CN1307071A - Smoke-inhibiting flame retardant composition - Google Patents
Smoke-inhibiting flame retardant composition Download PDFInfo
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- CN1307071A CN1307071A CN 00100709 CN00100709A CN1307071A CN 1307071 A CN1307071 A CN 1307071A CN 00100709 CN00100709 CN 00100709 CN 00100709 A CN00100709 A CN 00100709A CN 1307071 A CN1307071 A CN 1307071A
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- smoke
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- retardant composition
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Abstract
The composition, when added to polyvinyl chloride material, can reduce smoke amound of the material during burning. The composition consists of tin salt and molybdenum salt mixed powder as main component and one or several oxides of Sn, Sb, Zn or Zn-B or hydroxide of Al as supplementary material. It has optimized smoke inhibiting and flame retarding effect when the weight ratio between the main component and the supplementary material is 1 to 2.5-3.5.
Description
The invention relates to a kind of smoke-inhibiting flame retardant composition, refer to a kind of make an addition to polyvinyl chloride (PVC, polyvinyl chloride) and can effectively suppress the polyvinyl chloride amount of being fuming when burning, the smoke-inhibiting flame retardant composition of the anti-combustion characteristic of raising especially.
Polyvinyl chloride is a kind of synthetic thermoplastic polymer, has that the processing of high ductibility, great tolerant plasticity (Commodity thermoplastics) is good, a dielectricity, the difficult combustion of moisture resistance weather-proof, tool characteristic own, low price ... etc. advantage.The former scope of using is extremely wide, and is last to the insulation coating of electric wire, down to water pipe, furniture synthetic leather, door, window, foaming panel wall, raincoat, toy, floor, synthetic paper ... Deng, its application is all arranged.
Yet, because the polyvinyl chloride chlorinity is up to more than 56%, can discharge the poisonous dense smoke of high density during burning, go out when taking place in fire, not only hindered survivor's sight line, toxic gas directly causes the people especially in extremely.Though secondly polyvinyl chloride itself has flame retardancy, but produce foaming material, electric wire or sofa rubber with it ... Deng, manufacturer is in order to satisfy the demand of using and processing, often need to add auxiliary agents such as softening agent, stablizer or whipping agent, making pvc material lose the inherent difficulty fires characteristic and becomes flammable, and most particularly, produce a large amount of poisonous dense smoke during burning.
The relevant scholar in home and abroad, expert adopt several different methods for solving the problem that is produced when above-mentioned polyvinyl chloride burns at present.More (Moore F.W.1991 for example, Journal of VinylTechnology, 13 (3), Sep.) propose with zinc borate together additive (as phosphoric acid ester, bromination acid esters) be blended in the pvc material, but to reach the amount of being fuming when falling the polyvinyl chloride burning and to improve flame retardant resistance; Mai Maleier (McMurrer, M., 1991,9, Plastics Compounding) proposition applying boric acid zinc and ammonium molybdate mix jointly and add in the polyvinyl chloride, effectively reduce to be fuming to reach 50%; The card base of a fruit (Carty, P.1995,8 (4), Engineering Plastics) the amount of the being fuming when stannate of touching upon, alkali ferric oxide and ammonium molybdate can effectively suppress the pvc material burning; Bei Gelai etc. (R.G.Baggaley 1997, Vol.21, Fire and Materials) utilize hydroxyl pink salt and aluminium hydroxide and magnesium hydroxide pressing down fumicants and promoting its limited oxygen index (LOI) and reach 45.8 as pvc material.Aspect various countries' patent, (1976, US 3957723, Lawson) propose with Al (OH) as the labor life in addition
3But complement each other to fall the polyvinyl chloride amount of being fuming in when burning with ZnO; Uniroyal company (1984, US 4464502) then delivers the effect that multiplies each other with ZnO and MgO, the amount of being fuming when suppressing the polyvinyl chloride burning; Japanese Patent (1997 JP 9-227747) is with phosphorus compound and the expanded graphite anti-flaming smoke-inhibiting agent as pvc material; United States Patent (USP) (1997, US 5906679), the daily output chemistry is with ZnO/Sb
2O
5Melt adds in the pvc material mutually, reaches smoke suppressing effect; Recently, A Erkan company (US 5891571 in 1999, Alcan Inc.) utilizes ammonium octamolybdate, zinc and antimonous oxide to mix to add in the polyvinyl chloride, with the amount of being fuming of effective inhibition polyvinyl chloride.
