• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method of preparing a stable latex having two substantially monodisperse populations of vinyl chloride polymer particles, which method comprises polymerizing, in aqueous emulsion, vinyl-polymerizable monomers containing at least 60% by weight vinyl chloride, in the presence of both A. A VINYL CHLORIDE POLYMER SEED LATEX PROVIDING BETWEEN ABOUT 0.5 AND 20% OF DRY SOLIDS BASED ON TOTAL WEIGHT OF SAID MONOMERS, HAVING PARTICLES OF MEAN DIAMETER BETWEEN ABOUT 0.15 AND 0.6 MICRONS AND HAVING A "FIRST" SURFACTANT IN AMOUNT CORRESPONDING TO A SEED-PARTICLE SURFACE COVERAGE OF FROM 5% TO 100%, AND B. A "SECOND" SURFACTANT OF DIFFERENT CHEMICAL TYPE IN AMOUNT CORRESPONDING TO FROM ABOUT 0.01% TO 2% BY WEIGHT OF TOTAL MONOMER, WHEREIN THE CHEMICAL TYPE OF EACH SURFACTANT IS NONIONIC OR CARBOXYLATE OR SULFONATE OR SULFATE OR SULFOSUCCINATE, BUT WHEREIN THE CHEMICAL TYPE OF THE "SECOND" SURFACTANT IS DIFFERENT FROM THE CHEMICAL TYPE OF THE "FIRST" SURFACTANT.
    公开号:SU833164A3
    申请号:SU752171406
    申请日:1975-09-17
    公开日:1981-05-23
    发明作者:Торте Жан-Пьерр
    申请人:Продюи Шимик Южин Кюльманн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the chemistry and technology of polymers, in particular to the method of water-emulsion polymerization of vinyl chloride or ethylenically unsaturated monomers. The closest in technical essence and achievable results to the proposed method is to obtain latexes (co) polymers of vinyl chloride by emulsion (co) polymerization of vinyl chloride or its mixture with vinyl acetate or propylene in the presence of germinal latex, emulsifier and initiator, according to which The bodies use a polyvinyl chloride latex containing an emulsifier of the same type as the emulsifier used in the polymerization process. Ul The disadvantage of this method is the impossibility of The formation of latexes with double particle size of particles, as well as the low stability of plastisols based on the obtained latexes. The purpose of the invention is to obtain lathes with a double particle size of particles, improved viscosity characteristics and increased stability of plastisols based on these latexB. The goal is achieved in the method of producing latex (co) polymers of vinyl chloride by emulsion polymerization of vinyl chloride or its mixture with vinyl acetate or propylene in the presence of germinal latex, emulsifier and initiator, as a germinal latex using an emulsifier other than the emulsifier used during (co) polymerization, the degree of coating of the latex particles with an emulsifier is from 25 to 80%, and also the fact that the amount of germinal latex is 0.520% and the dry matter of the weight of (co) Mons 4er, and the average particle diameter of the germinal latex is 0.15-0.6 microns. The proposed method allows to obtain the latex in the form of a double particle size monodisperse of the new family, without the need for mixing operations and with the implementation of only two operations of polymerization. Obtained by the proposed method latexes contain a monodspersed family with an average diameter
    particles from 0.1 to 0.5 microns and a monodispersed family with a particle diameter of more than O, 5, but less than 2 microns.
    The weight fraction of particles with a diameter of from 0.1 to 0.5 microns is from 5 to 50%, preferably from 10 to 40%. The method is particularly useful for preparing latexes with an increased solids content. The content of the latter can reach 65%, preferably 60%. The capacity of the plants from this increases significantly.
    To carry out the proposed method, classic polymerization autoclaves are used, equipped with a stirring system and any one necessary for regulation with a device for cooling and heating. Polymerization temperatures are used that are customary for aqueous emulsion polymerization of vinyl chloride, i.e. equal to 20-80s, preferably 35-65 C.
    The monomer can be injected completely at the start of work, either by sequentially administered doses or, finally, continuously throughout the operation.
