenyl monomer or this aromatic ethenyl monomer with another kind of can with the polymkeric substance of the monomeric mixture of this monomer copolymerization;
Resin (B) is shown in following general formula (1):
Wherein X represents a halogen atom, and the n representative is at least an integer of 0, and i represents an integer of 1 to 4, the R representative:
And/or Y ': hydrogen atom or
R wherein
1Be a phenyl group, can be replaced that the amount of Y is that benchmark is 100 to 40mol% with R by low-grade alkyl group and/or halogen atom.
2. composition as claimed in claim 1, wherein alkaline inorganic compound (D) is water-soluble material.
3. composition as claimed in claim 1 comprises 70 to 98wt.% (A), 30 to 2wt.% (B) and 1 to 800ppm (D).
4. composition as claimed in claim 1 comprises 75 to 90wt.% (A), 25 to 3wt.% (B) and 10 to 500ppm (D).
5. composition as claimed in claim 1, wherein alkaline inorganic compound (D) is selected from by NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3And KHCO
3The group of forming.
6. preparation is as the defined method for compositions of claim 1, and the step of this method comprises alkaline inorganic compound (D) is dissolved in the solvent and with gained solution and mixes with resin combination (C).
7. method as claimed in claim 6, wherein solvent is a water.
8. method as claimed in claim 6, wherein alkaline inorganic compound (D) is selected from by NaOH, KOH, Na
2CO
3, K
2CO
3, NaHCO
3And KHCO
3The group of forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104505 CN1163907A (en) | 1996-03-26 | 1997-03-18 | Flame-retardant thermoplastic resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP69735/96 | 1996-03-26 | ||
| CN 97104505 CN1163907A (en) | 1996-03-26 | 1997-03-18 | Flame-retardant thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1163907A true CN1163907A (en) | 1997-11-05 |
Family
ID=5167412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97104505 Pending CN1163907A (en) | 1996-03-26 | 1997-03-18 | Flame-retardant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1163907A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735654B (en) * | 2003-01-13 | 2010-04-28 | 溴化物有限公司 | Flame-retardant for engineering thermoplastic applications |
| CN105244107A (en) * | 2015-10-16 | 2016-01-13 | 安徽蓝德集团股份有限公司 | Impact-resistant flame-retardant control cable |
-
1997
- 1997-03-18 CN CN 97104505 patent/CN1163907A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735654B (en) * | 2003-01-13 | 2010-04-28 | 溴化物有限公司 | Flame-retardant for engineering thermoplastic applications |
| US8067497B2 (en) | 2003-01-13 | 2011-11-29 | Bromine Compounds Ltd. | Flame-retardant for engineering thermoplastic applications |
| CN105244107A (en) * | 2015-10-16 | 2016-01-13 | 安徽蓝德集团股份有限公司 | Impact-resistant flame-retardant control cable |
| CN105244107B (en) * | 2015-10-16 | 2017-10-03 | 安徽蓝德集团股份有限公司 | A kind of shock resistance flame-proof control cable |
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