CN1038421C - Supertough master-pellets for polypropylene plastics and making method thereof - Google Patents
Supertough master-pellets for polypropylene plastics and making method thereof Download PDFInfo
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- CN1038421C CN1038421C CN95112772A CN95112772A CN1038421C CN 1038421 C CN1038421 C CN 1038421C CN 95112772 A CN95112772 A CN 95112772A CN 95112772 A CN95112772 A CN 95112772A CN 1038421 C CN1038421 C CN 1038421C
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Abstract
The present invention relates to a super tough modified material used for polypropylene plastics and a making method thereof. The super tough modified material is made by mixing, plasticizing and granulating inorganic filling materials, a compound coupling agent and an elastic body, wherein the average particle diameter of the inorganic filling materials is from 0.5 mu m to 5 mu m. The compound coupling agent is prepared from a coupling agent and an auxiliary coupling agent, the coupling agent is a polyfunctional group compound which at least comprises two types of functional groups, and the auxiliary coupling agent is a polyfunctional group compound having certain intermiscibility with the coupling agent and at least comprising one functional group capable of acting with one of the functional groups in the coupling agent. The elastic body is a rubber substance having certain intermiscibility with polypropylene and a blending substance thereof.
Description
The present invention relates to super tough modified master batch and manufacture method thereof that a kind of plasticizing mother particle and manufacture method thereof, particularly acrylic plastering are used.
In existing polyolefin plastics material, polypropylene is a kind of plastics variety that the application development potentiality are arranged very much.Compare with polyethylene, its light weight, stretching, flexural strength and modulus height, good combination property, and also cheap and easy to get, be easy to processing.Now engineering plastics have been substituted in a lot of application scenarios through modification.So also become at present one of world today's output maximum, most widely used plastics variety.But polypropylene material has a key weakness, and promptly material is crisp, and notch shock toughness is lower.Must pass through modification in most of application scenarios, as adding lime carbonate, talcum powder, wollastonite or kaolin etc. are made the tailored version modifying material and are used.Though under this application scenario, because the requirement of material notched Izod impact strength is not very high (＜20KJ/M
2), can adopt toughening mother particle for polyolefine plastics (patent publication No.: CN1124747A) solve in the reality.But have the application scenario of particular requirement at some, as: be applied to car collision bumper, bearing circle, seat, washing machine chassis, bike fender etc., its material notched Izod impact strength requires than higher (〉=40KJ/M
2) time, then generally all can only adopt the method for the rubber that adds more deal to make super tough modified version polypropylene dedicated material use.Though this method of modifying is technical feasible, material modified manufacturing energy consumption and production cost have objectively been increased.And because the adding of the rubber composition of more deal, the modulus of polypropylene material and resistance toheat more, the material modified raw materials cost that also descends also improves a lot.Therefore this is not a kind of effective and economic method.
Purpose of the present invention is exactly in order to address the above problem, and has proposed a kind ofly can effectively improve the polypropylene material notched Izod impact strength and the Supertough master-pellets for polypropylene plastics and the manufacture method thereof of other performance and not obvious reduction.
Technical solution of the present invention:
A kind of Supertough master-pellets for polypropylene plastics, it is characterized in that it by inorganic fill out grain, composite coupler, elastomerics through mix, plasticate, granulation makes, the weight percent of its each composition is:
Mineral filler 60-90%
Elastomerics 10-40%
Composite coupler 1-4% (mineral filler weight relatively)
Wherein: the median size of mineral filler is 0.5-5 μ m; Described elastomerics is selected from polypropylene has certain rubber-like material of capacitive mutually, or the blend of itself and high density polyethylene(HDPE) or new LDPE (film grade).Composite coupler is by coupling agent and help coupling agent to form, and their amount ratio is 1: 0.5-3, coupling agent is for containing two types of (a of functional group at least
1, a
2) polyfunctional compound, functionality 〉=3, a kind of (a of functional group wherein
1) can (OH) have an effect, and the another kind of (a of functional group with the hydroxyl of inorganic filler surface
2) then can with help the corresponding functional group (b) in the coupling agent to have an effect; Help coupling agent be have certain intermiscibility with coupling agent and contain at least a kind of can with (a of functional group in the coupling agent
2) polyfunctional compound of the functional group (b) that has an effect, its functionality 〉=3, molecular weight is 1000-8000.
