CN1082527C - Flame-retarding styrene-series resin compositions - Google Patents
Flame-retarding styrene-series resin compositions Download PDFInfo
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- CN1082527C CN1082527C CN98102518A CN98102518A CN1082527C CN 1082527 C CN1082527 C CN 1082527C CN 98102518 A CN98102518 A CN 98102518A CN 98102518 A CN98102518 A CN 98102518A CN 1082527 C CN1082527 C CN 1082527C
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Abstract
The present invention provides a flame retardancy styrene resin composition. The flame retardancy styrene resin composition comprises the following components: (A) 100 parts by weight of styrene resins which are modified by rubber, (B) 1 to 15 parts by weight of fire-retardant additives and (C) 1 to 10 parts by weight of rosin substances. The flame retardancy styrene resin composition can greatly enhance melting drip flame retardancy under the conditions without reducing impact resistance performance and heat resistance performance.
Description
The invention relates to a kind of flame-retarded phenylethylene series resin composition with excellent heat resistance and shock-resistance.
Press, phenylethylene resin series is owing to have excellent in impact resistance and thermotolerance, and its processibility is good again, has therefore been used widely on various uses such as auto parts, household appliance components and OA machine parts so far; Yet, limited the scope of its use owing to the inflammable characteristic of phenylethylene resin series; The phenylethylene resin series of acrylonitrile-butadiene-styrene (ABS) (being ABS) resin etc. has the characteristic of difficult burning in order for example to make, the method that extensively adopts is that a large amount of halogen of interpolation is an incombustible agent at present, but known to this case contriver etc., the heavy addition halogen is that incombustible agent can cause damage by fume when fire.
Again in invention cases such as day disclosure communique flat 8-120162 number and flat 9-183886 number, disclose a kind of rubber-modified phenylethylene resin series that contains the particular configuration factor, and the resin combination that contains special organophosphorus incombustible agent, known to only waiting with regard to this case contriver, a large amount of interpolation organophosphorus incombustible agent in constituent can cause resin thermotolerance, shock-resistance significantly to reduce.
On the other hand, in order to give the method for styrene-series resin compositions flame retardancy, still there be a kind of being established in together to drip with spark after making the resin fusion of having caught fire, to prevent that resin from prolonging the viewpoint of burning, under this viewpoint, it is a kind of under the situation that does not lower its rigidity and shock-resistance to give resin, and order catches fire that the resin at place melts and the character that drops easily (this character be designated hereinafter simply as fusion drip flame retardancy).But give and technology still is not fully in the flame retardancy that at present in fact is established in this viewpoint, the fusion that therefore how the to improve resin flame retardancy of dripping is the problem of demanding urgently breaking through for the field of flame-retarded phenylethylene series resin composition.
The present invention is in order to reduce the consumption that causes thermotolerance and shock-resistance to reduce the incombustible agent at reason place, except that adding the incombustible agent that also lacks than known technology, add a certain amount of rosin series material in the concurrent present flame-retarded phenylethylene series resin composition, can significantly reduce the addition of incombustible agent, and keep rubber-modified phenylethylene resin series thermotolerance and shock-resistance originally, the fusion that more can significantly the improve resin flame retardancy of dripping based on this discovery, is finished the present invention finally.
So main purpose of the present invention is to provide a kind of under the prerequisite that does not lower thermotolerance and shock-resistance, significantly improve the drip styrene-series resin compositions of flame retardancy of fusion.
That is the present invention is characterized in: this flame-retarded phenylethylene series resin composition includes:
The rubber-modified phenylethylene resin series of A 100 weight parts,
The incombustible agent of B 1～15 weight part, and,
The rosin based material of C 1～10 weight part.
＜A composition 〉
The A composition is rubber-modified phenylethylene resin series, rubber-modified phenylethylene resin series used in the present invention includes: use the polystyrene graft resin separately, and mix two kinds of situations such as use with styrenic with the polystyrene graft resin.Wherein, the polystyrene graft resin usually can be in the presence of rubber-like elastic body, add styrenic monomers and be less than styrenic monomers and can with the monomer of the necessary amount of this styrenic monomers copolymerization, and the condition of giving both copolymerizations makes it copolymerization and gets it, the rubber-modified phenylethylene resin series of gained has dispersive rubber-like elastic body particle in the matrix of its styrenic according to this.
