CN1069679C - Thermoplastic rubber-type water-proof coiled material - Google Patents
Thermoplastic rubber-type water-proof coiled material Download PDFInfo
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- CN1069679C CN1069679C CN 98102553 CN98102553A CN1069679C CN 1069679 C CN1069679 C CN 1069679C CN 98102553 CN98102553 CN 98102553 CN 98102553 A CN98102553 A CN 98102553A CN 1069679 C CN1069679 C CN 1069679C
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Abstract
The present invention provides a thermoplastic rubber-type waterproof coiled material which is a rubber-type waterproof coiled material using a thermoplastic elastic body as a base body. Ethene-octene copolymer is adopted as base-body rubber; the components of the ethene-octene copolymer comprise 100 portions of ethene-octene copolymer, 8.8 to 223 portions of filled reinforcing agent, 1.7 to 100 portions of softened plasticizer and 0.5 to 4 portions of anti-aging agent according to weight portions, and 5 to 7.5 portions of activator and 0.05 to 0.7 portions of cross-linking agent can also be added. A vulcanization machining process step is not needed for producing the rubber-type waterproof coiled material, leftover bits and pieces of industrial material, waste material and used products during the production process can be recovered and utilized, and heat adhesion can be adopted for joint seams of construction; the anti-aging performance of the thermoplastic rubber-type waterproof coiled material can reach or exceed the anti-aging performance of the rubber waterproof coiled material prepared by ethylene propylene terpolymer rubber.
Description
The present invention relates to a kind of building waterproof coil, is to be the rubber-type water-proof coiled material of matrix with the thermoplastic elastomer ethylene-octene copolymer.
Rubber-type water-proof coiled material is the new type waterproof coiled material of developing along with elastomeric development, rubber-type water-proof coiled material is compared with traditional felt asphalt type waterproof roll, it have in light weight, intensity is high, elongation good, tear strength and ageing-resistant performance is good, thermal adaptability is strong, long service life, advantage that construction pollution is few.Rubber-type water-proof coiled material be with rubber be matrix and filling modifying agent routinely the work program of rubber item carry out processing and manufacturing.The course of processing comprises that rubber plasticates, and sizing material is mixing, processing in flakes, operations such as sulfuration.The fundamental property that the waterproof roll of rubber-type should have is: water resisting infiltration of energy and infiltration; Water absorbability is little; Has stability to temperature variation; The certain physical mechanical property is arranged; Corrosion to weather, acid, alkali and microorganism has anti-preferably patience; Good adhesiveproperties or the like is arranged.The used base rubber kind of rubber-type water-proof coiled material has chloroprene rubber, isoprene-isobutylene rubber, terpolymer EP rubber, urethanes, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, and between them and use kind.Chloroprene rubber is the rubber that is applied to waterproof roll the earliest, it is having good performance aspect ageing-resistant, resistance to chemical attack, fire-retardant, the oil resistant, but thermal adaptability is relatively poor, can continue crosslinked during high temperature, the hardening because crystallization and second-order transition temperature are higher during low temperature, processing characteristics is also undesirable, though be one of rubber-type water-proof coiled material principal item at present, has by other rubber-type water-proof coiled material alternate trend.The isoprene-isobutylene rubber waterproof roll has high degree of saturation to determine it to have good ageing-resistant performance owing to isoprene-isobutylene rubber, and has splendid anti-gas permeability energy.Its price height, processing characteristics is bad, must use adhesive specially ability bonding.Because it is replaced these defectives by EPDM rubber waterproof rolling material gradually.The macromolecular structure of terpolymer EP rubber has determined it to have better ageing-resistant performance than above-mentioned two kinds of rubber-type water-proof coiled materials, better high temperature performance, and good to the anti-patience of acid, alkali, water vapor, processing characteristics is also more satisfactory.It develops very soon as the rubber-type water-proof coiled material of top grade, because its price is more expensive, widespread use is subjected to certain limitation.Chinese patent CN1097435A discloses a kind of production method of styrene-butadiene block copolymer modified asphalt waterproof coiled material, this waterproof roll still belongs to the asphaltic base waterproof roll that thermoplastic elastomer is made properties-correcting agent, still relatively poor aspect ageing-resistant performance and strength and extension property, its performance can not be compared with EPDM rubber waterproof rolling material.Czech patents CS271,374 disclose a kind of waterproof roll composition, and it contains mixture, carbon black or mineral filler, mineral oil and the cross-linking system of chloroprene rubber/ethylene-propylene rubber(EPR) blend and polyvinyl chloride (PVC) RESINS or vinyl chloride-vinyl acetate resin.It is compared with the ethylene-propylene rubber(EPR) waterproof roll, and better oil resistance has been arranged, but this waterproof roll still needs sulfuration.The shortcoming of thermoset rubber maximum is just can have use value through over cure, and vulcanization process has not only increased machining complexity and cost, and the recovery of the goods after the tailing after the sulfuration, waste material and the use is very difficult with utilizing.