    - Germinal latex is prepared by the usual methods of water-emulsion polymerization, ensuring monodispersed production; about latex. The average particle size of the germinal latex can range from 0.15 to 0.6 microns, preferably from 0.2 to 0.45 microns. The amount of seed used may be from 0.5 to 20% by weight of dry matter (relative to the monomers). Preferably this amount is from 1 to 10% by weight. The amount of germinal lating surfactant used should provide a coating ratio of between 25 and 80%. (The degree of coating is the ratio of the surface of the emulsifier to the total surface of the latex particles),
    Surfactant. . the chemical nature of which differs from the nature of the surface-active substances protecting the embryo, is contained in the reaction medium in an amount of 0.01-2 wt.%, preferably from up to 1% (to monomers). The surfactant and the germinal latex can be introduced into the reaction medium together or separately at the beginning of the polymerization, however, it is preferable to introduce them before applying the monomer. The surfactant g South also forms on-site prior to polymerization.
    A different chemical nature is understood as surfactants that do not belong to one particular chemical group, for example, a chemical group of non-ionic surfactants, a chemical group of metal salts of carboxylic acids, a chemical group of sulfonic acids, a chemical group of metal salts of sulfur esters, a chemical group of sulfonic salts acid.
    Cellulose derivatives such as methylcellulose, carboxymethylcellulose, etc., the products of hydrolysis of polyvinyl acetate particles, known by n. the name of polyvinyl alcohol, alkylene oxide adducts to alcohols, phenols, fatty acids, etc., fatty acid esters, for example, sorbitol monolaurate.
    The chemical group of metal salts of carboxylic acids includes alkali metal salts, for example, sodium, potassium, lithium, ammonium. Acids can be saturated linear or branched acids containing from 8; up to 24 (preferably from 10 to 18) carbon atoms, for example, lauric , myristic, palmitic, stearic acids, or acids obtained by oxosynthesis, for example, cacanoic acid, unsaturated acids, for example, oleic acid, modified fatty acids, for example, fatty acids, sulfonated in alpha- position
    The chemical group of metal salts of sulfonic acids includes alkali metal salts, for example, sodium, potassium, lithium, ammonium. Sulfonic acids can be sulfonated paraffins containing from 10 to 22 carbon atoms, sulfonated alkyls, aryls, for example alkyl benzenes, alkyl naphthalenes, simple alkyl diphenyl ethers, etc.- ..
    The chemical group of metal salts of sulfuric esters includes, preferably, alkali metal salts of sulfuric esters such as fatty acid sulfates containing from 10 to 20 carbon atoms, for example sodium lauryl sulfate.
    The chemical group of metal salts of sulfo-succinic acid is preferably alkali metal salts of sulfoalkyl succinic acid, the alkyl residue of which contains from 4 to 20 carbon atoms, for example, the sodium salt of dioctyl sulfo succinate.
    In the water emulsion polymerization process, one third of the surfactant can be added to protect the particles. This third surfactant may (without creating a chemical order of difficulty) be identical to one of the previously used surfactants. If this surfactant is identical to the surfactant used to protect the germinal latex, or if it is identical to a medium whose chemical nature is different from among those used to protect the germinal latex, then the amount is not included in the amount defined above. This third surfactant may be formed in situ during the polymerization process. By monomer is understood not only vinyl chloride, but also a mixture containing at least 60% by weight, preferably 80% by weight, of vinyl chloride with vinyl acetate or propylene. Radical polymerisation initiators can be water-soluble peroxides, such as sodium potassium or ammonium persulfate, hydrogen peroxide, perborates, hydroxyl trevrybutyl, or any water-soluble peroxide, used alone or in conjunction with a reducing