US3645775A - Process for production of an artificial leather and product - Google Patents
Process for production of an artificial leather and product Download PDFInfo
- Publication number
- US3645775A US3645775A US3645775DA US3645775A US 3645775 A US3645775 A US 3645775A US 3645775D A US3645775D A US 3645775DA US 3645775 A US3645775 A US 3645775A
- Authority
- US
- United States
- Prior art keywords
- polyurethane
- artificial leather
- silicone oil
- percent
- microporous
- 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.)
- Expired - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/904—Artificial leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
Definitions
- ABSTRACT Process of producing an artificial leather by coagulating or hardening a polyurethane gel applied to a substrate into a microporous layer which is permeable to 'water vapor, wherein a silicone oil is added to the initial gelable solution of the polyurethane in an organic solvent.
- a synthetic or artificial leather can be produced from a nonwoven web or fleece which has been bonded with a polymeric elastomeric binder such as a polyurethane.
- Nonwoven webs or fabrics which have been treated in this way are generally capable of storing water vapor and then giving it off again at the surface of the web. This is of the greatest importance for an artificial leather which is to be used in the manufacture of shoes because the upper leather of a shoe must absorb water vapor as perspiration from the foot and then pass it to the outside at the exposed surface. If the upper leather does not fulfill this function, the water vapor accumulates inside the shoe and causes discomfort to the wearer.
- Nonwoven webs or fabrics treated in this way are also highly porous and permeable to liquid so that, for example, rain water can enter the shoe from outside.
- the porous bonded web or fleece, also termed the substrate must therefore be provided with a microporous covering layer which although permeable to water vapor is impermeable to liquid water.
- this covering layer must give the shoe material the appearance of a leather surface and a leathery handle. Properties such as compression strength, bending or flexing resistance, resistance to cold, scuff resistance and the like of the finished material also depend largely on the quality of this surface covering layer.
- covering layers for an artificial leather from polyurethanes.
- These layers can be produced for example from solutions of polyurethanes in dimethylformamide or other suitable organic solvents, the polyurethane in the solution being converted into a gel by the addition of a nonsolvent such as water and the gel then being coated onto the bonded nonwoven web or fabric. After coagulation of the polyurethane, washing to remove the solvent and drying, polyurethane surface layers with improved permeability to water vapor are obtained.
- a nonsolvent such as water
- the general object of the present invention is to provide an initial gellable polyurethane composition and an improvement in the conventional process of providing a microporous surfacing of artificial leathers based on polyurethane whereby a number of important properties are enhanced in a relatively simple and economical manner.
- an artificial leather with improved properties can be produced particularly advantageously by the application of a polyurethane layer to a substrate, if there is used a gellable solution of polyurethane in an organic solvent which contains about 1 to l percent and preferably 2 to 4 percent by weight of a silicone oil, based on the weight of the dissolved polyurethane.
- the organic solvent is preferably dimethylformamide.
- Polyurethanes used in the process according to the invention are generally known. They may be obtained, for example,-
- the polyurethane film-forming or coating material should be one which consists predominately of the polyurethane, preferably 65 percent by weight or more, and may contain one or more other film-formweight thereof, and the total weight of such polymer mixtures is considered the weight of the polyurethane for purposes of the present invention. 4
- the organic solvent normally used is dimethyl formamide but other welLknown solvents for polyurethane are also suitable, for example dimethyl sulphoxide, dimethylacetamide and mixtures of such solvents.
- the quantity of the polyurethane in the solution may vary within wide limits in the process according to the invention. In general, concentrations of the polyurethane in the solvent of 15 to 40 percent by weight are found to be suitable.
- the polyurethane solution may also contain up to 30 percentby weight, based on the polyurethane, of other polymers such as polyvinyl chloride. Other additives such as stabilizers, pigments or dyes may of course also be included.
- Silicone oils which may be used within the scope of the invention are generally known liquid substances. They are polymeric organosilicon compounds in which silicon atoms are linked together via oxygen atoms and the remaining valencies of the silicon atoms are saturated with hydrocarbon radicals.