Thermoplastic elastomer is a kind of material that combines rubber and plastics advantage, its plastics at high temperature are flowable mutually, then play the effect of physical crosslinking point at normal temperatures, this physical crosslinking is hot reversible, therefore it both the machine-shaping mode of available heat thermoplastic plastic process and moulding, it has the elasticity of rubber again in wide temperature range.Its processing can be saved sulfuration process complicated and that power consumption is big.Consider the ageing-resistant performance of thermoplastic elastomer and the problem of raw materials cost aspect, the application on waterproof roll is very limited, and up to now, does not see thermoplastic elastomer successfully is used in waterproof roll as base rubber report as yet.
The objective of the invention is to propose a kind of ageing-resistant performance and the good new type waterproof coiled material of processing characteristics.The employing ethylene-octene copolymer is a base rubber, is aided with appropriate filling-modifiedly, obtains the waterproof roll that performance and cost are taken into account.
A kind of thermoplastic rubber-type water-proof coiled material provided by the present invention is made up of base rubber and filling-modified material, and base rubber is an ethylene-octene copolymer; It forms parts by weight: (1) ethylene-octene copolymer: 100 parts; (2) packing strengthening agent: 8.8～223 parts; (3) softening softening agent: 1.7～100 parts; (4) anti-aging agent: 0.5～4 part.Preferably scope is: (1) ethylene-octene copolymer: 100 parts: (2) packing strengthening agent: 30～138 parts; (3) softening softening agent: 30～60 parts; (4) anti-aging agent: 0.6～2 part.Can also add (5) activator: 5～7.5 parts; (6) linking agent is 0.05～0.7 part.
Ethylene-octene copolymer of the present invention is a kind of thermoplastic elastomer, but it has the thermoplastic processibility and ageing-resistant performance is also good unusually, but prepare waterproof roll with it also must add packing strengthening agent, softening softening agent and anti-aging agent to solve the processing shrinkability of improving it bigger, thermotolerance is bad, problems such as ultraviolet light scarce capacity can also reduce cost simultaneously effectively.The Engage product that ethylene-octene copolymer of the present invention can select for use commercially available Du Pont-Dow Chemical Company to produce, it is the ethylene-octene copolymer that adopts metallocene catalyst to make.This thermoplastic elastomer is a polymkeric substance of ethene and octene are arranged being formed and have the polyethylene crystallization phases (be plasticity mutually) and ethylene-octene pars amorpha (be elasticity mutually) by the viewpoint of molecular designing, because its tertiary carbon atom number is less, therefore its saturation ratio absolutely has good aging properties.The Engage product of Du Pont-Dow Chemical Company has the trades mark such as 8150,8003,8200,8401 can be for selecting for use according to the hardness difference.The hardness of Engage product high-melting-point more is also high more, and heat-drawn wire is high more, and it is also low more that elasticity becomes relatively.Along with the degree of crystallinity of the raising Engage of hardness is also high more, its ability of holding packing strengthening agent is also poor more, and the ability that absorbs softening agent is also more little.The consumption of ethylene-octene copolymer of the present invention is 100 parts (identical below the parts by weight), and when consumption is too low, packing strengthening agent will form external phase in composition, thereby the elongation of sheet material and elasticity are descended greatly, and winter hardiness also can not meet the demands.The usage ratio of ethylene-octene copolymer is too high, and the shortcoming of its inherent material property aspect can come out again, and cost also can increase.Packing strengthening agent among the present invention plays the processing that solves the ethylene-octene polymkeric substance on the one hand and shrinks problem, to improve processing characteristics, has improved creep resistance, heat