CN101565550B - Nucleating agent master batches used for foaming of thermoplastic resin and its manufacture method - Google Patents
Nucleating agent master batches used for foaming of thermoplastic resin and its manufacture method Download PDFInfo
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- CN101565550B CN101565550B CN2009100486396A CN200910048639A CN101565550B CN 101565550 B CN101565550 B CN 101565550B CN 2009100486396 A CN2009100486396 A CN 2009100486396A CN 200910048639 A CN200910048639 A CN 200910048639A CN 101565550 B CN101565550 B CN 101565550B
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Abstract
The invention relates to a nucleating agent and a method for preparing the nucleating agent, wherein the nucleating agent is used for reducing the dimension of the foaming hole and improving the density of the foaming hole when a supercritical fluid foaming agent (such as carbon dioxide or nitrogen) is used for producing thermoplastic foaming products. The raw materials of the nucleating agent mainly consists of an organic montmorillonite, a thermoplastic resin and a supercritical fluid foaming agent; the specific weight of the nucleating agent master batches is controlled within 100+/-5% of that of the thermoplastic resin. The method has the advantages that a supercritical fluid foaming method is adopted to prepare the nucleating agent master batches which have approximate specific weights to the resin material adopted by the subsequent foam forming, thus facilitating the subsequent injection foam forming and extrusion foam forming; and the carbon dioxide or nitrogen in supercritical state is used for reducing the viscosity of the carrier resin during the mixing process, the dispersion uniformity of the peeled sandwich montmorillonite in the carrier resin is reinforced, the process temperature is reduced, the layer spacing of the sandwich nano-montmorillonite which may be not peeled is increased and the sufficient peeling is realized.
Description
Technical field
Be to reach to reduce abscess-size and improve nucleator that cell density adopts and the manufacture method of nucleator when the present invention relates to adopt supercritical fluid aerating powder (as carbonic acid gas or nitrogen) to produce thermoplastic expanded goods.
Technical background
When the polymer foaming moulding, particularly adopt supercutical fluid, for example nitrogen or carbonic acid gas are as whipping agent, and nitrogen or carbonic acid gas can be dissolved in and form a single phase soln in the polymer melt.When the big and fine cellular material goods of injection moulding, extrusion moulding or blow molding cell density, must in moulding process, in melt, form a large amount of nucleation sites, otherwise very easily cause abscess big and size is uneven.From above-mentioned a single phase soln, form a large amount of nucleation sites and need produce huge thermodynamic phase, for example temperature variation or immense pressure reduction of speed rate fast.This has proposed too high requirement to a forming mould or a mouthful mould, is difficult to sometimes realize.Another method that forms a large amount of nucleation sites is to adopt heterogeneous nucleation, promptly introduces a large amount of solid nucleation sites.But adopt inorganic part of body such as lime carbonate, talcum, titanium dioxide usually.The nucleator of for example having described employing median dose (2.5%-7%) among the patent ZL98813127.7 " extrusion molding/blow moiding method of microcellular foam and the goods of made thereby " increases the mode of cell density and minimizing abscess-size.The nucleator that is adopted is a lime carbonate, talcum powder, and titanium dioxide etc., granular size is between 0.1 micron-1 micron.But when adopting these inorganic nucleators,, reduce the function of nucleator and the local performance of material if one side nucleator particle very thin (for example below 1 micron) because specific surface area is big, in the course of processing, agglomeration takes place easily; If the nucleator particle is bigger on the other hand, can't reach the effect that improves nucleation site quantity, if increase consumption, very big negative effect can be arranged to the performance of material.Also have a factor to be, when adopting these inorganic nucleators, also need add auxiliary agents such as toughener, fire retardant, softening agent, foam stabilizers in the foam material, cause the weight of goods to increase.
