CN100436524C - Flame-retardant resin composition, process for producing the same, and method of molding the same - Google Patents
Flame-retardant resin composition, process for producing the same, and method of molding the same Download PDFInfo
- Publication number
- CN100436524C CN100436524C CNB2004800274504A CN200480027450A CN100436524C CN 100436524 C CN100436524 C CN 100436524C CN B2004800274504 A CNB2004800274504 A CN B2004800274504A CN 200480027450 A CN200480027450 A CN 200480027450A CN 100436524 C CN100436524 C CN 100436524C
- Authority
- CN
- China
- Prior art keywords
- resin
- composition
- flame retardant
- flame
- resin combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
At least one resin ingredient selected among biodegradable resins and resins derived from plants is kneaded together with an ingredient imparting flame retardancy to obtain a flame-retardant resin composition. This resin composition enables biodegradable or plant-derived resins friendly to the global environment, such as polylactic acid and polybutylene succinate, to be applied to the housings of domestic electrical appliances, etc. In particular, when polylactic acid is used, use of acetylacetonatoiron as the flame retardant can provide a resin composition with excellent flame retardancy as a halogen-free material.
Description
Technical field
The present invention relates to Biodegradable resin with the plant resources be the resin of the raw material resin combination of having given flame retardant resistance, its manufacture method, with and manufacturing process.
Background technology
The resin (perhaps plastics) that can decompose under the effect of bacterium after in recent years, being embedded in the soil has received concern.These resins that are called as Biodegradable resin (perhaps biodegradable plastic), the existence that has on the aerobism bacterium issues the water (H that separates and resolve into estranged
2O) and carbonic acid gas (CO
2) characteristic.Biodegradable resin has obtained practicability in agriculture field, in addition, also be practical as the wrapping material of disposable commodities and compost (compost) material with refuse bag etc.
When utilize Biodegradable resin by soil in bacterial degradation character and when it is carried out waste treatment, compare with burning disposal in the past, can significantly reduce CO
2Output.Therefore, as preventing one of countermeasure of global warming, the use of Biodegradable resin has received concern.Used the commodity of Biodegradable resin, for example when in agriculture field, using, need not reclaim the plastics that use, so also more convenient sometimes for the user.Based on these reasons, the market of Biodegradable resin enlarges gradually at present.
And then in recent years, the resin that comes from plant gets most of the attention in electronics and automotive field.Coming from the resin of plant, is by making the monomer that obtains from plant material carry out polymerization or copolymerization obtains.The resin that comes from plant has been subjected to attention based on following reason as the resin that is of value to global environment, does not promptly rely on petroleum resources and makes; As the plant absorbing carbonic acid gas of raw material and grow up; Even and by burning disposal with its depleted situation under, its burn calories is also less usually, the CO of generation
2Measure less etc.The resin that comes from plant has biological degradability usually, but only from preventing the viewpoint of petroleum resources exhaustion, not necessarily needs to possess biological degradability.That is,, except Biodegradable resin, also contain the resin that comes from plant with biological degradability helping to protect in the resin of environment.Therefore, in this specification sheets that comprises following explanation, illustrate but the resin that do not have a biological degradability is composed with general name in order to give Biodegradable resin (comprising the resin that comes from oil and come from plant) and to come from plant, used what is called " environment resin " such term.
At present, roughly to be divided into poly lactic acid series (below, abbreviate " PLA " as), PBS system (polybutylene succinate (1, the copolymer resins of 4-butyleneglycol and succsinic acid)), PET be (polyethylene terephthalate) three kinds to the resin that is used as the environment resin.Feature separately is shown in following table 1.
Table 1
In the middle of these resins, PLA belongs to the above-mentioned resin that comes from plant.The sugar that PLA can make with plants such as corn or sweet potatoes as raw material by the chemosynthesis manufacturing, can be in industrial production.This plastics that contain the resin that comes from plant are also referred to as biological plastics.It is the raw material mass production that PLA has begun at present with the corn, thus noticeable especially, except the purposes of need biological degradability, also wish to develop the technology that can in multiple use, use PLA.
But, use these environment resins if will replace known material, need improve its characteristic.In following table 2, show the rerum natura of polystyrene (PS) as general resin, acrylonitrile-butadiene-styrene resin (below, be designated as ABS) and as the poly(lactic acid) (PLA) of environment resin and the rerum natura of polybutylene succinate (PBS)." bending elastic modulus " and " flexural strength " expression rigidity, the big more rigidity of its numerical value is high more." Emhorn shock strength " expression test film is subjected to shock load and failure energy when being destroyed, and its numerical value is big more, is difficult to more split applying when impacting." heat-drawn wire " is the temperature that resin begins to be out of shape, and its numerical value is high more, can use under hot conditions more.
Table 2
By this table as can be known, PLA is hard and crisp, the PBS softness.In addition, when the comparative heat characteristic, PLA lacks thermotolerance as can be known, and PBS has the above thermotolerance of ABS.
As the method for the characteristic of improving such environment resin, proposed to cooperate the method for other compositions.For example, open the method that has proposed in PLA, to cooperate the synthetic mica about 0.5～20wt% in the 2002-173583 communique (patent documentation 1) the spy for the thermotolerance of improving PLA.The spy opens in the 2002-173583 communique and also proposes, the additive (for example, carbodiimide) that can cooperate the hydrolysis (biological degradation) to Biodegradable resin to suppress.
In addition, there is report to point out, for example by in PLA, cooperating kenaf, can be applied to exterior body (the celery pool etc. of PC, " kenaf is strengthened the exploitation of poly(lactic acid) " (pre-original text collection is given a lecture in the annual meeting of the 14th plastics forming processing association, the 161st page～162 pages, 2003 (non-patent literature 1))).Particularly, wherein mention the scheme of after making the PLA ester moulding that is combined with kenaf, appending annealing operation, can improve the thermotolerance of PLA resin thus, improved the possibility that PLA is applied to the PC exterior body.
