CA1110384A - Plastics based composition - Google Patents
Plastics based compositionInfo
- Publication number
- CA1110384A CA1110384A CA311,368A CA311368A CA1110384A CA 1110384 A CA1110384 A CA 1110384A CA 311368 A CA311368 A CA 311368A CA 1110384 A CA1110384 A CA 1110384A
- Authority
- CA
- Canada
- Prior art keywords
- starch
- granules
- wax
- lubricant
- grams
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
Abstract
ABSTRACT
In the manufacture of products made of starch filled plastics the polymer and starch granules are mixed with a lubricant immediately prior to forming. A feedstock material in accordance with the invention comprises particles of starch granules in admixture with a lubricant such as an oil or wax.
In the manufacture of products made of starch filled plastics the polymer and starch granules are mixed with a lubricant immediately prior to forming. A feedstock material in accordance with the invention comprises particles of starch granules in admixture with a lubricant such as an oil or wax.
Description
D~.SCRIP~ION
This invention relates to compositions includ~
ing plastics, i.e. s~nthetic polymers and organic biodegradable fillers particularly natural starch granules. ~xamples of such compositions are pub-lished in U.E. Patent Specifications Nos. 1,485,8~3and 1,487,050.
The present invention is concerned with the incorporation of the filler part of the formulation.
As tha primary application of the invention is to compositions based on plastics and natural starch granule formulations we shall hereinafter, in the descriptive part of the specification, refer to the filïer as starch. ~he use of other granular organic fillers such as lactose is not excluded~
We ha~e proposed incorporating starch composi-tions by fluxing the plastic material and then adding the starch in a special purpose machine such as a mill having two rollers or an internal mixer~
Because this fluxing and adding constitutes an extra operatio~ before the plastics composition can be processed in a final conversion operatlon such as film extiusion t pipe extrusion, or injection mould-ing, it adds an extra processin~ cost to ~he o~rerall operation and i~ is custo~ary to minimise this extra ,....................................................... ~.
., - . .. .. : . . ~ .
, . - .
, ., . ...
...
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: . ~ .......
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, ~ . . .: , .
.
3~
:., cost by making the initial mixing at a high starch concentration referred to as a "masterbatch" which ; is subsequently diluted with unfilled polymer at the final conversion, thus reducing the tonnage passing through the masterbatching stage.
It has occasionally proved possible to add : limited amounts, of the order of 1 - ~/o, of starch directly to the polymer entering the final conver-sion operation~ where the heat softening and mixing part of the machinetakes the form of an extruder screw in a heated barrel, but this soon gives rise to mixing and dispersing problems as the ~oncentra~
tion is raised and, in the case of natural starch, when the added concentration reaches 15 - 30% an extra complication is revealed in the form of dry friction between the relatively large sta.rch granules.
It has now ~een discovered that this latter problem can be readily overcome by pre~mixing a small amount of a fluid lubricating substance, ultimately compatible with the pol~mer, with the starch whereupon at least ~ of starch can be directly : blended, immediately prior to final con~ersion, ~ with most thermoplastics. ~he lubricating substance ~, .
i/
which is plastic in state may be a liquid oil or a wax meltable into a liquid. The substance will h.ereinafter be referred to as a lubricant. It has further been observed that, when the dry friction is eliminated by the addition of a lubricant as described the extreme ease of dispersion of dry natural starch in molten polymers is developed to its full, this ease of dispersion being attributable to the virtual absence of ~ery fine particles.
Further in accordance with the invention the starch is preformed with the lubricant into discrete particles or pellets which particles or pellets are mixed with the plastics prior to final conversion.
This is particularly advantageous when the starch granules are rendered hydrophobic in accordance with the teachings of U.X. Patent No. 1,487,050.
Such granules are difficult to handle and store in the raw state and the present invention makes it possible for the hydrophobic starch to be supplied to converters, extruders etc. as particles or pellets comprising a blend of starch and lubricant.
