AU620934B2 - A thermoplastically processable starch and a process for making it - Google Patents

Abstract

In the manufacture of thermoplastically processable starch, an additive is essentially mixed with native or natural starch and the mixture is caused to melt by the application of heat and mechanical energy. The additive is a substance which lowers the melting point of the starch so that the melting point of the starch together with this additive lies below the decomposition temperature of the starch while, in addition, the additive has a solubility parameter of over 15 cal<1/2>cm<-3/2>. Once the starch-additive mixture has melted, the molten substance is mixed until it is at least virtually homogenous. In the melting range of the starch-additive mixture, the vapour pressure of the additive should be lower than 1 bar.

Description

(JPJ DATE 28/05/90 APPLN. I D 44279 89 AOJP DATE 05/07/90 PCT NUMBER PCT/CH89/00185 (21) Internationales Patcnzicasaich n 5 C/H9015 (11neratioses aet), usummr S.0056 (22) Internationales Anmeldedatum: 27. Oktober 1989 (27.10.89) Ver~ffentlicht Alit internalionalein Rec/ierclwnberich.

Priori tiitsd aten: 4083/88-1 3. November 1988 (03,11,88) CH (71)(72) Anmelder und Erflnder: TOMKA, Ivan [CH/CH]; Sch~tzenmattstrasse 1, CH-5600 Lenzburg (CH).

(74) Anwalt: DR. TROESCH AG; Walchestrasse 19, CH-8035 Z~rich (CR).

(81) Bestimmungsstaaten: AT (europiiisches Patent), AU, BE (europ~iisclies Patent), BR, CH (europilisches Patent), DE (europflisches Patent), DK, F1, FR (europilisches Patent), GB (europiiisches Patent), HU, IT (europiisches Patent), JP, KR, LU (europiiisches Patent), NL (europlisches Patent), NO, (54)Title: A THERMOPLASTICALLY PROCESSABLE STARCH AND A PROCESS FOR MAKING IT (54) Bezeichnung: THERMOPLASTISCH VERARBEITBARE STARKE SOWIE VERFAHREN ZU DEREN HERSTEL-

LUNG

(57) Abstract In the manufacture of thermoplastically processable starch, an additive is essentially mixed with native or natural starch and the mixture is caused to melt by the application of heat and mechanical energy. The additive is a substance which lowers the melting point of the starch so that the melting point of the starch together with this additive lies below the decomposition temperature of the starch while, in addition, the additive has a solubility parameter of over 15 cal 1 2

CM-

3 2 once the starch-additive mixture has melted, the molten substance is mixed until it is at least virtually homogenous. In the melting range of' the starch-additive mixture, the vapour pressure of the additive should be lower than I bar.

(57) Zusammenfassung Urn thermoplastisch verarbeitbare Stairke herzustellen, wird im wesentlichen nativer oder natflrlicher Stalrke emn Zuschlagstoff beigemischt und das Gemisch durch Zuftlhren von Wtlrme und mechanischer Energie in Schmelze gebracht. Beim Zuschlagstoff handelt es sich urn eine Substanz, welche die Schmelztemperatur der Stalrke erniedrigt, so dass die Schmelztemperatur der Stairke zusammen mit diesem Zuschlagstoff unterhalb der Zersetzungstemperatur der Stalrke liegt, und zudem weist der Zuschlagstoff einen Li~slichkeitsparameter auf von gr6sser als,15 cal 1 2 cm- 3 2 Nach demn Aufschmelzen des Gemisches aus Stairke und Zuschlagstoff wird die Schmelze so lange gemischt, bis sie wenigstens nahezu homogen ist. Der Dampfdruck des Zuschlagstoffes sollte im Schmelzbereich der Mischung aus Starke und Zuschlagstoff kleiner 1 bar sein.

1~

I)

TRANSLATIC

from.

(54) Title:

)N

I

THERMOPLASTICALLY PROCESSABLE STARCH AND A METHOD OF MAKING IT (57) Abstract In order to produce thermoplastically processable starch an additive is essentially mixed with native or natural starch and the mixture is caused to melt by the application of heat and mechanical energy. The additive is a substance which lowers the melting point of the starch so that the melting point of the starch together with this additive lies below the decomposition temperature of the starch and the additive furthermore has a solubility parameter of over call 2 cm" 3 2 After the mixture of starch and additive is molten the melt is mixed until it is at least almost homogeneous. The vapor pressure of the additive within the melting range of the mixture of starch and additive should be less than one bar.

i LAWYERS' MERCHANTS' TRANSLATION BUREAU S7 ranrslaritn Service Bureau) r v C' orl V Brtache iIRl lW961 Est 1908 Wrn. Bertlche, Ch. A.C.S.

*t -cv THERMOPLASTICALLY WORKABLE STARCH AND A METHOD FOR THE MANUFACTURE THEREOF BACKGROUND OF THE INVENTION The present invention relates to thermoplastically workable starch, to a method of manufacturing thermoplastically workable starch, to a method of manufacturing granulates, flakes, etc. and shaped bodies, extrudates, sheets, etc. of starch as well as to shaped bodies, fillers and vehicle materials consisting essentially of starch.

Natural or so-called native starch, such as obtained by washing and drying the raw starch, for instance of potatoes, grain, corn, etc., has a pronounced macromolecular structure, the macromolecules penetrating into each other only In part or not at all. This structure causes the niative

S'

o starch to be very heterogeneous and the heterogeneity is normally retained, at least in part, also upon the melting of the starch.

i As part of the increased use of so-called hydrophilic polymers, which also include starch, as so-called natural plastics in diversified fields of use, it has been attempted to work the starch by the known plastic processing techniques, for Instance, by injection molding and extrusion.

20 As a result of the above-described properties of native starch, however, it is not possible to produce shaped bodies of starch which have sufficient mechanical properties, such as for instance strength. In accordance with the known methods of working or processing of hydrophilic .polymers, such as for instance gelatins or cellulose, an attempt to homogenize starch having a water content on the order of magnitude of 20%, based on the total weight, has been made for instance in a screw extruder of an injection molding machine and followed by working the extrudate.

GB Patent 1 014 801 describes a method in accordance with which a cooled mixture of native starch containing 12% to 15% water, or a not substantially smaller content of water, and a gelatinization promoter Is processed to form a plastic-like product. In accordance with the method described, it is essential that the starch have a sufficient ;;ater content.

S• TMS/1691R II._ W M IilM I I 1 it -2- Federal Republic of Germany OS 3 712 029 describes a method for the pressure molding of molded bodies of starch In which a mixture of native starch with, inter alia, 0.5% of a lubricant and 10% to 22% water is melted In an Injection molding machine within a temperature range of to 240 0 C and then processed. It Is essential here that the water content by retained during the entire process.