Patent documentation 1: the spy opens the 2002-173583 communique
Non-patent literature 1: celery pool etc., " kenaf is strengthened the exploitation of poly(lactic acid) " (pre-original text collection is given a lecture in the annual meeting of the 14th plastics forming processing association, and the 161st page～162 pages, 2003 years)
But it is to be the composition that purpose proposes to improve thermotolerance that the resin put down in writing in above-mentioned document is formed, and still not mentionedly whether gives indispensable flame retardant resistance when being used for the exterior body of household appliances.In fact, the resin of putting down in writing in the above-mentioned file is formed and is not had flame retardant resistance.Therefore, the PLA composition that in the past proposed can't be used for the exterior body that inside has the electrochemical products such as televisor of high-voltage part.In addition, electrochemical product in recent years trends towards safety-sensitive, even do not have in the machine of high voltage devices in inside, the tendency that adopts the resin with flame retardant resistance is arranged also.Therefore, even the environment resin has gratifying characteristic at aspects such as rigidity, shock strength and thermotolerances, only otherwise have flame retardant resistance, its availability is also extremely low.
Summary of the invention
The present invention In view of the foregoing finishes just, and its purpose is, provides the environment resin is given flame retardant resistance and is used for for example environment resin combination of the exterior body of electrochemical product.
In order to address the above problem, the inventor etc. concentrate on studies, and found that the flame retardant resistance of environment resin is identical with common resin, can be by adding and mixing fire retardant and improved.That is, the invention provides and contain from Biodegradable resin and come from least a resinous principle of selecting the resin of plant and the resin combination of giving the composition of flame retardant resistance, the described composition of giving flame retardant resistance is supported by inorganic porous plastid.
Here, " Biodegradable resin " is meant, become low molecular compound by microbiological degradation and finally resolve into the resin of water and oxygen at occurring in nature after using, " coming from the resin of plant " is to instigate the monomer generation polymerization that is generated by plant material or make this monomer the resin that obtains with other monomers (can be the non-monomer that comes from plant) generation copolymerization.Comprise resin with biological degradability and the resin that does not have biological degradability in coming from the resin of plant, the resin that comes from plant with biological degradability can be categorized as said " Biodegradable resin " here., put down in writing this 2 kinds of resins side by side here, its objective is, clearly use resin or come from the characteristics of the resin of plant, so please be careful this point as component of polymer with biological degradability from point of view of environment protection.In addition, in this manual, so-called " resin " this term is used in reference to the polymkeric substance in the resin combination, and " resin combination " is meant the composition that contains resin at least.Plastics are meant and contain the material of polymkeric substance as neccessary composition.Resin combination of the present invention contains resinous principle and gives the composition of flame retardant resistance, so can be referred to as plastics.
" flame retardant resistance " is meant the character that does not burn away or do not produce the leftovers after a fire after removing ignition source.The composition of giving flame retardant resistance is specially fire retardant.The fire retardant of Shi Yonging for example is 1 or the multiple fire retardant of selecting from halogen flame retardant, phosphorus flame retardant, inorganic flame retardant, silicone-based fire retardant and metal complex in the present invention.As the environment resin, particularly come from the fire retardant of the resin of plant, preferably use metal complex.Particularly ferric acetyl acetonade, acetylacetone cobalt and acetylacetone copper can be given excellent flame retardancy to the resin that comes from plant, so preferred the use.
The present invention is preferred for containing poly(lactic acid) (PLA), lactic acid copolymer or polybutylene succinate (PBS) or their mixture as the situation of resinous principle, is particularly preferred for containing the situation of poly(lactic acid) as resinous principle.As mentioned above, about poly(lactic acid) (PLA), existing people proposes its framework that can be used for household appliances as the resin that can mass-producedly come from plant etc.Therefore, by giving flame retardant resistance, can further improve its practicality to it.
The present invention also provides the manufacture method of flame retardant resin composition in addition, comprising carrying out mixing step at least a resin selected the resin of plant from Biodegradable resin and coming from by the composition of giving flame retardant resistance that inorganic porous plastid supported.Mixing operation be when making plastics or when shaping requisite operation, be in the operation that resinous principle dissolving back is implemented.Therefore, give the composition of flame retardant resistance, then need not establish other operations that are used to cooperate the composition of giving flame retardant resistance in addition, can under the condition of avoiding cost significantly to increase, obtain flame retardant resistance environment resin if in mixing operation, mix.
And then, the present invention also provides the manufacturing process of flame retardant resin composition, comprising: with the step that composition utilizes injection forming or compression forming method to be shaped, described composition is to from Biodegradable resin with come from least a resin selected the resin of plant and carried out mixing obtaining by the composition of giving flame retardant resistance that inorganic porous plastid supported.That is, flame retardant resin composition of the present invention can be under the situation of the production unit that does not have the conventional formed products that uses of bigger change to use, and forms according to the method for routine.Therefore, if use flame retardant resin composition of the present invention, then can be easily raw material be transformed into biodegradable plastic or comes from the plastics of plant from general thermoplastics.
By the present invention, can be under the situation that does not increase manufacturing process, give the Biodegradable resin of global environment gentleness and come from the resin of plant with flame retardant resistance.Its result can be with the plastics that contain these resins exterior body as electrochemical product etc., so with regard to flame retardant resin composition of the present invention, its industrial value is big and useful.
Description of drawings
Fig. 1 is the schema that the method for flame retardant resin composition of the present invention is made in expression
Embodiment
As previously mentioned, in the flame retardant resin composition of the present invention, contain from Biodegradable resin and come from a kind or the several resins of selecting the resin of plant as resinous principle, and then contain the composition of giving flame retardant resistance.At first, resinous principle is described.