Take a broad view of above-mentioned various polyvinyl chloride and press down cigarette, flame-retardant formulations composition, we can find:
(1) adds Al (OH)
3, Mg (OH)
2Deng inorganic hydrate, need heavy addition (general addition is 50-150phr, the umber in per hundred parts of resins of phr=or the rubber) just can show and press down cigarette, fire-proof function.So a large amount of interpolation not only increases the degree of difficulty of manufacturing processed, and the polyvinyl chloride performance easily is damaged, and often can't satisfy the coml demand.
(2) add zinc borate system, subtract that to fall cigarette dose-effect fruit limited, and flameproof effect is not good.
(3) add inorganicss such as stannate, ammonium molybdate and cost an arm and a leg, smoke suppressing effect is not obvious at least as if addition, increases progressively (maximum is about 50% and subtracts the amount of falling) if addition＞5phr then presses down hood and inequality.
(4) add zinc oxide/weisspiessglanz system, can promote the flame retardancy of polyvinyl chloride, but but can't effectively fall the amount of being fuming, and have the problem of discharging metaantimmonic acid gas when burning.
(5) adding phosphoric acid salt with expanded graphite is, fire-proof function is obvious, but the amount of being fuming subtract fall limited.
(6) with hydroxyl pink salt lining aluminium hydroxide or magnesium hydroxide, smoke suppressing effect is still good, and 40phr is above just a unusual effect but fire line need be added.
More than comprehensive, the shortcoming of prior art or be that addition is big influences performance; Or for cost an arm and a leg, smoke suppressing effect is less than 50%, can not satisfy business-like demand.
Therefore, the utmost point need be developed a kind of novel fire-retardant constituent that presses down cigarette, and it can make an addition in the pvc material reaching the purpose that presses down cigarette and high flame retardant, and can reach and suppress the effect of polyvinyl chloride burning fuming amount more than 50% at a small amount of add (3-25phr).
The inventor in line with the spirit of actively inventing, conceives a kind of " smoke-inhibiting flame retardant composition " that can address the above problem for these reasons, and several times research experiment has been finished this invention eventually.
Main purpose of the present invention provides a kind of smoke-inhibiting flame retardant composition, the amount of being fuming in the time of effectively suppressing the pvc material burning, and the limited oxygen index (Limit OxygenIndex) of lifting pvc material.
Smoke-inhibiting flame retardant composition of the present invention comprises the main body powder of (A) pink salt powder and molybdenum salt powdered mixture, and (B) the auxilliary body powder of any two or more mixture of Sn oxide powder or aluminium hydroxide powder or zinc and boron oxide powder or sb oxide powder or its.
Because the present invention forms novelty, can provide on the industry and utilize, and truly have the enhancement effect, so apply for patent of invention in accordance with the law.