This processing technique results in an Improvement of the mechanical properties of the shaped starch bodies but the homogenizing effect in the molten starch is realized only if the water in the entry zone of the screw plunger Is not heat expelled from the starch in the i form of steam but remains in the starch along the entire length of the plunger. A prerequisite for this is also that excellent mixing takes place, such as that which takes place for instance in a kneader or a twin-shaft extruder with correspondingly long plunger lengths. The shaft •l 15 plunger or kneader plunger in this case forms a quasi-closed space, the plunger length and the temperature control along the plunger being critical in order for a sufficient homogenizing effect to be produced.

This procedure for the production of homogeneous starch, or better, thermoplastically workable starch, is obviously complicated and critical since various processing parameters, such as the maintaining of a sufficient water content, temperature, processing, type of machine, length of screw, etc. must be accurately maintained. It Is therefore not surprising that in the known method according to EP-A-0 304 401, it Is recommended to separate the homogenizing step, also called the destructuring step, and the following working of the starch melt from each other so as to obtain sufficient properties in shaped starch bodies. In accordance with said process, it is essential that the first process step be carried out in a closed system so that the water cannot escape, for instance, in the form of steam.

The high water content of 10 20% necessary in said method is, as is generally known in the processing of plastics, not entirely advantageous for the working and also not for the character of the shaped body to be produced. In particularly, for instance, a water content on the order of magnitude of 17%'or more prevents reasonable extrusion of TMS/1691R

A

I!

-3the starch for the production of sheets, profiled sections or tubes. It may be said, in general, that an open working method, such as Is present for instance upon extrusion, is made impossible as a result of the high vapor pressure of water, which is definitely greater than 1 bar.

Therefore, one object of the present invention is to create thermoplastically workable starch and a method of manufacturing it without the above-mentioned disadvantages and to permit a simpler carrying out of the process thereby making possible a non-problematic thermoplastic working of the starch in accordance with known polymer processing techniques. However, if the water content is at least 25 wt%, the mixture can be processed in the "open" system at 108°C. However, the extrudate is tacky and not stable in form at 20 0

C.

J DESCRIPTION OF THE INVENTION In accordance with the invention, this is achieved by mixing and 15 melting starch with an additive having certain characteristics until the j melt is at least substantially homogeneous.

According to a first embodiment of the present invention there is provided a thermoplastically processable starch, characterized by the I fact that it consists essentially of an at least substantially 20 homogeneous mixture which is at least substantially anhydrous and consists of starch and/or a starch derivative and at least 5% of at least one additive, the additive or additives having the following properties: the solubility parameter is more than 15 (cal I 2 cm 3 2 I upon the mixing of the starch with the additive, the melting point of the starch is reduced in such a manner that the melting point of the starch together with the additive is below the decomposition temperature of the starch; and i the vapor pressure of the additive or additives in the mixture consisting of additive and starch is less than 1 bar within the temperature range close to the melting point of the homogeneous mixture within which the starch is thermoplastically processed.

%T stlypMS/1691 R 4 According to a second embodiment of the present Invention there 1s provided a method of preparing thermoplastically processable starch, characterized by the fact that substantially native or natural starch, tcgether with at least one additive, is brought into molten state by the feeding of heat, the additive being at least one substance which reduces the melting point of the starch so that the melting point of the starch together with this additive is below the decomposition temperature of the starch, and the additive having a solubility parameter of more than (cal/2 cm-3/ 2 and the vapor pressure of said at least one additive in the mixture of additive and starch is less than 1 bar in a temperature 'least one additive, and thereupon the mixture of starch and additive is mixed until the melt is at least substantially homogeneous.

According to a third embodiment of the present Invention there is 15 provided a molded body consisting essentially of starch, characterized by the fact that it comprises at least 5% of an additive which has a solubility parameter of more than 15 call 2 cm 3 2 within a temperature range of 100 to 300 0 the portion 6p of the solubility parameter 5 corresponding to the polar interactions and the portion

O

H corresponding to the hydrogen-bridge bonds being at least twice as great as the portion 6 d of the solubility parameter 5 of said at least one additive corresponding to the dispersion forces, and which, upon admixture to the starch, reduces the melting point of the latter so that the melting point of the starch together with the additive is below the decomposition temperature of the starch, the additive furthermore having in the mixture of additive and starch a vapor pressure of less than 1 bar in the region of the said melting point.

According to a fourth embodiment of the present invention there is provided a method for the controllable adjusting of the properties of fillers, consisting essentially of thermoplastically processable starch, characterized by the fact that this is obtained substantially via the selection of the molecular weight distribution of said starch.

4^ !TMS/l 691 R I According to a fifth embodiment of the present invention there Is provided a method of binding water in an environment of low water content and/or on a water-pervious substrate by means of thermoplastically processable starch, the starch being used preferably in the form of a sheet, large-surface foils, a network or some other extrudate.

There is thus provided a thermoplastically workable starch which is i of an at least substantially homogeneous mixture of starch and/or starch derivative with at least 5% of at least one addition substance, the additive substance having solubility parameter greater than 15 (ca 11 /2 cm and, upon mixing with the starch, lowering the melting i temperature thereof in such a manner that the melting temperature of the I starch together with the additive substance is below the decomposition I temperature of the starch.

Furthermore, the additive or additives have a vapor pressure of 15 less than 1 bar within a temperature range close to the melting point of I the homogeneous mixture in which the starch is thermoplastically I" processed.

It is furthermore provided that the gram-molecular weight of the starch used be in a range of more than 1 million, and preferably in the li 20 range of 3 10 million.

I. The thermoplastically workable starch can be present in the form of i granulates, flakes, pills, tablets or powder or in the form of fibers.

There is furthermore provided a method of manufacturing thermoplastically workable starch in which essentially native or natural starch is melted together with at least one addition substance by applying heat, whereupon the mixture of starch and additive substances Is mixed until the melt is substantially homogeneous. The addition substance is a substance which, when mixed with starch, lowers the melting temperature thereof so that the melting temperature of the starch together with this addition substance lies below the decomposition temperature of the starch, and the addition substance furthermore has a solubility parameter of more than 15 (cal1/ 2 cm-3/ 2 Ms/1691R -6- The solubility parameter of the addition substance within a temperature range of 100° to 300°C is preferably on the order of magnitude of 15 to 25 cal I 2 cm- 3 2 The solubility parameter 5, as Is known, consists essentially of the three portions, namely a polar portion 6p, a portion 6

H

corresponding to the hydrogen-bridge bonds, and a dispersion portion I or is a function of these three values. In accordance with the I4 invention, it is proposed that the portion 6p of the solubility parameter 8 corresponding to the polar Interactions and the portion 8 H corresponding to the hydrogen-bridge bonds are greater than the portion 8 d of the solubility parameter 5 of the at least one additive corresponding to the dispersion forces. 6p and 6 d are i preferably twice as great as the dispersion portion 56 d !j There Is furthermore proposed a method of preparing 15 thermoplastically processable starch in which substantially native or natural starch, together with at least one additive, is brought Into t *fe molten state by the feeding of heat and thereupon the mixture of starch and additive is mixed until the melt is at least substantially j homogeneous. The additive is a substance which, upon mixing with starch, 20 reduces the melting point of the latter so that the melting point of the starch together with this additive is below the decomposition temperature of the starch, the additive furthermore having a solubility parameter of :more than 15 (cal 1 2 cm 3 2 Furthermore, the additive or additives have a vapor pressure which is less than 1 bar In the temperature range close to the melting point of the homogeneous mixture in which the mixture of starch and additive Is thermoplastically processed.