Further and in accordance with another aspect of the invention it has been found possible to use the starch as a ~ehicle for introducing into plastics compositions a variety of modifying sub-stances such as fire retardants, smoke suppressants, fertilisers, crop nutrients such as nitrates and phosphates and insecticides and the like.
", : , -:
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It is necessary that these added substances should be soluble in a solvent which is not a solvent for starch ~rains, thus enabling the starch yrains to be coated with a substantially uniform layer of 5 the additive by blending together the additive solution at an appropriate concentration and the starch material followed by a drying staye to remove the solvent. This dry stage can conveniently be r achieved by the well known process of spray drying or 10 the operations of mixing and drying can be combined by introducing the additive solution into the starch ~ which is being maintained in the form of a fluid bed ; by a stream of gas which is at a temperature appropriate to accomplish the drying action.
The following Examples illustrate the two aspects of the present invPntion:
.~
;' ', EXAMPLE 1 - Comparative tests compa ing the extrusion characteristics of a s*arch/plastics blend wi-th-and without lubricant.
.. .. .
A dry blend o~ natural maize starch'grains and polyethylene granules where the polyethylene had a melt flow index of 2 and a density of .918 was introduced into the hopper of an extrusion machine of screw diameter 45mm and L:D ratio 20:1. The screw was a normal 3 section diminishing depth configuration designed for the extrusion of polyethylene, and the machine settings of temperature and speed were also appropriate to the extrusion of poly-ethylene. With a starch concentration of 25~
by weight the starch friction produced much noise and the product was obviously imperfectly mixed and contained many particles of burnt and discoloured starch. When this operation was repeated using the techniques of the present invention but using a starch which had been cold pre-blended with a 10%
of ethyl oleate, an oily material, calculated on the weight of the starch together with 4~ of calcium stearate, another oily material, calculated on the weight of the starch then the extrusion operation worked normally, producing a smooth and uniform product with no discolsuration. The ethyl oleate is an autoxidisable material as described in our Patent Specifications Nos. 1,485,833 and :
, , ,~
,. . ::, . ;
..
.: . . .:, , ,: ' , 1,487,050. The starch granules may be untreated but preferably have the surfaces thereof modified (rendered hydrophobic) by reaction with a compound which readily reacts with hydroxyl groups to form an ester or an ether. This is in accordance with the teachings of Patent No. 1,487,050.
400 grams of a lubricant, refined paraffin wax of melting range 50 - 55C was ~used in a water jac]~etted pan and maintained at a temperature about 10C above its melting point. 600 grams of corn starch dried to ~elow 1% moisture content and pre-heated to 70C was added smoothly whilst agitating the mass with a slow speed stirrer. When all the starch was dispersed and no lumps or agglomerates remained the resulting fluid paste was poured into shallow metal trays and allowed to cool and solidify in the form of layers some 3 mm thick which were sub-sequently broken into fr~gments and sieved through a s~reen with 4 mm s~uare apertures yielding uniform particles or pellets. These granules when mixed with low density polyethylene of density 0.912 and melt flow index 2 in the ratio of 8.33 parts by weight of starch concentrate to 91.67 parts by weight ~ . . . . . .
of polyethylene could he fed to the hopper of a conventional film blowing extrusion machine (a 45 mm screw diameter with.L : D ratio of 20 : 1 and made by Samafor Limited, ~rance) could be converted to plastic film of 50 micrometre thickness in which the starch could be seen to be uniformly dispersed and was present at a concentration of 5% by weight.
400 grams o refined paraffin wax of melting ~ 10 range 50 - 55C was fused in a water jacketted ; kettle and maintained at a temperature of about 10C
above its melting point. 600 grams of warm dry hydrophobic corn starch (prepared as described in British Patent Specification No. 1,487,050)was then mixed into the fluid wax by low speed stirring followed by 50 grams of iso-octyl oleate, 50 grams .
I of calcium oxide of particle size 5 micrometres and below, and 200 grams of rutile titanium dioxide.
The resulting fluid paste was xefired by passing it through a Pascall & Co. 9" x 3" triple roll mill with its rolls heated to 60C, the output being received in shallow trays where it was allowed to cool and solidify in sheets about 3 mm thick before being broken into fragments and screened through . .