- the preferred silicone oils have a predominately linear structure with recurring units of the formula sometimes expressed as (SiR O), in which the side groups R represent a hydrocarbon radical of one to 12 carbon atoms, preferably one to six carbon atoms, such as lower alkyl, e.g., methyl, or aryl, e.g., phenyl.
- silicone oils are generally quite similar in their chemical structure, corresponding to the above noted formula of the individual recurring unit in the polymer, although minor modifications can be made without affecting the essential properties of these silicone oils.
- Their viscosity is primarily determined by the chain length of the linear polyorgano-siloxane structure, although there may occasionally occur a cross-linking of individual chains by a silicon-oxygen-silicon linkage.
- Such minor variations of the well-known silicone oils are to be included within the scope of the invention.
- Silicone oils which have a viscosity of to 1,000 centipoise (c?) are found to be particularly suitable for purposes of the invention.
- the silicone oils may be soluble or insoluble in the organic solvent such as dimethylformamide employed in the preparation of the polyurethane gel.
- the silicone oil selected for purposes of the invention is added in a quantity of from about 1 to 10 and preferably about 2 to 4 percent by weight, based on the dissolved polyurethane. Addition of the silicone oil is best carried out when the polyurethane is already dissolved in the organic solvent. Care should be taken to ensure that the silicone oil is uniformly distributed in finely divided or finely dispersed form in the solution at the point where the dissolved polyurethane is converted into a gel,'e.g., by the addition of a suitable non-solvent such as water. This uniform distribution is particularly applicable when using a silicone oil which is insoluble inthe dimethylformamide or other solvent.
- the gel can be applied to a porous nonwoven web or fleece, for example with the aid of a doctor blade, and is then coagulated, washed and dried. After drying, the microporous covering layer on the substrate preferably has a thickness of about 0.3 to 0.6 mm. and especially 0.3 to 0.4 mm.
- the substrate itself is bonded with a polyurethane solution or any suitable elastomer solution by impregnating the'nonwoven web or fabric and hardening the elastomeric binder in a conventional manner.
- a suitable nonwoven web can be obtained for example by the process according to British Pat. specification No. 1,017,023. Many techniques are known for the manufacture of nonwoven webs and their bonding into a flexible, porous substrate capable of providing the body or primary layer of an artificial leather, and the present invention is not limited'to the use of any particular substrate.
- the addition of a silicone oil according to the invention substantially improves the microporous covering or surface layers.
- a silicone oil according to the invention it is possible by means of the silicone oil to substantially eliminate the tendency of certain polyurethanes, -e.g., as 7 obtained by the process according to French Pat. No.'1,546,169, to disintegrate when drying the covering layer so as to yield a film or surface layer which is nonporous and impermeable to water vapor.
- the covering layers obtained according to the invention are extremely stable.
- Polyurethane solutions which contain 30 to 40 percent by weight of the polyurethane and about 1 to 10 percent by weight, based on the dissolved polyurethane, of a silicone oil therefore represent a preferred embodiment of the invention, these solutions being gelled and subsequently coagulated, washed and dried to yield the desired microporous layer.
- microporous polyurethane layer is particularly advantageous because less solvent needs to be recovered.
- the microporous layers produced according to the invention can be easily washed out very thoroughly before they are dried and no residues remain which could subsequently cause difficulties, such as collapse of the microporous or fine cellular structure of the covering layer or discoloration of the polyurethane. Furthermore, covering layers with improved physical or mechanical properties are obtained when higher concentrations of the initial solution are used.
- the process according to the invention moreover makes it possible to produce colored surface coatings or layers in which 'adye or pigment is very uniformly distributed.
- the covering layers produced according to the inventio are also notable for a very uniform pore structure and increased compressive strength.
- the bending resistance is also improved.
- Low-temperature mechanical properties, particularly the response to bending, are likewise superior in comparison to previous products.