As Biodegradable resin and the resin that comes from plant, can use known resin arbitrarily.As Biodegradable resin, for example can enumerate polycaprolactone (PCL), polybutylene succinate (PBS) and the polyethylene terephthalate (PET) made by the petroleum chemistry raw material and by the polyhydroxybutyrate (PHB) of microorganism generation etc.PCL, PBS and PET make the monomer generation polymerization that obtains from plant material and the resin that obtains.As the resin that comes from plant, representative is poly(lactic acid) (PLA) and lactic acid copolymer.PLA and lactic acid copolymer be, will ferment the lactic acid that obtains as raw material to starch or carbohydrate, makes it carry out polymerization and the resin that obtains, and wherein said starch or carbohydrate are obtained by corn or sweet potato etc.PLA is the Biodegradable resin of hydrolysis-type, and in the purposes that does not need biological degradability, interpolation sometimes makes the compound of water-disintegrable reduction and uses.At this moment, biological degradability is low or do not have a biological degradability.But; as previously mentioned, nonbiodegradability is arranged no matter come from the resin of plant, all have do not utilize petroleum resources, heat output few, be absorbing carbon dioxide advantage such as grow up as the plant of raw material; therefore from the viewpoint of environment protection, can preferably use in the present invention.
In the present invention, preferably use PBS or PLA, especially preferably use PLA or mixed PLA and resin that other resins form as resinous principle.PLA has the outstanding transparency and rigidity, so the molding of Gou Chenging can be used for various uses thus.On the other hand, the shortcoming that PLA has thermotolerance and shock-resistance is low and injecting formability is also low slightly.For this reason, particularly under the situation of injection forming, preferably in PLA, mix other resins and/or properties-correcting agent use.For example, the thermotolerance of PBS is outstanding and himself have biological degradability, so be fit to mix with PLA.Particularly, PLA and PBS preferably mix with the ratio of 95: 5～55: 45 (weight ratio).Perhaps, can use commercially available polylactic acid modified dose as properties-correcting agent, PLA is carried out modification.
In the resinous principle, can contain Biodegradable resin as required and come from resin beyond the resin of plant (for example, do not have biological degradability and be the resin of raw material) with the petrochemical materials.The ratio of such resin preferably accounts for below the 45wt% of whole resinous principle.Consider that from point of view of environment protection do not wish to contain in a large number and do not have biological degradability and the non-resin that comes from plant, in addition, when metal complexes such as use ferric acetyl acetonade described later were given flame retardant resistance, the flame retardant resistance of composition descended sometimes.
Then, the composition of giving flame retardant resistance is described.As the composition of giving flame retardant resistance (being also referred to as " flame-retardant composition "), can enumerate as previously mentioned as fire retardant and in addition known halogen flame retardant, phosphorus flame retardant, inorganic flame retardant and silicone-based fire retardant can also enumerate superpower hydrochlorate, dehydrogenation catalyst and metal complex.
As the halogen flame retardant, particularly, for example can use tetrabromo-bisphenol (TBBA), decabromodiphynly oxide (DBDPO), hexabromocyclododecane (HBCD), octabromodiphenyl ether (OBDPO), two tribromophenoxy ethane (BTBPE), tribromophenol (TBP), ethylenebis tetrabromo-benzene dicarboximide, the TBA polycarbonate oligomer, brominated Polystyrene, the TBA epoxy oligomer, the TBA epoxy polymer, the two bromopropyl ethers of TBA, ethylenebis pentabromo-biphenyl, poly-bromobenzene ether, bromide fire retardants such as hexabromobenzene, and chlorinated paraffin, chlorine-based flame retardants such as perchloro cyclopentadecane and the acid of chlorine mattress.
As phosphorus flame retardant, particularly, for example can use TPP, triphosphoric acid allyl ester, aromatic phosphoric ester, phosphoric acid 2-ethylhexyl diphenyl, triethyl phosphate, TCP, tricresyl phosphate base phenylester, tricresyl phosphate (chloroethene) ester, tricresyl phosphate-β-chlorine propyl ester, tricresyl phosphate (dichloro third) ester, halogen-containing condensed phosphoric acid esters, aromatic condensation phosphoric acid ester, poly-phosphate and red phosphorus etc.
As inorganic flame retardant, for example can use Mg (OH)
2, Al (OH)
3, Sb
2O
3, guanidine acid, Sb
2O
5, zinc borate, molybdenum compound and zinc etc.
Flame-retardant composition beyond following illustration is above-mentioned.When with superpower hydrochlorate when the flame-retardant composition, can use fluorine butane sulfonic acid potassium salt, fluoromethane sulfonic acid potassium salt, fluoromethane sulfonate sodium, sulfuric acid supports ferric oxide and wolframic acid supports ferric oxide etc.In addition, flame-retardant composition as dehydrogenation catalyst system can use chromic oxide, copper chromium, cupric oxide, ferric oxide, lanthanum trioxide, manganese oxide, molybdenum oxide, nickel oxide, copper-chromium catalyst, palladous oxide, stannous pyrophosphate, tantalum oxide, titanium oxide, tetra-sodium titanium, Tungsten oxide 99.999, zinc pyrophosphate, zirconium pyrophosphate, vanadium oxide and zinc oxide etc.In addition, when with metal complex when the flame-retardant composition, can use ferric acetyl acetonade, acetylacetone cobalt, acetylacetone copper, dimethyl thiocarbamate iron, benzoyl contract acetone iron, three (dibenzoyl methyl) iron and cupric ethylene diamine tetraacetate etc.Flame-retardant composition as clay system for example can use montmorillonite (smectite) and montmorillenite (montmorillonite) etc.Flame-retardant composition as foaming (intumescent) is for example can use the combination of polyphosphoric acid ammonium salt (APP) and tetramethylolmethane (PER).When using resin, can use polyphenylene oxide (PPE) and polycarbonate (PC) etc. as flame-retardant composition.And then, as other flame-retardant compositions, for example can enumerate silicone-based fire retardants such as dimethyl silscone and Methylphenylsilanone, brominated aromatic triazine and composite fire retardant.Even the compound in above-mentioned beyond the compound of particular instantiation as long as can give the flame retardant resistance that needs to resin combination, just can use.In addition, in resin combination of the present invention, can be used in combination the fire retardant more than 2 kinds, at this moment, the ratio of each fire retardant can be set arbitrarily according to required flame retardant resistance.