resistance, uvioresistant performance, the tear resistance of sizing material on the other hand.Packing strengthening agent can be selected well-known carbon black, white carbon black, lime carbonate, potter's clay or their mixture etc. for use.The consumption of packing strengthening agent is mainly determined according to the physical and mechanical properties of its kind and waterproof roll, generally is controlled in 8.8～223 parts of scopes, is preferably in 30～138 parts of scopes.The consumption that improves packing strengthening agent can reduce the waterproof roll cost, but consumption too much can worsen the flowing property of sizing material, and reduces the unit elongation and the winter hardiness of material, and the subduing property of coiled material also will descend.Softening softening agent among the present invention can improve the processing characteristics of ethylene-octene copolymer on the one hand, improve mobile, reduce relaxation shrinkage, strengthen infiltration and the coating effect of ethylene-octene copolymer to packing strengthening agent, it can also improve the unit elongation of sizing material on the other hand, and the hardness of reduction sizing material, the winter hardiness of raising sizing material.Can select the conventional various softening softening agent that uses of Rubber processing for use.According to the polar phase approximately principle, the present invention selects paraffin oil, naphthenic oil or their mixture for use.Softening plasticizer consumption is controlled in 1.7～100 parts the scope, is preferably in 30～60 parts of scopes.Softening softening agent too much can reduce the intensity of sizing material, and the thermotolerance of sizing material, creep-resistant property also can variation.The anti-aging agent that adopts among the present invention (containing ultraviolet absorbers) can further improve the ageing-resistant performance of sizing material.Phenols, amines antioxidants or the ultraviolet absorbers that can select for use conventional rubber to use.For example commercially available antioxidant 1010, antioxidant 264, antioxidant D OPC or anti-aging agent 1076 all can.Consumption is controlled in 0.5～4 part of scope, is preferably in 0.6～2 part of scope.
Can also in forming, the waterproof roll that above-mentioned the present invention proposes add activator and linking agent.The effect of activator is to improve rate of crosslinking to increase cross-linking density.Activator can be selected zinc oxide and stearic mixture for use, and their weight ratio is 1: 1～5: 1, totally 5～7.5 parts.Linking agent can be selected dicumyl peroxide, 2 for use, 5-dimethyl-2,5 bis(t-butylperoxy) hexane or di-t-butyl peroxide.Because the crystallization phases of this thermoplastic elastomer of ethylene-octene copolymer is the polyethylene phase, under the influence of pars amorpha polymer thermal motion, the fusing point of this crystallization phases is lower.Although packing strengthening agent can improve its thermal deformation resistant ability effectively, improve its use temperature, also have certain difficulty medium-term and long-term use of 80 ℃～100 ℃ environment.The peroxide cross-linking agent that adds trace, generation is little crosslinked in polymer phase in mixing process, and this moment is the thermoplasticity of remarkably influenced composition neither, can effectively improve the thermal deformation resistant ability of composition simultaneously again.When the peroxide cross-linking agent amount that adds is too much, then can obviously lose the thermoplasticity of polymkeric substance.The peroxide cross-linking agent add-on is controlled in 0.05～0.7 part of scope.
Embodiment 1
Forming parts by weight is:
Base rubber
8,150 100 parts of Engage
The weighting agent strengthening agent
40 parts of carbon blacks (N330)
40 parts in lime carbonate
Softening softening agent
25 parts of naphthenic oils
15 parts of paraffin oils
Anti-aging agent
Anti-aging agent
1 part of above-mentioned ligand of antioxidant 1010 ties up in the Banbury mixer mixing, mixing time 3～15 minutes, and 100 ℃～120 ℃ of material temperature, in blocks with the four-roll calender calendering under 100 ℃～120 ℃ then, cooling, rolling, packing.