The detailed description of preferred embodiment
Flame-retardant smoke inhibition composition of the present invention is the main body powder that comprises (A) pink salt powder and molybdenum salt powdered mixture, and (B) the auxilliary body powder of any two or more mixture of Sn oxide powder or aluminium hydroxide powder or zinc and boron oxide powder or sb oxide powder or its.Wherein (A) main body powder and (B) the content ratio of auxilliary body powder can be 1: 1-5 (weight ratio): preferablely can be 1: 2.5-3.5 (weight ratio).The pink salt in the present invention (A) main body powder and the ratio of molybdenum salt are preferably 1: 0.2-5.0.Pink salt in the flame-retardant smoke inhibition composition main body powder of the present invention is preferably the mixture of sodium stannate, zinc, magnesium stannate or its any two or more pink salts.And the molybdenum salt in the flame-retardant smoke inhibition composition main body powder of the present invention, the preferable mixture that can be molybdic oxide, zinc molybdate, ammonium molybdate or its any two or more molybdenum salt.Main body powder median size of the present invention is preferably 0.1 to 50 μ m.And the pink salt content in the smoke-inhibiting flame retardant composition of the present invention is preferably and contains 5% to 20%, and its pink salt median size is preferably 0.1 to 50 μ m, and the best is 0.1 to 5 μ m.Molybdenum salts contg in the smoke-inhibiting flame retardant composition of the present invention is preferably and contains 2% to 20%, and its molybdenum salt powder median size is preferably 0.1 to 50 μ m, and measuring good is 0.1 to 5 μ m.If the auxilliary body powder tin-oxide of smoke-inhibiting flame retardant composition of the present invention then is preferably SnO
2, SnO or its mixture, best median size is the SnO less than 6 μ m
2If the auxilliary body powder sb oxide of smoke-inhibiting flame retardant composition of the present invention then is preferably Sb
2O
3, Sb
2O
5Or its mixture, best median size is the Sb less than 5 μ m
2O
5Powder.If the auxilliary body powder zinc oxide of smoke-inhibiting flame retardant composition of the present invention, then preferable median size is the ZnO powder less than 5 μ m.If the auxilliary body powder aluminium hydroxide of smoke-inhibiting flame retardant composition of the present invention, then preferable median size are the Al (OH) less than 3 μ m
3Powder.If the auxilliary body powder zinc and boron oxide of smoke-inhibiting flame retardant composition of the present invention, then preferable median size is for containing the hydrate zinc borate powder less than 2 μ m.
Smoke-inhibiting flame retardant composition of the present invention is in order to be added in the pvc material, so that the pvc material after adding reaches the effect that presses down smoke high flame retardant.The tobacco composition that presses down of the present invention adds consumption in the polyvinyl chloride, is to add pure pvc material (containing soft or hard matter) with 3 to 35phr addition, and the amount of being fuming when it can effectively suppress the pvc material burning also promotes its flame retardant resistance.And join consumption in the polyvinyl chloride, be preferably 5 to 25phr additions and join in the pure pvc material and (contain soft or hard matter).
For making those skilled in the art person more understand technology contents of the present invention, especially exemplified by preferable concrete
Embodiment is described as follows.
Soft, the herd polyvinyl chloride material that each embodiment is made is all measured the LOI value of various polyvinyl chloride samples earlier with limited oxygen index (LOI) survey meter, measure every amount of being fuming always (TSR, Total Smoke Release) with tapered calorimeter (ConeCalorimeter) or NBS again.
Embodiment 1 (soft PVC that does not contain inorganic fillings)
According to composition consumption weight ratio, utilize kneader and thermocompressor with its uniform mixing and be pressed into several different smoke-inhibiting PVC constituent test specimens of forming polyvinyl chloride, dioctyl phthalate (DOP) (DOP softening agent), oxidized petroleum waves, stablizer, processing aid (as Ingawax) and smoke-inhibiting flame retardant agent (A-F) * as table one.
Table one
*The composition explanation of A-F is referring to table two
| Composition | Addition (phr) |
| Polyvinyl chloride | ??????100 |
| Dioctyl phthalate (DOP) (softening agent) | ???????40 |
| Chlorinated wax | ???????20 |
| Stablizer | ???????3 |
| Processing aid (as Ingawax) | ???????0.7 |
| Smoke-inhibiting flame retardant agent (A-F) * | ???????20 |
The limited oxygen index that does not contain the soft PVC of inorganic fillings reaches always is fuming value as shown in Table 2:
Table two
Embodiment 2 (polyvinyl chloride that contains inorganic fillings)
| Specimen coding | Always the amount of being fuming ( *10 4) | Limited oxygen index | The smoke-inhibiting flame retardant agent |
| ??A | ?????38.1 | ????19 | Do not add |
| ??B | ?????24.1 | ????28 | ????????????????????Sb 2O 5 |
| ??C | ?????19.0 | ????30 | ????????????????Sb 2O 5+Na 2SnO 3??????(Sb 2O 5∶Na 2SnO 3Both weight ratios are=1: 1) |
| ??D | ?????21.2 | ????30 | ???????????????????Sb 2O 5+MoO 3????????(Sb 2O 5∶MoO 3Both weight ratios are=3: 1) |
| ??E | ?????34.5 | ????22 | ????????????????????Al(OH) 3 |
| ??F | ?????11.2 | ????33 | ??????????????Sb 2O 5+MoO 3+Na 2SnO 3(Sb 2O 5∶MoO 3∶Na 2SnO 3Three's weight ratio is=6: 1: 1) |
With polyvinyl chloride, dioctyl phthalate (DOP) (softening agent), chlorinated wax, Ba/Zn stablizer, processing aid (as Ingawax) and press down cigarette, fire retardant (G-K)
*And CaCO
3According to composition consumption weight ratio, utilize kneader and thermocompressor with its uniform mixing and be pressed into several different smoke-inhibiting PVC constituent test specimens of forming as table three.
