CN1389514A - Fire-retardant thermoplastic resin composite and its application - Google Patents
Fire-retardant thermoplastic resin composite and its application Download PDFInfo
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- CN1389514A CN1389514A CN 01118649 CN01118649A CN1389514A CN 1389514 A CN1389514 A CN 1389514A CN 01118649 CN01118649 CN 01118649 CN 01118649 A CN01118649 A CN 01118649A CN 1389514 A CN1389514 A CN 1389514A
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Abstract
The invention refers to a kind of combustion-preventing thermoplastic resin combination which includes: (a) the thermoplastic rosin; (b) the compound of phenolic aldehyde resin containing the nitrous mixed ring and phosphor and which serves the combustion-preventing agent. Because the invention's combustion-prevention thermoplastic resin combinstion doesn't contain the halogen and has especially fine combustion-prevention quality and high hot-resistant quality, it can be used to manufacture the things of the electronic machine, the electric products, the components and parts of the automobile, and so on.
Description
The present invention relates to a kind of fire-retardant thermoplastic resin composite, it comprises: (a) thermoplastic resin, and (b) as the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of fire retardant.
Thermoplastic resin is widely used in various fields, but thermoplastic resin has a very big shortcoming, that is easy firing and dripping hangs down when meeting fire.In order to overcome these shortcomings, normally in thermoplastic resin, add fire retardant to improve its inflammableness.Yet, these additives can bring additional problem again during burning, for example, if when containing halogenide such as bromine compounds in the fire retardant that is added, when burning and high temperature, easily discharge deleterious flue dust and gas, for example the aromatics of high bromine content can produce the bromination furans and the Xiuization dioxin compound of severe toxicity when burning and high temperature, badly influences people's health and environment.Even not burned, use the waste of these fire retardants in a large number, its recovery and handle environment and Yan Junhui throws into question.Therefore, for thermoplastic resin, the utmost point need be developed a kind of not halogen-containing fire retardant.And in the present not halogen-containing flame retardant system of developing, what attract most attention is that phosphorus is and the nitrogen flame retardant.
Phosphorus series compound is as the fire retardant of thermoplastic resin, and known have No. 491,986, European patent and No. 685,518, European patent and a USP5, and 733,957, it discloses use aromatic phosphoric acid ester oligomer as fire retardant.Use aromatic phosphoric acid ester oligomer is disclosed for Japanese patent laid-open 10-60160 number as fire retardant and cooperate other fire retardant or flame retardant such as silicon compound.Japanese patent laid-open 10-251497 number and spy open flat 11-21458 and then disclose use red phosphorus and small molecules phosphate compound respectively as fire retardant.In addition, the phosphate compound that uses as phenolic aldehyde is then disclosed as fire retardant for Japanese kokai publication hei 7-292050 number.And USP 4,278,591 and 5,618,865 items disclose and have used derived from the compound nitrogen series of the trimeric cyanamide fire retardant as thermoplastic resin.In addition, the flame retardant system that more thermoplastic resin is arranged then is in conjunction with phosphorus system and compound nitrogen series, so as to strengthening its flame retardant effect and improving thermal properties and melt-processed character, as USP5,814,690, Japanese kokai publication hei 10-175,985 and the spy open flat 9-296120.
On the basis of existing technology, the object of the present invention is to provide a kind of new fire-retardant thermoplastic resin composite, it is not halogen-containing, can improve the flame-retardant nature of thermoplastic resin, processibility, physical properties and the mechanical properties of resin kept or promoted, good especially flame retardant resistance and high heat resistance had.
A further object of the present invention is to provide described composition, in the application of making electric machine articles for use, e-machine articles for use, medical machine articles for use, Automobile Products, mechanical aspects.
A kind of fire-retardant thermoplastic resin composite of the present invention, it comprises: (a) thermoplastic resin, and (b) as the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of fire retardant.
Thermoplastic resin among the present invention is meant the resin that has flowability and machine-shaping according to this after the heating.The specific examples of thermoplastic resin of the present invention comprises: polyester, as polyethylene terephthalate (PET), polybutylene terephthalate (PBT); The liquid crystal type polyester; Wholly aromatic polyester; Polycarbonate; Polymeric amide; Fully aromatic polyamide; Polyimide; Polystyrene; Polyphenylene oxide; Polyethersulfone; Polysulfones; Acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer etc.These resins can be separately or are used with two or more the form of mixture.