Above-mentioned rubber-like elastic body means, glass transfer temperature is at sub-zero polymkeric substance, its object lesson has: butadiene-based rubber, ethylene-propylene are rubber (ethylene-propylene that for example is called for short EPDM is the binary polymerization body of rubber), and acrylic ester rubber etc.; And aforementioned styrenic monomers can be the styrene derivatives that vinylbenzene and nuclear and side chain are substituted, and above-mentioned substituting group can be low alkyl group and halogen, and lower alkyl is to refer in particular to contain 1～4 carbon atom person, and halogen is preferable with chlorine and bromine especially; Therefore, styrenic monomers of the present invention, its concrete example has: vinylbenzene, alpha-methyl styrene, neighbour-vinyl toluene, to monochlorostyrene, 2,4,6-tribromo-benzene ethene etc. wherein, are preferable with vinylbenzene and alpha-methyl styrene particularly.Above-mentioned copolymerizable monomer can be for example: vinyl cyanide, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, maleic anhydride, N-phenylmaleimide, wherein, be preferable particularly with vinyl cyanide and N-phenylmaleimide.
Being used in the ratio of making the rubber-like elastic body in the polystyrene graft resin is 6～80% of graftomer weight, and all the other are styrenic monomers and copolymerizable monomer.In the present invention, can use the graftomer of making, also can be as above-mentioned, the styrenic that does not contain rubber-like elastic body mixes use, and in rubber-modified phenylethylene resin series, the ratio of rubber-like elastic body is good with 5～25 weight %, when the content of rubber-like elastic body is lower than 5 weight %, the effect that can't manifest shock-resistance, if when surpassing 25 weight %, the fusion of the constituent flame retardancy of dripping can reduce.And with the balance between shock-resistance and appearance, in the dispersion particle diameter of rubber-like elastic body of the present invention, its weight average particle diameter serves as appropriate with 0.1～5 μ m, when disperseing particle diameter to be lower than 0.1 μ m, can not represent shock-resistance, if when surpassing 5 μ m, then impact and surface luster will significantly be reduced, aforementioned weight average particle diameter is that TEM is measured.
The present invention can adopt block polymerization, solution polymerization process, emulsion polymerization method, suspension polymerization when graft polymerization, and the combination of above-mentioned polymerization, for example: carry out methods such as suspension polymerization after the block polymerization again.The rubber-modified phenylethylene resin series of gained has according to this: rubber-modified polystyrene, ABS resin (acrylonitrile-butadiene-styrene (ABS)), AES resin (are vinyl cyanide-ethene basically, propylene-styrene), AAS resin (being acrylonitrile-acrylate-styrene basically), and MBS resin (being methyl methacrylate-butadiene-styrene basically) etc., with regard to shock-resistance and thermotolerance, be preferable with ABS resin especially.
＜B composition 〉
B composition of the present invention is an incombustible agent, and it can be the phosphorus series flame-resisting agent and halogen is an incombustible agent, wherein, with the phosphorus series flame-resisting agent is preferable, above-mentioned phosphorus series flame-resisting agent is especially with the aromatic phosphoric ester monomer, and the aromatic phosphoric ester condensation body is good, also can adopt the mixture of above-mentioned composition; B composition of the present invention is more so that with having the aromatic phosphoric ester shown in the following structural 1 for better.
In the aforementioned structural formula 1, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, respectively be independent, it can be hydrogen atom or carbonatoms at 1～4 alkyl or hydroxy, X is the above organic radicals of two valencys, n is the integer more than 0 or 0.
The above organic radical of above-mentioned two valencys is alkylidene group and nuclear phenols residue etc., wherein again to have 1～4 carbon atom person for preferable, phenylene for example, its concrete example are then with Resorcinol, Resorcinol, dihydroxyphenyl propane, Bisphenol F etc., and the residue of aforementioned derivative is preferable.
Can be used in concrete fragrant family phosphoric acid ester of the present invention for example is: triphenyl, trimethylphenol phosphate, three (xylyl) phosphoric acid ester, the cresylol diphenyl phosphoester, the xylyl diphenyl phosphoester, three (2, the 6-dimethyl benzene) phosphoric acid ester, two (2, the 6-xylyl) phenyl phosphate ester, single (2, the 6-dimethyl benzene) diphenyl phosphoester, Resorcinol two (diphenyl phosphoester), Resorcinol two (2,6-xylyl phosphoric acid ester), dihydroxyphenyl propane two (2,6-xylyl phosphoric acid ester), dihydroxyphenyl propane two (diphenyl phosphoester), Resorcinol two (2,6-xylyl phosphoric acid ester), Resorcinol two (2-tolyl phosphoric acid ester), two phenyl two (diphenyl phosphoester) etc. and composition thereof, with regard to thermotolerance, You Yisan (2, the 6-xylyl) phosphoric acid ester, and Resorcinol two (2,6-xylyl phosphoric acid ester) is good.