; ~ :, " !
~ . -~, . , a 4 mm aperture sieve. The sieved particles or pellets were blended with low density polyethylene o~ density 0.912 and MFl 2 in the ratio 11 parts by weight of granules to 89 parts by weight of polyeth~lene before extruding as described in Example 2 to give a white smooth film 50 micrometres thick and containing 6~ starch, 2~ pigment, 0.6%
oleic ester autoxidant and 0.5~ calcium oxide dessicant.
EXAMPLE_4 600 grams of dry hydrophobic starch prepared as described in British Patent No. 1,487,050 was placed in a hi-gh speed fluidizing mixer made by Henschel AG and having a mixing chamber capacity of about 20 litres. In the mixer were also placed 50 grams of iso-octyl oleate/ 50 grams of calcium oxide powder of particle size 5 m:icrometres and less, and 150 grams of roughly powdered paraffin wax of melting range 50-55C. The mixer was run at high speed until the wax fused, and then at lower speed allowing the temperature to fall to about 40C when the blend could be discharged as a warm dry powder which could be fed to a single punch tabletting machine by Manesty & Co. The product from the tabletting machine was in the form of small ,: ~ , .,.:, .,: : : : :
'' ' " ;,','' , ' :,,:;'''::
firm uniform tablets (pellet or granule) of dimensions similar to customary plastics granules. A blend of the starch concentrate granules with polyethylene in such proportions as to give a starch concentxation of 6% by weight in the final product was converted into plastic film as in the previous examples.
.
A warm blend of starch, iso-octyloleate, calcium oxide and wax dispersed in a high speed mixer and discharged warm as described in Example 4 was transferred to a Manesty Co. 'Rotogran' oscillating bar granulating machine in which it was forced by moving steel bars through a coarse screen. The product was a coarse granular powder which could be blended with low density polyethylene and extruded into uniform film as described in Example 3.
In the above examples 2 to 5 paraffin wax could be replaced for example by a low molecular weight polyethylene wax. There is no limitation to low density polyethylene, successful films could be blown from High Density polyethylene.
~r :' ,' ,"~''', ': '" ' ' There is no limitation to film blowing, thick sections were extruded in other polyolefins and also starch filled polypropylene film was prepared by extrustion casting onto a chilled casting roller.
EXA~lPLE 6 - A plastics/starch foxmulation includin_ a fire ret_rdant.
A slurry was prepared of corn starch in water by suspending 220 grams of undried maize starch in 1 litre of water. Sufficient ammonium molybda-te was then dissolved in the suspension water to cor-respond to a final concentration of 12% of the -weight of the starch. This slurry was then intro-duced into the spray system of a laboratory spray drying unit by compressed air at 4 kg/cm2 and with the chamber air inlet temperature of 165 and outlet temperature of 65C. The product recovered from the output cyclone was a free flow dry white powder which was used as a filler for plasticised PVC compositions containing 50 p.h.r. of D.O.P.
plasticiser and 0.5 p.h~r. of lead stearate stabiliser, the modified starch concentration being adjusted to 30~ by weight of the whole formulation.
., - - . - - . , - . . . .
~he mixing was accomplished on a steam heated 2-roll mill at 150C, ~he product in the form of a sheet approximately 2.5 mm thick when compared with a similar formulation except for the ommission of 5 the ammo~ium mol~bdate gave rise to a much lower .
generation of smoke in a combustion test. Again the starch granules are preferably rendered hydro-phobic in accordance with the teachings of Patent No. 1,487,050.
: , , '
This invention relates to compositions includ~
ing plastics, i.e. s~nthetic polymers and organic biodegradable fillers particularly natural starch granules. ~xamples of such compositions are pub-lished in U.E. Patent Specifications Nos. 1,485,8~3and 1,487,050.
The present invention is concerned with the incorporation of the filler part of the formulation.