agent to form a system known as redox oxide (the acid). - a reducing system), for example sodium formaldehyde sulfoxide (rongalite, etc., which can be used by metal ions, for example copper or iron. pH can be indicated with bicarbonate soda, sodium sulphate, borax, sodium acetate, alkaline phosphates. Polymerization can also take place in the presence of a base, such as ammonia, soda or potash. You can also use molecular weight control means, such as mercaptan, chloroform, carbon tetrabromide. , dichlorethylene or trichloroethylenia and halogenated derivatives of methane. The essence of the invention is disclosed by the following specific examples. Example 1. In the autoclave from no. rusting steel with a capacity of 3 liters, supplied with a stirrer, rotating at a speed of 250 rpm is loaded; g: Waters800 Germinal latex (1% dry material relative to the monomer) 33 Potassium sulphate 3 Potassium persulfate 2. Diamyl sulfosuccinate (0.1% of monomer) 1 Granulometry: 0.15 µm, dry matter content - 30% 55% degree of coating is provided with sodium lauryl sulfate (Texapon). After a vacuum of 600-70.0 mm Hg is formed. Art. served by transferring, 1000 Vinyl chloride and the temperature of the autoclave is increased to. Then, in four equal portions, 10 g of atri lauryl sulfate (Texapon) dissolved in 00 cm of water (after 1 h, 1 h 30 min, 2 h and 2 h 30 min reaction) are served. The dry matter content of the resulting latex is 45%. Latex consists of WU monodispersed granulometric families: a fraction of 0.6 microns is 66%, and a fraction of 0.3 microns — 33%. Yarimer 2. In a stainless steel autoclave with a capacity of 3 liters, equipped with a stirrer, rotating at 150 revolutions per minute, load, g: Water 700 Germ latex (2.3% dry matter relative to the monomer) Potassium persulfate soda Dauctyl sulfosuccinate (0.15 % of monomer) Granulometry:, 0, 2 microns, dry matter content by weight - 37%, 30% degree of coating is provided by sodium laurate. 8 autoclave pressure is reduced to 600-700 mm Hg, after this load 150 g of vinyl chloride. The temperature of the autoclave is raised to 45c. After the pressure drops, 850 g of vinyl chloride, as well as a solution of 7 g of sodium sulfonate of sulfonated alkyl diphenyl ether (Loufax 2A1), pacTBopejiHoro in 250 g of water, are continuously supplied for three hours. The solid content of the resulting latex is 48%. Latex consists of two monodispersed granulometric families; the content of the fraction 0.65 micron is 81%, the content of the fraction 0.25 micron is 19%. EXAMPLE 3 A stainless steel autoclave with a capacity of 3 liters, equipped with a stirrer rotating at a speed of 100 rpm, is loaded with g: Waters4 Zerodiaceous latex (3% by weight of dry material to the monomer) 75 Sodium perborate. 4 Drills3. Sodium myristate (0.2% of monomer) 2 Granulometry 0.3 micron, dry matter content by weight - 40%, 45% coverage by sodium alkyl sulfate (Mersolat). After a vacuum of 600-700 mm Hg is formed in the autoclave. Art. load 200 g of vinyl chloride. The autoclave is heated to 50 seconds. After dropping the volume by 0.5 kg / cm, 800 g of vinyl chloride are introduced in such a way that the pressure in the autoclave always remains 0.5 kg / cm lower than the elasticity of the saturated vapor of lorous in the nila with a temperature of 50 C. In the same Time to inject a solution of 10 g of sodium dodecyl sulfosulfate in 200 cm of water. The solids content in the resulting latex is 60%. It contains two monodispersed particle size distribution families: 0.9 micron fractions - 71% and 0.2 micron fractions - 2 Example 4 (comparative). The reaction is carried out as in the previous example, using germinal latex with a 120% coverage level. During the reaction, the latex coagulates. Electron-microscopic examination revealed a particle size distribution distributed between 0.05 and 0.8 μP Pr and measure 5. In the autoclave from: Non-Rusting steel with a capacity of 3 liters, g: Germ-latex (10% dry material, to monomer) Ammonium persulphate 30% ammonia Ammonium ethylhexonate (0.1% of monomer) Granulometry: 