The spendable halogen of the present invention is the object lesson of incombustible agent, can be divided into following six classes:
One, brominated phosphoric acid salt: three (tribromo neo-pentyl) phosphoric acid ester etc. for example.
Two, bromination ring-type fats: hexabromocyclododecane etc. for example.
Three, halogenation phenols: as tetrabromo-bisphenol.
Four, the derivative of tetrabromo-bisphenol: tetrabromobisphenol two (2,3-dibromo propyl ether) etc. for example.
Five, bromination epoxy low-grade polymer class: low-grade polymer of bromination phenols and epichlorohydrin etc. for example.
Six, brominated diphenyl base ethers: decabrominated dipheny base ether etc. for example.
The addition of B composition is the A composition with respect to 100 weight parts among the present invention, must be good with 3～10 weight parts especially between 1～15 weight part; When the addition of B composition is lower than 1 weight part, can't make the flame retardancy of resin combination reach remarkable and significant effect,, not only can undermine original thermotolerance of resin and impact strength if when the addition of B composition is higher than 15 weight parts, also can cause the raising of cost, so undesirable.
＜C composition 〉
The C composition that the present invention uses is the rosin series material, it can be: natural rosins such as gum resin, tar rosin and wood rosin, or the modified rosin of nilox resin that above-mentioned natural rosin disproportionation, hydrogenation, dehydrogenation are formed, staybelite, westvaco rosin etc., and the rosin ester that these rosin and alkylol cpd and/or epoxy compoundss constituted etc., above-mentioned modified rosin also comprises these rosin distillations is refining and get.Can in each group and/or each group, get one or more during use separately and mix use; For the present invention, be to have the carboxyl of natural rosin, nilox resin, staybelite, westvaco rosin with use (COOH) person is for good.
The alcoholization that can be used for the formation of rosin ester contains thing and without particular limitation, it can use various known alcohols, for example: monovalent alcohol, saturated and unsaturated various known divalent alcohol, or in divalent alcohol, trivalent alcohol and the polyether glycol etc. of dihydroxyphenyl propane additional ring oxidative ethane or propylene oxide gained, above-mentioned alkylol cpd can and/or can be used alone between each group in each group, perhaps makes up two or more uses; Wherein, the object lesson of monovalent alcohol has: methyl alcohol, 2-Ethylhexyl Alcohol, hexalin, toluene alcohol etc., and saturated and unsaturated divalent alcohol, and the divalent alcohol of additional oxyethylene of two A or propylene oxide gained, for example: ethylene glycol, Diethylene Glycol, triethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentane diol, 3-methyl isophthalic acid, 5-pentane diol, 1,6-hexane diol, octane glycol, 1,4-butynediol and dipropylene glycol etc.; And trivalent alcohol can be for example: glycerine (being glycerol), trimethylolethane and TriMethylolPropane(TMP) etc.; Tetravalence alcohol then can be: the isoamyl tetrol, and polyether glycol can be for example: the polymkeric substance of oxyethane, propylene oxide and tetrahydrofuran (THF) etc. or multipolymer etc.
Can be used for the epoxide of formation of rosin ester and without particular limitation, it can use various known monobasic epoxy compoundss or multivalence epoxy compounds etc., and above-mentioned monobasic epoxy compounds can be given an example as the monocarboxylic acid glycidyl esters class of the fragrant glycidyl ether of the alkyl glycidyl base ether of N-butyl glycidyl base ether and 2-ethylhexyl diglycidyl ether etc., phenylglycidyl ether etc., koch's acid glycidyl esters etc., Styrene oxide 98min., cyclohexene oxide etc.Above-mentioned binary epoxy compounds can give an example as:
One, non-annularity aliphatics diglycidyl ether class: for example the ethylene glycol bisthioglycolate glycidyl ether,
Diethylene Glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyoxyethylene glycol
Diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol 2-glycidyl
Base ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, new
Pentanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether etc.