As the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of fire retardant, it is characterized by this compound and have following repeating unit in the fire-retardant thermoplastic resin composite of the present invention:
R wherein
1And R
2For identical or different, and represent H, C
1-20Alkyl, phenoxy group, phenyl (C
1-4Stretch alkyl), the phenyl (C that replaces through hydroxyl on the phenyl ring
1-4Stretch alkyl);
R
aFor can be through C
1-4Alkyl replaces stretch phenyl, singly-bound,
Or-C (R
3) R in the H-[formula
3Be H, C
1-4Alkyl, CH
2=CH-, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl].
(b) be selected from following formula (b1) or (b2) the phosphorous repeating unit of any one
R wherein
1, R
2And R
aDescribed as defined above, and
X is Sauerstoffatom or electron pair,
T is Sauerstoffatom or chemical bond
R ' and R " can be identical or different, and be C
1-18Alkyl, phenyl or phenyl (C
1-6) alkyl, or
It can close and be expressed as
R wherein
iAnd R
jFor identical or different, and be hydrogen or C
1-18Alkyl; And
Wherein each substituent definition as mentioned above.
Wherein
R
bBe H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4Alkyl phenyl or the C that replaces through hydroxyl
1-4Alkyl phenyl;
R
cBe NH
2, OH, C
1-10Alkyl, phenyl or benzoyl.
R among the present invention
aAnd R
bRepresented " C
1-4Alkyl " reach " C
1-4Alkyl phenyl " or " C that replaces through hydroxyl on the phenyl ring
1-4Alkyl phenyl " in C
1-4The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, second butyl, tributyl etc.
R ' and R " represented " phenyl (C
1-6) alkyl " and in C
1-6The example of alkyl comprises above-mentioned C
1-4The cited person of alkyl reaches amyl group, hexyl etc.
R
cShown C
1-10The example of alkyl comprises above-mentioned C
1-6The described person of alkyl reaches heptyl, octyl group, nonyl, decyl etc.
R ' and R " represented C
1-18The example of alkyl comprises above-mentioned C
1-10The cited person of alkyl reaches 11 carbon backs, ten dicarbonyls, 13 carbon backs, 14 carbon backs, 15 carbon backs, 16 carbon backs, 17 carbon backs, 18 carbon backs etc.
R
1And R
2Represented C
1-20The example of alkyl comprises above-mentioned C
1-18The cited person of alkyl reaches 19 carbon backs, 20 carbon backs etc.
Repeating unit (a) in the phosphorous polymer with phenolic structure of the present invention is derived from phenolic resinoid, for example the polyphenol shown in resol, cresol novolac resin, xylenol resol, phenol resol, isobutyl-phenol resol, nonyl phenol resol, bisphenol A phenolic resin, bisphenol F phenolic resin, bis-phenol resol, melamine resin etc. and the following formula:
R in the formula
1And R
2Described as defined above, and Z is 1-10.
Repeating unit (b1) in the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of the present invention is the reaction product derived from the compound of above-mentioned phenolic resinoid and the reaction of the phosphorated compound shown in following formula gained:
W represents halogen or OR in the formula " ' (R in the formula " ' expression alkyl, aryl or aralkyl), the foregoing definition of the implication of other symbol.
Repeating unit (b2) in the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of the present invention is the reaction product derived from the compound of above-mentioned phenolic resinoid and the reaction of the P contained compound shown in following formula gained:
W represents halogen or OR in the formula " ' (R in the formula " ' expression alkyl, aryl or aralkyl), the foregoing definition of the implication of other symbol.
Repeating unit (c) in the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of the present invention is derived from trimeric cyanamide (melamines) compound, cyanuric acid (cyanuric acid) compound and guanamines class (guanamine) compound, for example benzene guanidine (bcnzoquanamine) etc.
W represents halogen atom in the formula, or aforementioned
Shown P contained compound also can be following formula: compound:
Hal represents halogen atom in the formula, the foregoing definition of the implication of other symbol.