Embodiment 2
Base rubber
8,150 100 parts of Engage
The weighting agent strengthening agent
40 parts of carbon blacks (N330)
80 parts in lime carbonate
Softening softening agent
26 parts of naphthenic oils
16 parts of paraffin oils
Anti-aging agent
2 parts of processing conditionss of antioxidant 1010 are with embodiment 1.
Embodiment 3
Base rubber
8,150 100 parts of Engage
The weighting agent strengthening agent
90 parts of carbon blacks (N330)
33 parts in lime carbonate
Softening softening agent
100 parts of naphthenic oils
Anti-aging agent
0.5 part of processing conditions of salicylic acid tert-butyl phenyl acetate is with embodiment 1.
Embodiment 4
Base rubber
8,200 100 parts of Engage
The weighting agent strengthening agent
40 parts of carbon blacks (N330)
30 parts in potter's clay
Softening softening agent
35 parts of naphthenic oils
25 parts of paraffin oils
Anti-aging agent
0.6 part of processing conditions of salicylic acid tert-butyl phenyl acetate is with embodiment 1.
Embodiment 5
Base rubber
8,003 100 parts of Engage
The weighting agent strengthening agent
40 parts of carbon blacks (N330)
98 parts in lime carbonate
Softening softening agent
30 parts of naphthenic oils
Anti-aging agent
2 parts of processing conditionss of salicylic acid tert-butyl phenyl acetate are with embodiment 1.
Embodiment 6
Base rubber
8,180 100 parts of Engage
The weighting agent strengthening agent
43 parts of carbon blacks (N330)
52 parts in lime carbonate
Softening softening agent
30 parts of naphthenic oils
Anti-aging agent
4 parts of antioxidant 264s
Promoting agent
5 parts in zinc oxide
2.5 parts of stearic acid
Linking agent
0.7 part of above-mentioned ligand of dicumyl peroxide ties up in the Banbury mixer mixing, finished in mixing 3～15 minutes down at 150 ℃ needed dynamically little crosslinked and mixing, under 100 ℃～120 ℃ with the four-roll calender calendering in flakes, cooling, rolling is packed.
Embodiment 7
Base rubber
8,003 100 parts of Engage
The weighting agent strengthening agent
8.8 parts in lime carbonate
Softening softening agent
15 parts of naphthenic oils
Anti-aging agent
0.6 part of processing conditions of antioxidant 1010 is with embodiment 1.
Embodiment 8
Base rubber
8,200 100 parts of Engage
The weighting agent strengthening agent
16 parts of carbon blacks (N330)
14 parts in lime carbonate
Softening softening agent
1.7 parts of naphthenic oils
Anti-aging agent
1.9 parts of antioxidant 264s
Promoting agent
4 parts in zinc oxide
1 part of stearic acid
Linking agent
0.05 part of processing conditions of dicumyl peroxide is with embodiment 6
Embodiment 9
Base rubber
8,003 100 parts of Engage
The weighting agent strengthening agent
66 parts of carbon blacks (N330)
157 parts in lime carbonate
Softening softening agent
5 parts of paraffin oils
Anti-aging agent
3 parts of processing conditionss of antioxidant 264 are with embodiment 1.Comparative example
Base rubber
100 parts of terpolymer EP rubbers (EPDM)
The weighting agent strengthening agent
Fast 20 parts of the carbon blacks that extrude
100 parts of hard (china) claies
Softening softening agent
12.5 parts of naphthenic oils
Anti-aging agent
1.5 parts of anti-aging agent C
Promoting agent
5 parts in zinc oxide
1.0 parts of stearic acid
Promotor
0.5 part of captax
1.5 parts of TM monex TD
2 parts of above-mentioned ligands of linking agent (sulphur) tie up in the Banbury mixer mixing, and mixing time 15～25 minutes is extruded slice with forcing machine then, with drum vulcanizer sulfuration 25 minutes, cool off rolling, packing under 160 ℃.