Two, aromatic series or annular aliphatic diglycidyl ether class: for example 2, two (the 4-hydroxyls of 2-
Phenyl) propane diglycidyl ether, two (4-hydroxy phenyl) methane 2-glycidyl
Base ether, two (4-hydroxy phenyl) the ethane diglycidyl ether, 2 of 1-, the two (hydroxyls of 2-
The basic ring hexane) propane diglycidyl ether, 3,3 ', 5,5 '-tetramethyl--4,4
'-dihydroxybiphenyl base diglycidyl ether, 2,2-two [4-beta-hydroxy handle oxygen base phenyl]
Propane diglycidyl ether etc.
Three, annular aliphatic ring-type ethylene oxide: for example 3,4-epoxycyclohexyl-3,4-epoxy hexamethylene
Alkane carbonic ether, ethene basic ring (epidioxy hexane) etc.
And the triatomic ring oxygen compound can have for example: trihydroxy methyl propane triglycidyl group ether, trihydroxy-ethyl chlorinated isocyanurates triglycidyl group ether etc.; And the tetra-atomic ring oxygen compound can be for example: 1,1,2, and 2-four (4-hydroxy phenyl) ethane four glycidyl group ether; Other polyepoxides still has: the poly epihydric alcohol base ether of Sorbitol Powder poly epihydric alcohol base ether, phenol novolac-type resin etc.; Above-mentioned epoxy compounds can be a kind of separately or be made up two or more uses.
C composition of the present invention no doubt can use at this point, but in order to improve the stability that this composition is supplied with when mixing, so that the mixing of resin combination is more even, aforementioned C composition is with before other compositions mix, and is good to perform being treated to of preventing to lump earlier.
Be rosin based materials such as most solid state natural rosin, nilox resin, staybelite, owing to be therefore strip increases the weight of to be easy to generate down caking in weight phenomenon, if this moment is directly when being used for making styrene-series resin compositions, large-scale production be out of question though in small-scale laboratory, produce, if can be caused the supply variation of the device that mixes, be difficult to make uniform resin combination, therefore, make the C composition prevent to handle through caking in advance, can solve this problem points.Aforementioned small pieces are to mean broken thing, pill, globule, lamellar body, particle and powder etc. to be beneficial to and to store or miniature that processing such as the device feeding that mixes are carried out, and its size is generally at 2.0～0.001 centimeters, and are preferable with 1.0～0.01 centimeters.
Aforementioned caking prevents to handle more specifically, be to make chemical substance be covered in the surface of rosin based material, perhaps for example behenic acid, ethene bis-stearamides are melted the surface of mixing or spread upon material with the rosin series material, prevent that the rosin series material from producing the phenomenon of caking, aforementioned chemical substance includes:
One, inanimate matter micropartical, for example talcum, silica particle.
Two, polymeric microsphere, for example fine powder of acrylonitrile-styrene copolymerized zoarium.
Three, slide the property material powder, for example the two stearic amides of ethene, Magnesium Stearate etc.
With respect to the A composition of 100 weight parts, the addition of aforementioned C composition needs between 1～10 weight part, and is good with 3～8 weight parts; When the addition of C composition is lower than 1 weight part, promptly can not make the difficult burning of resin combination reach remarkable and significant effect, if the addition of C composition is higher than 10 weight parts, then can undermine original thermotolerance of resin and shock-resistance.
＜D composition 〉
In the present invention, if desire further to promote the flame retardancy of constituent, can add the difficulty combustion auxiliary agent of D composition according to need again, above-mentioned difficult combustion auxiliary agent can be the difficult combustion of various known organic system difficult combustion auxiliary agents or inorganic system auxiliary agent, it can use separately, also two kinds of auxiliary agents can be mixed and use; Preferable difficulty combustion auxiliary agent has: the antimony of ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, sodium antimonate and butter of antimony is incombustible agent, and in addition, the present invention also can adopt difficult combustion auxiliary agent such as zinc borate, zirconium white, magnesium oxide and trimeric cyanamide system.
With respect to the A composition of 100 weight parts, the addition of aforementioned D composition needs between 1～5 weight part, when the addition of D composition during greater than 5 weight parts, can undermine the original shock-resistance of resin.