The mixing of the starch with the additive is preferably effected substantially free of water or moisture present in the mixture of starch and additive Is at least substantially removed from it.

The solubility parameter of the additive is preferably on the order of magnitude of 15 to 25 cal /2 cm 312 within a temperature range of U 100°C to 300°C.

691R

I'

-7- In particular, if the melting and mixing of the starch with said at least one addition substance takes place in an open environment, i.e. not under pressure, the vapor pressure of the addition substance must be less than one atmosphere In the melting range of addition substance and starch at which the mixing or working of the thermoplastically workable starch takes place in order for the additioit substance to escape in controlled fashion or not at all from the mixture with the starch.

It is furthermore provided that said at least one addition substance be so selected that the interfacial surface energy between addition substance and starch be not greater than 20% of the individual interfacial surface energies with respect to air. If the addition I substance satisfies this requirement, then assurance is had that the i interaction between addition substance and this starch is sufficient.

Preferably 5 to 35% of addition substances are admixed to the 15 starch, based on the total weight of the mixture.

It is provided that the mixing of the starch melt with the addition substance be effected with in a temperature range of 1000 to 300 0 and preferably 1200 to 220°C and most preferably 1500 to 170 0

C.

Y The mixing of the natural or native starch with the addition substances can be effected in the manner that the mixture is fed to a plastic-processing machine, such as for instance a single-shaft or twin-shaft extruder or to a kneader, and that the mixture is mixed in it, as for instance in the shaft plunger or the kneader plunger, to a thermoplastic mass which is at least substantially homogeneous. If the vapor pressure of the addition substance in the temperature range at which the mixing Is effected is less than 1 atmosphere, the mixing can be carried out in any open or closed vessel. Only if the vapor pressure of the addition substance is greater than 1 atmosphere in the temperature range of the mixing must the vessel be closed so that the addition substances does not escape from the mixture.

It is furthermore provided that at least one of the following substances be used as addition substance: (t tS/1691R

A

L\ ^i ,-7 8 1,3-butanediol, glycerin, ethyleneglycol, propyleneglycol, diglyceride, diglycolether, formamide, and/or N-methylformamide.

However, there is also suitable as addition substance at least one substance in accordance with the following formulas: RI-[(-O-CH-CH- k]-RI S n km z R RI RV with R' -H or -alkyl; R I -RVI -OH -NH 2 in which at least one RII VI must be equal to -OH, and j *i n 1, 2 5; m, k 0, 1, 2, provided that n 0 if m, k 0 as well as z 1, 2 o) 15 R i or C 0 with R 1

R

2 -alkyl or S

R

3 20

R

4 and in which R 3

R

4 -alkyl; but without R1 R 2

-H;

R R -alkyl; R R 2

-NH

2 -H and simultaneously R 2 -alkyl; R -H and simultaneously R 1 -alkyl.

R

2 -H and simultaneously R l -alkyl.

The preferred additives indicated by way of example above have substantially a solubility parameter 5 which is either approximately equal to 15 cal/2 cm 3 2 or else, as required, greater than this value. Thus, for instance, the solubility parameter of ethylene glycol is 16.3 cal 2 cm 3 formamide 17.8, glycerine 21.1, and N-methylformamide 16.1, diglyceride 15.8, etc.

For the determination of the solubility parameter, reference is had furthermore to the following Titerature: J. Brandrup, E.H. Immergut, Polymer Handbook, Second Edition, 1975, John Niley, pages IV 337 et seq., in particular Table 3.

S T/1691R 9 In said book, reference Is had to Table 3.3 In which both the solubility parameters 5, as well as the portions 6p, 6 H and 6 d are individually listed.

It is provided, moreover, that at least one further additive, such as for instance a filler, lubricant, plasticizing agent, flexibilizing agent, pigmenting agent or some other colorant and/or mold-release agent be added to the mixture of starcn and addition substances.

The following materials are particularly suitable as fillers: gelatin, protein, polysaccharide, a derivative of cellulose, a synthetic polymer which is at least substantially soluble in an addition substance for the starch, and/or a gelatin phthalate.

S: It is proposed that 0 to 50% by weight of filler, and preferably 3 to 10 be added based on the total weight of the mixture of starch and addition substance.

15 It is furthermore provided that at least one inorganic filler, such as for instance, an oxide of magnesium, aluminum, silicon, titanium, etc.

be added in a concentration of 0.02 to 3 and preferably 0.02 to 1 based on the total weight.

I As plasticizing agent there are particularly suitable polyalkylene 20 oxide, glycerol, glycerin mono-, di- or triacetate, sorbitol as well as S citrate, which is added to the mixture of starch and addition substance j in a concentration within the range of 0.5 to 15 and preferably 'to 5 based on total weight.

For the coloring of the mixture of starch and addition substance, there are suitable, in particular, organic or inorganic pigments in a concentration on the order of magnitude of 0.001 to 10 and preferably 0.5 to 3 wt.%.

In order to improve the flowability there are suitable, in lj particular, animal or vegetable fats and/or lecithins, which are preferably used in hydrogenated form, these fats and other fatty acid derivatives preferably having a melting point of more than 1iR r TlS/1691R

OZ

a X{~ 10 In order to reduce the hydrophilic nature and thus the water instability of the thermoplastically workable starch during and after its working, a cross-linking agent or an agent for chemically modifying the starch, such as alkylsiloxanes, can be added to the mixture of starch and addition substance.

The following substances are particularly suitable as cross-linking i agents: bivalent and polyvalent carboxylic acids as well as their I anhydrides, acid halides and/or acid amides of bivalent and polyvalent 10 carboxylic acids, derivatives of bivalent or polyvalent inorganic acids, epoxides, formaldehyde and/or urea derivatives, divinylsulfones, S divinylsulfones of the general formula I II 15 X-CH 2

-S-CH

2

-X

i 0 isocyantes, oxo compounds such as acetone, formaldehyde or polyvalent oxo compounds and/or cyanamide. When using acid amides of carboxylic acids, 20 one acid group should be present as a free carboxyl group.

The methods of producing thermoplastically workable starch described above are suitable, in particular, for the production of granulates, flakes, pills, powders, tablets, fibres, etc. from thermoplastically workable starch.

The thermoplastically workable starch prepared in accordance with the methods described above can be worked directly in accordance with the customary known plastic processing methods. To be sure, particularly upon extrusion of tubes, sheets and the like, the addition substance must d have a vapor pressure of less than 1 atmosphere at the processing temperature in order to prevent foaming of the starch. With too high a water content, the production of blown sheets, tubes, etc., for instance, is not possible. By the addition of a sufficient amount of addition substance, the absorption of water in the starch, which in itself is natural, is at least partially 'prevented.