In the middle of above-mentioned flame-retardant composition, as be added to Biodegradable resin and come from the resin of plant, can be when particularly coming from the resin of plant with the composition of a small amount of performance high flame retardant effect, can enumerate zinc oxide and vanadium oxide and ferric acetyl acetonade, cupric ethylene diamine tetraacetate, acetylacetone copper and the benzoyl metal complexes such as acetone iron that contract.Therefore,, can reduce the addition of flame-retardant composition, change (for example decline of flexural strength and Young's modulus) so can reduce the rerum natura physically of the resin combination that the interpolation by flame-retardant composition causes if use these flame-retardant compositions.In addition, when reducing the addition of flame-retardant composition, recovery is used this resin combination to become and is more prone to.Ferric acetyl acetonade (Fe (acac)
3) compare with phosphorus flame retardant with known halogen flame retardant, especially can give higher flame retardant effect for the resin that comes from plant (being specially poly(lactic acid)), so preferred the use.
The rerum natura variable quantity of the resin combination that the blending ratio of flame-retardant composition can cause according to the interpolation of the degree of the required flame retardant resistance of kind, the kind of resinous principle, the resin combination of flame-retardant composition and flame-retardant composition is determined.Particularly, for example in resin combination, flame-retardant composition preferably accounts for about 5wt%～40wt%.When the ratio of flame-retardant composition during less than 5wt%, the flame retardant resistance effect that is difficult to be significantly improved, when surpassing 40wt%, the detrimentally affect that is caused by the mixing of flame-retardant composition (for example the plasticity that is caused by the decline of flowability is bad) will become remarkable.
The blending ratio of above-mentioned flame-retardant composition is one of its example, different according to the kind of the kind of resinous principle and flame-retardant composition, and the optimum range of the blending ratio of flame-retardant composition is also inequality.For example, when with poly(lactic acid), lactic acid copolymer, perhaps the mixture of at least a resin in the middle of them and other resins is as resinous principle, with metal complex (particularly ferric acetyl acetonade) during as flame-retardant composition, preferably according to making metal complex account for the mode hybrid metal coordination compound of 1～15wt% of resin combination, when with the halogen flame retardant during as flame-retardant composition, preferably mix flame-retardant composition according to the mode that makes flame-retardant composition account for 10～30wt% of resin combination, when phosphorus flame retardant during as flame-retardant composition, is preferably mixed flame-retardant composition according to the mode that makes flame-retardant composition account for 20～40wt% of resin combination.
Flame-retardant composition preferably is dispersed in the resin with the state that is supported by inorganic porous plastid.Particularly, preferably flame-retardant composition is scattered in the resin by following method, promptly in inorganic porous plastid, support flame-retardant composition after, itself and resinous principle is mixing, when inorganic porous plastid is ground into particulate, be scattered in the resin.By also using inorganic porous plastid, can obtain flame-retardant composition dispersive resin combination more equably, so can further reduce the addition of flame-retardant composition.Promptly, when using inorganic porous plastid, be that the granular solid with the size that is unlikely to cause cohesion is carried out interpolation when beginning is mixing, in mixing process, be ground into fine particle homodisperse afterwards, so compare with the situation of only adding flame-retardant composition, can improve the dispersiveness of flame-retardant composition.In addition, inorganic porous plastid itself has the character that can give flame retardant resistance to resin, can act synergistically with the flame-retardant composition that has supported to improve the flame retardant resistance of resin combination.
Inorganic porous plastid for example is made of silicon oxide and/or aluminum oxide, is that the ratio with 45～55vol% has the porous plastid that the aperture is the pore of 10～50nm.Inorganic porous plastid like this is preferably the granular solid of the particle diameter with 100～1000nm when supporting flame-retardant composition.If particle diameter is too small, cohesion takes place sometimes and cause the particle gigantism.On the other hand, when particle diameter was excessive, the particle diameter of the inorganic porous plastid after pulverizing in mixing operation increased, sometimes can not homodisperse.Inorganic porous plastid (has promptly carried out mixing back to inorganic porous plastid) and has preferably had the particle diameter of 25～150nm in the resin combination that finally obtains.When using inorganic porous plastid, for example, preferably support flame-retardant composition 3～50 weight parts with respect to inorganic porous plastid 100 weight parts.So support the inorganic porous plastid of flame-retardant composition, for example can add, mixing according to the mode of the 1～40wt% that accounts for whole resin combination.The loading of the flame-retardant composition here and the addition of inorganic porous plastid are one of examples, can be located at according to the kind of flame-retardant composition outside these scopes.
Inorganic porous plastid for example can support flame-retardant composition by following method, promptly, make inorganic porous plastid impregnated in the flame-retardant composition that need are supported and (for example be dissolved or dispersed in the liquid that forms in the solvent, when using metal complex, be the aqueous solution of metal complex) in, make the method for solvent evaporation then by heating.Itself can adopt the known method manufacturing inorganic porous plastid, for example, can be (for example with pore-forming agent, water-soluble inorganic salt) be dissolved in the silicon sol and make its drying after burn till, pore-forming agent is dissolved in the hot water and removes pore-forming agent, obtain inorganic porous matter thus from the particle that obtains.Perhaps, inorganic porous plastid can be porous glass or zeolite etc.