Table three
*The composition explanation of G-K is referring to table four
| Composition | Addition (phr) |
| Polyvinyl chloride | ??????100 |
| The Ba/Zn stablizer | ???????5 |
| Chlorinated wax | ???????20 |
| Dioctyl phthalate (DOP) | ???????30 |
| Processing aid (as Ingawax) | ???????1 |
| ?????????CaCO 3 | ???????60 |
| Smoke-inhibiting flame retardant agent (A-F) * | ???????20 |
Table four
Embodiment 3
| Specimen coding | Always the amount of being fuming ( *10 4) | Limited oxygen index | The smoke-inhibiting flame retardant agent |
| ??G | ?????3.0 | ????22 | Do not add |
| ??H | ?????2.9 | ????27 | ???????????????????SnO 2 |
| ??I | ?????2.3 | ????24 | ???????????2ZnO·3B 2O 3·3.5H 2O |
| ??J | ?????2.7 | ????23 | ??????????????????Al(OH) 3 |
| ??K | ?????1.0 | ????23 | ?????????SnO 2+Al(OH) 3+Na 2SnO 3+MoO 3(weight ratio (SnO between each compound 2∶Al(OH) 3∶MoO 3∶ ?????????Na 2SnO 3Be=5: 10: 1: 4) |
With polyvinyl chloride, shock-resistant modifying agent, calcium stearate, epoxidised soybean oil, tin is the smoke-inhibiting flame retardant agent of stablizer and different ratios, utilizes kneader and thermocompressor with the tool uniform mixing and be pressed into several different smoke-inhibiting PVC constituent test specimens of forming.
Table five
| Composition | Addition (phr) |
| Polyvinyl chloride | ???????100 |
| Shock-resistant modifying agent | ????????8 |
| Stearyl ester calcium | ????????2 |
| Epoxidised soybean oil | ????????3 |
| Tin is stablizer | ????????2 |
| Press down cigarette, fire retardant | ???????0-20 |
Wherein press down cigarette, fire retardant is Sn
2O
3+ Al (OH)
3+ SnO
2+ MoO
3+ Na
2SnO
3Weight ratio between it is: Sb
2O
3: Al (OH)
3: SnO
2: MoO
3: Na
2SnO
3=8: 3: 4: 3: 2
Table six
| Press down fumicants addition (phr) | Limited oxygen index | The amount of being fuming D m(90 seconds) |
| ?????????0 | ??????32 | ??????250 |
| ?????????5 | ??????43 | ??????150 |
| ?????????10 | ??????44 | ??????130 |
| ?????????15 | ??????43 | ??????120 |
| ?????????20 | ??????42 | ??????115 |
By in table two, table four and the table six as can be known, the smoke-inhibiting flame retardant composition of the composition of various embodiments of the present invention, after tested after, limited oxygen index all obviously promote and always the amount of being fuming decline to a great extent.
In sum, no matter the present invention in every respect shows it fully be different from the feature of known techniques with regard to purpose, means and effect, is a quantum jump of " smoke-inhibiting flame retardant composition ".Only it should be noted that above-mentioned many embodiment only give an example for convenience of explanation, the claim scope that the present invention advocated certainly should be with described being as the criterion of claim scope of application.But not only limit to the foregoing description.
Claims (12)
1. smoke-inhibiting flame retardant composition is characterized in that including:
(A) the main body powder of the pink salt powder of 1 weight part and molybdenum salt powdered mixture, and
(B) at least a auxilliary body powder that is selected from the group that is formed by Sn oxide powder, aluminium hydroxide powder, zinc and boron oxide powder and sb oxide powder of 1 to 5 weight part.
2. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that wherein the part by weight of main body powder and auxilliary body powder is 1: 2.5-3.5.
3. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that including the pink salt of 5% to 20% weight part, and wherein pink salt is at least a group that is made up of sodium stannate, zinc and magnesium stannate that is selected from.
4. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that including the molybdenum salt of 2% to 20% weight part, and wherein molybdenum salt is at least a group that is made up of molybdic oxide, zinc molybdate and ammonium molybdate that is selected from.
5. smoke-inhibiting flame retardant composition as claimed in claim 1, the median size that it is characterized in that main body powder wherein is between 0.1 μ m to 50 μ m.
6. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that wherein tin-oxide is at least a being selected from by SnO
2And the group of SnO composition, and median size is less than 6 μ m.
7. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that wherein sb oxide is at least a being selected from by Sb
2O
3And Sb
2O
5The group that forms, and median size is less than 5 μ m.
8. smoke-inhibiting flame retardant composition as claimed in claim 1 it is characterized in that wherein zinc oxide is ZnO, and median size is less than 5 μ m.
9. smoke-inhibiting flame retardant composition as claimed in claim 1 it is characterized in that wherein zinc and boron oxide for containing hydrate zinc borate, and median size is less than 2 μ m.
10. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that wherein aluminium hydroxide is Al (OH)
3, and median size is less than 3 μ m.
11. smoke-inhibiting flame retardant composition as claimed in claim 1 is characterized in that its consumption is to be added in the pvc material with 3 to 35phr addition.
12. smoke-inhibiting flame retardant composition as claimed in claim 11 is characterized in that its addition that is added in the polyvinyl chloride is 5 to 25phr.
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|---|---|---|---|
| CN 00100709 CN1307071A (en) | 2000-02-01 | 2000-02-01 | Smoke-inhibiting flame retardant composition |
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|---|---|---|---|
| CN 00100709 CN1307071A (en) | 2000-02-01 | 2000-02-01 | Smoke-inhibiting flame retardant composition |
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|---|---|
| CN1307071A true CN1307071A (en) | 2001-08-08 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017311A (en) * | 2014-06-21 | 2014-09-03 | 苏州金刚防火钢型材系统有限公司 | Steel-plastic high-flame-retardant fireproof door and window profile and manufacturing method thereof |
| CN105733133A (en) * | 2016-04-25 | 2016-07-06 | 浙江尤夫高新纤维股份有限公司 | Flame-retarding and smoke-suppressing polyvinyl chloride membrane structure material |
| CN107540988A (en) * | 2017-10-12 | 2018-01-05 | 钱艺博 | One kind suppression cigarette base polyvinyl chloride material and preparation method thereof |
| CN109593243A (en) * | 2018-12-07 | 2019-04-09 | 赢胜节能集团有限公司 | A kind of low cigarette heat-insulating material and preparation method thereof |
| CN111662538A (en) * | 2020-06-15 | 2020-09-15 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
| CN111748179A (en) * | 2020-06-15 | 2020-10-09 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
-
2000
- 2000-02-01 CN CN 00100709 patent/CN1307071A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017311A (en) * | 2014-06-21 | 2014-09-03 | 苏州金刚防火钢型材系统有限公司 | Steel-plastic high-flame-retardant fireproof door and window profile and manufacturing method thereof |
| CN105733133A (en) * | 2016-04-25 | 2016-07-06 | 浙江尤夫高新纤维股份有限公司 | Flame-retarding and smoke-suppressing polyvinyl chloride membrane structure material |
| CN107540988A (en) * | 2017-10-12 | 2018-01-05 | 钱艺博 | One kind suppression cigarette base polyvinyl chloride material and preparation method thereof |
| CN109593243A (en) * | 2018-12-07 | 2019-04-09 | 赢胜节能集团有限公司 | A kind of low cigarette heat-insulating material and preparation method thereof |
| CN111662538A (en) * | 2020-06-15 | 2020-09-15 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
| CN111748179A (en) * | 2020-06-15 | 2020-10-09 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
| CN111662538B (en) * | 2020-06-15 | 2022-04-19 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
| CN111748179B (en) * | 2020-06-15 | 2022-04-19 | 金发科技股份有限公司 | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof |
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