- Microporous covering layers produced according to the invention may be grained and provided with one or more coatings, e.g., an undercoat containing a polyurethane and a top lacquer containing nitrocellulose.
- the surface coatings which are applied when finishing the covering layer of the invention have a total thickness of only a few microns. 1
- silicones in polyurethane-containing dressings or finishing agents for synthetic leather, the use of silicones in this limited way does not achieve the advantages of this invention. Moreover, it is extremely surprising that the use of silicone oils in the production of a microporous covering layer which is several hundred microns in thickness results in an artificial leather which has many improved properties.
- the resistance of the product to bending stresses at -20 C. is above 100,000 but is only about 40,000 when no silicone oil is used. Flexing numbers of over 360,000 are obtained in a Bally Flexometer at a temperature of -5 0, whereas the same covering layer without the addition of silicone exhibits a flexing number of only about 180,000.
- EXAMPLE 2 A 30 percent polyurethane solution in dimethyl formamide is initially prepared, wherein the polyurethane is obtained from a polybutylene adipate having a molecular weight of 1,000 and diphenylmethane-4,4-diisocyanate in the molar ratio of 2:3 while providing a chain lengthening with diethanolamine and ethylene diamine in the molar ratio 0.15:0.70.
- This preparation corresponds to that disclosed in French Pat. specification No. 1,546,169.
- the covering layer collapses on drying to give a film or layer which is nonporous and impermeable to water vapor.
- EXAMPLE 3 A 35 percent polyurethane solution in dimethylformamide is prepared in known manner from polyethylene adipate (molecular weight 2,000), diphenylmethane-4,4-diisocyanate and ethylene glycol in the molar ratio of 1:4.3 3.3. 20.5 grams of water, 22.5 grams of dimethylformamide, 1.0 grams of a commercial metal complex dye consisting of equal'parts of Savinyl dyes Brown GLS and Yellow RLS (Sandoz AG, Basle, Switzerland) and 2.2 grams of a commercial silicone oil (Getren 4, available from Th. Goldschmidt AG,-Essen, Germany) are added successively to 207 grams of this polyurethane solution at 50 C. with stirring.
- the solution is homogenized, converted into a gel by cooling it to room temperature, and directly applied to a substrate which is permeable to water vapor to provide a surface layer having a thickness of 0.8 mm.
- the polyurethane layer is stored for 6 minutes at room temperature and 60 percent relative humidity and then coagulated in water at 20 C. and washed. When the polyurethane surface layer has been dried at 100 C., it is very smooth and of completely uniform color.
- the bending numbers of the product at 20 C. are higher than 300,000; in the flexometer at 5 C. and +20 C., the sample shows no damage after 1,000,000 flexes.
- Organopolysiloxane emulsion used as a release material.
- Viscosity 2,100 clP Water-soluble .polydimethylsiloxane
- Water-soluble organopolysiloxane a release material for the rubber and plastic industry. Used for special release problems.