Preparation method as the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of fire retardant among the present invention is: can make phenolic resinoid and at least a compound reaction that is selected from melamine class, cyanuric acid class and guanamines compounds earlier, formation contains nitrogenous heterocyclic novolac polymer, again with formula (I) or (II) represented P contained compound reaction.
Above-mentioned phenolic resinoid is the known reaction of polymer arts with the reaction that is selected from least a compound of melamine class, cyanuric acid class and guanamines compounds, does not repeat them here.
Formed contain nitrogenous heterocyclic novolac polymer and formula (I) or (II) shown in the reaction of P contained compound, can enumerate following two kinds of methods at this:
Method A: dehalogenation hydrochlorate method (when W represents halogen in formula (I) or the P contained compound (II))
Make and contain nitrogenous heterocyclic novolac polymer and formula (I) or P contained compound (II) 100 to 300 ℃ temperature of reaction, preferably 120 to 260 ℃ temperature of reaction and in the reaction pressure of 0.1-600mmHg, preferably under 0.1 to 100mmHg reaction pressure, reacted 0.5 to 20 hour, be preferably 1 to 15 hour.
In the superincumbent reaction, the P contained compound reactive functional group base (that is W yl) with respect to 1 mole uses the hydroxyl-functional base of 0.1 to 20 mole resol, is preferably 0.5 to 15 mole hydroxyl-functional base.
Above-mentioned reaction can be reacted under the condition of catalyzer existence or catalyst-free.But add catalyzer and can promote its speed of reaction effectively.The example of suitable catalyzer comprises aluminum chloride, magnesium chloride, aluminium hydroxide, magnesium hydroxide, lead chloride (I) etc.
The usage quantity of catalyzer be the reactant gross weight 0.001 to 5wt%, be preferably 0.01 to 2wt%.
Above-mentioned reaction can be carried out in solvent or under solvent-free condition.Solvent can use any solvent, as long as reaction is had no adverse effects.The example of spendable solvent is for example toluene, dimethylbenzene, vinyl-acetic ester, tetrahydrofuran (THF) etc.
Method B: ester-interchange method (when W in formula (I) or the P contained compound (II) represents OR " ' time)
Make and contain nitrogenous heterocyclic novolac polymer and formula (I) or P contained compound (II) 100 to 300 ℃ temperature of reaction, preferably 120 to 260 ℃ temperature of reaction and in 0.1 to 600mmHg reaction pressure, preferably under 0.1 to 100mmHg reaction pressure, reacted 0.5 to 20 hour, and be preferably 1 to 15 hour.
In above-mentioned reaction, the P contained compound reactive functional group base (that is W yl) with respect to 1 mole uses the hydroxyl-functional base of 0.1 to 20 mole resol, is preferably 0.5 to 15 mole hydroxyl-functional base.
Above-mentioned reaction can be reacted under the condition of catalyzer existence or catalyst-free.But add catalyzer and can promote its speed of reaction effectively.The example of suitable catalyzer comprises aluminum chloride, magnesium chloride, lead chloride (I), triethylamine, four titanium butoxide, yellow soda ash, salt of wormwood, zinc acetate etc.
The catalyzer usage quantity be the reactant gross weight 0.001 to 5wt%, be preferably 0.01 to 2wt%.
Above-mentioned reaction can be carried out in solvent or under solvent-free condition.Solvent can use any solvent, as long as reaction is had no adverse effects.The example of spendable solvent is for example toluene, dimethylbenzene, vinyl-acetic ester, tetrahydrofuran (THF) etc.
In fire-retardant thermoplastic resin composite of the present invention, consumption as the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus (b) of fire retardant, with respect to 100 parts by weight of thermoplastic resin (a), use the compound (b) of 1 to 100 weight part, preferred 2 to 85 weight parts that use reach and more preferably use 5 to 70 weight parts.Because as the consumption of compound (b) very little, then can't reach desired flame-retarding characteristic; If consumption is too many, then forming process and the mechanical properties to thermoplastic resin has detrimentally affect.
