CN1049363A - Rubber mass - Google Patents

Rubber mass Download PDF

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Publication number
CN1049363A
CN1049363A CN 89107026 CN89107026A CN1049363A CN 1049363 A CN1049363 A CN 1049363A CN 89107026 CN89107026 CN 89107026 CN 89107026 A CN89107026 A CN 89107026A CN 1049363 A CN1049363 A CN 1049363A
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CN
China
Prior art keywords
rubber
weight
tectum
rubber mass
sulphur
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.)
Pending
Application number
CN 89107026
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Chinese (zh)
Inventor
塞帕克·姆·白勃洛夫
伊利娜·格·康亚夫科
伊利娜·本·沙夫拉卡亚
亚克夫·阿·古维奇
加利娜·伊·鲁丹科
阿拉·尼·弗洛什纳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imerys Minerals Ltd
Alma-Atinsky Arkhitektarno-Stroiteiny Institut
Original Assignee
Alma-Atinsky Arkhitektarno-Stroiteiny Institut
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alma-Atinsky Arkhitektarno-Stroiteiny Institut filed Critical Alma-Atinsky Arkhitektarno-Stroiteiny Institut
Publication of CN1049363A publication Critical patent/CN1049363A/en
Pending legal-status Critical Current

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Classifications

    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00Flooring
    • E04F15/12Flooring or floor layers made of masses in situ, e.g. seamless magnesite floors, terrazzo gypsum floors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00Flooring
    • E04F15/22Resiliently-mounted floors, e.g. sprung floors

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to rubber industry.
Rubber mass of the present invention contains the component of following ratio (weight %);
Based on rubber 48.0~52.0 sulphur 08~1.1 stearic acid 0.4~0.6 specific surface of divinyl silicon-dioxide 2.5~5.5 toxilic acids 0.3~0.6 mineral oil 2.0~3.0 2-mercaptobenzothiazoles 0.3~0.4 tetramethyl-thiuram disulfide 0.2~0.3 pigment 1.0~1.5 kaolin rest parts greater than 50 meter 2/ gram
The present invention can be used for preparing the tectum of playground.