As concrete example, the following describes and select poly(lactic acid) or lactic acid copolymer as resinous principle, selection ferric acetyl acetonade and/or acetylacetone copper situation as flame-retardant composition.At this moment, as inorganic porous plastid, the preferred porous plastid that constitutes by silicon oxide (silicon-dioxide) that uses, wherein the ratio with 45～55vol% has the pore that the aperture is 10～50nm, and particle diameter is 100～500nm.Ferric acetyl acetonade and/or acetylacetone copper are preferably supported by silica porous body with respect to the ratio of silica porous body 100 weight parts with 5～45 weight parts, and more preferably the ratio with 10～35 weight parts is supported.Supported the silica porous body of ferric acetyl acetonade and/or acetylacetone copper, preferably added, more preferably added according to the mode that accounts for 5～15wt% according to the mode of the 5～40wt% that accounts for the integrally combined thing.Adding this inorganic porous plastid and carrying out mixing and in the resin combination that obtains, in resin, ferric acetyl acetonade and/or acetylacetone copper are that mixed with 0.5～5.25wt% is in resin combination as the microparticulate of the particle diameter with 25～150nm for inorganic porous plastid.By the inorganic porous plastid of use like this, can reduce the adding proportion of flame-retardant composition.
Except containing flame-retardant composition, can also contain flame retardant in the resin combination of the present invention.Flame retardant can not become flame-retardant composition when using separately, but when adding with flame-retardant composition, has the effect that the flame retardant resistance that can further improve flame-retardant composition is improved effect.Therefore, by using flame retardant, can further reduce the addition of flame-retardant composition.As flame retardant, for example can use from organo-peroxides such as ketone peroxide, ketal peroxide, hydroperoxide, dialkyl peroxide, peroxyester and peroxide two carbonic ethers, a kind of selecting in dimethyl one diphenyl butane and their derivative or multiple compound.When using organo-peroxide, infer that in resin combination, organo-peroxide discharges oxygen, has improved the flame retardant resistance of resin combination thus as flame retardant.In addition, when using dimethyl-diphenyl butane, infer dimethyl-diphenyl butane and brought into play the free radical capture effect, improved the flame retardant resistance of resin combination thus as flame retardant.But, these are inferred and can't impact scope of the present invention.When using multiple compound, its ratio of mixture is not particularly limited, can select arbitrarily to obtain required flame-retarding characteristic.The flame retardant amount can be set according to the kind and the addition of flame-retardant composition, for example can add 5～45 weight parts with respect to flame-retardant composition 100 weight parts.In addition, the total amount of flame retardant and flame-retardant composition is preferably the amount of the 5～40wt% that is equivalent to whole resin combination.Its reason is as the explanation of being done in the content of relevant flame-retardant composition.
Resin combination of the present invention can also contain other compositions except containing outside the above-mentioned composition (that is, resinous principle, flame-retardant composition (containing inorganic porous plastid when being supported by inorganic porous plastid) and blended flame retardant as required).For example, be the color of needs, can contain tinting material etc. in order to make resin combination.In addition, reach required rerum natura for the rerum natura that makes resin combination etc. in case of necessity, for example can contain butadiene-based rubber etc. to improve shock-resistance.
Resin combination of the present invention can be by carrying out mixing the manufacturing to resinous principle and flame-retardant composition.For example under the situation of the resin combination of making particle shape, mixing can before obtaining particle, enforcement.Perhaps, can after the resin (or resin combination) of particle shape and flame-retardant composition is mixing, form particle shape once more.Perhaps, can also in forming process, in not containing the resin of dissolved of flame-retardant composition, mix flame-retardant composition.When usually making the exterior body of electrochemical product, can adopt the compression forming method that uses upper die and lower die to exert pressure behind the method that is shaped with mold injects behind the dissolving resin, the dissolving resin with regulation shape by the shaping of plastics.In these manufacturing process, implement to use kneading machine etc. that dissolved resin is carried out mixing operation.Therefore, in its mixing process, flame-retardant composition can be mixed into and obtain the molding that constitutes by flame retardant resin composition in the resinous principle.If so add flame-retardant composition, do not need to add other operations of flame-retardant composition, so can obtain resin combination of the present invention with high-level efficiency.
Resin combination of the present invention is to have given the composition of flame retardant resistance to environment mild resin, as molding, can be used in the framework or the part of various electrochemical products.Resin combination of the present invention specifically can be used as computer, portable phone, audio product (for example, receiving set, cassette recorder, CD player, MD player) microphone, keyboard and the framework of portable audio players or the member of part.Perhaps, resin combination of the present invention can also be used for automobile inside material, two-wheel car exterior material and home-use various chandleries etc.
Embodiment
(embodiment 1)
Use the twin shaft mixing roll mixing, make particle carrying out as raw material synthetic poly(lactic acid) (PLA) 70wt% and polybutylene succinate (PBS) 30wt% with corn.Here, the purpose of mixing PBS is in order to improve thermotolerance.
In this embodiment, as the ferric acetyl acetonade (Fe (acac) of flame-retardant composition
3) by SiO
2Porous plastid supports.Fe (acac)
3The ratio that supports, be 60 weight parts with respect to porous plastid 100 weight parts.Use the twin shaft mixing roll, under 185 ℃, to the particle 90wt% that obtains by step 1 with supported Fe (acac)
3SiO
2Porous plastid 10wt% carries out mixing (step 2), and die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid, its voidage is about 45～50vol%, has the particle diameter of about 100nm～1000nm.This SiO
2Porous plastid with resin when mixing, be broken by the effect of shearing force, the finer particle that finally becomes the particle diameter (median size is about 75nm) with about 25nm～150nm is scattered in the resin.In addition, the Fe in the resin combination that calculates (acac)
3Content be 3.75wt%.
With UL (Underwriters Laboratories)-94 is benchmark, and this test film has been implemented the 20mm testing vertical flammability.The results are shown in the table 3.Be be evaluated as the V0 of UL standard according to this sample of test-results.
(embodiment 2)
In the particle that in the step 1 of embodiment 1, obtains, mixing not by SiO
2The ferric acetyl acetonade that porous plastid supports (Fe (acac)
3) powder, obtained the required Fe (acac) of flame retardant resin composition that obtains being suitable for UL standard V0
3Blending ratio.