691R 11 The thermoplastically workable starch prepared in accordance with the methods described above is suitable, in particular, as filler or formulating aid for addition to thermoplastic or thermosetting polymers.

The suitability as filler for formulating aid is a result, in particular, of the fact that the properties of the thermoplastlcally workable starch can be controlled via the gram-molecular weight distribution of the starch, which is relatively narrow.

Furthermore, the thermoplastically workable starch is suitable, for 4 instance, as vehicle material for active substances, such as for instance, drug active principles, and reagents, such as for instance, flocculating agents for waste waters.

SThermoplastically processable starch is also suitable for binding water in a low-water environment and/or on a water-pervious substrate.

The starch is extruded, for instance, in the form of a sheet, 15 large-surface foils or networks and placed on the substrate consisting, for instance, of sand or gravel. Due to its hydrophilic nature, the starch binds water so that watering of the earth can be effected more efficiently, for instance, in desert-like territories.

a 1691R

TRANSLATION

from: The method of the invention will now be explained further on basic of a few basic test results with reference to tables.

i In this connection Table I shows the effect of additives on the melting point of native starch; Table II shows the homogenization process with different amounts of additive and different homogenization conditions, as well as the effects thereof on the molar weight and icrystallinity of the starch; i Table III shows selected mechanical values of homogenized and insufficiently homogenized starch, and Table IV shows the dependence of the shear viscosity on the homogenization temperature and the composition of the starch.

In order to investigate the influence of additives on the native starch, it is necessary to remove the water content of about 17% which is naturally present in the starch. This is done, on the one hand, by adding addition substances, particularly upon the melting and the mixing, and, on the other hand, by the customary methods of drying.

Depending on the properties desired for the shaped body to be produced, such as thermal and mechanical properties in particular, about 10 to 25% additive is preferably added to the native starch, the water content of the starch being LAWYERS' MERCHANTS' TRANSLATION BUREAU M Tnstatin Service Bureul Carl V Rertiche RIAls.tO Est 1908 Wm,. Bertsche, Ch. A.C.S.

TRANSLATION 13 from: -treduced by the addition of the additives. The melting point of the starch can also be substantially influenced thereby, which has an effect, on the one hand, on the processing of the starch and, on the other hand, on the dimensional stability under heat of the shaped bodies produced.

This influence was studied further by adding five preferred additives. First of all the native starch was completely dried so as to exclude the influence of water.

Thereupon 10 wt.% of addition substance was admixed in each case to the dried starch and the mixture slowly heated, the feeding of the heat being precisely observed. In this way, the thermal conversion of the mixture could be accurately followed up and a conclusion reached as to the temperature range in which the mixture is completely melted. As additives, DMSO, glycerin, ethylene glycol, propylene glycol and butalene glycol were used. The thermal conversion regions measured and thus the influence of the additives on the melting point of the starch are set forth in Table I. In this connection it may additionally be pointed out that the bottom starting point of a "peak" is related to the glass temperature while melting takes place in the region at the upper end of the "peak." Of the additives used, ethylene glycol reduces the melting point of the starch most, while the use of butalene glycol gives a relatively high melting region of about 200 0

C.

LAWYERS' MERCHANTS' TRANSLATION BUREAU Traniaring Service Burcu) CIrl V Rertche IRRl-1NrA6l Est. I908 Wmin. Bertche. Ch. A.C.S.

t--t

TRANSLATION

from.

There was also examined an addition of propylene carbonate, in which case the starch decomposes before melting. The reduction of the melting point evidently is related to the influencing of the molecular structure in the native starch, but this effect was not further examined for the time being.

If the mixture of starch and additive is processed further, then attention must be paid to the resultant melting point upon the homogenization process, i.e. upon the mixing of the melt of starch and additive.

Thus, for instance, mixtures of propylene glycol and native starch with amounts of propylene glycol in the range of 10 to 20% were fed to a kneader and then mixed at 175'C.

Depending on the amount of additive, the dwell time of the mixture in the kneader was 40 to 100 seconds, in which connection the processing temperature could be decreased by admixing more additive so as to achieve sufficient homogeneity in the melt. In another example, glycerin was r addcl and the processing temperature was correspondingly lowered in the kneader. It was found by experience that the addition of 1% additive gives a reduction of the melting range of about 10*C and that for the same shearing velocity, the same viscosity of the mixture is obtained with 1% more additive already at a temperature which is about 10'C lower.

The average power in the kneader in the above-mentioned test was about 10 kW per 100 kg of mixture of starch and i LAWYERS' MERCHANTS' TRANSLATION BUREAU S1 (71anslatrit Servi e Buremu) rl V o.rtrh. lt 1.lI(w Estll 1908 Wmn. Brtsche. Ch. A.C.S.

zz_ 4~,i TRANSLATION from

-A-

N

I~1 additive. The homogeneity of the melt was tested by producing test pieces and subjecting them to stress/strain tests. In the region where the mechanical properties measured, i.e. the tensile strength or tear strength, could not be substantially further improved, it could accordingly be concluded that the melt had sufficient homogeneity. Based on this stress/strain test, sufficient reference data can be obtained in order to conclude, with a given composition of the melt of starch and additive, what a suitable dwell time in the extruder or kneader is.

Table II shows the homogenizing of starch carried out under different homogenization conditions and the effects thereof on the homogeneity of the resultant thermoplastically processable starch.

Potato starch is used, the potato starch P 3 together with 15% additive having a melting range of about 180'C and potato starch P 4 together with 15% additive having a melting range of about 190'C.

Column A indicates the composition of the starch/ additive mixture, the value A being grams of additive per (grams of starch grams of additive). A value of A 0.15 therefore means 15 grams of additive to 100 grams of mixture of starch additive. As additive there is used a mixture of the aforementioned additives of preferred use, the mixture having a solubility parameter of 20 ca1 1 /cm'3/ 2 at 150C.

I1 A-i LAWYERS' MERCHANTS' TRANSLATION BUREAU (7(Tansarlt Strvlct Burtu) rirt V t rtsche ,IlRI.ll Vt Est 1008 Wm. Berttche, J.D..Ch. A.C.S.

Ii

TRANSLATION

from The temperatures T 3 to T 6 represent desired temperature values of the controlled temperatures of the individual zones of the homogenization device. The homogenization device used is a kneader.

T

E is the temperature of the mass upon emergence from the kneader.

B is the speed of rotation of the kneader shaft in rpm.

C is the power introduced into the mass in the form of mechanical work in kW.

D is the mass flow in the kneader, i.e. the rate of flow of the melt through the kneader in kg/hr.

E is the intrinsic viscosity of the thermoplastic starch after leaving the kneader, measured in solution in 0.1N KOH at 60 0 C after a dissolving time of one hour at 110°C in an Ubelhode capillary viscosimeter, measured in cm 3 per gram. E is a measure of the molar weight of the thermoplastic starch in gram/mol). The corresponding correlation is E 0.2 x MG 04 weight average of the molecular weight).