＜allocate composition arbitrarily 〉
Flame-retarded phenylethylene series resin composition of the present invention, except aforementioned composition, significantly do not undermining under the effect of the present invention, can suitably allocate the composition that adds other, above-mentioned other compositions include: as colorant, the benzotriazole of titanium oxide is that UV light absorber, steric barrier amine are lubricant, for example Hinered phenols of light stability, for example higher fatty acid amides, hardened castor oil etc., the antioxidant of phosphorous acid esters, and the plasticizer of phthalic ester, inclined to one side two acid esters of benzene, benzoic ether etc. for example; Above-mentioned additive can be used alone or make up two or more uses.
Again in phenylethylene resin series of the present invention, under the not obvious scope that undermines effect of the present invention, can suitably allocate and add other various polymkeric substance, for example polymeric amide, polybutylene terephthalate, poly-(2, the 6-dimethyl is stretched benzene) ether, aromatic copolycarbonate and methyl-methacrylate resin etc.
The manufacturing of＜fireproof styrene resin 〉
Flame-retarded phenylethylene series resin composition of the present invention is with composition A, B, C, D, and arbitrarily composition various compositions according to above-mentioned allotment proportional arrangement it; And with the general mixing muller manufacturing of Bradley Bender plastometer, Banbury muller, the mixing machine of kneading, roller press, single shaft or biaxial extruder etc.; Normally mat mixing such as these forcing machines are mixed and the extrudate that extrudes cooling pillization and it.Above-mentioned mixing normally carried out under 170～250 ℃ temperature, and be comparatively desirable with 190～230 ℃ especially, and the mixing of aforementioned various configuration compositions is mixed, and order is not special to be limited.
＜purposes 〉
The styrene-series resin compositions of the present invention of gained because very excellent on flame retardancy, shock-resistance, thermotolerance and flowability, so can be used on various industrial goods by expectation, particularly can be widely used in the field of household electrical appliance and OA furniture according to this.
＜embodiment 〉
Embodiment shown below and comparative example are for further specifying the concrete example that the present invention proposes; But scope of the present invention is not exceeded with these embodiment, and evaluation described later then is to be undertaken by following testing method or machine.
One, flame retardancy: be VB method (the upright burning that is as the criterion with UL-94, Vertical Burning) estimates, and use 1/16 o'clock testing plate, with long 5 o'clock, wide 1/2 o'clock sample hanging and catch fire in the lower end, be divided into V-0, V-1, V-2 etc. with this method and according to nonflammable order, for V-0, V-1, the dropping that is dropped when burning need not make and place 12 at present absorbent cotton to catch fire, but for V-2, even if it is also harmless to make absorbent cotton fire burns.
Two, melt turnover rate (MFR, melt flow rate): measuring method is to be the index of benchmark as flowability with ASTM-D1238, and records the thawing turnover rate (increase the weight of 5 kilograms, melt temperature be 200 ℃) of resin.
Three, Emhorn shock strength: the method for measurement is to be the index of benchmark as shock-resistance with ASTM-D256, and measures Emhorn shock strength (have breach on 23 ℃, testing plate, its thickness is) at 1/4 o'clock.
Four, heat-drawn wire: be to be benchmark with ASTM-D648, to measure the temperature (18.6Kgf/cm of thermal distortion
2, 1/4 o'clock testing plate).
The rubber-modified phenylethylene resin series of A composition is to use the ABS resin of applicant company manufacturing commodity PA-756S by name, and the rubber content in the above-mentioned resin is 17 weight %, and its rubber grain is 0.25 μ m, hereinafter to be referred as A-1).
Two (2, the 6-xylyl phosphoric acid ester) commodity of Resorcinol " PX-200 " (hereinafter to be referred as B-1) by name that the fragrant family phosphoric acid ester of B composition is to use Japan big eight chemical limited-liability company to make.
Disproportionation gum resin and staybelite that the rosin based material of C composition is to use the chemical limited-liability company in Japanese waste river to make, wherein disproportionation rubber rosiny commodity are called " the silk R of dragon ", and the commodity of staybelite " Gao Peier CH " by name.
With above-mentioned composition respectively with after the mixed shown in the table 1, mix with high-speed mixer, melt down at 210 ℃ with twin shaft extruding machine (gear directly is 30mm φ) afterwards and mix the back, can make particulate state flame-retarded phenylethylene series resin composition of the present invention as particulate state.With this particle ejection formation and as testing plate, measure it according to aforementioned evaluation method, measured result is as shown in table 1.