The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, use the twin shaft mixing roll, under 185 ℃, to the particle that in step 1, obtains with as the Fe (acac) of flame retardant resistance composition
3Carry out mixing (step 2), die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).In the present embodiment, change particle and Fe (acac)
3Mixture ratio, made a plurality of test films, and respectively it carried out the flame retardant resistance evaluation.Fe (acac)
3Be with not by SiO
2Porous plastid supports and is used for the form of powder of particle diameter with about 2～80 μ m.At this moment, powder is by mixing and pulverized, and is scattered in the resin with the powder size at initial stage.Therefore, if will obtain the flame retardant resistance of UL standard V0 similarly to Example 1, need make particle and Fe (acac)
3Proportioning reach 88: 12 (weight ratio).Contain Fe (acac) for ratio with 12wt%
3The result of the UL-94 testing vertical flammability implemented of test film, as the results are shown in the table 3 of present embodiment.
(embodiment 3)
According to the step identical with embodiment 1, poly(lactic acid) (PLA) and polybutylene succinate (PBS) are carried out mixing, made particle (step 1).
The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, by SiO
2The flame-retardant composition that porous plastid supports is a zinc borate.Zinc borate is supported with respect to the ratio of porous plastid 100 weight parts with 42 weight parts.Use the twin shaft mixing roll, under 185 ℃, to the particle 90wt% that in step 1, obtains, supported the SiO of zinc borate
2Porous plastid 10wt% carries out mixing (step 2), and die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid and the SiO that in embodiment 1, uses
2Porous plastid is identical, by mixing, finally becomes nano level microparticulate in resin.The content of the zinc borate in the resin combination that calculates in addition, is 3.0wt%.
Adopt the method identical, the test film that obtains has been implemented the UL-94 testing vertical flammability with embodiment 1.The results are shown in the table 3.According to the result of table 3, this sample is be evaluated as UL standard V0.
(embodiment 4)
In the particle that in the step 1 of embodiment 1, obtains, mixing not by SiO
2The powder of the zinc borate that porous plastid supports has been obtained the blending ratio of the required zinc borate of the flame retardant resin composition that obtains being suitable for UL standard V0.
The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, use the twin shaft mixing roll, under 185 ℃, carry out mixing (step 2) to the particle that in step 1, obtains with as the zinc borate of flame retardant resistance composition, die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).In the present embodiment, change the mixture ratio of particle and zinc borate, made a plurality of test films, and respectively it has been carried out the flame retardant resistance evaluation.Zinc borate is with not by SiO
2Porous plastid supports and has that the form of powder of the particle diameter of about 5～100 μ m is used.At this moment, powder is by mixing and pulverized, and is scattered in the resin with the powder size at initial stage.Therefore, if will obtain the flame retardant resistance of UL standard V0 similarly to Example 3, need make the proportioning of particle and zinc borate reach 86: 14 (weight ratio).Contain the result of the UL-94 testing vertical flammability that the test film of zinc borate implements for ratio, as the results are shown in the table 3 of present embodiment with 14wt%.
(embodiment 5)
According to the step identical with embodiment 1, poly(lactic acid) (PLA) and polybutylene succinate (PBS) are carried out mixing, made particle (step 1).The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, by SiO
2The flame-retardant composition that the porous plastid particle supports is TBBA (tetrabromo-bisphenol).TBBA is supported with respect to the ratio of sub 100 weight parts of porous plasmid with 20 weight parts.Use the twin shaft mixing roll, under 185 ℃, to the particle 90wt% that in step 1, obtains, supported the SiO of TBBA
2Porous plastid particle 10wt% carries out mixing (step 2), and die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid particle and the SiO that in embodiment 1, uses
2Porous plastid is identical, by mixing, finally becomes nano level microparticulate in resin.In addition, the content of the TBBA in the resin combination that calculates is 1.7%.
Adopt the method identical, the test film that obtains has been implemented the UL-94 testing vertical flammability with embodiment 1.The results are shown in the table 3.According to the result of table 3, this sample is be evaluated as UL standard V0.
(embodiment 6)
In the particle that in the step 1 of embodiment 1, obtains, mixing not by SiO
2The powder of the TBBA that porous plastid supports has been obtained the blending ratio of the required TBBA of the flame retardant resin composition that obtains being suitable for UL standard V0.
The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, use the twin shaft mixing roll, under 185 ℃, carry out mixing (step 2) to the particle that in step 1, obtains with as the TBBA of flame retardant resistance composition, die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).In the present embodiment, change the mixture ratio of particle and TBBA, made a plurality of test films, and respectively it has been carried out the flame retardant resistance evaluation.TBBA is with not by SiO
2Porous plastid supports and has that the form of powder of the particle diameter of about 20～100 μ m is used.At this moment, powder is by mixing and pulverized, and is scattered in the resin with the powder size at initial stage.Therefore, if will obtain the flame retardant resistance of UL standard V0 similarly to Example 5, need make the proportioning of particle and TBBA reach 85: 15 (weight ratio).Contain the result of the UL-94 testing vertical flammability that the test film of TBBA implements for ratio, as the results are shown in the table 3 of present embodiment with 15wt%.
(embodiment 7)
Be produced on and only mixed SiO in the particle that obtains in the step 1 of embodiment 1
2The sample of porous plastid particle.The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, use the twin shaft mixing roll, under 185 ℃, to particle 70wt%, the SiO that in step 1, obtains
2Porous plastid particle 30wt% carries out mixing (step 2), and die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid particle and the SiO that in embodiment 1, uses
2Porous plastid is identical, by mixing, finally becomes nano level microparticulate in resin.
Adopt the method identical, the test film that obtains has been implemented the UL-94 testing vertical flammability with embodiment 1.The results are shown in the table 3.According to the result of table 3, this sample is be evaluated as UL standard V2.