A kind of manufacture method of Supertough master-pellets for polypropylene plastics, it is characterized in that making composite coupler with coupling agent and after helping coupling agent to mix earlier, again composite coupler and mineral filler are mixed in super mixer, temperature is 60-80 ℃, time is 10-15 minute, obtain the good mineral filler of surface treatment, this mineral filler mixed on mixing roll with elastomerics plasticate, plasticating temperature is 140-160 ℃, plasticated time 10-15 minute, obtain the melt of plasticating, after in flakes, cooling, granulation promptly make Supertough master-pellets of the present invention.
It is a kind of new for, the i.e. manufacturing of toughness reinforcing method of master batch and Supertough master-pellets thereof that the present invention is that the super tough modification of polypropylene (PP) plastics provides.That is before the polypropylene material product molding, as long as an amount of Supertough master-pellets is simply mixed with polypropylene, and by injection, extrude or forming method such as hollow blow molding is made plastics, then the notched Izod impact strength of resulting product material promptly reaches super high impact strength level (〉=40KJ/M
2).And the material compared of material modified modulus in flexure and resistance toheat and employing modified rubber has also obtained obvious improvement.Manufacture super tough type polypropylene dedicated material with modification, and then the method for moulding compares, the inventive method has been saved the step of making PP Pipe Compound, has reduced material modified manufacturing energy consumption, has made things convenient for user's modification requirement.And because the material cost of this Supertough master-pellets is lower, add the obvious increase that can not cause material modified material cost among the PP, compare, then obviously reduce, obtain better economic benefit so can be the user with rubber toughened type PP Pipe Compound.The present invention is aspect the surface treatment of Supertough master-pellets filler, adopt coupling agent and the method that helps the coupling agent Combined Processing first, they also evenly are coated on the master batch filling surface with the form connection of chemical bond, have formed half interpenetrating network structure with elastomerics again simultaneously, have strengthened the interfacial phase connection.So make that the toughening effect of this Supertough master-pellets is particularly evident.
At ambient temperature, the coupling agent in the composite coupler that the present invention adopts and help coupling agent not have an effect mutually, thus can be dispersed in inorganic filler surface by means of thinner, with the viscosity of reduction composite coupler.Mineral filler can be selected lime carbonate, kaolin, talcum powder, wollastonite, barium sulfate, aluminum oxide etc. for use, and its median size is preferably 1-3 μ m, and its consumption the best is the 70-80% of total amount.Yet under the hot conditions of mineral filler and elastomer composite, a of functional group in the coupling agent
1When having an effect with inorganic filler surface, a of its functional group
2Chemical action has also taken place with helping the b of functional group in the coupling agent.Promptly with this understanding, help coupling agent to connect with the form of chemical bond and evenly be coated on inorganic filler surface, and crosslinked action has taken place with coupling agent by coupling agent.Obviously, this moment is because mineral filler and elastomerics melt are in the tight contact condition under the mixing condition, so it helps coupling agent when crosslinked action takes place, also must twine, network resilience body molecular chain, promptly forming half interpenetrating network structure at the interface, thereby strengthened the interfacial phase connection effectively, improved the modified effect of Supertough master-pellets.
Coupling agent among the present invention for silicane, can be selected N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan (A-1120) for use, γ-An Bingjisanyiyangjiguiwan (A-1100) or γ-glycidyl ether oxygen propyl trimethoxy silicane (A-187) etc.Can select isopropyl tri (dioctylpyrophosphato)titanate (TTOPP-38S) or two (dioctyl pyrophosphoryl oxygen base) oxo acetic acid titanium (KR-138S) etc. for use for titanate ester.The functionality of coupling agent is preferably 4-5, and the consumption of its relative mineral filler is preferably 0.8-1.2%.
The coupling agent that helps among the present invention can be selected polyether compound for use.The kind of terminal functionality is then looked a in the coupling agent in its polyethers
2The character of functional group and determining.So, can select end carboxyl class polyethers for use to the above-mentioned silane coupling agent that contains amino or epoxy group(ing).Then can select end amino, terminal hydroxy group or end oxazoline acyclic polyether etc. for use for the titante coupling agent that contains phosphate groups.And actual proof, coupling agent and help the functional group reactions activity between coupling agent high more, then its coupling effect is also good more.