- organic solvent is dimethyl formamide
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1815043A DE1815043B2 (de) | 1968-12-17 | 1968-12-17 | Verfahren zur Herstellung von Kunstleder |
Publications (1)
Publication Number | Publication Date |
---|---|
US3645775A true US3645775A (en) | 1972-02-29 |
Family
ID=5716407
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US3645775D Expired - Lifetime US3645775A (en) | 1968-12-17 | 1969-12-12 | Process for production of an artificial leather and product |
Country Status (17)
Country | Link |
---|---|
US (1) | US3645775A (fi) |
JP (1) | JPS5312561B1 (fi) |
AT (1) | AT296218B (fi) |
BE (1) | BE739674A (fi) |
BR (1) | BR6914292D0 (fi) |
CH (1) | CH503831A (fi) |
DE (1) | DE1815043B2 (fi) |
ES (1) | ES372448A1 (fi) |
FI (1) | FI53327C (fi) |
FR (1) | FR2026352A1 (fi) |
GB (1) | GB1285214A (fi) |
HU (1) | HU163696B (fi) |
LU (1) | LU59990A1 (fi) |
NL (1) | NL6915267A (fi) |
NO (1) | NO131250C (fi) |
PL (1) | PL80381B1 (fi) |
RO (1) | RO58673A (fi) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894165A (en) * | 1973-05-23 | 1975-07-08 | G S Staunton & Co Inc | Coated flexible reticulate structures and method for the preparation thereof |
US3932337A (en) * | 1974-04-25 | 1976-01-13 | The Richardson Company | Thermoplastic urethane compound having low compression set and high modulus |
US4011189A (en) * | 1975-08-08 | 1977-03-08 | Dow Corning Corporation | Urethanes modified with siloxanes |
US4059659A (en) * | 1974-11-01 | 1977-11-22 | Chemie-Anlagenbau Bischofsheim Gmbh | Process for producing finished and/or irreversibly embossed microporous sheet structures |
US4137360A (en) * | 1973-09-07 | 1979-01-30 | Bayer Aktiengesellschaft | Microporous sheets and a process for making them |
US4543144A (en) * | 1983-04-13 | 1985-09-24 | Bayer Aktiengesellschaft | Aqueous polyurethane compositions containing crosslinking agents and their use for heat-active one-coat reverse coating |
US4547423A (en) * | 1982-07-15 | 1985-10-15 | Sony Corporation | Textile for clothes |
US4554198A (en) * | 1982-01-14 | 1985-11-19 | Bluecher Hubert | Waterproof and air-tight, moisture-conducting textile material |
US4714652A (en) * | 1984-06-06 | 1987-12-22 | Lorica S.P.A. | Process for fire-proofing porous synthetic sheet material particularly artificial leather |
WO2006000044A1 (en) * | 2004-06-24 | 2006-01-05 | Ezio Margiotta | Liquid impermeable material |
US20070179031A1 (en) * | 2006-01-27 | 2007-08-02 | Shuo-Hsiu Chang | Weight trainer |
US20110071448A1 (en) * | 2004-06-24 | 2011-03-24 | Ezio Margiotta | Liquid impermeable material |
CN103015173A (zh) * | 2012-12-24 | 2013-04-03 | 建德市顺发化工助剂有限公司 | Pu革用泡孔调直剂及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3190766A (en) * | 1961-10-31 | 1965-06-22 | Du Pont | Method of making vapor permeable sheet materials |
US3211674A (en) * | 1961-08-22 | 1965-10-12 | Mobay Chemical Corp | Polyurethane foam from hydroxylated tall oil |
US3243475A (en) * | 1960-05-27 | 1966-03-29 | Bayer Ag | Polyurethanes |
US3450791A (en) * | 1966-09-20 | 1969-06-17 | Desoto Inc | Modified polyurethane-silicone polymers |
-
1968
- 1968-12-17 DE DE1815043A patent/DE1815043B2/de not_active Ceased
-
1969
- 1969-09-24 GB GB4693669A patent/GB1285214A/en not_active Expired
- 1969-09-25 NO NO382469A patent/NO131250C/no unknown
- 1969-09-25 FI FI275669A patent/FI53327C/fi active
- 1969-09-29 CH CH1461169A patent/CH503831A/de not_active IP Right Cessation
- 1969-10-01 BE BE739674D patent/BE739674A/xx unknown