As tha primary application of the invention is to compositions based on plastics and natural starch granule formulations we shall hereinafter, in the descriptive part of the specification, refer to the filïer as starch. ~he use of other granular organic fillers such as lactose is not excluded~
We ha~e proposed incorporating starch composi-tions by fluxing the plastic material and then adding the starch in a special purpose machine such as a mill having two rollers or an internal mixer~
Because this fluxing and adding constitutes an extra operatio~ before the plastics composition can be processed in a final conversion operatlon such as film extiusion t pipe extrusion, or injection mould-ing, it adds an extra processin~ cost to ~he o~rerall operation and i~ is custo~ary to minimise this extra ,....................................................... ~.
., - . .. .. : . . ~ .
, . - .
, ., . ...
...
: . ~. .. ;, .
: . ~ .......
.: . ~. . .
, ~ . . .: , .
.
3~
:., cost by making the initial mixing at a high starch concentration referred to as a "masterbatch" which ; is subsequently diluted with unfilled polymer at the final conversion, thus reducing the tonnage passing through the masterbatching stage.
It has occasionally proved possible to add : limited amounts, of the order of 1 - ~/o, of starch directly to the polymer entering the final conver-sion operation~ where the heat softening and mixing part of the machinetakes the form of an extruder screw in a heated barrel, but this soon gives rise to mixing and dispersing problems as the ~oncentra~
tion is raised and, in the case of natural starch, when the added concentration reaches 15 - 30% an extra complication is revealed in the form of dry friction between the relatively large sta.rch granules.
It has now ~een discovered that this latter problem can be readily overcome by pre~mixing a small amount of a fluid lubricating substance, ultimately compatible with the pol~mer, with the starch whereupon at least ~ of starch can be directly : blended, immediately prior to final con~ersion, ~ with most thermoplastics. ~he lubricating substance ~, .
i/
which is plastic in state may be a liquid oil or a wax meltable into a liquid. The substance will h.ereinafter be referred to as a lubricant. It has further been observed that, when the dry friction is eliminated by the addition of a lubricant as described the extreme ease of dispersion of dry natural starch in molten polymers is developed to its full, this ease of dispersion being attributable to the virtual absence of ~ery fine particles.
Further in accordance with the invention the starch is preformed with the lubricant into discrete particles or pellets which particles or pellets are mixed with the plastics prior to final conversion.
This is particularly advantageous when the starch granules are rendered hydrophobic in accordance with the teachings of U.X. Patent No. 1,487,050.
Such granules are difficult to handle and store in the raw state and the present invention makes it possible for the hydrophobic starch to be supplied to converters, extruders etc. as particles or pellets comprising a blend of starch and lubricant.
Further and in accordance with another aspect of the invention it has been found possible to use the starch as a ~ehicle for introducing into plastics compositions a variety of modifying sub-stances such as fire retardants, smoke suppressants, fertilisers, crop nutrients such as nitrates and phosphates and insecticides and the like.
", : , -:
, , : ,;. : :
: : : " ~ , : ': :', " , , :: .. , ":
':''' " , : ~ , , :
,, ,," ~, "", "
It is necessary that these added substances should be soluble in a solvent which is not a solvent for starch ~rains, thus enabling the starch yrains to be coated with a substantially uniform layer of 5 the additive by blending together the additive solution at an appropriate concentration and the starch material followed by a drying staye to remove the solvent. This dry stage can conveniently be r achieved by the well known process of spray drying or 10 the operations of mixing and drying can be combined by introducing the additive solution into the starch ~ which is being maintained in the form of a fluid bed ; by a stream of gas which is at a temperature appropriate to accomplish the drying action.
The following Examples illustrate the two aspects of the present invPntion:
.~
;' ', EXAMPLE 1 - Comparative tests compa ing the extrusion characteristics of a s*arch/plastics blend wi-th-and without lubricant.
.. .. .