0.4 microns, dry content by weight - 33% 50% degree of coverage is provided by sodium alkyl naphthalene sulfonate After the pressure in the auto clave decreases, up to 600-700 mm Hg, 1000 g of vinyl chloride is introduced. The temperature of the autoclave is increased to. After three hours of reaction, a solution of sodium alkyl naphthalisulfonate 9 diluted in 300 g of water is introduced continuously for three hours. Get latex containing 41% solids. It consists of two monodispersed granulometric families: a fraction of 0.83 microns — 89% and a fraction of 0.25 microns — 11%. Example 6. An autoclave of 16 liter vitrified steel, equipped with a stirrer rotating at a speed of 150 rpm, was placed: g: Germinal latex (5% dry matter to monomer) Trisodium phosphate ammonium persulfate Sodium sulfate Iron sulfate Dodecyl benzene sulfonate sodium , 05% of the monomer) 1.5, Granulometry: 0.6 microns, dry content by weight - 30%, the degree of coating is provided by ethoxylated nonylphenyl with 10 ethylene oxides. After a vacuum of 600,700 mm Hg. load 600 ml of vinyl chloride and the autoclave is heated to 45 ° C. After the pressure drops, 2400 g of vinyl chloride are introduced into the autoclave and a solution of 30 g of sodium dodecylbenzrllsulfonate dissolved in 1 kg of water is continuously injected for three hours. Latex is obtained, with 30% dry matter content. It contains two monodispersed granulometric families: 1.7 microns fractions - 84% and 0.17 microns fractions - 16%. Example 7. Into an autoclave of vitrified, 16-liter steel, equipped with a stirrer, are loaded with: Water4000 Germinal latex (5% dry matter relative to the monomer) 390 Sodium acetate 6 Potassium persulfate 15 Sodium lauryl sulfate (0.06% of monomers) 2 Granulometers : 0.25 micron, solids by weight 42%, 25% coverage; provided by sulfosuccinate (A20 Aerosol). After a vacuum in the autoclave forms from 600 to 700 mm Hg. 3000 g of vinyl chloride and 300 g of vinyl acetate are introduced into it. The autoclave is heated to. After 2 hours, a solution of 30 g of sodium lauryl sulfate in 1 kg of water was continuously introduced within two hours. The obtained latex with a content of .37% dry matter. Latex consists of two monodispersed granulometric families: the fraction of 0.75 microns is 68%, and the fraction of 0.14 microns is 32%. Example 8. Into an autoclave of vitrified steel with a capacity of 16 liters, g: Water 3500 Germ Latex (6% dry matter relative to the monomer). . 400 Lauric acid 30 Ammonium laurate (0.2% of monomer) Ammonium persulphate. Granulometry: 0.4 microns, contains dry; substances - 40%, 35% degree of coating is provided by dioctyl sulfosuccinate Granulometry: 0.5 microns, percentage of dry matter content is 35–30% (Level of coverage is provided by the sodium salt of oxo acid) After a rarefaction of 600-700 mm Hg in aktoklav of rarefaction. injection of 3,000 g of vinyl chloride, the autoclave is heated to 50 ° C, after 1 h, 100 g of 3% ammonia is added in two and a half hours, and a latex containing 41% of dry matter is obtained. perforated granulometric actions: fractions 0.65 micron - 59%, - and fractions 0.3 microns - 41%. ep 9. Into a 16 liter vitrified steel autoclave, g, water: 5000 Gravity latex (9% dry matter relative to monomer) 770 Hydroxyethyl nonylphenol with 10 ethylene oxide, (1% of monomer) 30 Sodium carbonate 8 Sodium persulfate 10 After purging the reactor 4000 g of chloride of nyl is charged with nitrogen. The temperature is increased to 25 g of sodium lauryl sulfate diluted in 1 l of water in four different portions (the injection was done after 30 min, 1 h, 1 h 30 min, and 2 Latex containing 31% solid substances. Latex consists of two monodispersed granulometric families: 0.6 microns - 61 and 0.45 microns - 39%. Example 10. A stainless steel autoclave with a capacity of 2 m, equipped with a stirrer, was loaded with: Water 700 kg Zarch latex (4 wt.