The performance of the waterproof roll of embodiment and comparative example and the Ministry of Chemical Industry's standard (HG2402-92) is relatively listed in the table.The performance index of the waterproof roll that proposes of the present invention meet and exceed the requirement of HG2402-92 standard as can be known from table.Compare with common rubber-type water-proof coiled material, it has the advantage of thermoplastic elastomer, do not need to vulcanize manufacturing procedure, goods after tailing in the production process, waste material and the use can be recycled, it is bonding that Construction Joint does not need particular adhesive to carry out, can adopt hot stickyly, so cost is lower.And also good at aspect of performance than terpolymer EP rubber thermoset rubber type waterproof roll, be all excellent new type waterproof coiled materials of a kind of ageing-resistant performance and processing characteristics.
The performance of embodiment and comparative example relatively
Annotate: be with * number data representation ozone ageing condition: ozone ageing (100pphm; 40 ℃ * 168h; Elongation 40%, static state)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example | HG2402-92 | ||
| Acceptable end product | Salable product | |||||||||
| Tensile strength (MPa) | 11 | 9.5 | 8.0 | 8.4 | 11.2 | 10.8 | 22 | 13.4 | ≥8 | ≥7 |
| Tensile yield (%) | 500 | 480 | 512 | 580 | 523 | 506 | 700 | 500 | ≥450 | |
| Angle tear strength (KN/m) | 37.4 | 33.8 | 37.2 | 35 | 47.5 | 39.6 | 50 | 30 | ≥28 | ≥24.5 |
| Hot air aging condition: 80 ℃ * 168h | ||||||||||
| The tensile strength velocity of variation, % tensile yield velocity of variation, % tear strength velocity of variation, % | -7 | -9 | 0 | -4.7 | -6.3 | 13 | -18 | -20 | -20～40 | -20～50 |
| -6.4 | -6.3 | -7.8 | -8.6 | -5.2 | -2 | -8.6 | -26.8 | ≥-30 | ||
| 2.9 | 0.6 | 4.6 | 5.7 | 1.3 | 4.8 | 4 | -3.3 | -40～40 | -50～50 | |
| Ozone ageing (500pphm; 40 ℃ * 168h; Elongation 40%, static state) | Flawless | Flawless | Flawless | Flawless | Flawless | Flawless | Flawless | Flawless | Flawless | Flawless |
| Temperature limit of brittleness (℃) | -48 | -50 | -43 | -48 | -48 | -48 | -50 | - | -45 | -40 |
| Watertightness (0.3MPa * 30min) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Processing mode | Thermoplasticity is not vulcanized | Thermoplasticity is not vulcanized | Thermoplasticity is not vulcanized | Thermoplasticity is not vulcanized | Thermoplasticity is not vulcanized | Thermoplasticity, dynamic crosslinking | Thermoplasticity is not vulcanized | Thermoset, sulfuration | Thermoset, sulfuration | Thermoset, sulfuration |
| Seam | Hot sticky | Hot sticky | Hot sticky | Hot sticky | Hot sticky | Hot sticky | Hot sticky | Tackiness agent | Tackiness agent | Tackiness agent |
Claims (2)
1. a thermoplastic rubber-type water-proof coiled material is made up of base rubber and filling-modified material,
It is characterized in that: base rubber is an ethylene-octene copolymer; It forms parts by weight: (1) ethylene-octene copolymer: 100 parts; (2) packing strengthening agent: 8.8-223 part; (3) softening softening agent: 1.7-100 part; (4) anti-aging agent: 0.5-4 part; Packing strengthening agent is carbon black, white carbon black, lime carbonate, potter's clay or their mixture; Softening softening agent is paraffin oil, naphthenic oil or their mixture; Anti-aging agent is phenolic type antioxidant, amines antioxidants or ultraviolet absorbers.