Fire-retardant thermoplastic resin composite of the present invention, except The compounds of this invention (b), still can add known not halogen-containing fire retardant, for example trimeric cyanamide phosphoric acid ester (melaminephosphate), ammonium polyphosphate (ammonium polyphosphate), tricyanic acid-melamine mixture and the P contained compound that is shown below:
J is 0 to 10 integer in the formula, Ar
1To Ar
4Can be identical or different, and for phenyl, phenolic group, be substituted phenyl or be substituted phenolic group; Q for do not replace or be substituted stretch phenyl stretch xenyl or following formula shown in group:
In the formula G be-O-,-S-,-SO
2-,-C (CH
3)
2-,-CH
2-or-CH (Ph)-, R
11-R
4For identical or different, and expression hydrogen or C
1-4Alkyl.
In fire-retardant thermoplastic resin composite of the present invention, also can add metal oxide or metal hydroxides, so as to its flame-retarding characteristic of further raising.The example comprises for example aluminum oxide, magnesium oxide, magnesium hydroxide, aluminium hydroxide, lead hydroxide (I) etc.
The usage quantity of this metal oxide or metal hydroxides with respect in 100 weight part thermoplastic resin compositions, is used 0 to 100 weight part, is preferably 0.1 to 80 weight part, more preferably 2 to 70 weight parts.
In fire-retardant thermoplastic resin composite of the present invention, also can add the known additive that is customarily used among the thermoplastic resin composition, only otherwise halogen-containing getting final product.These additives comprise for example thermo-stabilizer, antioxidant, UV light absorber, plasticizer, releasing agent, dyestuff, pigment and tinting material etc.
Be the physical strength of strengthening fire-retardant thermoplastic resin composite of the present invention and rigidity etc., can in composition of the present invention, add fibrous or granulous inorganic filling material, for example glass fibre, sheet glass, granulated glass sphere, carbon fiber, steel fiber, aromatic polyamide fibre (aramide), barium sulfate, mica, talcum powder etc.
Thermoplastic polyester composition of the present invention can known forming method such as method such as injection molding, extrusion moulding, compression moulding, is made into electrical appliances such as junctor, rly., switch, sheating material, transformer material, coil method, appliance and electronic, medical machine articles for use, Automobile Products, mechanical machine articles for use etc.
As from the foregoing, fire-retardant thermoplastic resin composite of the present invention is not because halogen-containing and have special excellent flame-retardant performance matter and a high heat resistance, and can be in order to make e-machine articles for use, electric product articles for use, automobile spare part articles for use etc.
Fire-retardant thermoplastic resin composite of the present invention has the flame-retarding characteristic standard that reaches UV94V-O and has high heat resistance owing to not halogen-containing and antimonous oxide.Fire-retardant thermoplastic resin composite of the present invention has the hanging low property of resin and the fire retardant of improvement separates out, and has kept the workability of thermoplastic resin and good physical property.
Illustrate in greater detail the present invention below with reference to synthesis example and embodiment, but these synthesis examples and embodiment are only in order to explanation the present invention but not in order to limit the scope of the invention.
In the following example, used following commercially available prod:
P contained compound A: produced by Akzo Nobel chemical company, sell with trade(brand)name PhosflexTPP, its structural formula is as follows:
P contained compound B: being produced by Akzo Nobel chemical company, is that PhosflexCDP sells with commodity, and its structural formula is as follows:
P contained compound C: electrochemical company is produced by the Japanese rising sun, is that FP-6000 sells with commodity, and its structural formula is as follows:
Synthesis example 1: phenol-formaldehyde A synthetic that contains nitrogen heterocyclic ring and phosphorus
Have in 3 liter of four neck flask reaction vessel of temperature and pressure-controlling and indicating unit one, add phenol 470 grams, 37.4% formalin 200 grams, water 174 grams, triethylamine 3.8 grams and trimeric cyanamide 50 grams, 80 ℃ of following reactions are warming up to 120 ℃ of following reactions 1 hour, reclaim unreacted phenol and water after 2 hours after, promptly get and contain nitrogenous heterocyclic resol.Have in 3 liter of four neck flask reaction vessel of temperature and pressure-controlling and indicating unit one, what add 500 grams aforementionedly contains nitrogenous heterocyclic resol, the Magnesium Chloride Anhydrous of the P contained compound A of 750 grams and 1.6 grams, be warming up to 200 ℃, and be decompressed to 1mmHg, at 6 hours internal reactions, promptly get the phenol-formaldehyde A that contains nitrogen heterocyclic ring and phosphorus after the reaction, phosphorus content 6.8wt%, nitrogen content 4.5wt%.