Help the functionality size of coupling agent also very important, when its functionality＜3, owing to be difficult for producing crosslinked action, can not effectively twine, network resilience body molecular chain, therefore actual coupling effect is bad.But too high as functionality, crosslinked action is strong excessively, then helps the coupling agent molecule chain to be difficult for being difficult for winding, network resilience body molecular chain, so its coupling effect is also bad to the elastomer molecules diffusion.Effect is better when selecting for use functionality to be 3-4 in the reality.
Help the molecular weight of coupling agent that modified effect is also had significant effects.Less as molecular weight, then help coupling agent twine at the interface, the quantity of network resilience body molecular chain is on the low side, interface binding intensity is not high.Excessive as molecular weight, then help the mutual solubility variation between coupling agent and elastomerics, its coupling effect is also bad.Select the compound of molecular weight between 3000-6000 in the reality for use, effect is better.The consumption that helps coupling agent is preferably 1 with the ratio of coupling agent: 0.5-2.
Mutual capacitive between elastomerics of the present invention and polypropylene, dispersiveness also have a significant impact its toughening effect.Preferably select for use in the reality with polypropylene and have better the segmented copolymer thermoplastic elastomers such as (SBS) of ethylene-propylene rubber(EPR) (EPR), terpolymer EP rubber (EPDM), cis-1,4-polybutadiene rubber (BR), isoprene-isobutylene rubber (IBR), styrene-butadiene rubber(SBR) (SBR) or the vinylbenzene and the divinyl of capacitive mutually.Perhaps select suitable (its melting index is at the 0.5-15g/10min) high density polyethylene(HDPE) (HDPE) of above-mentioned elastomerics and molecular weight or the blend of new LDPE (film grade) (LDPE) for use.
Owing to the adding of a large amount of mineral fillers, caused the increase of material melt flow resistance, the processing flowability variation of the material that is modified among the present invention.To this can be that the flow ability modifying agent of 0.5-2% improves by adding relative total amount.This stream properties-correcting agent can be selected solid paraffin, whiteruss or polyethylene wax etc. for use, and its optimum amount is the 0.8-1.2% of total amount.
For guaranteeing the stability of master batch of the present invention in manufacturing processed and moulding process, in the master batch manufacturing, can add an amount of thermo-stabilizer and photostabilizer, consumption is the 0.1-1.0% of total amount.
Modification theory of the present invention mainly is to have utilized inorganicly to fill out that a particle is little, surface-area is big, easy dispersive characteristic in polypropylene matrix, and strengthened interface associativity between filler particles and rubber phase by compound link coupled surface treatment method, thereby make in its moulding process, when master batch and matrix dispersion, easily forming with the inorganic filler particle is the center, elastomerics then is coated on the dispersion particle of " core-shell structure " around it, and elastomerics is dissociated out by inorganic filler surface, and the tendency that forms the free rubber phase particles then reduces.So both improved the volume parts of composite elastic body disperse phase effectively; can make and be modified material under less elastomer content condition; can reach higher notched Izod impact strength; simultaneously the homodisperse of rubber phase in matrix more easily carried out, the master batch process of the super tough modification technology of polypropylene material is achieved.
Embodiment 1 (is example to produce 100 kilograms of Supertough master-pellets):
Get 70 kilograms of lime carbonate mineral fillers, its median size is 1.51 μ m, and distribution variance is 0.23 μ m
2, dried for standby.Get 0.7 kilogram of isopropyl tri (dioctylpyrophosphato)titanate (TTOPP-38S) coupling agent, its molecular structural formula is:
Qu Duan oxazoline polyethers ON347 (three-functionality-degree, molecular weight 4700) helps 0.7 kilogram of coupling agent again, and its molecular structural formula is:
Wherein:
Or-CH
2-CH
2-
With above-mentioned coupling agent with help coupling agent to mix, simultaneously can add an amount of isopropanol agent, obtain composite coupler after they mix.