(embodiment 8)
According to the step identical with embodiment 1, poly(lactic acid) (PLA) and polybutylene succinate (PBS) are carried out mixing, made particle (step 1).The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, by SiO
2The flame-retardant composition that porous plastid supports is a cupric ethylene diamine tetraacetate.Cupric ethylene diamine tetraacetate is supported with respect to the ratio of sub 100 weight parts of porous plasmid with 17.6 weight parts.Use the twin shaft mixing roll, under 185 ℃, to the particle 90wt% that in step 1, obtains, supported the SiO of cupric ethylene diamine tetraacetate
2Porous plastid particle 10wt% carries out mixing (step 2), and die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid particle and the SiO that in embodiment 1, uses
2Porous plastid is identical, by mixing, finally becomes nano level microparticulate in resin.The content of the cupric ethylene diamine tetraacetate in the resin combination that calculates in addition, is 1.5wt%.
Adopt the method identical, the test film that obtains has been implemented the UL-94 testing vertical flammability with embodiment 1.The results are shown in the table 3.According to the result of table 3, this sample is be evaluated as UL standard V0.
(embodiment 9)
According to the step identical with embodiment 1, poly(lactic acid) (PLA) and polybutylene succinate (PBS) are carried out mixing, made particle (step 1).The cooperation of the composition in the present embodiment is same as embodiment 1 in proper order, can use the flowcharting of Fig. 1.In the present embodiment, by SiO
2The flame-retardant composition that porous plastid supports is ferric acetyl acetonade (Fe (acac)
3).Fe (acac)
3Supported with respect to the ratio of porous plasmid 100 weight parts with 60 weight parts.Use the twin shaft mixing roll, under 185 ℃, to the particle 90wt% that in step 1, obtains, supported (Fe (acac)
3) SiO
2Porous plastid particle 5wt%, carry out mixing (step 2) as tertiary butyl trimethyl silane superoxide (t-butyl-trimethylsil peroxide) (the Japanese grease system PERBUTYL SM) 5wt% of flame retardant, die forming is that (forming temperature is 180 ℃, and pressure is 120kg/cm for the test film of 125mm * 13mm * 3.2mm
2) (step 3).The SiO of Shi Yonging in the present embodiment
2Porous plastid particle and the SiO that in embodiment 1, uses
2Porous plastid is identical, by mixing, finally become nano level particulate and is scattered in the resin.In addition, the Fe in the resin combination that calculates (acac)
3Content be 1.9wt%.
Adopt the method identical, the test film that obtains has been implemented the UL-94 testing vertical flammability with embodiment 1.The results are shown in the table 3.According to the result of table 3, this sample is be evaluated as UL standard V0.
At first, from the result of embodiment 7 as can be known, SiO
2Self becomes flame-retardant composition porous plastid.Therefore, with regard to the sample that obtains by embodiment 1,3 and 5, SiO
2Porous plastid and improved the flame retardant resistance of resin combination by its flame-retardant composition that supports by synergy.In addition, embodiment 1～4,8 and 9 result represent that PLA is given fire-retardantization by the material of non-halogen.And then the ferric acetyl acetonade that uses in embodiment 1 and 2 is compared with the flame-retardant composition of use in other embodiments, can guarantee the flame retardant resistance of UL standard V0 with ratio still less, and the expression ferric acetyl acetonade is suitable for fire-retardantization of PLA.In addition, embodiment 9 is illustrated under the situation of using flame retardant, can further reduce the blending ratio of flame-retardant composition.
(embodiment 10)
Stem portion with pulverizing mestha such as hammers adds water then, uses stirrer to stir, and reaches about 100 μ m up to staple length.Then, the mixture of mestha and water is launched to be positioned on the porcelain dish, put into drying oven (60 ℃), dry 48 hours.After the drying, scrape mestha, obtained and poly(lactic acid) blended mestha from porcelain dish.With the ratio of 70: 30 (weight ratio) poly(lactic acid) (PLA) particle and kenaf are put into the twin shaft mixing roll and carry out mixingly, make particle.Then, cooperate this particle 70wt%, Mg (OH) with the step identical with embodiment 1
230wt% has made the test film that is made of flame retardant resin composition, by the step identical with embodiment 1, it has been carried out the UL-94 vertical test, and the result has the flame retardant resistance that is suitable for the V0 standard.
(embodiment 11)
With poly(lactic acid) (PLA) 50wt%, polybutylene succinate 22.5wt%, TBBA 12.5wt% and Mg (OH)
215wt% puts into the twin shaft mixing roll, with 500rpm and carry out mixingly under 195 ℃, makes particle.The particle that obtains is put in the injection machine, and the mould that uses televisor developing device back cover to use has been implemented injection forming.At this moment, forming temperature is 180 ℃, for fear of the wash-out of the flame-retardant composition that is caused by quenching, die temperature is made as 80 ℃.After shaping, cooling die takes out molding under room temperature state, obtain the back cover of televisor developing device.
The rerum natura of the back cover that obtains is compared with the rerum natura of the back cover of the televisor developing device that uses the resin combination shaping in the past that the mixing fire retardant forms in PS (polystyrene), does not have very big-difference.
Industrial utilizability
Resin combination of the present invention, be for raw material obtain easness or with after discarded angle Say and given anti-flammability to the little Biodegradable resin of the load of environment and/or the resin that comes from plant Composition, at industrial practicality height. Therefore, this resin combination is fit to consist of various article, Particularly very useful as the constituent material of the exterior body of electrochemical product etc.
Claims (8)
1. resin combination, wherein contain:
From Biodegradable resin and come from least a resinous principle of selecting the resin of plant and the composition of giving flame retardant resistance, the described composition of giving flame retardant resistance is supported by inorganic porous plastid.
2. resin combination as claimed in claim 1, wherein,
As resinous principle, contain at least a resin in poly(lactic acid), lactic acid copolymer and the polybutylene succinate.
3. resin combination as claimed in claim 1, wherein,
The composition of giving flame retardant resistance is to be selected from least a fire retardant in halogen flame retardant, phosphorus flame retardant, inorganic flame retardant and the silicone-based fire retardant.