A dry blend o~ natural maize starch'grains and polyethylene granules where the polyethylene had a melt flow index of 2 and a density of .918 was introduced into the hopper of an extrusion machine of screw diameter 45mm and L:D ratio 20:1. The screw was a normal 3 section diminishing depth configuration designed for the extrusion of polyethylene, and the machine settings of temperature and speed were also appropriate to the extrusion of poly-ethylene. With a starch concentration of 25~
by weight the starch friction produced much noise and the product was obviously imperfectly mixed and contained many particles of burnt and discoloured starch. When this operation was repeated using the techniques of the present invention but using a starch which had been cold pre-blended with a 10%
of ethyl oleate, an oily material, calculated on the weight of the starch together with 4~ of calcium stearate, another oily material, calculated on the weight of the starch then the extrusion operation worked normally, producing a smooth and uniform product with no discolsuration. The ethyl oleate is an autoxidisable material as described in our Patent Specifications Nos. 1,485,833 and :
, , ,~
,. . ::, . ;
..
.: . . .:, , ,: ' , 1,487,050. The starch granules may be untreated but preferably have the surfaces thereof modified (rendered hydrophobic) by reaction with a compound which readily reacts with hydroxyl groups to form an ester or an ether. This is in accordance with the teachings of Patent No. 1,487,050.
400 grams of a lubricant, refined paraffin wax of melting range 50 - 55C was ~used in a water jac]~etted pan and maintained at a temperature about 10C above its melting point. 600 grams of corn starch dried to ~elow 1% moisture content and pre-heated to 70C was added smoothly whilst agitating the mass with a slow speed stirrer. When all the starch was dispersed and no lumps or agglomerates remained the resulting fluid paste was poured into shallow metal trays and allowed to cool and solidify in the form of layers some 3 mm thick which were sub-sequently broken into fr~gments and sieved through a s~reen with 4 mm s~uare apertures yielding uniform particles or pellets. These granules when mixed with low density polyethylene of density 0.912 and melt flow index 2 in the ratio of 8.33 parts by weight of starch concentrate to 91.67 parts by weight ~ . . . . . .
of polyethylene could he fed to the hopper of a conventional film blowing extrusion machine (a 45 mm screw diameter with.L : D ratio of 20 : 1 and made by Samafor Limited, ~rance) could be converted to plastic film of 50 micrometre thickness in which the starch could be seen to be uniformly dispersed and was present at a concentration of 5% by weight.
400 grams o refined paraffin wax of melting ~ 10 range 50 - 55C was fused in a water jacketted ; kettle and maintained at a temperature of about 10C
above its melting point. 600 grams of warm dry hydrophobic corn starch (prepared as described in British Patent Specification No. 1,487,050)was then mixed into the fluid wax by low speed stirring followed by 50 grams of iso-octyl oleate, 50 grams .
I of calcium oxide of particle size 5 micrometres and below, and 200 grams of rutile titanium dioxide.
The resulting fluid paste was xefired by passing it through a Pascall & Co. 9" x 3" triple roll mill with its rolls heated to 60C, the output being received in shallow trays where it was allowed to cool and solidify in sheets about 3 mm thick before being broken into fragments and screened through . .
; ~ :, " !
~ . -~, . , a 4 mm aperture sieve. The sieved particles or pellets were blended with low density polyethylene o~ density 0.912 and MFl 2 in the ratio 11 parts by weight of granules to 89 parts by weight of polyeth~lene before extruding as described in Example 2 to give a white smooth film 50 micrometres thick and containing 6~ starch, 2~ pigment, 0.6%
oleic ester autoxidant and 0.5~ calcium oxide dessicant.
EXAMPLE_4 600 grams of dry hydrophobic starch prepared as described in British Patent No. 1,487,050 was placed in a hi-gh speed fluidizing mixer made by Henschel AG and having a mixing chamber capacity of about 20 litres. In the mixer were also placed 50 grams of iso-octyl oleate/ 50 grams of calcium oxide powder of particle size 5 m:icrometres and less, and 150 grams of roughly powdered paraffin wax of melting range 50-55C. The mixer was run at high speed until the wax fused, and then at lower speed allowing the temperature to fall to about 40C when the blend could be discharged as a warm dry powder which could be fed to a single punch tabletting machine by Manesty & Co. The product from the tabletting machine was in the form of small ,: ~ , .,.:, .,: : : : :
'' ' " ;,','' , ' :,,:;'''::
firm uniform tablets (pellet or granule) of dimensions similar to customary plastics granules. A blend of the starch concentrate granules with polyethylene in such proportions as to give a starch concentxation of 6% by weight in the final product was converted into plastic film as in the previous examples.