According to a large amount of disclosed nano imvites at the research document aspect the polymer modification, the nano imvite of good distribution not only has aspects such as strengthening and improve flame retardant resistance to polymkeric substance and has good result, and the crystallization nucleation of semi-crystalline polymer and crystalline polymer (as nylon, PP etc.) is had good effect.The nano lamellar body of peeling off is solid phase in polymer melt, length and width direction size is between the 100-200 nanometer, and thickness only is 1 nanometer, has very big specific surface area.This structure provides splendid nucleation site for foaming.Go out millions of nanometer laminated structures owing to 1 gram nano imvite is peelable,, just can produce the nucleation site that has more the order of magnitude than method described in the ZL98813127.7 even in polymkeric substance, disperse 1% the nano imvite of peeling off attitude like this.However, but how to solve in forming process, especially will be in the short period of time and the finite space when injection moulding, making nano imvite is to need the problem that solves to peel off that form is dispersed in the thermoplastic matrix.Wherein adopting nano imvite to concentrate master batch is a kind of mode very easily.According to existing disclosed technical literature, make concentrated master batch and comprise two steps, at first polynite is purified and the processing that organises, carry out mixing or compound with thermoplastic resin then.Wherein polynite concentrates and the intercalation processing that organises has a lot of prior aries, and commercialization.For example disclose a kind of organo montmorillonite of in polar organic solvent, using the long-chain quaternary amine salt intercalation processing that comprises hexadecyl trimethyl ammonium bromide among the patent publication No. CN1807507A of Institute of Chemistry, Academia Sinica " a kind of preparation method of nanometer montmorillonite organic phase intercalation ", contained the montmorillonite of 85-93% in the raw material polynite described in this patent.And the business-like organo montmorillonite DK series that Zhejiang Feng Hong clay chemical industry company limited releases has higher smectite content (96%-98%).The granularity of the polynite after handling is still at micron order but these organise, and be intercalation configuration, can not form in the plasticizing mixing process in shaper and fully peel off dispersive nano imvite lamella and can not form the required a large amount of nucleation site of microporous foam, more can not improve the performance of material or goods; Uneven owing to disperseing on the contrary, thus the not even performance thin spot of abscess in material or the goods caused.These micron-sized organo montmorillonites need just can be peeled off to form a large amount of nano level montmorillonite layer structures and be distributed in the thermoplastic matrix after compound through melting mixing or original position and go with polymkeric substance, could realize with a large amount of nucleation site of the polynite acquisition of a small amount of and improve material or the performance of goods.
Concentrate master batch and making method and in patent WO2005/056644, disclosed a kind of nano imvite, adopt the organic montmorillonoid and the polymer melt calendering process of the purification of U.S. Nanocor company.The method that this patent discloses mainly is that the proportional range by regulation organo montmorillonite and compatible dispersion agent defines this nano imvite enriched material, thermoplastic carrier resin is wherein refered in particular to further and is polyolefine, and when nano imvite further polyolefin elastomer that adds behind the matrix polymer thorough mixing.Master batch according to described method production, when the content of nano imvite is higher, the proportion of prepared concentrated master batch will be much larger than the proportion of thermoplastic resin particle commonly used, be more suitable in the molding device of the charging equipment that adopts accurate measurement, otherwise in the material loading process, concentrate master batch and thermoplastic resin particle skewness in hopper, and then cause the unsteady phenomenon of quality of injection-molded item or extruded product.
Summary of the invention
Purpose of the present invention, the one,, make the close nucleator master batch of resin material proportion that is adopted with follow-up foaming by the method that adopts the supercutical fluid foaming, convenient follow-up injection foaming moulding and foam shaping by extrusion; The 2nd,, adopt supercritical carbon dioxide or nitrogen to reduce the viscosity of vector resin in the mixing process, strengthen and peel off the dispersing uniformity of back stratiform polynite in vector resin, reduce technological temperature; The 3rd,, by foaming, the interlamellar spacing of the unstripped laminar nano polynite that may exist strengthens, and realizes peeling off.