4. resin combination as claimed in claim 1, wherein,
The composition of giving flame retardant resistance is a ferric acetyl acetonade.
5. resin combination as claimed in claim 1, wherein,
The composition of giving flame retardant resistance is an acetylacetone copper.
6. molding, it is made of resin combination, contain in the described resin combination from Biodegradable resin and come from least a resinous principle of selecting the resin of plant and the composition of giving flame retardant resistance, the described composition of giving flame retardant resistance is supported by inorganic porous plastid.
7. the manufacture method of a resin combination wherein, comprising:
Carry out mixing step at least a resinous principle selected the resin of plant from Biodegradable resin and coming from by the composition of giving flame retardant resistance that inorganic porous plastid supported.
8. the manufacturing process of a resin combination, wherein, by injection molding method or compression forming method resin combination is shaped, described resin combination is to make by the method that comprises the steps, and described step is for to from Biodegradable resin with come from least a resinous principle selected the resin of plant and carried out mixing step by the composition of giving flame retardant resistance that inorganic porous plastid supported.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP329631/2003 | 2003-09-22 | ||
| JP2003329631 | 2003-09-22 | ||
| JP038212/2004 | 2004-02-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1856543A CN1856543A (en) | 2006-11-01 |
| CN100436524C true CN100436524C (en) | 2008-11-26 |
Family
ID=37195977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800274504A Expired - Fee Related CN100436524C (en) | 2003-09-22 | 2004-09-17 | Flame-retardant resin composition, process for producing the same, and method of molding the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100436524C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216648B (en) * | 2017-07-28 | 2020-02-07 | 杭州本松新材料技术股份有限公司 | Flame-retardant polyamide composite material |
| GB2591121A (en) * | 2020-01-16 | 2021-07-21 | Floreon Transf Packaging Limited | Polylactic acid flame resistant blend |
| CN116003980B (en) * | 2022-10-27 | 2023-10-13 | 宁波家联科技股份有限公司 | Polylactic acid 3D printing material with heat resistance, high strength and stable size and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53127484A (en) * | 1977-04-13 | 1978-11-07 | Toyobo Co Ltd | Phosphorus-containing chelate compound |
| DE4325849A1 (en) * | 1993-07-31 | 1995-02-02 | Basf Ag | Flameproofed polylactide and copolylactide |
| JP2000086965A (en) * | 1998-09-14 | 2000-03-28 | Dainichiseika Color & Chem Mfg Co Ltd | Coloring agent composition |
| JP2001164463A (en) * | 1999-12-03 | 2001-06-19 | Nicca Chemical Co Ltd | Flameproof processing agent for polylactic acid fiber and method for flameproof processing of polylactic acid fiber structure |
| JP2001172489A (en) * | 1999-12-20 | 2001-06-26 | Mitsubishi Gas Chem Co Inc | Biodegradable resin composition |
| CN1412250A (en) * | 2001-10-19 | 2003-04-23 | 松下电器产业株式会社 | Polymer composition |
-
2004
- 2004-09-17 CN CNB2004800274504A patent/CN100436524C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53127484A (en) * | 1977-04-13 | 1978-11-07 | Toyobo Co Ltd | Phosphorus-containing chelate compound |
| DE4325849A1 (en) * | 1993-07-31 | 1995-02-02 | Basf Ag | Flameproofed polylactide and copolylactide |
| JP2000086965A (en) * | 1998-09-14 | 2000-03-28 | Dainichiseika Color & Chem Mfg Co Ltd | Coloring agent composition |
| JP2001164463A (en) * | 1999-12-03 | 2001-06-19 | Nicca Chemical Co Ltd | Flameproof processing agent for polylactic acid fiber and method for flameproof processing of polylactic acid fiber structure |
| JP2001172489A (en) * | 1999-12-20 | 2001-06-26 | Mitsubishi Gas Chem Co Inc | Biodegradable resin composition |
| CN1412250A (en) * | 2001-10-19 | 2003-04-23 | 松下电器产业株式会社 | Polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1856543A (en) | 2006-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4705471B2 (en) | Exterior body | |
| EP1724304B1 (en) | Flame-retardant styrene resin composition | |
| KR101317503B1 (en) | Flame-retardant resin composition, process for producing the same, method of molding the same | |
| CN102153820B (en) | Preparation method of flame retarding styrene polymer composite material | |
| TW201111425A (en) | Flame-retarded, foam-producing styrene-based resin compositions | |
| JP5279966B2 (en) | Recycled resin and method for producing recycled resin | |
| CN109401232A (en) | Flame-proof polylactic acid composition and its expanded bead | |
| CN100436524C (en) | Flame-retardant resin composition, process for producing the same, and method of molding the same | |
| JPS62220546A (en) | Semi-hard thermoplastic polyester composition | |
| JP5484632B2 (en) | Exterior of electrical equipment | |
| JP4209217B2 (en) | Polylactic acid resin composition | |
| JP4691908B2 (en) | Appliance exterior | |
| JP2004137388A (en) | Styrenic flame-retardant resin composition and method for producing the same | |
| JPWO2008004546A1 (en) | Flame retardant resin composition, production method thereof and molding method thereof | |
| KR20130082222A (en) | Methylmethacrylate-butadiene-styrene impact modifier and environment-friendly polylactic acid resin composition comprising the same | |
| Vahidi | Application of Cellulose Nanocrystals and Zinc Oxide as a Green Fire Retardant System in High Density Polyethylene | |
| JPH0550539B2 (en) | ||
| Oradei | Formulation and Study of New Eco-Friendly Intumescent Polylactic Acid Based Materials | |
| US8779049B2 (en) | Outer casing and method for producing the same | |
| JPH075804B2 (en) | Flame-retardant styrene resin composition and flame retardant for styrene resin | |
| JPH0689202B2 (en) | Flame-retardant styrene resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |