NO135871B - - Google Patents
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- Publication number
- NO135871B NO135871B NO1320/70A NO132070A NO135871B NO 135871 B NO135871 B NO 135871B NO 1320/70 A NO1320/70 A NO 1320/70A NO 132070 A NO132070 A NO 132070A NO 135871 B NO135871 B NO 135871B
- Authority
- NO
- Norway
- Prior art keywords
- resin
- granules
- phenol
- beads
- polystyrene
- Prior art date
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 18
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000002657 fibrous material Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000007931 coated granule Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011324 bead Substances 0.000 description 13
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/236—Forming foamed products using binding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/206—Using expandable particles or beads as starting material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/207—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising impregnating expanded particles or fragments with a binder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
Oppfinnelsen angår skumplastprodukter som er dannet av ekspanderte granuler av termoplast, særlig polystyren, og fenol/formaldehydharpiks som opptar mellomrommene mellom granulene og danner et ubrutt, stivt nettverk mellom nevnte granuler. The invention relates to foam plastic products which are formed from expanded granules of thermoplastic, in particular polystyrene, and phenol/formaldehyde resin which occupies the spaces between the granules and forms an unbroken, rigid network between said granules.
Oppfinneren har konstatert at denne struktur tilveie-bringer bemerkelsesverdige mékaniske egenskaper og særlig en meget god kompresjonsmotstand. The inventor has established that this structure provides remarkable mechanical properties and in particular a very good compression resistance.
Produktene egner seg særlig godt for varmeisolasjon av bygninger. The products are particularly suitable for thermal insulation of buildings.
Den anvendte harpiks som danner nettverket har følgende egenskaper: The resin used to form the network has the following properties:
- den fukter granulene jevnt, - it moistens the granules evenly,
- den har høy herdningshastighet ved den anvendte temperatur, - den hefter godt til granulene i herdet tilstand, - it has a high curing speed at the temperature used, - it adheres well to the granules in the cured state,
-'den sikrer en stiv og ubrutt struktur. - it ensures a rigid and unbroken structure.
Gjenstanden for foreliggende oppfinnelse er altså en kontinuerlig fremgangsmåte til fremstilling av et stivt, plate-, formet skumplastprodukt, omfattende a) en kjerne av ekspandert termoplast, fortrinnsvis polystyren, i form av granuler som er innleiret i fenol/formaldehydharpiks, og b) to yttersjikt av et fibermateriale, fortrinnsvis vevet glassfiberduk, og fremgangsmåten karakteriseres ved at man påfører fullt ekspanderte termoplast-granuler et homogent belegg av fenol/formaldehyd-harpiksen på i og for seg kjent måte ved pådusjing av en oppløsning av harpiksen, fører de belagte granuler inn mellom de to baner av fibermateriale som skal danne yttersjiktene, og sammenpresser denne' lagstruktur til endelig The object of the present invention is thus a continuous method for the production of a rigid, plate-shaped foam plastic product, comprising a) a core of expanded thermoplastic, preferably polystyrene, in the form of granules embedded in phenol/formaldehyde resin, and b) two outer layers of a fiber material, preferably woven glass fiber cloth, and the method is characterized by applying a homogeneous coating of the phenol/formaldehyde resin to fully expanded thermoplastic granules in a manner known per se by spraying on a solution of the resin, the coated granules introduce between the two webs of fiber material which will form the outer layers, and compress this layer structure to the end
■ form under samtidig oppvarming til herdning av harpiksen. ■ form while simultaneously heating to harden the resin.
Por fremstilling av de ekspanderte granuler blir Por production of the expanded granules becomes
utgangsmaterialet,fortrinnsvis polystyrengranuler, som inneholder et jevnt fordelt ekspanderingsmiddel, først utsatt for vanndamp. Under denne innvirkning mykner .termoplasten og ekspanderings-midlet fordamper. Dette trinn, den såkalte forekspansjon, blir fulgt av et annet trinn i hvilket man bringer granulene i en sterkere ekspandert tilstand ved å utsette dem for en ny damp-ekspansjon..• the starting material, preferably polystyrene granules, containing a uniformly distributed expanding agent, first exposed to water vapour. During this impact, the thermoplastic softens and the expanding agent evaporates. This step, the so-called pre-expansion, is followed by another step in which the granules are brought into a more strongly expanded state by subjecting them to a new steam expansion..•
Ifølge en annen utførelsesform blir granulene for-varmet med luft til en temperatur på 90-100°C eller høyere, før de utsettes for behandling med damp. En ■slik fremgangsmåte er beskrevet i norsk patent nr. 131.919. According to another embodiment, the granules are preheated with air to a temperature of 90-100°C or higher, before they are subjected to treatment with steam. Such a method is described in Norwegian patent no. 131,919.
Ifølge en annen ,utførelsesform blir granulene forekspandert ved atmosfæretrykk ved å utsettes for en damp-behandling, og deretter blir de behandlet med damp i autoklaven. Man kan utføre flere behandlinger. Dette er beskrevet i norsk patent nr. 131-920. Ekspanderingen av granuler skal være full-stendig før de bringes under kompresjon. According to another embodiment, the granules are pre-expanded at atmospheric pressure by being subjected to a steam treatment, and then they are treated with steam in the autoclave. Several treatments can be performed. This is described in Norwegian patent no. 131-920. The expansion of granules must be complete before they are brought under compression.
Fra norsk patent,nr. 91.715, eksempel 1, og tysk patent nr. 964.217, er det i og for seg kjent å fremstille pla-ter av oppskummede polystyrenpartikler som er innleiret i en herdeplast. From Norwegian patent, no. 91,715, example 1, and German patent no. 964,217, it is known per se to produce sheets of foamed polystyrene particles which are embedded in a thermosetting plastic.
Fra norsk patent nr. 68.486' er det kjent å omgi stfumplastplater med glassfiberduk som er impregnert med bitumen. From Norwegian patent no. 68,486, it is known to surround Stfumplast sheets with glass fiber cloth which is impregnated with bitumen.
Fra den ålment tilgjengelige norske søknad 168.325 (tilsvarende tysk utlegningsskrift 1.669.648)' er det kjent å blande oppskummede polyetylenpartikler med epoksyharpiks og sammentrykke blandingen til mindre enn halvparten av det opp-rinnelige volum, hvorpå blandingen herdes. En lignende prosess hvor polystyrenpartikler brukes, men hvor sammentrykningen er liten, er beskrevet i US-patent 3-251.916..■' From the widely available Norwegian application 168,325 (corresponding to German explanatory document 1,669,648) it is known to mix foamed polyethylene particles with epoxy resin and compress the mixture to less than half of the original volume, after which the mixture is hardened. A similar process where polystyrene particles are used, but where the compression is small, is described in US Patent 3-251,916..■'
I det følgende beskrives en utførelsesform av fremgangsmåten ifølge oppfinnelsen. In the following, an embodiment of the method according to the invention is described.
Man ekspanderer med vanndamp polystyren-granuler med en diameter på 0,5 - 2 mm inneholdende 5-7 % pentan. Man erhol-der på den måte ekspanderte perler .med en volumvekt på. 12-25kg/m^ etter modning, avhengig1 av oppholdstiden i damp. Polystyrene granules with a diameter of 0.5 - 2 mm containing 5-7% pentane are expanded with steam. Expanded pearls with a volume weight of 12-25kg/m^ after ripening, depending1 on the residence time in steam.
Man fremstiller parallelt, en fenol-trioksymetylen-harpiks med et ekvivalent molekylært forhold formaldehyd/fenol = 2/1 ved hjelp av en kjent kondensasjons-prosess i alkalisk medium. Den nøytraliserte harpiks har et tørrekstrakt av 72- 75% og en viskositet på ca. 14 poise ved 20°C. Harpiksen blir aktivert med 1-2 vekt-% saltsyre med 17 % konsentrasjon. Blandingen har en begrenset holdbarhet. In parallel, a phenol-trioxymethylene resin with an equivalent molecular ratio of formaldehyde/phenol = 2/1 is produced using a known condensation process in an alkaline medium. The neutralized resin has a dry extract of 72-75% and a viscosity of approx. 14 poise at 20°C. The resin is activated with 1-2% by weight hydrochloric acid with a 17% concentration. The mixture has a limited shelf life.
Belegningen av.de ekspanderte perler kan skje i en horisontal sylinder som roterer om sin akse og som er forsynt med på akselen anbragte skovler som sikrer en effektiv omrøring. Man innfører perlene ved en ende av sylinderen og innsprøyter samtidig den katalyserte harpiks. The coating of the expanded beads can take place in a horizontal cylinder which rotates about its axis and which is equipped with paddles placed on the axis which ensure efficient stirring. The beads are introduced at one end of the cylinder and the catalyzed resin is injected at the same time.
Etter belegningsprosessen innfører man perlene i en luft-oppvarmet presse mellom to baner av fibermateriale, fortrinnsvis glassfiberduker. Man utsetter det hele for en strøm av luft av 115-125°C i løpet av 1-5 min., og man komprimerer. Man minsker fordelaktig volumet med 30-50 %. Man oppnår derved en tiltetting av mellomrommene mellom perlene.. Kompresjonsgraden beregnes slik at perlene bringes'nær hverandre uten å drive ut harpiksen. After the coating process, the beads are introduced into an air-heated press between two webs of fiber material, preferably glass fiber cloths. The whole is exposed to a stream of air of 115-125°C for 1-5 min., and compressed. The volume is advantageously reduced by 30-50%. You thereby achieve a sealing of the spaces between the beads. The degree of compression is calculated so that the beads are brought close to each other without driving out the resin.
Ved siden av at de har gode mekaniske egenskaper, er de. fremstilte skumplastprodukter, inneholdende herdet fenol/- formaldehydharpiks, lite brennbare. Man kan forbedre denne egenskap ytterligere hvis man erstatter perlene av normal polystyren med perler av polystyren'som er gjort ubrennbare med kjemiske midler. In addition to having good mechanical properties, they are manufactured foam plastic products, containing hardened phenol/formaldehyde resin, low inflammability. One can further improve this property if one replaces the beads of normal polystyrene with beads of polystyrene that have been made non-flammable by chemical means.
I motsetning til produkter av normal polystyren som er gjort ubrennbare på vanlig måte, har endelig oppfinneren med overraskelse konstatert at de nye produkter, når de utsettes for flammer og flammen fjernes, ikke avgir brennende tjærestoffer, hvilket representerer en betydelig fordel i tilfelle av brann. Finally, in contrast to products of normal polystyrene which have been made non-flammable in the usual way, the inventor has finally found with surprise that the new products, when exposed to flames and the flame is removed, do not emit burning tar substances, which represents a significant advantage in case of fire.
Glassfiberduken som befinner seg på overflaten av produktet kan med fordel inneholde et impregneringsmateriale, f.eks. bitumen som danner et tettende belegg. Denne anvendelse er meget fordelaktig når det gjelder isolasjon av takterrasser. . Fig. 1 viser eksempelvis ét apparat for kontinuerlig fremstilling av polystyren-skum hvis mellomrom er fylt med The fiberglass cloth that is on the surface of the product can advantageously contain an impregnation material, e.g. bitumen which forms a sealing coating. This application is very advantageous when it comes to the insulation of roof terraces. . Fig. 1 shows, for example, an apparatus for the continuous production of polystyrene foam whose spaces are filled with
-f enolharpiks. -f enol resin.
De ekspanderte granuler eller perler blir innført kontinuerlig ved 1 og de passerer i en blandingssylinder 2 omfattende en Arkimedes-skrue 3 samt forstøvningsdyser 4 og tilførselsrør 5- Disse rør blir matet med flytende katalysert The expanded granules or beads are introduced continuously at 1 and they pass in a mixing cylinder 2 comprising an Archimedes screw 3 as well as atomizing nozzles 4 and supply pipes 5- These pipes are fed with liquid catalyzed
fenolharpiks. phenolic resin.
De ekspanderte granuler eller perler som er dekket The expanded granules or beads that are covered
med fenolharpiks, passerer en trakt 6 som fører dem mellom to baner av glassfiberduk I- la., som blir avviklet fra spoler 8-8a. with phenolic resin, pass a funnel 6 which leads them between two webs of glass fiber cloth I-la., which are unwound from coils 8-8a.
Det hele passerer en oppvarmningsinnretning som omfatter to transportbånd 9~9a med metallmasker. Deretter føres det i en kompresjonsinnretning som omfatter to transportbånd 10-lOa, It all passes through a heating device comprising two conveyor belts 9~9a with metal meshes. It is then fed into a compression device comprising two conveyor belts 10-10a,
forsynt med lameller. provided with slats.
Dette apparat kan kompletteres med en impregnerings-innretning (med f.eks. bitumen) over hele bredden av det erholdte produkt 11. This device can be completed with an impregnation device (with e.g. bitumen) over the entire width of the obtained product 11.
Fig. 2 er et snitt etter linjen II-TI av fig. 1, og viser ved 7' og 7a glassfiberbanen, ved 12 perler av ekspandert polystyren og ved 13 fornettet fenolharpiks mellom perlene. Fig. 2 is a section along the line II-TI of fig. 1, and shows at 7' and 7a the fiberglass web, at 12 beads of expanded polystyrene and at 13 cross-linked phenolic resin between the beads.
Anvendelseseksempel av apparatet Application example of the device
Man innfører i blanderen 2 perler av polystyren ekspandert til 18 kg/nr 3 i en 'mengde av 60 kg/time. Man fordeler i en mengde av 60 kg/time ved hjelp av dyser 4, en blanding av fenoltrioksymetylen-harpiks med et ekvivalent molekylært forhold formaldehyd/fenol = 2/1 og saltsyre med en konsentrasjon av 17 %, således at vektforholdet syre/harpiks er 1,5 %. Perlene blir omhyllet med harpiksen ved hjelp av skruen 3 og ført mot trak- 2 beads of polystyrene expanded to 18 kg/no. 3 in a quantity of 60 kg/hour are introduced into the mixer. A mixture of phenoltrioxymethylene resin with an equivalent molecular ratio of formaldehyde/phenol = 2/1 and hydrochloric acid with a concentration of 17% is distributed in a quantity of 60 kg/hour using nozzles 4, so that the weight ratio of acid/resin is 1.5%. The beads are coated with the resin by means of the screw 3 and guided towards the
ten 6 og deretter gjennom maskinen 9~9a. Produktet holdes mellom de to glassfiberbaner 7~7a som veier 60 g/m . ten 6 and then through the machine 9~9a. The product is held between the two fiberglass webs 7~7a which weigh 60 g/m.