For achieving the above object, the present invention realizes by following technical proposal:
Raw material of the present invention mainly is made up of organo montmorillonite, thermoplastic resin and supercritical fluid aerating powder, wherein, and by weight ratio:
Organo montmorillonite accounts for 100-500
Thermoplastic resin accounts for 500-900
Supercritical fluid aerating powder accounts for 0.5-90
The specific gravity control of the nucleator master batch that above-mentioned raw materials is made is between 100+/-5% of the proportion of thermoplastic resin; Further prioritization scheme is, raw material mainly is made up of organo montmorillonite, thermoplastic resin and supercritical fluid aerating powder, wherein, and by weight ratio:
Organo montmorillonite accounts for 300-400
Thermoplastic resin accounts for 600-700
Supercritical fluid aerating powder accounts for 0.6-70
The specific gravity control of the nucleator master batch that above-mentioned raw materials is made is between 100+/-5% of the proportion of thermoplastic resin; The shape of master batch comprises cylindricality, the sphere in different shape cross section or approaches the spheric particle, and particle can be 1 millimeter-5 millimeters sieve aperture by diameter; Described organo montmorillonite particle be by smectite content the polynite between the 95%-99% in polar organic solvent or inorganic solvent by comprising that the cetyl trimethylammonium bromide long chain quaternary handled, and can pass through 400 mesh sieves; Described thermoplastic resin is meant polyethylene, polypropylene, maleic anhydride modified polypropylene, polyvinyl chloride, acrylic resin, styrene resin, poly terephthalic acid hexylene glycol ester, polybutylene terephthalate, polyacrylic ester, polyhenylene ether, the modified polyphenylene ether resin, full-aromatic polyester, polyacetal resin, polycarbonate, polyetherimide, polyethersulfone, polyamide-based resin, polysulfones, polyether-ether-ketone, polyetherketone, thermoplastic polyurethane, a kind of or two kinds or multiple thermoplastic resin identical or compatible or mixture in the thermoplastic polyolefin elastomer with matrix resin; Described supercritical fluid aerating powder is meant supercritical co or overcritical nitrogen; The production method of described used for foaming of thermoplastic resin nucleator master batch is characterized in that comprising the following steps:
1) temperature with thermoplastic resin is increased to its fusing point or an interior temperature value of temperature of fusion ± 20 ℃ scope;
2) again the organo montmorillonite particle is added in the fused thermoplastic resin;
3) thermoplastic resin and organo montmorillonite are carried out melting mixing and form mixture at the fusing point or a temperature value in ℃ scope of temperature of fusion ± 20 of thermoplastic resin;
4) then to 3) described in mixture in introduce supercritical fluid aerating powder, and with temperature maintenance 3) described in temperature value, the uniform mixture of further mixing formation;
5) behind the extrusion foaming and be cut into particulate state.
Advantage of the present invention is, make the close nucleator master batch of resin material proportion that is adopted with follow-up foaming by the method that adopts the supercutical fluid foaming, convenient follow-up injection foaming moulding and foam shaping by extrusion, by adopting supercritical carbon dioxide or nitrogen to reduce the viscosity of vector resin in the mixing process, strengthen and peel off the dispersing uniformity of back stratiform polynite in vector resin, reduce technological temperature, pass through foaming, the interlamellar spacing of the unstripped laminar nano polynite that may exist strengthens, and realizes fully peeling off.
Description of drawings
Fig. 1 is a manufacturing process synoptic diagram of the present invention
Fig. 2 is for realizing that a kind of device used in the present invention is the parallel dual-screw extruding machine synoptic diagram;
Fig. 3: a kind of extruding pelletization mouth mould synoptic diagram of suitable technology of the present invention;
Embodiment
Detailed description of the present invention will be described further by the drawings and specific embodiments.
As accompanying drawing 1,2,3,4, label is wherein represented respectively: 1-forcing machine driving mechanism, 2-first opening for feed, 3-second opening for feed, 4a-wherein first screw arbor assembly, 4b-wherein on second screw arbor assembly, the 5-screw rod reverse screw element, 6-the 3rd opening for feed, 7-supercutical fluid measuring apparatus, 8-supercritical fluid source, 9-mouth mould, 10-pellet device, 11-master batch particle, 9a-melten gel inlet part, 9b-extrude passage, the 9c-passage of finalizing the design;
A parallel dual-screw extruding machine is set, length be screw diameter 38-40 doubly between, three opening for feeds are set on forcing machine, be separately positioned on screw rod zero position, be the fluxing zone position of ending and be the exhaust section position apart from the about 9-10 of first opening for feed times screw diameter apart from the about 28-29 of first an opening for feed times screw diameter.By metering thermoplastic resin particle, organo montmorillonite particle, supercritical foaming agent are incorporated in the extruder barrel respectively by these three opening for feeds.Wherein share is as follows by weight ratio for these three kinds of raw materials:
Organo montmorillonite adopts the DK5 product of Zhejiang Feng Hong clay chemical industry company limited, and by 400 mesh sieves, proportion is at 2.1g/cm
3, 400g, smectite content 98%;
Thermoplastic resin adopts nylon 6, and its proportion is at 1.14g/cm
3, 600g;
Supercritical fluid aerating powder adopts carbonic acid gas 20g.