SE of the native untreated starch is 260, from which a value for MG of the native untreated starch of 6 x 107 results.

F is the crystalline portion in percent. By means of the crystallinity of the starch it can be determined whether the homogenization has been effected sufficiently and the /T LAWYERS' MERCHANTS' TRANSLATION BUREAU Translaring Service Bureau) Sar' Cr V Rertche ,IRl.R166O Est 108 Wm. Bertache. Ch. A.C.S.

'e ii

TRANSLATION

from: starch is thus thermoplastically processable. Native starch is highly crystalline, while thermoplastically processable starch has practically no crystalline content any longer.

Measurement of the Crystalline Content: Method of measurement: X-ray diffraction on powder Measurement value: Intensity of the scattered dispersion as a function of the scatter angle Native potato starch: sharp reflections at the dispersion angles (degrees) 6, 14, 17, 20, 22, 24, 26.

Measure of the crystallinity: Fx surface content of the scatter intensity/scatterangle function for the sharp reflections of the treated starch, Fn surface content as above for the native untreated starch F F x 100 Fn The F values of the treated starch in the homogeneous thermoplastic state are less than Discussion of Table II: The criterion for evaluation as to how well or poorly the homogenization of the starch has been effected is the value F for the crystalline portions. Values of between 0 and 5 are optimal while values of more than 5% already permit the conclusion that there is insufficient homogeneity of the thermoplastic starch.

LAWYERS' MERCHANTS' TRANSLATION BUREAU c(rl th .Tanslating Service Bureau) 0 iC; rl V Bertlche 'tI .10 1 Est 1908 Wm, Bertche. Ch. A.C.S.

•4

TRANSLATION

from: The values found for E, i.e. for the intrinsic viscosity, lie within a reasonable range but even the lowest value found for E gives an average molecular weight MG of million.

If one compares the different values for A, i.e. for the composition of the starch mixtures with P 3 and with P 4 it is clear that the values pass through an optimum within a region of 0.25 to 0.3. Thus, for instance, mixtures of the starch P3 with A values of 0.35 and 0.4 after the homogenization still have high crystalline percentages while values for A of 0.3 and 0.25 show practically no crystalline portions any longer. The same picture results furthermore also for starch mixtures from potato starch P4 with additive. This statement can of course not be generalized, but the homogenization effect depends, not least of all, also on the composition or properties of the additive or additives.

One essential criterion for the homogenization is the power introduced, it being clear from the experiments that the greater the power introduced into the kneader, the better the homogenization of the starch. This can be noted for instance from samples 3a, 3b and 3c, where the homogenization takes place practically within the same temperature range and where the composition of the starch mixture is also the same, namely with a value of A 0.35. rhe same effect can also be noted from a comparison of Samp' s 9 and 10, where Sample LAWYERS' MERCHANTS' TRANSLATION BUREAU I( fTanslatig Service Burem) t Carl V Bertsche H#Rlt i661 Est. 190 Wnm. Bertiche. Ch. A.C.S.

I~

c

TRANSLATION

from: with a higher amount of power introduced into the kneader gives sufficient homogeneity while Sample 9 shows a crystallinity content of For the obtaining of sufficient homogeneity in the thermoplastic starch there is also essential the selection of the temperatures in the homogenization apparatus, as can be noted, for instance, from a comparison of Samples 5a and Thus for example, Sample 5b results in better homogeneity even though although less power has been introduced into the kneader. The better homogeneity results here substantially from the definitely higher temperatures selected in the kneader.

The measured values set forth in Table II however clearly show that no prediction can be generalized as to composition, temperatures selected in the kneader and power introduced. Therefore, for each starch/additive mixture selected it is a question of optimizing the conducting of the I process in order to obtain a thermoplastic starch. In the V final analysis, the question is also essential as to whether one wishes to obtain a high or low molecular weight. This question depends in the final analysis on the requirements as to whether the thermoplastic starch is to be used for injection molding or extrusion. As is known, polymers of higher viscosity are more suitable for extrusion while polymers of lower viscosity are more suitable for injection u; LAWYERS' MERCHANTS' TRANSLATION BUREAU IMnsiari: lr Serice Burea) r~rlV Rsrtsce i RRIA i Es. 1908 Wm. Bertsch, 1. Ch. A.CS.

TRANSLATION

from molding.

Referring again to the homogenization of the starch, it should also be mentioned that, of course, the dwell time of the material in the homogenizing apparatus or kneader can affect the homogeneity of the material.

Comments on Table III: Table III shows the influence of the homogeneity or crystallinity of the thermoplastic starch on mechanical properties based on the illustrative description of the influence on elongation and fracture behavior of the starch.

Sample I concerns test pieces of thermoplastic starch material which is sufficiently or almost ideally homogenized and is suitably thermoplastically processable. Sample II is a sample of starch which is insufficiently homogenized and accordingly contains too high a percentage of crystallinity.

The modulus column sets forth the modulus of elasticity of the two materials, which interestingly enough is A practically the same for both materials. Column A sets forth the composition of the samples, Column E, in the same way as in Table II, the intrinsic viscosity of the samples, and Column F the value of the crystalline percentage.

G is the relative elongation of the material upon rupture in percent and H is the amount of energy which was fed to the material until its fracture. The dimension of H is KJ/m 2 T S v LAWYERS' MERCHANTS' TRANSLATION BUREAU S fTonlartin Service Bureau) Carl V, Bertiche IR81.t- Estl 1Q08 Wm. Bertsche. Ch. A.C.S.

TRANSLATION

from, In line 1 there are set forth the values of various measurements for samples I which comprise a crystalline percentage on the order of magnitude of 0 to max. There are concerned here therefore materials which are almost ideally homogenized and accordingly can be excellently thermoplastically processed.

In corresponding manner there are set forth in line II various measurements for Materials II which are insufficiently homogenized.

From Column G it can clearly be noted that the starch materials from line II are essentially more brittle than the materials in line I. Furthermore, substantially more energy must, as shown in Column H, be fed to the starch materials of line I in order to elongate them to rupture.

Based on the stress/strain tests which are numerically set forth in Table II, the improvement in the mechanical properties of thermoplastically processable starch can be clearly noted. Based on the reduction in the crystallinity of the material to less than 5% one thus obtains starch materials having sufficient to good mechanical properties.

These mechanical properties can, of course, be further improved by the amount of additive and by suitable selection of addition substances.

Since shearing forces in the molten mixture of starch and additive are obviously responsible for the homogenization t LAWYERS' MERCHANTS' TRANSLATION BUREAU (Transating Service Buretu) .4 Carl V.Bertache lRRI-.lC I6 Est., 908 Wm. Bertsche. A.C.S.

'^L^V

I_

TRANSLATION

from: -2 effect and thus lead to a material of low crystallinity, the relationship between the shear viscosity of the melt and the shearing action of the homogenizing apparatus will be discussed in more detail. For this purpose, the structure viscosity of the molten starch, i.e. the dependence of the shear viscosity on the shearing rate, is examined in a capillary rheometer.