% Dry matter relative to the monomer) 71 kg Soda 300 g Potassium persulfate 600 g Sodium Laurate, 0.2% relative to the monomer 1, 6 kg. Granulometry: 0.16 micron, dry matter content by weight - 45–60% coverage by dodecylbenzenesulfate sodium (HANZA). After a vacuum of 60000 mm Hg, st. 800 kg of chlorine vinyl are introduced. The temperature of autolava is reduced to 40 ° C. After two acas, continuously, for 8 hours, add 200 kg of a 3% aqueous solution of dioctyl ultrafusion succinate. A mixture containing two monodiyoperirovannyh granulometric seedlings is obtained: fractions 0.62 microns - 84% and fractions 0.22 microns-16%. Example; 11 (comparative). Wire: as in Example 10, amen sodium laurate is equivalent to i dodecylbenzenesulfonate (Hansa). Latex of the same content is obtained, but with one predominantly family with close to 0.65 micron gradation (96%) plus 4% of asters from 0.02 to 0.1 micron. Example 12. A stainless steel autoclave with a capacity of 6 liters, equipped with a stirrer rotating at a speed of 200 rpm, is loaded with: Water 1500 Germinal latex (3 wt.% Dry matter to monomer) 120 Dicarbonate soda 1 Ammonium persulphate 25 Lipine J acid 3 Myristic acid 12. Granulometry: 0.45 microns, weight percent dry matter content - 40%; The 30% step of coating is provided with sulfonated sodium alkyl diphenyl ether (2A1). After a vacuum has been formed, 600700 mm Hg. load 100 g of propylene and 1500 g of vinyl chloride. The temperature of the autoclave is raised to 35 ° C. After 3 hours, 150 g of a 2% soda solution is continuously added over a period of 6 hours. A latex containing 45% by weight of a solid is obtained, consisting of two monodispersed granules of etheric families with a fraction of 0.9 microns - 74% and a fraction of 0.2 microns - 26%. Example 13. In an autoclave made of vitrified steel, with a capacity of 16 liters, equipped with a stirring system, rotating at 75 rev / min, are introduced, g: WATER 5000 Germ latex (5% dry matter relative to the monomer) 500 Potassium hydroxide 5 Potassium persulphate 18 Potassium dodecylbenzenesulphonate (0.05% of the monomer) 1.75 Granulometric composition: 0.5 micron, dry matter content by weight - 30%, degree of coating 80%, provided with mycetum calmis.
    A vacuum of 700 mm Hg is created in the autoclave, after which 3000 g of vinyl chloride are charged. The mixture is heated to a temperature of 53 ° C, and after 2 hours, a solution of 40 g of sodium dodecyl sulfate in 1 l of water is continuously introduced over b. A latex is obtained, the dry matter content of which is 31%. This latex is represented by two monodisperse granulometric compositions with a fraction of 0.9 μm78% - and a fraction of 0.2 μm - 22%.
    The latexes obtained according to examples 10 and 11 are finely ground, the resulting powder is triturated under the same conditions with a plasticizer (dioctyl phthalate) in a polyvinyl chloride / dioctyl phthalate ratio of 100: 50 parts by weight. The viscosity values of the pastes, as determined on a Brookfield RVT viscometer at 20 rpm (in puaz), are presented in the table.
    From the data of the table, it follows that the polymers obtained by the proposed method are distinguished by lower viscosity values in plastisols and form more stable plastisols. .
    Thus, carrying out the process of (co) polymerizing vinyl chloride according to the proposed method allows one to obtain latexes with a double particle size distribution and possessing improved properties.
    权利要求:
    Claims (2)
    [1]
    1. A method of producing latex (co) polymers of vinyl chloride by emulsion polymerization of vinyl chloride or its mixture with vinyl acetate or propylene in the presence of germinal latex, emulsifier and initiator, different in that in order to obtain latexes with double particle size, as germinal latex use a latex containing an emulsifier that is different from. the emulsifier used in (co) polymerization, the degree of coating of the latex particles by the emulsifier is from 25 to 80%.
    [2]
    2. A method according to claim 1, characterized in that the amount of germinal latex is 0.5 to 20% based on the dry matter by weight
    (co) monomers, and the average particle diameter of germinal latex is 0.15-0.6 microns.