Seksjonen 9~9a er forsynt med varmluft-opphetnings-kasser. Produktet holdes 2 min. ved ll8°C ved sirkulasjon av varm luft. Produktet føres deretter i seksjonen 10-10a hvor dets tykkelse minskes med 33 %• Etter avkjøling oppnår, man produktet 11. Dets volumvekt er 42 kg/rn^. Sections 9~9a are provided with hot air heating boxes. The product is kept for 2 min. at ll8°C by circulation of hot air. The product is then fed into section 10-10a where its thickness is reduced by 33%• After cooling, product 11 is obtained. Its volume weight is 42 kg/rn^.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR6913264A FR2041478A5 (en) | 1969-04-25 | 1969-04-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO135871B true NO135871B (en) | 1977-03-07 |
NO135871C NO135871C (en) | 1977-06-15 |
Family
ID=9033092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO1320/70A NO135871C (en) | 1969-04-25 | 1970-04-09 |
Country Status (16)
Country | Link |
---|---|
AT (1) | AT311053B (en) |
BE (1) | BE749540A (en) |
CA (1) | CA973673A (en) |
CH (1) | CH515110A (en) |
DE (1) | DE2020125A1 (en) |
DK (1) | DK135776B (en) |
ES (1) | ES379027A1 (en) |
FI (1) | FI54247C (en) |
FR (1) | FR2041478A5 (en) |
GB (1) | GB1292195A (en) |
IE (1) | IE34091B1 (en) |
LU (1) | LU60801A1 (en) |
NL (1) | NL7005310A (en) |
NO (1) | NO135871C (en) |
SE (1) | SE365748B (en) |
ZA (1) | ZA702732B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2354186A1 (en) * | 1976-06-11 | 1978-01-06 | Saunier Jean Pierre | Insulation blocks of polystyrene beads moulded in phenol! resin - for shaped forms with good strength and insulation characteristics |
WO1993016129A1 (en) * | 1992-02-05 | 1993-08-19 | Siemens Aktiengesellschaft | Syntactic foam |
ITPO20110010A1 (en) * | 2011-05-11 | 2012-11-12 | Leandro Bigalli | NEW SYSTEM AND INDUSTRIAL PLANTS FOR THE PRODUCTION OF COATING ON ELEMENTS IN THERMOPLASTIC FOAMS AND / OR THERMO-HARDENERS TO PRODUCE ELEMENTS OF VERY SPECIFIC WEIGHT AND WITH HIGH MECHANICAL AND AESTHETIC PERFORMANCES. |
-
1969
- 1969-04-25 FR FR6913264A patent/FR2041478A5/fr not_active Expired
-
1970
- 1970-03-19 AT AT259770A patent/AT311053B/en not_active IP Right Cessation
- 1970-04-08 DK DK176070AA patent/DK135776B/en unknown
- 1970-04-09 NO NO1320/70A patent/NO135871C/no unknown
- 1970-04-10 GB GB07204/70A patent/GB1292195A/en not_active Expired
- 1970-04-13 IE IE469/70A patent/IE34091B1/en unknown
- 1970-04-14 NL NL7005310A patent/NL7005310A/xx unknown
- 1970-04-14 FI FI1025/70A patent/FI54247C/en active
- 1970-04-22 SE SE05583/70A patent/SE365748B/xx unknown
- 1970-04-23 ZA ZA702732A patent/ZA702732B/en unknown
- 1970-04-23 CH CH612470A patent/CH515110A/en not_active IP Right Cessation
- 1970-04-24 CA CA081,069A patent/CA973673A/en not_active Expired
- 1970-04-24 LU LU60801D patent/LU60801A1/xx unknown
- 1970-04-24 DE DE19702020125 patent/DE2020125A1/en active Pending
- 1970-04-24 ES ES379027A patent/ES379027A1/en not_active Expired
- 1970-04-24 BE BE749540D patent/BE749540A/en unknown
Also Published As
Publication number | Publication date |
---|---|
ES379027A1 (en) | 1973-02-01 |
CH515110A (en) | 1971-11-15 |
IE34091L (en) | 1970-10-25 |
ZA702732B (en) | 1971-02-24 |
NL7005310A (en) | 1970-10-27 |
LU60801A1 (en) | 1970-11-17 |
FI54247C (en) | 1978-11-10 |
GB1292195A (en) | 1972-10-11 |
BE749540A (en) | 1970-10-26 |
DK135776B (en) | 1977-06-20 |
DK135776C (en) | 1977-11-21 |
IE34091B1 (en) | 1975-02-05 |
FR2041478A5 (en) | 1971-01-29 |
CA973673A (en) | 1975-09-02 |
SE365748B (en) | 1974-04-01 |
NO135871C (en) | 1977-06-15 |
FI54247B (en) | 1978-07-31 |
AT311053B (en) | 1973-10-25 |
DE2020125A1 (en) | 1970-11-12 |
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