.
A warm blend of starch, iso-octyloleate, calcium oxide and wax dispersed in a high speed mixer and discharged warm as described in Example 4 was transferred to a Manesty Co. 'Rotogran' oscillating bar granulating machine in which it was forced by moving steel bars through a coarse screen. The product was a coarse granular powder which could be blended with low density polyethylene and extruded into uniform film as described in Example 3.
In the above examples 2 to 5 paraffin wax could be replaced for example by a low molecular weight polyethylene wax. There is no limitation to low density polyethylene, successful films could be blown from High Density polyethylene.
~r :' ,' ,"~''', ': '" ' ' There is no limitation to film blowing, thick sections were extruded in other polyolefins and also starch filled polypropylene film was prepared by extrustion casting onto a chilled casting roller.
EXA~lPLE 6 - A plastics/starch foxmulation includin_ a fire ret_rdant.
A slurry was prepared of corn starch in water by suspending 220 grams of undried maize starch in 1 litre of water. Sufficient ammonium molybda-te was then dissolved in the suspension water to cor-respond to a final concentration of 12% of the -weight of the starch. This slurry was then intro-duced into the spray system of a laboratory spray drying unit by compressed air at 4 kg/cm2 and with the chamber air inlet temperature of 165 and outlet temperature of 65C. The product recovered from the output cyclone was a free flow dry white powder which was used as a filler for plasticised PVC compositions containing 50 p.h.r. of D.O.P.
plasticiser and 0.5 p.h~r. of lead stearate stabiliser, the modified starch concentration being adjusted to 30~ by weight of the whole formulation.
., - - . - - . , - . . . .
~he mixing was accomplished on a steam heated 2-roll mill at 150C, ~he product in the form of a sheet approximately 2.5 mm thick when compared with a similar formulation except for the ommission of 5 the ammo~ium mol~bdate gave rise to a much lower .
generation of smoke in a combustion test. Again the starch granules are preferably rendered hydro-phobic in accordance with the teachings of Patent No. 1,487,050.
: , , '
Claims (4)
1. In a process of manufacturing a plastic based product which includes the step of feeding a feedstock to a shaping apparatus which develops heat and pressure, said feedstock comprising polymer granules and natural starch granules with the surfaces thereof rendered hydrophobic, the improvement comprising incorporating a lubricant which is an oily material with the said granules, whereby the granules of starch are coated with said lubricant when undergoing the shaping.