Description

Rubber mass
The present invention relates to rubber industry, relate to rubber mass or rather, the present invention especially can be used for preparing the tectum of playground.
Building playground needs covering layer material, and this material should have the deformation ability of bearing, and is characterized in having certain elongation, permanent set, elasticity, tensile strength, hardness and water-intake rate.Tectum to flat playground has following requirement:
Ultimate tension, MPa is not less than 1.2
Shore hardness, the 30-60 of the unit of regulation
(this paper continues to use regulation later on
The Shore hardness of unit)
Rebound resilience, % 35-60
Elongation, % 200-450
Permanent set (permanent elongation), % 4-40
24 hours water-intake rate, % is not more than 1
In addition, in the playground of top cover was arranged, this tectum should be nontoxic, did not promptly emit the toxic volatile compound of the safe level amount that oversteps the extreme limit towards periphery in the environment.
In global practice, be extensive use of with resilient material, particularly be that the basis is formed as above-mentioned materials with rubber.
A kind ofly be used to prepare the tectal known prescription of playground and comprise butylbenzene thermoelastic material, shredded rubber, hydrophobic chalk, pigment and nanotesla rubber based adhesives.(weight %) is as follows for the ratio of its original components:
Butylbenzene thermoelastic material 1.0-4.8
Shredded rubber 36.5-49.8
Hydrophobic chalk 0.1-10.0
Pigment 0.4-1.5
Nanotesla rubber based adhesives 21.0-46.0 (SU, A, 678123).
This prescription contains butylbenzene thermoelastic material and nanotesla rubber based adhesives as matrix material, and shredded rubber and hydrophobic chalk are as filler.
Tectum based on this batching of obtaining of filling a prescription has snappiness (62-72%), and the result has reduced the sportsmen especially along the tectum running speed; This tectum is vulnerable to the effect of extraneous factor, promptly has low weather resistance and tint retention.Owing to lack tenderizer in this batching, make the rubber mass hardening, be aplastic, thereby make rubber mass be difficult to processing.
In addition, the tectum of making according to above-mentioned batching has very high water-intake rate (1.51-4.1%).
Except above-mentioned shortcoming, with the butylbenzene thermoelastic material is that the tectum that make on the basis also has the low characteristics of sanitation performance, because in use, from wherein discharging healthy people there is dysgenic volatile matter, i.e. vinylbenzene, S-contained substance, hydrochloric ether etc.
Also have a kind of known prescription, it contains thermoplastic elastic butadiene-styrene block copolymer, rosin, stearic acid, zinc oxide, and specific surface is a 175-380 rice 2Silicon-dioxide, kaolin or wood chip and the pigment of/gram, (weight %) is as follows for the ratio of its original components:
Butadiene-styrene block copolymer 64.0-67.0
Rosin 1.0-2.6
Stearic acid 1.0-2.6
Zinc oxide 1.0-2.6
Specific surface is a 175-380 rice 2The silica 1 .0-2.6 of/gram
Kaolin (wood chip) 24.6-29.2
Pigment 0.1-0.4
This prescription contains butadiene-styrene block copolymer as matrix material, and specific surface is a 175-380 rice 2The silicon-dioxide of/gram.Kaolin or wood chip are as filler, and rosin and stearic acid are as tenderizer.
Characteristics of this batching are the vinylbenzene that discharges a large amount, and this has just limited with the possibility of its goods of making in indoor use.
Also have a kind of known tectal prescription of runway that is used for, it contains nanotesla rubber, asbestos powder, stearic acid, zinc oxide and SULPHUR POWDER, and (weight %) is as follows for the ratio of each component:
Nanotesla rubber 60.0-75.0
Asbestos powder 15.0-30.0
Stearic acid 5.0-12.0
Zinc oxide 0.2-0.6
SULPHUR POWDER 0.8-1.5 (SU, A, 306151).
This prescription contains chloroprene rubber-nanotesla rubber as matrix material, and asbestos powder is as filler, and SULPHUR POWDER is as vulcanizing agent, and zinc oxide is as vulcanization accelerator.
The tectum of being made by this known batching has following physical and mechanical properties: the Shore hardness 65-70 unit of regulation, ultimate tension 0.5-0.8 MPa, water-intake rate 1.5-4.0%.
This tectum is easy to premature aging, and this is owing in use its physical and mechanical properties and profile degenerate.
In addition, will discharge deleterious volatile compound to atmospheric environment by this tectum, acetylene, vinyl cyclohexene, hydrochloric ether, S-contained substance.
Task of the present invention is to obtain rubber mass by changing component and adding annexing ingredient, this rubber mass allows to obtain when reducing water-intake rate, have improved sanitary chemistry performance, physical and mechanical properties, resemble the tectum of ultimate tension, elasticity and hardness especially, and prolong the tectal work-ing life of making by this rubber mass.
Above-mentioned task is to solve like this, according to the present invention, contains synthetic rubber, filler, sulphur, stearic rubber mass, comprises rubber based on divinyl as synthetic rubber, and kaolin is as filler, and comprises that specific surface is greater than 50 meters 2Silicon-dioxide, toxilic acid, mineral oil, 2-mercaptobenzothiazole, tetramethyl-thiuram disulfide and the pigment of/gram, (weight %) is as follows for the ratio of each component:
Rubber 48.0-52.0
Sulphur 0.8-1.1
Stearic acid 0.4-0.6
Silicon-dioxide 2.5-5.5
Toxilic acid 0.3-0.6
Mineral oil 2.0-3.0
2-mercaptobenzothiazole 0.3-0.4
Tetramethyl-thiuram disulfide 0.2-0.3
Pigment 1.0-1.5
The kaolin rest part