- 1969-10-08 RO RO6121269A patent/RO58673A/ro unknown
- 1969-10-08 AT AT947469A patent/AT296218B/de not_active IP Right Cessation
- 1969-10-09 NL NL6915267A patent/NL6915267A/xx unknown
- 1969-10-13 ES ES372448A patent/ES372448A1/es not_active Expired
- 1969-11-18 BR BR21429269A patent/BR6914292D0/pt unknown
- 1969-11-18 JP JP9183969A patent/JPS5312561B1/ja active Pending
- 1969-12-08 PL PL1969137380A patent/PL80381B1/pl unknown
- 1969-12-10 LU LU59990D patent/LU59990A1/xx unknown
- 1969-12-12 US US3645775D patent/US3645775A/en not_active Expired - Lifetime
- 1969-12-16 FR FR6943581A patent/FR2026352A1/fr not_active Withdrawn
- 1969-12-17 HU HUGA000987 patent/HU163696B/hu unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3243475A (en) * | 1960-05-27 | 1966-03-29 | Bayer Ag | Polyurethanes |
US3211674A (en) * | 1961-08-22 | 1965-10-12 | Mobay Chemical Corp | Polyurethane foam from hydroxylated tall oil |
US3190766A (en) * | 1961-10-31 | 1965-06-22 | Du Pont | Method of making vapor permeable sheet materials |
US3450791A (en) * | 1966-09-20 | 1969-06-17 | Desoto Inc | Modified polyurethane-silicone polymers |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894165A (en) * | 1973-05-23 | 1975-07-08 | G S Staunton & Co Inc | Coated flexible reticulate structures and method for the preparation thereof |
US4137360A (en) * | 1973-09-07 | 1979-01-30 | Bayer Aktiengesellschaft | Microporous sheets and a process for making them |
US3932337A (en) * | 1974-04-25 | 1976-01-13 | The Richardson Company | Thermoplastic urethane compound having low compression set and high modulus |
US4059659A (en) * | 1974-11-01 | 1977-11-22 | Chemie-Anlagenbau Bischofsheim Gmbh | Process for producing finished and/or irreversibly embossed microporous sheet structures |
US4011189A (en) * | 1975-08-08 | 1977-03-08 | Dow Corning Corporation | Urethanes modified with siloxanes |
US4554198A (en) * | 1982-01-14 | 1985-11-19 | Bluecher Hubert | Waterproof and air-tight, moisture-conducting textile material |
US4547423A (en) * | 1982-07-15 | 1985-10-15 | Sony Corporation | Textile for clothes |
US4543144A (en) * | 1983-04-13 | 1985-09-24 | Bayer Aktiengesellschaft | Aqueous polyurethane compositions containing crosslinking agents and their use for heat-active one-coat reverse coating |
US4714652A (en) * | 1984-06-06 | 1987-12-22 | Lorica S.P.A. | Process for fire-proofing porous synthetic sheet material particularly artificial leather |
WO2006000044A1 (en) * | 2004-06-24 | 2006-01-05 | Ezio Margiotta | Liquid impermeable material |
US20110071448A1 (en) * | 2004-06-24 | 2011-03-24 | Ezio Margiotta | Liquid impermeable material |
US20070179031A1 (en) * | 2006-01-27 | 2007-08-02 | Shuo-Hsiu Chang | Weight trainer |
CN103015173A (zh) * | 2012-12-24 | 2013-04-03 | 建德市顺发化工助剂有限公司 | Pu革用泡孔调直剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
GB1285214A (en) | 1972-08-16 |
RO58673A (fi) | 1975-09-15 |
DE1815043B2 (de) | 1975-02-06 |
HU163696B (fi) | 1973-10-27 |
CH503831A (de) | 1971-02-28 |
JPS5312561B1 (fi) | 1978-05-02 |
DE1815043A1 (de) | 1970-06-25 |
ES372448A1 (es) | 1971-10-16 |
FI53327C (fi) | 1978-04-10 |
NO131250C (fi) | 1975-04-30 |
PL80381B1 (fi) | 1975-08-30 |
LU59990A1 (fi) | 1970-02-10 |
NL6915267A (fi) | 1970-06-19 |
BE739674A (fi) | 1970-03-16 |
FI53327B (fi) | 1977-12-30 |
NO131250B (fi) | 1975-01-20 |
AT296218B (de) | 1972-02-10 |
BR6914292D0 (pt) | 1973-01-16 |
FR2026352A1 (fi) | 1970-09-18 |
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