2. A process according to Claim 1 wherein the said oily material is a wax.
3. A process according to Claim 1 wherein the wax and starch granules are preformed into pellets.
4. A feedstock for carrying out the process of Claim 3 consisting essentially of polymer granules and preformed pellets of natural starch granules and a meltable wax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000377443A CA1189212A (en) | 1977-09-16 | 1981-05-12 | Plastics based composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB38772/77A GB1600496A (en) | 1977-09-16 | 1977-09-16 | Plasticsbased composition |
| GB38772/77 | 1977-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1110384A true CA1110384A (en) | 1981-10-06 |
Family
ID=10405606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA311,368A Expired CA1110384A (en) | 1977-09-16 | 1978-09-15 | Plastics based composition |
Country Status (23)
| Country | Link |
|---|---|
| US (2) | US4218350A (en) |
| JP (1) | JPS5490248A (en) |
| AR (2) | AR230840A1 (en) |
| AT (1) | AT368770B (en) |
| AU (1) | AU537455B2 (en) |
| BE (1) | BE870457A (en) |
| BR (1) | BR7806072A (en) |
| CA (1) | CA1110384A (en) |
| CH (2) | CH644880A5 (en) |
| DE (1) | DE2839908A1 (en) |
| DK (1) | DK407778A (en) |
| ES (1) | ES473389A1 (en) |
| FI (1) | FI782826A (en) |
| FR (1) | FR2403354B1 (en) |
| GB (1) | GB1600496A (en) |
| IE (1) | IE47745B1 (en) |
| IL (2) | IL55559A0 (en) |
| IT (1) | IT1109078B (en) |
| NL (1) | NL7809320A (en) |
| NO (1) | NO783106L (en) |
| NZ (1) | NZ188382A (en) |
| SE (2) | SE7809716L (en) |
| ZA (1) | ZA785208B (en) |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337181A (en) * | 1980-01-17 | 1982-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable starch-based blown films |
| CH669201A5 (en) * | 1986-05-05 | 1989-02-28 | Warner Lambert Co | AT ROOM TEMPERATURES FIXED AND FREE-FLOWING BASIC COMPOSITION FOR PRINTING. |
| CA1252586A (en) * | 1987-03-12 | 1989-04-11 | Alphons D. Beshay | Silane bonding agent grafts and bonds a mixture consisting of a cellulosic and an inorganic materials to be applied for bonding with thermoplastic polymers |
| GB8712009D0 (en) * | 1987-05-21 | 1987-06-24 | Folk Drive Eng Ltd | Degradable plastics |
| GB2208651B (en) * | 1987-08-18 | 1991-05-08 | Warner Lambert Co | Shaped articles made from pre-processed starch |
| US5095054A (en) * | 1988-02-03 | 1992-03-10 | Warner-Lambert Company | Polymer compositions containing destructurized starch |
| GB2214918B (en) * | 1988-02-03 | 1992-10-07 | Warner Lambert Co | Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material |
| US5035930A (en) * | 1988-12-30 | 1991-07-30 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
| US5043196A (en) * | 1989-05-17 | 1991-08-27 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
| US5009648A (en) * | 1989-03-22 | 1991-04-23 | E. R. Squibb & Sons, Inc. | Starch containing film ostomy pouches |
| EP0473726A4 (en) * | 1989-05-19 | 1992-07-15 | Agri-Tech Industries, Inc. | Injection molded biodegradable starch polymer composite |
| JP2900402B2 (en) * | 1989-05-26 | 1999-06-02 | エヌオーケー株式会社 | Biodegradable rubber composition |
| US5288765A (en) * | 1989-08-03 | 1994-02-22 | Spherilene S.R.L. | Expanded articles of biodegradable plastics materials and a method for their production |
| FI88724C (en) * | 1989-10-05 | 1993-06-28 | Biodata Oy | Biologically untreated backing film and foil production |
| US4985024A (en) * | 1989-12-01 | 1991-01-15 | Minnesota Mining And Manufacturing Company | Disposable diaper having fastening means that are degradable |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH340626A (en) * | 1955-09-13 | 1959-08-31 | Lonza Ag | Plastic compound containing vinyl polymer or copolymer and filler |