In order to improve the tectal work-ing life of being made by above-mentioned batching, preferably make the additional SP styrenated phenol (С т и р о с л и р о В а Н Н Н й Ф e н о Л) that contains of the batching that is proposed, this moment, the ratio (weight %) of each component was as follows:
Rubber 48.0-52.0
Sulphur 0.8-1.1
Stearic acid 0.4-0.6
Silicon-dioxide 2.5-5.5
Toxilic acid 0.3-0.6
Mineral oil 2.0-3.0
2-mercaptobenzothiazole 0.3-0.4
Tetramethyl-thiuram disulfide 0.2-0.3
Pigment 1.0-1.5
SP styrenated phenol 0.5-1.0
The kaolin rest part
Above-mentioned rubber mass has high-tensile and rebound resilience, low water absorption and hardness.
In addition, the rubber mass that is proposed has high sanitary chemistry characteristic, and is nontoxic, and not towards periphery environment discharge the toxic and volatile substances go beyond the limit of the safe level amount.
In the case, the tectal usage period limit for length who makes according to the rubber mass that is proposed.
Above-mentioned all allow to the rubber mass prescription that will be proposed, for example be used for indoor and open-air type playground tectum.
The batching that is proposed is in the standard equipment of producing technical rubber goods enterprise, and the method for conventional mixing each component of employing obtains.In order to make tectum by the batching that is proposed, above-mentioned rubber mass is under 140-155 ℃ temperature, heat-treat with the self-vulcanizing method.
Once used rubber based on divinyl as synthetic rubber, it is the mixture of styrene-butadiene rubber(SBR), divinyl-alpha-methyl styrene rubber, elastoprene (buna) and synthetic polyisoprene and elastoprene.
When adding rubber mass in the rubber mass batching proposed, can cause reducing and hardness too improves by its tectal elasticity of making less than 48% (weight).When the rubber mass that adds during, under the situation of not improving its physical and mechanical properties, improved the price of covering layer material, and made this tectal sanitary chemistry performance depreciation greater than 52% (weight).
Add the specific surface that is proposed in the batching and be higher than 50 meters 2The silica volume of/gram can reduce tectal intensity and make its sanitary chemistry performance depreciation during less than 2.5% (weight), also improves water-intake rate.The silica volume that adds can cause too being improved by the tectal hardness that this batching is made during greater than 5.5% (weight), and the result has reduced the speed that the sportsmen is run along tectum especially.
The toxilic acid amount in the rubber mass batching proposed of adding is during less than 0.3% (weight), causes by its tectal sanitary chemistry performance depreciation of making and increases curing time, and the result has increased power consumption because toxilic acid in above-mentioned batching as linking agent.The toxilic acid amount can improve tectal hardness greater than 0.6% (weight).
The stearic acid amount that adds is less than 0.4% (weight), and mineral oil (is T BoilWhen=300-600 ℃ high boiling hydrocarbon) amount is less than 2.0% (weight), the processing performance of this rubber mass in the course of processing degenerated, hardness increases, and tectum hardness improves and reduce its elasticity.The stearic acid amount that adds is greater than 0.6% (weight), and the mineral oil mass causes the processing performance and the tectal sanitary chemistry performance depreciation of rubber mass during greater than 3.0% (weight) equally.In this case, mineral oil is harmful volatile compound source that emits, the alkyl cyclic hydrocarbon that this mineral oil is high boiling hydrocarbon, obtain when mainly being petroleum refining and the liquid form mixt of alkyl aromatics.
The sulphur amount in the rubber mass batching proposed of adding causes curing time to increase during less than 0.8% (weight), and sulphur content can significantly improve tectal hardness during greater than 1.1% (weight).
The 2-mercaptobenzothiazole amount in the rubber mass batching proposed of adding is less than 0.3% (weight), and the tetramethyl-thiuram disulfide amount can increase the time length of sulfidation during less than 0.2% (weight), reduces tectal intensity, increases its elongation.
The 2-mercaptobenzothiazole amount that adds is greater than 0.4% (weight), and the tetramethyl-thiuram disulfide amount improves tectal hardness and reduces its elasticity during greater than 0.3% (weight).
In addition, the percentage composition that increases these materials can cause the sanitary chemistry performance significantly to degenerate, because these materials are source of releases of dithiocarbonic anhydride and thiomethyl alcohol.
Add SP styrenated phenol in the rubber mass batching proposed (be one-, two-and three-(α-Jia Bianji) phenol mixtures) when measuring less than 0.5% (weight), can reduce tectal work-ing life, because the premature aging of covering layer material takes place, the result has reduced its physical and mechanical properties.The add-on of said components can cause the tectum price to improve, and not improve its physical and chemical performance during greater than 1.0% (weight).
In the rubber mass batching that is proposed, can use inorganic and pigment dyestuff as tinting material with wide color range, the amount of pigment that adds is during less than 1.0% (weight), can not provide desired tone, the amount of pigment that adds is during greater than 1.5% (weight), tectal tone variation becomes low key tone.
Use kaolin as filler in the rubber mass that proposed batching, it is that complicated aluminium is for silicate.The kaolin amount that adds causes tectum intensity to reduce during less than 28% (weight), and water-intake rate improves, and the processing performance of rubber mass degenerates.The kaolin amount that adds causes tectal hardness to improve during greater than 46% (weight).