According to above-mentioned weight proportion share, adopt suitable metering and conveying device evenly these three kinds of main raw materials to be transported in the parallel dual-screw extruding machine tube with method in the following order, make the foaming nucleation masterbatch:
(1) thermoplastic resin pellet is passed through first opening for feed that forcing machine is sent in metering by weight ratio, begin the fusing point or an interior temperature of temperature of fusion ± 20 ℃ scope of carrying and heating up and reaching thermoplastic resin;
(2) the organo montmorillonite powder is sent to by second opening for feed by weight ratio after metering carries out mixingly in the melten gel, and keep temperature in the machine barrel in the fusing point of the thermoplastic resin described in (1) or a temperature in ℃ scope of temperature of fusion ± 20;
(3) and then with the supercritical fluid aerating powder carbonic acid gas, be incorporated in the mixture of fused thermoplastic resin and polynite by the 3rd opening for feed by weight ratio;
(4) molten resin, polynite, supercritical gas are continued to mix the uniform mixture of formation
(5) be cut into particle shape behind the through port mould extrusion foaming.
Further specify
As attached illustrated in figures 1 and 2, adopting a screw diameter D is 30 millimeters parallel dual-screw extruding machine, and spiro rod length is 40D.Wherein first opening for feed 2, second opening for feed 3, the 3rd opening for feed 6 be separately positioned between the 1D-2D, between the 9D-10D and between the 28D-29D.Wherein first opening for feed 2 is connected with pellet or powder weight metering drawing-in device respectively with second opening for feed 3.Wherein first opening for feed 2 is introduced thermoplastic resin particle, and second opening for feed 3 is introduced the organo montmorillonite powder.And the 3rd opening for feed 6 is connected with supercutical fluid measuring apparatus 7.Wherein the supercutical fluid measuring apparatus adopts the device described in the ZL200620049021.3, and further is connected with supercritical fluid source 8.Outlet at forcing machine connects a mouth mould 9, as shown in Figure 3.Connect pellet device 10 after the mouth mould 9, extrudate is cut into the particle 11 of certain-length.
Wherein the melts in mouthful mould 9 is extruded passage and is comprised three parts, and wherein colloidal sol inlet part 9a is connected with the outlet of forcing machine, extrudes passage 9b and the passage 9c that finalizes the design.Wherein the finalize the design cross section of passage 9c is that pellet diameter commonly used is the elliptical shape that 3 millimeters circular hole or sectional area are equivalent to 3 mm dia garden hole areas.The cross-sectional shape that is adopted of extruding passage 9b wherein is identical with the cross-sectional shape that typing passage 9c is adopted, but extrudes passage 9b sectional area then less than the sectional area of typing passage 9c.
In the present embodiment, thermoplastic resin adopts nylon 6, and its proportion is at 1.14g/cm
3And organo montmorillonite adopts the DK5 product of Zhejiang Feng Hong clay chemical industry company limited, and proportion is at 2.1g/cm
3The weight proportion of nylon 6 is 600g, and the mass parts of organo montmorillonite is 400g, adds by first opening for feed 2 and second opening for feed, 3 metering backs respectively.And measure the supercritical carbon dioxide gas that input is about the 20g weight part by the 3rd opening for feed 6.
By heating and the temperature control unit (not expressing in the synoptic diagram) that is installed on the machine barrel barrel zone temperature is stabilized in (fusing point of nylon 6 is 225 ℃) between 225 ℃-230 ℃.Adopting this temperature design mainly is to make base resin have higher viscosity, thereby can effectively the montmorillonite layer structure be peeled off in mixing process, and is distributed in the nylon resin.And carry out supercharging by the direction screw element 5 that is arranged on the mixing section closing position, strengthen mixing effect.
Introduce the supercritical co of about 12g then by the 3rd opening for feed 6.The 3rd opening for feed 6 is arranged on reverse screw element 5 position about 1D afterwards, the exhaust section of promptly common parallel dual-screw extruding machine.Within the distance of about 10D after this, carbonic acid gas disperses to be added in the mixture of nylon 6 and nano imvite gradually.Dissolved the viscosity degradation of the nylon 6 of carbonic acid gas, improved the dispersive ability of laminar nano polynite, thereby under the situation that does not improve temperature, the nano imvite of being stripped from is evenly dispersed in resin matrix, obtains nylon 6, nano imvite and carbonic acid gas three's uniform mixture.