The following equation was found as correlation between the two values: S= K y Herein, r is the shear viscosity of the melt in Pa x sec, and y is the sheer velocity in sec 1 K is a physical constant which is at times also referred to as the consistency. K is calculated from the following equation: EA 1 1 K exp )-a(A-Ao R T To 0 For the term EA/R a value of 5.52 x 104 Kelvin was found, R being the gas constant and EA the thermal activation energy of the change-of-place process of the molecules upon the flowing of the melt.

T is the temperature of the melt (in degrees Kelvin) and To is a reference temperature of 458 Kelvin.

a is also a constant having the value of 2.76 x 102 and A is, as is known, the composition of the starch/additive mixture. A0 is the composition of a reference mixture having LAWYERS' MERCHANTS' TRANSLATION BUREAU S(T7anharing Service Bureau) S Crl V. Bertiche R81-1961) Est. 1908 Wm. Bertsche, Ch. A.C.S.

.r TRANSLATION 23 from: -afa value of A 0.1.

In this connection it is now found that the term m is a function of the temperature of the melt and of the composition of the starch/additive mixture.

Table IV lists values of m as a function of T (degrees Kelvin) and of A, these values having been obtained in the manner that the shear viscosity established itself suitably with a predetermined y, i.e. the shear velocity in the measurement device. For m there is thus obtained a function of the general formula m f(A) r The values of Table IV emphasize the already suspected fact that, at elevated temperature of the melt, the shear velocity can be reduced in order to obtain the same shear viscosity in the melt and, with increased proportion of additive, the temperature of the melt can be reduced in order to obtain the same shear viscosity in the melt.

The starch, or better, thermoplastic starch, which has now been homogenized in this manner can then be further processed directly in accordance with the customary methods of processing plastics, such as injection molding, extrusion, sheet blowing, spray blowing, deep drawing etc. In this connection, to be sure, it is necessary, particularly in the case of extrusion, tube blowing, injection blowing etc., that the additive have a vapor pressure which is definitely less than 1 bar at the temperature with which the melt leaves the SLAWYERS' MERCHANTS' TRANSLATION BUREAU rS (Transiating Service Bureau) Crl V. Bertwche IRR Est. 9O08 Wm. Bertsche. Ch. A.C.S.

Ti r

TRANSLATION

from:nozzle at the extruder. The same applies also with respect to the water content of the melt, which must not be too high.

It must therefore also be seen to it that sufficient additive is present in the melt to displace or replace the water.

With too high a water content or the use of an additive having too high a vapor pressure, the material foams upon leaving the nozzle.

By further addition of addition substances as described above, the properties of the moldings and extrudates can be further substantially affected. Thus, for instance, by the addition of inorganic fillers such as magnesium oxide, aluminum, silicon etc., the transparency can be reduced or entirely prevented. Additions of vegetable or animal fats improve the flow properties of the melt or serve to improve the removal from the mold. The affecting of the properties is, to be sure, not primarily an object of the present invention, so that further description hereof can be dispensed with.

Another important aspect consists in the adding of cross-linking agents to the starch'since shaped bodies and extrudates of pure starch are not water-resistant, due to the hydrophilic nature. By the addition of cross-linking agents and other chemical-modifying agents, parts made of starch become at least partially or almost completely waterresistant and can thus be used without difficulty in actual LAWYERS' MERCHANTS' TRANSLATION BUREAU (T aniarting Service Bureau) Carl V Rrtsche i 191-1W4I Est. 1q08 Wm. Bertsche. Ch. A.C.S.

T

TRANSLATION

from: practice. The selection and addition of one of the abovementioned cross- linking agents depends essentially on the additive and the amount thereof added to the native starch, in which connection the addition substances may also play a role. Temperature and dwell time in the extruder, i.e. upon the melting, homogenizing and processing, are therefore the essential criteria for the type of cross-linking agent to be selected. In principle, the cross-linking should not proceed so far during the processing of the starch that the thermoplasticity is so affected thereby that processing becomes problematical. This, however, is fully known from the processing of partially cross-linkable thermoplastics, from the production of powdered lacquers etc. in practice, so that it need not be g 'ne ?ito further.

The aforemention, tves and processing conditions used by way of example .'ve served only for further explanation of the invention and can be varied in accordance with the requirements in any desired way by the use of other materials and processing conditions. It is essential in this Sconnection that by the addition of an additive to the native starch and the mixing of these two materials in the melt, a thermoplastically processable starch can be obtained. It is furthermore essential that the additive have a cohesion energy density which makes it possible for it to affect the molecular structure of the native starch in such a manner LAWYERS' MERCHANTS' TRANSLATION BUREAU (Translating Service Buresi) Carl V Irtache I lRR.i IW Est. 1908 Wm. Bertache. Ch. A.C.S.

A

I

I II

TRANTSLATION

from. -r that the thermoplastic processability thereof can be obtained. Finally, another requirement is that the vapor pressure of the additives be less than 1 bar within the processing temperatut.c x znge, at least in the case of open processing.

LAWYERS' M4ERCHANTS' TRANSLATION BUREAU (T1ranheA ing Serdece Bureew4 gCarl V. Rertache 'IRR~II I Eat 1q0S Win. Bertsch@. I. Ch. A.C.S.

L

Claims (33)

1. A thermoplastically processable starch, characterized by the fact that it consists essentially of an at least substantially homogeneous mixture which Is at least substantially anhydrous and consists of starch and/or a starch derivative and at least 5% of at least one additive, the additive or additives having the following properties: the solubility parameter is more than 15 (cal1/2 cm3); upon the mixing of the starch with the additive, the melting point of the starch is reduced in such a manner that the melting point of the starch together with the additive is below the decomposition temperature of tho starch; and the vapor pressure of the additive or additives in the mixture consisting of additive and starch Is less than 1 bar within the temperature range close to the melting point of the homogeneous 15 mixture within which the starch is thermoplastically processed.

2. A thermoplastically processable starch according to claim 1, characterized by the fact that the molecular weight of the starch lies within a range of more than 1 million.

3. A thermoplastically processable starch according to claim 1 or 2, characterized by the fact that the molecular weight lies within the range of 3 million to 10 million.

4. A thermoplastically processable starch according to any of claims 1 to 3, characterized by the fact that it is In the form of granulates, flakes, pills and/or tablets or powder or fibers. 25 5. A thermoplastically processable starch according to any one of S* claims 1 to 4, characterized by the fact that the portion 6p of the S"solubility parameter 8 corresponding to the polar interactions and the portion 8 H corresponding to the hydrogen-bridge bonds are greater than the portion 8 d of the solubility parameter 8 of said at least one additive corresponding to the dispersion forces.

6. A method of preparing thermoplastically processable starch, characterized by the fact that substantially native or natural starch, together with at least one additive, is brought into molten state by the introduction of heat, the additive being at least one substance which reduces the melting point of the starch so that the melting point of the starch together with this additive is below the decomposition temperature of the starch, and the additive having a solubility parameter of more .k T T/1691R 28 than 15 (call 2 cm-3/2), and the vapor pressure of said at least one additive in the mixture of additive and starch is less than 1 bar in a temperature range close to the melting point of the starch together with said at least one additive, and thereupon the mixture of starch and additive is mixed until the melt is at least substantially homogeneous.

7. A method according to claim 6, characterized by the fact that the mixing of starch with said at least one additive is effected substantially free of water.

8. A method according to claim 6, characterized by the fact that upon the mixing of starch with said at least one additive moisture present in the mixture Is at least substantially removed from it.

9. A method according to any one of claims 6 to 8, characterized by the fact that said at least one additive has a solubility parameter of 15 to 25 (cal 112 cm 3 2 within a temperature range of 100 300°C. 15 10. A method according to any one of claims 6 to 9, characterized by the fact that said at least one additive is so selected that the Interfacial surface energy between additive and starch is not greater than 20% of the individual Interfacial energies of starch and additive with respect to air.

11. A method according to any one of claims 6 to 10, characterized by the fact that 5 to 357. additives, referred to the total weight of the mixture, are admixed to the starch.

12. A method according to any one of claims 6 to 11, characterized by the fact that the mixing of the molten starch with the additive Is I 25 effected within a temperature range of 100 to 300 0 C.

13. A method according to any one of claims 6 to 11, characterized by the fact that the mixing of the molten starch with the additive is effected within a temperature range of 120 to 220 0 C.

14. A method according to any one of claims 6 to 13, characterized by the fact that the mixing of the molten starch with the additive is effected within a temperature range of 150 170 0 C. A method according to any one of claims 6 to 14, characterized by the fact that substantially natural or native starch is fed together with the additive to a plastic processing machine such as, for Instance, a single-shaft or twin-shaft extruder or a kneader and mixed therein, as for instance in the shaft piston or the kneader piston, to form an at least approximately homogeneous thermoplastic mass. 691R 71 29

16. A method according to any one of claims 6 to 15, characterized by the fact that as additive there Is used at least one of the following substances: 1.3 butanediol glycerin ethylene glycol propylene glycol diglyceride diglycolether formamlde N-methyl formamide.

17. A method according to any one of claims 6 to 16, characterized by the fact that the starch is substantially mixed with glycerin as additive. 15 18. A method according to any one of claims 6 to 17, characterized by the fact that there is added to the starch as additive at least one substance in accordance with the following formulas: I VI R -(CH)k z-R I I R"R" RIV R with R -H or -alkyl; II-VI RIIVI -OH -NH 2 :i 25 in which at least one RIIVI, -OH, and n 1, 2 5; m, k O, 1, 2 and n 0 if m, k 0 as well as z 1, 2 oo) or R 0 with R 1 R 2 -alkyl, R2 R 3 -N R 4 with R 3 R 4 -alkyl; but without R. R 2 -H; 1/1691R R 1R 2 alkyl; R= R 2 =-NH 2 R 1 I -H and at the same time R 2 =-alkyl; R2=-H and at the same time R I -alkyl.

19. A method according to any one of claims 6 to 18, characterized by the fact that at least one further addition substance such as, for instance, a filler, a lubricant, a softening agent, a flexibilizing I agent, a pigmenting agent or other coloring substance and/or a mold removal agent is added to the mixture of starch and additive.

20. A method according to any one of claims 6 to 19, characterized by the fact that as filler at least one of the following materials is used: gelatin a protein a polysaccharide a cellulose derivative a synthetic polymer which is at least approximately soluble in an additive for the starch *e. a gelatin phthalate.

21. A method according to any one of claims 6 to 20, characterized by the fact that between 0 and 50% filler, and preferably 3 to referred to the total weight is admixed to the mixture of starch and :additive.

22. A method according to any one of claims 6 to 21, characterized 25 by the fact that at least one inorganic filler such as, for example, magnesium oxide, aluminum oxide, silicon dioxide and titanium dioxide etc. is used in a concentration of 0.02 to 3% referred to the total weight.

23. A method according to claim 22, characterized by the fact that the inorganic filler is used in a concentration of 0.2 to 1% referred to the total weight.

24. A method according to any one of claims 6 to 23, characterized by the fact that a softening agent such as for instance a polyalkylene oxide, glycerin, glycerinmono-, -di- or -triacetate, sorbitol, a citrate etc. is used in a concentration within the range of 0.5 to 15% referred to the total weight. S/1691R eA~A 31 A method according to claim 24, characterized by the fact that the softening agent is used in a concentration within the range of 0.5 to referred to the total weight.

26. A method according to any one of claims 6 to 25, characterized by the fact that an organic or inorganic pigment is used in a concentration in the order of 0.001 to 10% referred to the total weight.

27. A method according to any one of claims 6 to 26, characterized by the fact that an organic or inorganic pigment is used in a concentration in the order of 0.5 to 3% referred to the total weight.

28. A method according to any one of claims 6 to 27, characterized by the fact that an agent for improving the flowability is used.

29. A method according to claim 28, characterized by the fact that said agent for improving flowability is an animal or vegetable fat or fatty acid derivative thereof or a lecithin.

30. A method according to claim 29, characterized by the fact that said animal or vegetable fat or fatty acid derivative thereof or lecithin is in the hydrogenated form.

31. A method according to claim 28 or 29, characterized by the fact that said animal or vegetable fat or fatty acid derivative thereof or lecithin has a melting point of more than 50 0 C.

32. A method according to any one of claims 6 to 31, for the preparation of at least partially cross-linkable starch, characterized by the fact that at least one cross-linking agent is added to the mixture of starch and additive. 25 33. A method according to any one of claims 6 to 32, characterized S: by the fact that, as cross-linking agent, at least one of the following substances is used: S- a bivalent or polyvalent carboxylic acid and/or an anhydride thereof, a halide and/or an acid amide of a bivalent or polyvalent carboxylic acid, S- a derivative of a bivalent or polyvalent inorganic acid an epoxide, such as a polyvalent glycid ether formaldehyde and/or a urea derivative a divinyl sulfone of the general formula S3S/1691R 32 0 II X-CH 2 -CH 2 -X 2 11 0 an isocyanate an oxo compound, such as acetone formaldehyde or a polyvalent oxo compound cyanamide.

34. A method of preparing granulates, flakes, pills, powders, tablets, fibers, etc. from thermoplastically processable starch by the use of the method according to any of claims 6 to 33. A method of preparing moldings, extrudates, sheets etc. of starch by the use of the method according to any one of claims 6 to 34, 15 characterized by the fact that the homogeneous mixture is processed directly.