Synthesis example 2: bakelite B synthetic that contains nitrogen heterocyclic ring and phosphorus
According to the same procedure of synthesis example 1, but substitute trimeric cyanamide, substitute P contained compound A, make the bakelite B that contains nitrogen heterocyclic ring and phosphorus with P contained compound B with benzo guanamine (benzoquanamine).
Embodiment 1 to 6 and comparative example 1 to 4
After composition as shown in table 1 below mixed with listed amount, mix 260 ℃ of fusions with the single screw extrusion machine of 10 millimeters of diameters, resulting composition its flame retardant resistance, heat-drawn wire and fire retardant is after measured separated out check, and its result is as shown in table 1.
Table 1
Annotate: 1.PBT: polybutylene terephthalate, artificial resin factory in Changchun sells with commodity PBT 1100-2116, IV-0.94dl/g.
| Thermoplastic resin is formed | The result | |||||
| Thermoplastic resin (100 weight part) | P contained compound (weight part) | Flame retardant resistance | Heat-drawn wire | Fire retardant is separated out check | ||
| ? ????UL94 | ? ??(℃) | Surface phosphorus amount is than (before the thermal treatment/thermal treatment after) | ||||
| Embodiment 1 | ????PBT 1 | ??A-25 | ????V-0 | ????60 | ????1.00 | |
| Embodiment 2 | ????PBT 1 | ??B-25 | ????V-0 | ????59 | ????1.01 | |
| Embodiment 3 | ????PBT 1 | ??A-15 | ????C-15 | ????V-0 | ????60 | ????1.35 |
| Embodiment 4 | ????PC 2 | ??A-25 | ????V-0 | ????134 | ????1.01 | |
| Embodiment 5 | ????PC 2/ABS 3(75/25 weight ratio) | ??A-25 | ????V-0 | ????98 | ????1.00 | |
| Embodiment 6 | ????PC 2/ABS 3(75/25 weight ratio) | ??B-25 | ????V-0 | ????101 | ????1.00 | |
| Comparative example 1 | ????PBT 1 | ???- | ????A-30 | ????V-0 | ????55 | ????2.00 |
| Comparative example 2 | ????PC 2 | ???- | ????B-30 | ????V-0 | ????131 | ????1.85 |
| Comparative example 3 | ????PC 2/ABS 3(75/25 weight ratio) | ???- | ????A-30 | ????V-0 | ????86 | ????1.85 |
| Comparative example 4 | ????PC 2/ABS 3(75/25 weight ratio) | ???- | ??????- | Burning | ????86 | ?????- |
2.PC: the bisphenol type polycarbonate, sell with trade(brand)name EIPILONS-200 by Mitsubishi engineering plastics company.
3.ABS: acrylonitrile-butadiene-styrene copolymer.Sell with trade(brand)name TOYOLAK-500 by Japanese Toray company.
4. flame retardant resistance: test according to the UL-94 method.
5. heat-drawn wire: make test piece according to ASTM-638, under the 1.82MPa loading, measure.
6. fire retardant is separated out: test piece was handled in 100 ℃ of baking ovens after 24 hours, measured test piece surface phosphorus amount with fluorescent X-ray.