For a better understanding of the present invention, enumerate following examples.
Embodiment 1
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 50.000
Sulphur 0.900
Stearic acid 0.400
Specific surface is greater than 50 meters 2The silicon-dioxide 4.000 of/gram
Toxilic acid 0.500
Mineral oil, average (CP.) T Boil=360 ℃ 3.000
2-mercaptobenzothiazole 0.375
Tetramethyl-thiuram disulfide 0.275
Ferric oxide red colorant 1.500
Kaolin 39.050
Above-mentioned batching is in the standard equipment of producing technical rubber goods enterprise, and the method for conventional mixing each component of employing obtains.In order to make tectum by above-mentioned batching, this sizing material is under 140-155 ℃ of temperature, heat-treat with the self-vulcanizing method in jar.
Once use the rubber mass that is obtained to make the tectum sample, and carried out test determination tension (fracture) breakdown point, elongation, permanent set, Shore hardness, rebound resilience, water-intake rate and sanitary chemistry performance.
Use gas-liquid chromatography to check tectal sanitary chemistry performance.Be lower than the maximum acceptable concentration that these compounds are stipulated if disengage the discharging amount of (м и г р и р у ю щ и х) compound, then this material is considered to nontoxic.
Test-results is listed in the subordinate list.
Embodiment 2
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 48.000
Sulphur 0.900
Stearic acid 0.500
Specific surface is greater than 50 meters 2The silicon-dioxide 4.000 of/gram
Toxilic acid 0.500
The mineral oil average T Boil=420 ℃ 3.000
2-mercaptobenzothiazole 0.375
Tetramethyl-thiuram disulfide 0.275
Ferric oxide red colorant 1.500
Kaolin 40.950
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 3
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 52.0
Sulphur 1.00
Stearic acid 0.50
Specific surface is greater than 50 meters 2The silicon-dioxide 4.00 of/gram
Toxilic acid 0.50
The mineral oil average T Boil=450 ℃ 3.00
2-mercaptobenzothiazole 0.37
Tetramethyl-thiuram disulfide 0.28
Ferric oxide yellow pigment 1.50
Kaolin 36.85
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 4
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 48.0
Sulphur 0.8
Stearic acid 0.6
Specific surface is greater than 50 meters 2The silicon-dioxide 2.5 of/gram
Toxilic acid 0.3
The mineral oil average T Boil=410 ℃ 2.0
2-mercaptobenzothiazole 0.3
Tetramethyl-thiuram disulfide 0.3
Ferric oxide red colorant 1.5
SP styrenated phenol (one-, two-and three-
(α-Jia Bianji) phenol mixture) 0.5
Kaolin 43.2
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 5
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 50.0
Sulphur 0.90
Stearic acid 0.45
Specific surface is greater than 50 2The silicon-dioxide 4.50 of/gram
Toxilic acid 0.40
The mineral oil average T Boil=380 ℃ 2.80
2-mercaptobenzothiazole 0.35
Tetramethyl-thiuram disulfide 0.25
Ferric oxide yellow pigment 1.30
SP styrenated phenol 0.70
Kaolin 38.35
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 6
By the rubber mass that following component is formed, % (weight)
Styrene-butadiene rubber(SBR) 52.0
Sulphur 1.1
Stearic acid 0.4
Specific surface is greater than 50 meters 2The silicon-dioxide 5.5 of/gram
Toxilic acid 0.6
The mineral oil average T Boil=500 ℃ 3.0
2-mercaptobenzothiazole 0.4
Tetramethyl-thiuram disulfide 0.2
Phthalocyanine green pigment 1.0
SP styrenated phenol 1.0
Kaolin 34.8
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 7
By the rubber mass that following component is formed, % (weight)
Divinyl-alpha-methyl styrene rubber 48.000
Sulphur 1.000
Specific surface is greater than 50 meters 2The silicon-dioxide 3.500 of/gram
Toxilic acid 0.500
The mineral oil average T Boil=520 ℃ 2.500
2-mercaptobenzothiazole 0.375
Tetramethyl-thiuram disulfide 0.275
Phthalocyanine green pigment 1.500
SP styrenated phenol 1.000
Kaolin 40.850
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 8
By the rubber mass that following component is formed, % (weight)
Divinyl-alpha-methyl styrene rubber 50.000
Sulphur 1.000
Stearic acid 0.500
Specific surface is greater than 50 meters 2The silicon-dioxide 3.500 of/gram
Toxilic acid 0.500
Mineral oil on average boils down=and 580 ℃ 2.500
2-mercaptobenzothiazole 0.375
Tetramethyl-thiuram disulfide 0.275
Pthalocyanine blue pigment 1.500
SP styrenated phenol 1.000
Kaolin 38.850
Make tectum by the rubber mass that makes, be similar to embodiment 1 and carry out the tectum performance test.
Test-results is listed in the subordinate list.
Embodiment 9
By the rubber mass that following component is formed, % (weight)
Divinyl-alpha-methyl styrene rubber 52.000
Sulphur 1.000
Stearic acid 0.500
Specific surface is greater than 50 meters 2The silicon-dioxide 3.500 of/gram
Toxilic acid 0.500
The mineral oil average T Boil=400 ℃ 2.500
2-mercaptobenzothiazole 0.375
Tetramethyl-thiuram disulfide 0.275
Phthalocyanine green pigment 1.500
SP styrenated phenol 1.000
Kaolin 36.850
Make tectum by the rubber mass that makes, test is similar to embodiment 1 and carries out.
Test-results is listed in the subordinate list.
Subordinate list
Tectal performance based on rubber mass Embodiment By known schemes (SU, A, 306151)
??1 ?2 ??3 ??4 ?5 ??6 ?7 ??8 ??9
Shore hardness, the unit's of regulation rebound resilience, the % elongation, the % permanent set, the % ultimate tension, 24 hours water-intake rate of MPa, % is according to hydrocarbon/according to the toxicity overall performance of S-contained substance 40 44 39 42 38 36 42 39 37 50 48 52 54 56 58 48 50 52 400 360 420 430 400 380 260 340 400 18 12 20 18 8 16 8 10 14 3.2 3.5 3.2 3.0 3.2 3.5 4.0 3.8 3.7 0.83 0.80 0.85 0.9 0.85 0.95 0.84 0.87 0.94 less than 1/ less than 1 65-70 6-8--0.5-0.8 1.5-4 greater than 1/ greater than 1