Pearl filler added in the super mixer mix, add above-mentioned composite coupler in whipping process, whipping temp is 70 ℃, stirs promptly to obtain the good mineral filler of surface treatment in 15 minutes.The mineral filler that this surface treatment is good mixes, plasticates on two roller mixing rolls with 30 kilograms of terpolymer EP rubbers (EPDM2504); temperature is controlled at 150 ℃; in blocks again after plasticating 15 minutes, cooling also promptly obtains Supertough master-pellets of the present invention about 100 kilograms through flat dicing machine granulation.
The present invention in the process of plasticating, the titanium ester bond (a of functional group in the isopropyl tri (dioctylpyrophosphato)titanate coupling agent
1) and (a of phosphate radical functional group
2) respectively with the hydroxyl on pearl filler surface with Duan oxazoline polyethers helps coupling agent Zhong De oxazoline ring (b) that chemical action takes place, make and help coupling agent to connect with the form of chemical bond and evenly be coated on inorganic filler surface by coupling agent.And when helping coupling agent and coupling agent generation crosslinked action, also winding, network resilience body molecular chain make them form half interpenetrating network structure at the interface, so strengthened the interfacial phase connection effectively.
Supertough master-pellets of the present invention only needs simple the mixing by a certain percentage again with acrylic plastering can make the very high polypropylene plastics products of toughness of material by injection moulding or extrusion moulding moulding.
50 parts of Supertough master-pellets that will make by above-mentioned prescription and technology are with after 50 parts of polypropylene (PPF401) resins simply mix, through injection moulding sample preparation (about 210 ℃-230 ℃ of injection temperatures, injection pressure 50MPa).Sample is by standard GB1040-79, GB1042-79, GB1043-79 and GB3682-83 test performance.
Table 1 embodiment 1 and comparative example 1-6 result are relatively
The fusion of Charpy breach bend tension
Sequence number shock strength strength index
(KJ/M
2) (MPa) (MPa) (g/10min)
Embodiment 1 88.3 34.3 18.1 1.3
Comparative example 1 73.3 33.3 18.1 1.3
Comparative example 2 82.7 34.7 17.4 1.3
Comparative example 3 7.3 62.3 33.2 2.5
Comparative example 4 20.1 40.2 19.5 1.5
Comparative example 5 21.2 34.9 18.1 1.3
Comparative example 6 60.1 34.7 18.3 1.5
Except that helping coupling agent to adopt the Duan oxazoline polyethers ON330 (three-functionality-degree, molecular weight 3000), all the other are all identical with embodiment 1 in comparative example 1 master batch.
Except that helping coupling agent to adopt the Duan oxazoline polyethers ON337 (three-functionality-degree, molecular weight 3700), all the other are all identical with embodiment 1 in comparative example 2 master batches.
Do not add the Supertough master-pellets sample in comparative example 3 polypropylene (PPF401) resin.
CaCO3 median size d=3.2 μ m in comparative example 4 master batches, distribution variance s
2=1.1 μ m, all the other are all identical with example 1.
Does not handle on the CaCO3 surface in comparative example 5 master batches, and all the other are all identical with embodiment 1.
Save in comparative example 6 master batches and help coupling agent, all the other are all identical with embodiment 1.
Embodiment 1 and comparative example 1-6 gained material property are shown in Table 1:
Embodiment 2:
Mineral filler CaCO3 is identical with embodiment 1, and consumption is referring to table 2.
The CaCO3 surface treatment method, helps coupling agent and consumption thereof identical with embodiment 1 at coupling agent.
Elastomerics is selected the blend of terpolymer EP rubber (EPDM2504) and high density polyethylene(HDPE) (HDPE2200J) for use.Concrete consumption is referring to table 2.
Embodiment 2 master batches are formed the influence of polypropylene (PP) toughening effect referring to table 2.
Table 2 master batch is formed to be influenced the PP toughening effect
| Sequence number | Master batch is formed (%) | Master batch Charpy lacks bend tension fusion mouth shock strength strength index * consumption (KJ/M 2) (MPa) (MPa) (g/10min) |
| Base material is formed the CaCO3 consumption | ||
| Embodiment 2-1 embodiment 2-2 embodiment 2-3 embodiment 2-4 | EPDM 10% 80% HDPE 8% flow ability modifying agent 2% EPDM 14% 73% HDPE 12% flow ability modifying agents, 1% EPDM, 15% 73% HDPE 11% flow ability modifying agent 1% EPDM, 15% 73% HDPE 11% flow ability modifying agents 1% | 50％ 36.1 38.2 20.9 55％ 42.7 36.4 19.5 55％ 54.4 34.7 18.4 1.5(6.1) 55％ 55.3 32.1 17.4 3.6(15.2) |
Annotate: base material PP resin in the table, embodiment 2-1 to 2-3 is PPF401, embodiment 2-4 is: PPF40155%, PPMK55 45%.* melt index determination condition: 230 ℃, 2.16kg load; Data are the 5.0kg load-up condition in the bracket.