| ZA732749B (en) * | 1972-05-18 | 1974-11-27 | Coloroll Ltd | Improvements in synthetic resin sheet material |
| US4016117A (en) * | 1972-05-18 | 1977-04-05 | Coloroll Limited | Biodegradable synthetic resin sheet material containing starch and a fatty material |
| GB1485833A (en) * | 1973-11-28 | 1977-09-14 | Coloroll Ltd | Synthetic-resin-based compositions |
| US3952347A (en) * | 1973-12-13 | 1976-04-27 | Personal Products Company | Biodegradable barrier film and absorbent pad utilizing same |
| US4125495A (en) * | 1974-11-25 | 1978-11-14 | Coloroll Limited | Synthetic/resin based compositions |
-
1977
- 1977-09-16 GB GB38772/77A patent/GB1600496A/en not_active Expired
-
1978
- 1978-09-08 US US05/940,839 patent/US4218350A/en not_active Expired - Lifetime
- 1978-09-11 NZ NZ188382A patent/NZ188382A/en unknown
- 1978-09-12 AU AU39762/78A patent/AU537455B2/en not_active Expired
- 1978-09-12 IL IL7855559A patent/IL55559A0/en not_active IP Right Cessation
- 1978-09-13 BE BE190467A patent/BE870457A/en not_active IP Right Cessation
- 1978-09-13 ZA ZA00785208A patent/ZA785208B/en unknown
- 1978-09-13 NL NL7809320A patent/NL7809320A/en not_active Application Discontinuation
- 1978-09-14 DE DE19782839908 patent/DE2839908A1/en not_active Withdrawn
- 1978-09-14 NO NO783106A patent/NO783106L/en unknown
- 1978-09-14 JP JP11349578A patent/JPS5490248A/en active Pending
- 1978-09-14 FI FI782826A patent/FI782826A/en unknown
- 1978-09-15 ES ES473389A patent/ES473389A1/en not_active Expired
- 1978-09-15 CH CH968778A patent/CH644880A5/en not_active IP Right Cessation
- 1978-09-15 IE IE1873/78A patent/IE47745B1/en unknown
- 1978-09-15 SE SE7809716A patent/SE7809716L/en unknown
- 1978-09-15 DK DK407778A patent/DK407778A/en not_active Application Discontinuation
- 1978-09-15 CH CH338381A patent/CH644881A5/en not_active IP Right Cessation
- 1978-09-15 FR FR7826537A patent/FR2403354B1/en not_active Expired
- 1978-09-15 IT IT69138/78A patent/IT1109078B/en active
- 1978-09-15 BR BR7806072A patent/BR7806072A/en unknown
- 1978-09-15 AR AR273724A patent/AR230840A1/en active
- 1978-09-15 CA CA311,368A patent/CA1110384A/en not_active Expired
- 1978-09-18 AT AT0673778A patent/AT368770B/en not_active IP Right Cessation
-
1980
- 1980-02-20 US US06/122,851 patent/US4324709A/en not_active Expired - Lifetime
-
1981
- 1981-06-01 AR AR285542A patent/AR223433A1/en active
- 1981-06-04 IL IL63045A patent/IL63045A0/en not_active IP Right Cessation
-
1985
- 1985-07-31 SE SE8503650A patent/SE462284B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2403354B1 (en) | 1985-09-06 |
| NO783106L (en) | 1979-03-19 |
| SE8503650D0 (en) | 1985-07-31 |
| AR230840A1 (en) | 1984-07-31 |
| BR7806072A (en) | 1979-04-17 |
| IL63045A0 (en) | 1981-09-13 |
| DK407778A (en) | 1979-03-17 |
| ATA673778A (en) | 1982-03-15 |
| AU3976278A (en) | 1980-03-20 |
| NL7809320A (en) | 1979-03-20 |
| AU537455B2 (en) | 1984-06-28 |
| CH644881A5 (en) | 1984-08-31 |
| NZ188382A (en) | 1980-04-28 |
| US4324709A (en) | 1982-04-13 |
| DE2839908A1 (en) | 1979-03-29 |
| JPS5490248A (en) | 1979-07-17 |
| IT7869138A0 (en) | 1978-09-15 |
| ES473389A1 (en) | 1979-10-16 |
| SE7809716L (en) | 1979-03-17 |
| IE781873L (en) | 1979-03-16 |
| US4218350A (en) | 1980-08-19 |
| AR223433A1 (en) | 1981-08-14 |
| FI782826A (en) | 1979-03-17 |
| IL55559A0 (en) | 1978-12-17 |
| GB1600496A (en) | 1981-10-14 |
| SE462284B (en) | 1990-05-28 |
| CH644880A5 (en) | 1984-08-31 |
| ZA785208B (en) | 1979-08-29 |
| AT368770B (en) | 1982-11-10 |
| BE870457A (en) | 1979-01-02 |
| IE47745B1 (en) | 1984-06-13 |
| IT1109078B (en) | 1985-12-16 |
| FR2403354A1 (en) | 1979-04-13 |
| SE8503650L (en) | 1985-07-31 |
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