This uniform mixture is incorporated in mouthful mould 9, and mixture is through intake 9a, extrude passage 9b after, foaming and arrive pellet device 10 in the typing passage through cooling and shaping.After pelletizing, obtain nucleator master batch 11.Through measuring, the proportion of master batch is at 1.15g/cm
3, near the proportion 1.14cm of nylon 6
3
At this specific embodiment, typing passage 9c adopts the prototype passage of 3 mm dias in mouthful mould 9, also adopt circular passage and extrude passage 9b, but its diameter is set to 2.6 millimeters.
Contrastively, stop to introduce supercritical fluid aerating powder by opening for feed 6, the proportion of the master batch material of extruding is up to 1.5g/cm
3, far above the proportion of nylon 6.
Adopt the nucleator master batch of this proportion, when injection moulding or extrusion foaming processing nylon 6 foaming products, this master batch is easy to before material loading and in plasticizing apparatus and the even blending of nylon 6 pellets, can be in the material loading process, or in hopper, the situation of fluctuation appears in the ratio of two kinds of material (masterbatch and matrix thermoplastic resin).Cause the Products Quality instability further.
Adopt identical parallel dual-screw extruding machine with embodiment 1, but thermoplastic resin adopts polypropylene PP and maleic anhydride to improve polyacrylic mixture, the ratio weight average of two kinds of materials is at 0.9-0.91g/cm
3Between, and organic nano imvite adopts the DK4 organo montmorillonite of Zhejiang Feng Hong clay chemical industry company limited, and select with 400 mesh sieves, smectite content 96%, proportion is at 2.0g/cm
3
The parts by weight that polypropylene PP and maleic anhydride improve polypropylene mixture and DK4 nano imvite are 680g and 320g, wherein among the thermoplastic resin intermixture of 680g maleic anhydride to improve polyacrylic weight be 120g.And supercutical fluid adopts nitrogen, and weight is 13.6g.The barrel zone temperature of parallel dual-screw extruding machine is arranged between 170 ℃-175 ℃, and the fusing point of PP is 176 ℃.
The structure formation of mouthful mould 9 adopts the mouth mould 9 among the embodiment 1 in the present embodiment.The proportion of the nucleator master batch 11 of Sheng Chaning is 0.91g/cm according to the method described above
3About.Close with the proportion of the PP pellet of reality.Injection moulding that the aspect is follow-up and extrusion moulding.
Adopt identical parallel dual-screw extruding machine with embodiment 1, but thermoplastic resin adopts the mixture of nylon 6, polypropylene, maleic anhydride modified acrylic resin, and the total weight parts of this mixture is 650g, and wherein nylon 6 is 300g, polypropylene is 300g, and maleic anhydride modified polypropylene is 50g; And organo montmorillonite adopts the DK4 product of Zhejiang Feng Hong clay chemical industry company limited, and weight part is 350g, and by 400 mesh sieves, proportion is 2.0g/cm
3, smectite content is 96%; Supercritical fluid aerating powder adopts carbonic acid gas, and weight part is 6g.
Press embodiment 1 and the mixture of the identical priority of embodiment 2 adding methods with three kinds of thermoplastic resins, organo montmorillonite powder, and supercritical co.The temperature of mixing roll is set 205 ℃.
The proportion that obtains master batch by this proportioning is 1.1g/cm
3This master batch is suitable for the PA or the PA/PP alloy material foaming of high nylon 6 content.
Embodiment 4
With reference to embodiment 3, adopt the mixture 650g of three kinds of thermoplastic resins of identical proportioning, organo montmorillonite is DK4 product 350g, but the amount of supercritical co is 50g.The temperature of mixing roll is set at 205 ℃.The proportion of the nucleator master batch that obtains by this proportioning is 0.92g/cm
3This master batch is suitable for the PP or the PP/PA alloy material foaming of high polypropylene content.
Though below design and embodiment according to the object of the invention have been done to elaborate with reference to accompanying drawing; but those of ordinary skills can recognize; under the precondition that does not break away from the claim limited range; still can make various improvement and conversion to the present invention, and this improvement and conversion still should belong to protection scope of the present invention.