Embodiment 1～3 can be learnt that with respect to comparative example 1～6 constituent of the present invention is all very excellent on the harmony of flame retardancy, thermotolerance and shock-resistance by embodiment; The V-2 of flame retardancy then is presented at the back fire that drips of catching fire and can extinguishes in addition, and HB represents not belong to any of V-0, V-1, V-2.
Flame-retarded phenylethylene series resin composition of the present invention like this has excellent in impact resistance and thermotolerance really, can be described as material very useful on industry.
[table 1]
| Experiment numbers | Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 1 | 2 | 3 | 4 | 5 | 6 | |||
| Resin combination | A-1 | Weight part | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| B-1 | Weight part | 3 | 6 | 3 | 5 | 12 | 3 | 3 | 0.5 | 20 | |
| Disproportionation gum resin | Weight part | 4 | 2 | - | - | - | 0.5 | 15 | 5 | 5 | |
| Staybelite | Weight part | - | - | 4 | - | - | - | - | - | - | |
| Estimate | The UL94 incombustible agent | V-2 | V-2 | V-2 | HB | V-2 | HB | V-2 | HB | V-2 | |
| Melt turnover rate | g/10min | 12 | 13 | 12 | 10 | 14 | 10 | 15 | 11 | 22 | |
| Heat-drawn wire | ℃ | 83 | 82 | 82 | 83 | 75 | 83 | 77 | 84 | 70 | |
| The Emhorn shock strength | Kg-cm/cm | 14 | 13 | 14 | 14 | 9 | 14 | 8 | 14 | 6 | |
Claims (4)
1, a kind of fireproof styrene tree refers to it is characterized in that constituent: this constituent includes:
(A) the rubber-modified phenylethylene resin series of 100 weight parts,
(B) incombustible agent of 1～15 weight part, and
(C) the rosin based material of 1～10 weight part;
Wherein the incombustible agent of B composition is for having the aromatic phosphoric ester of following structural;
R in the above-mentioned formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9Be independence, it can be hydrogen atom or carbonatoms at 1～4 alkyl or hydroxy, and X is the above organic radical of divalence, and n is the integer more than 0 or 0.
2, flame-retarded phenylethylene series resin composition as claimed in claim 1 is characterized in that: wherein the rosin based material of C composition is a natural rosin, or the modified rosin that natural rosin disproportionation, hydrogenation or dehydrogenation are formed.
3, flame-retarded phenylethylene series resin composition as claimed in claim 1 or 2 is characterized in that: wherein the C composition is to prevent the processing of luming through bestowing.
4, flame-retarded phenylethylene series resin composition as claimed in claim 1 or 2 is characterized in that: wherein with respect to the rubber-modified resin combination of 100 weight parts, further allotment has the difficulty combustion auxiliary agent of 0～5 weight part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102518A CN1082527C (en) | 1998-06-17 | 1998-06-17 | Flame-retarding styrene-series resin compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102518A CN1082527C (en) | 1998-06-17 | 1998-06-17 | Flame-retarding styrene-series resin compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1239113A CN1239113A (en) | 1999-12-22 |
| CN1082527C true CN1082527C (en) | 2002-04-10 |
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| CN98102518A Expired - Fee Related CN1082527C (en) | 1998-06-17 | 1998-06-17 | Flame-retarding styrene-series resin compositions |
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| KR100816981B1 (en) * | 2006-06-29 | 2008-03-26 | 주식회사 엘지화학 | Flame Retardant Rubber-Modified Styrene Resin Composition |
| CN104192968B (en) * | 2014-08-28 | 2016-08-17 | 中山市宏科化工有限公司 | A kind of hyperbranched type heavy metal chelating agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997709A (en) * | 1988-11-07 | 1991-03-05 | The Kendall Company | Novel adhesives and tapes including same |
| JPH03124753A (en) * | 1989-10-11 | 1991-05-28 | Asahi Chem Ind Co Ltd | Method for extrusion molding polyvinylidene chloride resin |
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1998
- 1998-06-17 CN CN98102518A patent/CN1082527C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997709A (en) * | 1988-11-07 | 1991-03-05 | The Kendall Company | Novel adhesives and tapes including same |
| JPH03124753A (en) * | 1989-10-11 | 1991-05-28 | Asahi Chem Ind Co Ltd | Method for extrusion molding polyvinylidene chloride resin |
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| CN1239113A (en) | 1999-12-22 |
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