Data as seen from table 2: when the EPDM in the Supertough master-pellets was reduced to 15% left and right sides, its material modified performance still can reach the level of super high impact strength.And because the improvement of the effect of flow ability modifying agent and cooperation base material PP proportioning.So the manufacturing cost of master batch product is not high, and the application scenario of having relatively high expectations applicable to processing flowability.
Claims (8)
1. Supertough master-pellets for polypropylene plastics, it is characterized in that it by mineral filler, elastomerics, composite coupler through mix, plasticate, granulation makes, the weight percent of its each composition is:
Mineral filler 60-90%
Elastomerics 10-40%
Composite coupler 1-4% (mineral filler weight relatively)
Wherein: the median size of mineral filler is 0.5-5 μ m; Described elastomerics is selected from the blend that has the rubber-like material of certain capacitive mutually or itself and high density polyethylene(HDPE) or new LDPE (film grade) with polypropylene, composite coupler is by coupling agent and help coupling agent to form, their amount ratio is 1: 0.5-3, coupling agent is for containing two types of (a of functional group at least
1, a
2) polyfunctional compound, functionality 〉=3, a kind of (a of functional group wherein
1) can (OH) have an effect, and the another kind of (a of functional group with the hydroxyl of inorganic filler surface
2) then can with help the corresponding functional group (b) in the coupling agent to have an effect; Help coupling agent be have certain intermiscibility with coupling agent and contain at least a kind of can with (a of functional group in the coupling agent
2) polyfunctional compound of the functional group (b) that has an effect, its functionality 〉=3, molecular weight is 1000-8000; Described coupling agent is titanate ester or silane coupling agent, and the described coupling agent that helps is a polyether compound, and their amount ratio is 1: 0.5-3.
2. by the described Supertough master-pellets for polypropylene plastics of claim 1, it is characterized in that mineral filler is selected from lime carbonate, kaolin, talcum powder, wollastonite, barium sulfate, aluminum oxide, its median size is 1-3 μ m, and consumption is 70-80%.
3. by the described Supertough master-pellets for polypropylene plastics of claim 1, it is characterized in that its elastomerics is selected from the segmented copolymer (SBS) of ethylene-propylene rubber(EPR) (EPR), terpolymer EP rubber (EPDM), cis-1,4-polybutadiene rubber (BR), isoprene-isobutylene rubber (IBR), styrene-butadiene rubber(SBR) (SBR), vinylbenzene and divinyl, or the high density polyethylene(HDPE) (HDPE) of suitable (its melting index is at 0.5-15g/10min) of itself and molecular weight or the blend of new LDPE (film grade) (LDPE), their consumption proportion is 1: 0-2.
4. by the described Supertough master-pellets for polypropylene plastics of claim 1, the functionality that it is characterized in that coupling agent in the composite coupler is 4-5, and the consumption of its relative mineral filler is 0.8-1.2%; The functionality that helps coupling agent in the composite coupler is 3-4, and its molecular weight is 3000-6000, and its consumption is 1 with the ratio of coupling agent: 0.5-2.0.
5. by the described a kind of Supertough master-pellets for polypropylene plastics of claim 1, it is characterized in that adding an amount of rare dose when coupling agent mixes,, it is uniformly dispersed in inorganic filler surface so that reduce the viscosity of composite coupler.
6. by the described a kind of Supertough master-pellets for polypropylene plastics of claim 1, it is characterized in that when composite coupler mixes with mineral filler, add the flow ability modifying agent that relative total amount is 0.5-2%.
7. by the described a kind of Supertough master-pellets for polypropylene plastics of claim 6, it is characterized in that flow ability modifying agent selects solid paraffin, white oil or polyethylene wax for use, its consumption is 0.8-1.2%.