Claims (11)
1. fire-retardant thermoplastic resin composite, it comprises: (a) thermoplastic resin and (b) as the phenolic resin compound that contains nitrogen heterocyclic ring and phosphorus of fire retardant, wherein this contains the phenolic resin compound of nitrogen heterocyclic ring and phosphorus, it is characterized by to have following repeating unit:
R wherein
1And R
2For identical or different and represent H, C
1-20The phenyl that replaces through hydroxyl on alkyl, phenoxy group, phenyl, the phenyl ring,
R
aFor through C
1-4Alkyl replaces stretch phenyl, singly-bound,
Or-C (R
3) H-, R in the formula
3Be H, C
1-4Alkyl, CH
2=CH-, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl;
(b) be selected from following formula (b1) or (b2) the phosphorous repeating unit of any one
R wherein
1And R
2For identical or different and represent H, C
1-20The phenyl that replaces through hydroxyl on alkyl, phenoxy group, phenyl, the phenyl ring,
R
aFor through C
1-4Alkyl replaces stretch phenyl, singly-bound,
Or-C (R
3) H-, R in the formula
3Be H, C
1-4Alkyl, CH
2=CH-, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl; And
X is Sauerstoffatom or electron pair,
T is Sauerstoffatom or chemical bond,
R ' and R " can be identical or different and be C
1-18Alkyl, phenyl or phenyl C
1-6Alkyl or
Can close and be expressed as
R
iAnd R
jFor identical or different and be hydrogen or C
1-18Alkyl; And
R wherein
1And R
2For identical or different and represent H, C
1-20The phenyl that replaces through hydroxyl on alkyl, phenoxy group, phenyl, the phenyl ring,
R
aFor through C
1-4Alkyl replaces stretch phenyl, singly-bound,
Or-C (R
3) H-, R in the formula
3Be H, C
1-4Alkyl, CH
2=CH-, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl; And
X is Sauerstoffatom or electron pair,
T is Sauerstoffatom or chemical bond,
R ' and R " can be identical or different and be C
1-18Alkyl, phenyl or phenyl C
1-6Alkyl or
Can close and be expressed as
R
iAnd R
jFor identical or different and be hydrogen or C
1-18Alkyl; And
Wherein
R
bBe H, C
1-4Alkyl, CH
2=CH, phenyl, furyl, C
1-4The C that replaces through hydroxyl on alkyl phenyl or the phenyl ring
1-4Alkyl phenyl;
R
cBe NH
2, OH, C
1-10Alkyl, phenyl or benzoyl.
2. composition as claimed in claim 1 wherein uses 1 to 100 weight part composition (b) to 100 weight part compositions (a).
3. composition as claimed in claim 1, wherein said thermoplastic resin are selected from the cohort that polyester, liquid crystal type polyester, Wholly aromatic polyester, polycarbonate, polymeric amide, fully aromatic polyamide, polyimide, polystyrene, polyphenylene oxide, polyethersulfone, polysulfones and acrylonitrile-butadiene-styrene copolymer are become.
4. composition as claimed in claim 1, it further contains other not halogen-containing fire retardant.
5. composition as claimed in claim 1, it further contains granular or fibrous inorganic filling material.
6. composition as claimed in claim 1, wherein said thermoplastic resin are polyester.
7. composition as claimed in claim 6, wherein said polyester are polybutylene terephthalate and/or polyethylene terephthalate.
8. composition as claimed in claim 1, wherein said thermoplastic resin are polycarbonate.
9. composition as claimed in claim 1, wherein said thermoplastic resin are acrylonitrile-butadiene-styrene copolymer.
10. composition as claimed in claim 1, wherein thermoplastic resin is the mixture of polycarbonate and acrylonitrile-butadiene-styrene copolymer.
11. composition as claimed in claim 1 is in the application of making electric machine articles for use, e-machine articles for use, medical machine articles for use, Automobile Products, mechanical aspects.
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|---|---|---|---|
| CNB011186496A CN1164678C (en) | 2001-06-06 | 2001-06-06 | Fire-retardant thermoplastic resin composite and its application |
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|---|---|---|---|
| CNB011186496A CN1164678C (en) | 2001-06-06 | 2001-06-06 | Fire-retardant thermoplastic resin composite and its application |
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| Publication Number | Publication Date |
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Family
ID=4663339
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153107B (en) * | 2006-09-28 | 2011-02-16 | 长春人造树脂厂股份有限公司 | Fire retardant resin composition |
-
2001
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153107B (en) * | 2006-09-28 | 2011-02-16 | 长春人造树脂厂股份有限公司 | Fire retardant resin composition |
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| CN1164678C (en) | 2004-09-01 |
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