    Sources of information taken into account during the examination 1. USSR Author's Certificate No. 329187, cl. C 08 F 114/06, 1970 (prototype),
    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    NO753239L|1976-03-25|
    DK150904C|1988-02-01|
    NO143797B|1981-01-05|
    NL187687C|1991-12-16|
    SE7510680L|1976-03-25|
    BE833251A|1976-03-10|
    CH599255A5|1978-05-31|
    DK425775A|1976-03-25|
    DD120450A5|1976-06-12|
    BR7506124A|1976-08-03|
    US4046730A|1977-09-06|
    JPS5328349B2|1978-08-14|
    DK150904B|1987-07-13|
    FR2286152A1|1976-04-23|
    IE42016L|1976-03-24|
    DE2542283C2|1985-07-11|
    SE410317B|1979-10-08|
    DE2542283A1|1976-04-08|
    NL7511195A|1976-03-26|
    NL187687B|1991-07-16|
    FR2286152B1|1978-07-13|
    ES441213A1|1977-03-16|
    IT1047448B|1980-09-10|
    CA1061033A|1979-08-21|
    GB1505549A|1978-03-30|
    JPS5157792A|1976-05-20|
    IE42016B1|1980-05-21|
    LU73440A1|1976-04-13|
    NO143797C|1981-04-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB627265A|1945-11-16|1949-08-04|Goodrich Co B F|Improvements in or relating to highly stable vinyl polymer latices and method of preparing same|
    IT650198A|1961-03-24|
    NL6709139A|1966-07-07|1968-01-08|
    US3424706A|1966-07-08|1969-01-28|Staley Mfg Co A E|Vinylidene chloride copolymerization in presence of preformed seed latex|
    US3578647A|1968-05-06|1971-05-11|Grace W R & Co|Chemical crosslinking scorch preventing additives and process therefor|
    US3578648A|1968-06-18|1971-05-11|Nippon Carbide Kogyo Kk|Process for the preparation of vinyl chloride polymers|
    FR2044364A5|1969-05-19|1971-02-19|Pechiney Saint Gobain|US4150210A|1978-06-19|1979-04-17|Stauffer Chemical Company|Emulsion polymerization of vinyl chloride polymers using mixed emulsifier system|
    US4219454A|1978-09-05|1980-08-26|Air Products And Chemicals, Inc.|Vinyl acetate copolymer emulsions for paint|
    US4254004A|1979-05-09|1981-03-03|Scm Corporation|Emulsion process for polymer particles|
    DE2937223A1|1979-09-14|1981-04-02|Basf Ag, 6700 Ludwigshafen|METHOD FOR THE DISCONTINUOUS POLYMERIZATION OF VINYL CHLORIDE IN EMULSION|
    FR2468619B1|1979-11-06|1985-06-21|Rhone Poulenc Ind|PROCESS FOR THE PREPARATION OF VINYL CHLORIDE HOMO- AND CO-POLYMERS SUITABLE FOR GIVING PLASTISOLS FROM A LATEX CONTAINING TWO PARTICLE POPULATIONS|
    DE3017543A1|1980-05-08|1981-11-26|Bayer Ag, 5090 Leverkusen|AQUEOUS DISPERSIONS BASED ONACRYLIC ACID ALKYLESTER POLYMERISATES WITH TWO EXCELLENT, PRACTICALLY NOT OVERLAPPING MAXIMAS IN PARTICLE SIZE DISTRIBUTION WITHIN SPECIFIC PARTICLE LARGE RANGE|
    DE3036969A1|1980-10-01|1982-05-13|Hoechst Ag, 6000 Frankfurt|PROTECTIVE COLLOID-FREE PLASTIC DISPERSIONS WITH BIMODAL PARTICLE SIZE DISTRIBUTION|
    DE3147008A1|1981-11-27|1983-06-01|Röhm GmbH, 6100 Darmstadt|METHOD FOR PRODUCING AQUEOUS, HIGH-CONCENTRATED BIMODAL PLASTIC DISPERSIONS|
    US4461869A|1981-12-30|1984-07-24|The B. F. Goodrich Company|Process for making low fusion dispersion resins|
    US4474860A|1983-05-16|1984-10-02|The Dow Chemical Company|High solids latexes for paper coatings|
    US5106903A|1984-12-17|1992-04-21|Lehigh University|Preparation of large particle size monodisperse latexes|
    US4791162A|1984-12-17|1988-12-13|Lehigh University|Preparation of large particle size monodisperse latexes|
    BE1004570A3|1990-09-17|1992-12-15|Solvay|METHOD FOR PRODUCTION OF POLYMER LATEX multimodal VINYL CHLORIDE.|
    FR2752844B1|1996-08-27|1998-10-30|Atochem Elf Sa|BIPOPULA LATEX OF POLYMERS BASED ON VINYL CHLORIDE, ITS METHODS OF OBTAINING AND ITS APPLICATION IN PLASTISOLS WITH IMPROVED RHEOLOGY|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7432094A|FR2286152B1|1974-09-24|1974-09-24|
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