Claims (2)

1. contain synthetic rubber, filler, sulphur, stearic rubber mass, it is characterized in that, it contains rubber based on divinyl as synthetic rubber.Kaolin is as filler and contain specific surface greater than 50 meters 2The silicon-dioxide of/gram, toxilic acid, mineral oil, 2-mercaptobenzothiazole, tetramethyl-thiuram disulfide and pigment, (weight %) is as follows for each component ratio:
Rubber 48.0-52.0
Sulphur 0.8-1.1
Stearic acid 0.4-0.6
Silicon-dioxide 2.5-5.5
Toxilic acid 0.3-0.6
Mineral oil 2.0-3.0
2-mercaptobenzothiazole 0.3-0.4
Tetramethyl-thiuram disulfide 0.2-0.3
Pigment 1.0-1.5
The kaolin rest part
2. rubber mass according to claim 1 is characterized in that, it adds contains SP styrenated phenol, and (weight %) is as follows for the ratio of each component:
Rubber 48.0-52.0
Sulphur 0.8-1.1
Stearic acid 0.4-0.6
Silicon-dioxide 2.5-5.5
Toxilic acid 0.3-0.6
Mineral oil 2.0-3.0
2-mercaptobenzothiazole 0.3-0.4
Tetramethyl-thiuram disulfide 0.2-0.3
Pigment 1.0-1.5
SP styrenated phenol 0.5-1.0
The kaolin rest part
CN 89107026 1989-07-19 1989-08-10 Rubber mass Pending CN1049363A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19893923940 DE3923940A1 (en) 1989-07-19 1989-07-19 Coating mixt. e.g. for floors in sports facilities - contains butadiene] rubber, kaolin filler, sulphur, stearic acid, silica, maleic acid, mineral oil, and pigment

Publications (1)

Publication Number Publication Date
CN1049363A true CN1049363A (en) 1991-02-20

Family

ID=6385408

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Application Number Title Priority Date Filing Date
CN 89107026 Pending CN1049363A (en) 1989-07-19 1989-08-10 Rubber mass

Country Status (3)

Country Link
CN (1) CN1049363A (en)
DE (1) DE3923940A1 (en)
FR (1) FR2651002B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1692230B1 (en) * 2003-11-21 2008-12-31 Imerys Kaolin, Inc. Rapid dispersing hydrous kaolins

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2088466A1 (en) * 1970-05-10 1972-01-07 Ztki Zebra Synthetic floor cover to sports grounds

Also Published As

Publication number Publication date
DE3923940A1 (en) 1991-01-24
FR2651002B1 (en) 1991-11-29
FR2651002A1 (en) 1991-02-22

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