2. a thermoplastic rubber-type water-proof coiled material is made up of base rubber and filling-modified material,
It is characterized in that: base rubber is an ethylene-octene copolymer; It forms parts by weight: (1) ethylene-octene copolymer: 100 parts; (2) packing strengthening agent: 8.8-223 part; (3) softening softening agent: 1.7-100 part; (4) anti-aging agent: 0.5-4 part; (5) activator 5-7.5 part; (6) linking agent: 0.05-0.7 part; Packing strengthening agent is carbon black, white carbon black, lime carbonate, potter's clay or their mixture; Softening softening agent is paraffin oil, naphthenic oil or their mixture; Anti-aging agent is phenolic type antioxidant, amines antioxidants or ultraviolet absorbers; Activator is zinc oxide and stearic mixture; Linking agent is a dicumyl peroxide, 2,5-dimethyl-2,5 bis(t-butylperoxy) hexane or di-t-butyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102553 CN1069679C (en) | 1998-06-29 | 1998-06-29 | Thermoplastic rubber-type water-proof coiled material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102553 CN1069679C (en) | 1998-06-29 | 1998-06-29 | Thermoplastic rubber-type water-proof coiled material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1203257A CN1203257A (en) | 1998-12-30 |
| CN1069679C true CN1069679C (en) | 2001-08-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98102553 Expired - Fee Related CN1069679C (en) | 1998-06-29 | 1998-06-29 | Thermoplastic rubber-type water-proof coiled material |
Country Status (1)
| Country | Link |
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| CN (1) | CN1069679C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425649C (en) * | 2006-09-07 | 2008-10-15 | 浙江俊尔新材料有限公司 | Thermoplastic elastomer for filming dacron cloth |
| CN100434466C (en) * | 2007-03-15 | 2008-11-19 | 上海交通大学 | Prepn process of foamed ethylene-octene copolymer material |
| CN101735521B (en) * | 2009-12-18 | 2011-12-14 | 常熟市三恒建材有限责任公司 | Flame-retardant ethylene-propylene-diene waterproof sheet and preparation method thereof |
| CN101812199B (en) * | 2010-05-11 | 2012-01-11 | 赵军 | Plastic cement composition product and preparation method thereof |
| CN101831105B (en) * | 2010-05-11 | 2012-07-18 | 冯青连 | Ethylene-octene copolymer waterproof coil and preparation method thereof |
| CN101805477B (en) * | 2010-05-11 | 2012-05-09 | 赵根生 | Waterproof product containing linear low density polyethylene and preparation method thereof |
| CN101805476B (en) * | 2010-05-11 | 2012-11-28 | 赵新生 | Waterproof product containing plastic and rubber composition and preparation method thereof |
| CN101805478B (en) * | 2010-05-11 | 2012-05-23 | *** | Waterproof product containing ethylene-octylene copolymers and preparation method thereof |
| CN103538260A (en) * | 2012-07-09 | 2014-01-29 | 宏祥新材料股份有限公司 | Production process for self-exhausting waterproof coiled material of water conservancy project |
| CN103304867B (en) * | 2013-06-04 | 2016-06-15 | 云南海燕建设有限公司 | The sticky polymer membranes of non-bituminous reaction and its preparation method |
| CN103554629B (en) * | 2013-09-30 | 2015-09-16 | 潍坊市宏源防水材料有限公司 | A kind of TPO waterproof roll and production technique thereof |
| CN104817755A (en) * | 2015-03-31 | 2015-08-05 | 解忠深 | Vulcanized ethylene-octene copolymer waterproof coiled material and production method thereof |
| CN104745117B (en) * | 2015-03-31 | 2017-06-30 | 解飞 | Self-adhesion reaction-ity ethylene octene copolymer composite of water-proof coiled material and its production method |
| CN110317417A (en) * | 2018-03-31 | 2019-10-11 | 寿光市永昌防水材料有限公司 | A kind of root resistant waterproof roll and preparation method thereof |
| CN113320251A (en) * | 2021-05-26 | 2021-08-31 | 南京曼可新材料有限公司 | High-adhesion-strength waterproof coiled material composition and preparation method thereof |
-
1998
- 1998-06-29 CN CN 98102553 patent/CN1069679C/en not_active Expired - Fee Related
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| CN1203257A (en) | 1998-12-30 |
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