8. the manufacture method of a Supertough master-pellets for polypropylene plastics, it is characterized in that making composite coupler with coupling agent and after helping coupling agent to mix earlier, again composite coupler and mineral filler are mixed in super mixer, temperature is 60-80 ℃, time is 10-15 minute, obtains the good mineral filler of surface treatment.This mineral filler mixed on mixing roll with elastomerics plasticate, plasticating temperature is 140-160 ℃, plasticates time 10-15 minute, obtains the melt of plasticating, after in flakes, cooling, granulation promptly make Supertough master-pellets of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112772A CN1038421C (en) | 1995-11-17 | 1995-11-17 | Supertough master-pellets for polypropylene plastics and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112772A CN1038421C (en) | 1995-11-17 | 1995-11-17 | Supertough master-pellets for polypropylene plastics and making method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1131165A CN1131165A (en) | 1996-09-18 |
| CN1038421C true CN1038421C (en) | 1998-05-20 |
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|---|---|---|---|
| CN95112772A Expired - Fee Related CN1038421C (en) | 1995-11-17 | 1995-11-17 | Supertough master-pellets for polypropylene plastics and making method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100087C (en) * | 1998-06-18 | 2003-01-29 | 中国科学院化学研究所 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
| CN1312217C (en) * | 2004-02-02 | 2007-04-25 | 山西新阳新材料有限公司 | Preparation method of ABS (acrilonitrile-butadiene-phenyl ethylene copolymer) functional filling mother particle |
| BR112012000217B1 (en) * | 2009-06-22 | 2019-06-25 | Borealis Ag | POLYMERIC COMPOSITION, AND USE OF A INOSSYLYLATE ON THE SAME |
| CN102070918A (en) * | 2009-11-19 | 2011-05-25 | 台州市黄岩明江塑胶有限公司 | Preparation method of calcium carbonate masterbatch |
| CN102336949B (en) * | 2011-07-23 | 2013-05-01 | 佛山市衡龙科技有限公司 | PP (Polypropylene) spun-bonded non-woven fabric white master batch and preparation process thereof |
| CN102627806B (en) * | 2012-04-12 | 2013-09-18 | 上海瀚氏模具成型有限公司 | PP/HDPE (Polypropylene/High-Density Polyethylene) plastic for automobile interior and preparation method thereof |
| CN104356501A (en) * | 2014-12-02 | 2015-02-18 | 芜湖鑫诚模塑科技有限公司 | Nano complex-function master batch and preparation method thereof |
| CN104817774A (en) * | 2015-04-02 | 2015-08-05 | 扬翔(上海)环保科技有限公司 | Foaming master batch and preparation method thereof |
| CN109233095A (en) * | 2018-08-07 | 2019-01-18 | 江苏凯诺塑化有限公司 | Modified polypropylene material for refrigerator ice milk layer drawer |
| CN109320830B (en) * | 2018-09-13 | 2021-07-23 | 浙江钦堂钙业有限公司 | High-mesh-number powder filling master batch and preparation method thereof |
| CN110903520A (en) * | 2019-11-22 | 2020-03-24 | 浙江海啊汽车用品有限公司 | Color-changing bionic automobile seat cover material and manufacturing method thereof |
| CN110845804A (en) * | 2019-11-22 | 2020-02-28 | 怀化东庆科技有限公司 | Polyisobutylene talcum powder master batch and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2424949A1 (en) * | 1973-05-24 | 1974-12-12 | Sublistatic Holding Sa | PROCESS FOR DRY TRANSFER COLORING OF METALLIC OR RIGID SURFACES AND THE PRODUCTS THEREOF |
| SU861359A1 (en) * | 1979-11-01 | 1981-09-07 | Воронежский технологический институт | Method of producing rubber mixture |
-
1995
- 1995-11-17 CN CN95112772A patent/CN1038421C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2424949A1 (en) * | 1973-05-24 | 1974-12-12 | Sublistatic Holding Sa | PROCESS FOR DRY TRANSFER COLORING OF METALLIC OR RIGID SURFACES AND THE PRODUCTS THEREOF |
| SU861359A1 (en) * | 1979-11-01 | 1981-09-07 | Воронежский технологический институт | Method of producing rubber mixture |
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| CN1131165A (en) | 1996-09-18 |
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