Claims (8)
1. used for foaming of thermoplastic resin nucleator master batch is characterized in that, raw material mainly is made up of organo montmorillonite, thermoplastic resin and supercritical fluid aerating powder, wherein, and by weight ratio;
Organo montmorillonite accounts for 100-500
Thermoplastic resin accounts for 500-900
Supercritical fluid aerating powder accounts for 0.5-90
The specific gravity control of the nucleator master batch that above-mentioned raw materials is made is between 100+/-5% of the proportion of thermoplastic resin.
2. used for foaming of thermoplastic resin nucleator master batch according to claim 1 is characterized in that raw material mainly is made up of organo montmorillonite, thermoplastic resin and supercritical fluid aerating powder, wherein, and by weight ratio;
Organo montmorillonite accounts for 300-400
Thermoplastic resin accounts for 600-700
Supercritical fluid aerating powder accounts for 0.6-70
The specific gravity control of the nucleator master batch that above-mentioned raw materials is made is between 100+/-5% of the proportion of thermoplastic resin.
3. used for foaming of thermoplastic resin nucleator master batch according to claim 1 is characterized in that, the organo montmorillonite particle can pass through 400 mesh sieves.
4. used for foaming of thermoplastic resin nucleator master batch according to claim 1 is characterized in that, the shape of master batch comprises cylindricality, the sphere in different shape cross section or approaches the spheric particle, and particle can be 1 millimeter-5 millimeters sieve aperture by diameter.
5. used for foaming of thermoplastic resin nucleator master batch according to claim 1, it is characterized in that, described organo montmorillonite particle be by smectite content the polynite between the 95%-99% in polar organic solvent or inorganic solvent by comprising that the cetyl trimethylammonium bromide long chain quaternary handled.
6. used for foaming of thermoplastic resin nucleator master batch according to claim 1, it is characterized in that, described thermoplastic resin is meant polyethylene, polypropylene, maleic anhydride modified polypropylene, polyvinyl chloride, acrylic resin, styrene resin, poly terephthalic acid hexylene glycol ester, polybutylene terephthalate, polyacrylic ester, polyhenylene ether, the modified polyphenylene ether resin, full-aromatic polyester, polyacetal resin, polycarbonate, polyetherimide, polyethersulfone, polyamide-based resin, polysulfones, polyether-ether-ketone, polyetherketone, thermoplastic polyurethane, a kind of or two kinds or multiple thermoplastic resin identical or compatible or mixture in the thermoplastic polyolefin elastomer with matrix resin.
7. used for foaming of thermoplastic resin nucleator master batch according to claim 1 is characterized in that described supercritical fluid aerating powder is meant supercritical co or overcritical nitrogen.
8. the production method of used for foaming of thermoplastic resin nucleator master batch according to claim 1 is characterized in that comprising the following steps:
1) temperature with thermoplastic resin is increased to its fusing point or an interior temperature value of temperature of fusion ± 20 ℃ scope;
2) again the organo montmorillonite particle is added in the fused thermoplastic resin;
3) thermoplastic resin and organo montmorillonite are carried out melting mixing and form mixture at the fusing point or a temperature value in ℃ scope of temperature of fusion ± 20 of thermoplastic resin;
4) then to 3) described in mixture in introduce supercritical fluid aerating powder, and with temperature maintenance 3) described in temperature value, the uniform mixture of further mixing formation;
5) behind the extrusion foaming and be cut into particulate state.
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| CN115926238B (en) * | 2022-12-28 | 2023-10-24 | 湖北格霖威新材料科技有限公司 | Preparation method of high-tensile and high-toughness polypropylene foaming material |
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2009
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Address after: 102208 Beijing, Huilongguan, Beijing, Changping District Billiton machinery Refco Group Ltd Patentee after: Co., Ltd of mechanical group is opened up in Beijing Address before: 102208 Beijing, Huilongguan, Beijing, China Billiton Machinery Co., Ltd. Patentee before: Beijing Chn-Top Machinery Co., Ltd. |
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Application publication date: 20091028 Assignee: BEIJING CHN-TOP OPTICAL-ELECTRONIC TECHNOLOGY CO., LTD. Assignor: Co., Ltd of mechanical group is opened up in Beijing Contract record no.: 2018990000193 Denomination of invention: Nucleating agent master batches used for foaming of thermoplastic resin Granted publication date: 20110209 License type: Common License Record date: 20180727 |
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