36. A thermoplastically processable starch whenever prepared by the method according to any one of claims 6 to 33.

37. A molded body consisting essentially of starch, characterized by the fact that it comprises at least 5% of an additive which has a I solubility parameter of more than 15 cal 2 cm 3 2 within a temperature range of 100 to 300 0 C, the portion 6 p of the solubility I parameter 6 corresponding to the polar interactions and the portion 6 H corresponding to the hydrogen-bridge bonds being at least twice as 25 great as the portion 6 d of the solubility parameter 6 of said at least one additive corresponding to the dispersion forces, and which, upon admixture to the starch, reduces the melting point of the latter so that the melting point of the starch together with the additive is below the decomposition temperature of the starch, the additive furthermore having in the mixture of additive and starch a vapor pressure of less Sthan 1 bar in the region of the said melting point.

38. A filler for the filling and/or formulating of thermoplastic or thermosetting polymers, consisting essentially of thermoplastically processable starch, according to any one of claims 1 to 5 or 36.

39. A support material for receiving active substances and/or reagents, consisting essentially of thermoplastically processable starch according to any one of claims 1 to 5 or 36. *n i-i iTS/1691 R ,fri-fmll l-ll l /I II I IIII III 33 A method for the controllable adjusting of the properties of fillers, consisting essentially of thermoplastically processable starch according to any one of claims 1 to 5 or 36, characterized by the fact that this is obtained substantially via the selection of the molecular weight distribution of said starch.

41. A method of binding water in an environment of low water content and/or on a water-pervious substrate by means of thermoplastically processable starch according to any one of claims 1 to or 36, the starch being used preferably in the form of a sheet, large-surface foils, a network or some other extrudate. DATED this SECOND day of OCTOBER 1991 S" Ivan Tomka I 1 Patent Attorneys for the Applicant *SPRUSON FERGUSON i 4-* /1691 a TRANSLATION from: 34' TABLE I Additive Thermal conversion (Temp 'C) Peak from Center of Peak to propylene glycol. ethylene glycol glycerin DMS 0 Butylene glycol 78 40 45 65 180 142 80 110 80 190 175 120 140 150 200 wt.% additive 0 wt.% water LAWYERS' MERCHANTS' TRANSLATION BUREAU (Tra 'usaring Service Buredu) V4r, v R'rttche .t I i W Est, 0Q8 Win. Bertsche, Ch. A. C.S. TRANSLATION LAWYERS' MERCHANTS' TRANSLATION BUREAU (7ranjicring Service Bureau) Carl V Rauluche cRII Est 1908 Win. Bertsche. Ch. A.C.S. h TRANSLATION31 from: T1 LAX!YERS' MERCHANTS' TRANSLATION BUREAU (Thansladng Service Bureaij Carl V. Bertache i tggi. )661 Est. 0908 Win. Bertsche, J. Chi. A.C.S. INTERNATIONAL SEARCH REPORT International Application No PCT/CH 89/00185 I. CLASSIFICATION OF SUBJECT MATTER (II several classification symbols apply, Indicate fil) According to International Patent Classfication (IPC) or to both National Classfication and IPC Int. Cl. 5 C 08 J 5/00, C 08 L 3/00 II. FICLDS SEARCHED Minimum Documentation Searched 7 ClaesiflcationSystem I Classification Symbols Int. C1. 5 C 08 L, C 08 J, C 08 B Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Flals Searched III DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, it with indication, where approoriate, of the relevant passages 12 Relevant to Claim No, t1 X GB, A, 1014801 (THE RESEARCH ASSOCIATION OF BRITISH 1-35 FLOUR MILLERS) 31 December 1965, see the whole document A US, A, 4076846 (NAKATSUKA et al.) 28 February 1978 A BE, A, 654605 (DEPARTMENT OF AGRICULTURE AND INSPECTION OF THE STATE OF NEBRASKA) 20 April 1985 A US, A, 2788546 (MELLIES et al.) 16 April 1957 Special categories ot cited documents: to later document published after the international filing date document defining the general state of the art which is not or priority date and not In conflict with tne aPlication but considered to be of articular relevance cited to understand Ins principle or theory underlying the invention earlier document but publi l hed on or alter the international document of particular relevance: the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on Driority clalm(s) or involve an inventive step which i cited to establish the pubication date ot another document of particular relevancet the claimed invention citation or other special reason (at specified) cannot be considered to involve an inventive steo when the document reterring to an oral disclosure. usa, exhibition or document is combined with one or more otner such docu- otner means menta, sucn combination being obvious to a person skilled document oublilhed prior to the international filing date but in the art, later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this international Search Report 17 January 1990 (17.01.90) 12 February 1990 112.02.90) International Searching Authority Signature of Autnorized Officer SEUROPEAN PATENT OFFICE Form PCTIISAt210 isecono sheet) (January 1t985 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. CH 8900185 SA 31872 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 05/02/90 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date GB-A- 1014801 None US-A- 4076846 28-02-78 JP-A- 51070834 18-06-76 JP-A- 51061648 28-05-76 JP-A- 51070835 18-06-76 JP-A- 51069562 16-06-76 JP-A- 51073143 24-06-76 JP-A- 51077651 06-07-76 AU-A- 8677275 07-04-77 CA-A- 1061163 28-08-79 DE-A- 2552126 26-05-76 FR-A,B 2292005 18-06-76 GB-A- 1532783 22-11-78 NL-A- 7513527 25-05-76 BE-A- 654605 20-04-65 DE-A- 1470792 27-02-69 FR-A- 1413334 LU-A- 47186 21-12-64 NL-A- 6412198 26-04-65 US-A- 3243308 US-A- 2788546 None 0 0 C For more details about this annex :see Oficial Journal of the European Patent Ofie, N. 12/82 w. For more details about this annex :see Official Journal of the European Patent Office, No. 12/82 INTERNATIONALER RECHERCHENBERICHT InternationaisAktenzeichen PcT/CH 89 /00185 1. KLASSIFIKATION DES ANMELDUNGSGEGENSTANDS (bal mehrersn Klasslfikatlonsaymbolsn sind &Ile anzugeban) 6 Nach der internationlnfPatefltkiassiiktiof(PC) oder nch der natianalen Klassifikation und der IPC Int.-C1 5 C 08 J 5/00, C 08 L 3/00 11. RECHERCHIERTE SACHGEBIETE Recherchierter Mincdestpriifstaff 7 Recherchierte nicht zumn Mindestpniifstoff gehorende Ver6ff entlichungien, saweit diese unter die recherchierten Sachgebiete fallen 8 IlL EINSCHLAGIGE VEROFFENTLICHULNGEN 9 Art* Kennzeichnung der Veraffentlichungll,soweit erforderlich unter Angabe der malgeblichen Teile 1 2 Betr. Anspruch Nr. 13 X GB, A, 1014801 (THE RESEARCH ASSOCIATION OF 1-35 BRITISH FLOUR MILLERS) 31. Dezember 1965, siehe das ganze Dokunient A US, A, 4076846 (NAKATSUKA et al.) 28. Februar 1978 A BE, A, 654605 (DEPARTMENT OF AGRICULTURE AND INSPECTION OF THE STATE OF NEBRASKA) April 1985 A US, A, 2788546 (MELLIES et al.) 16. April 1957 *Basandera Kategorien von angegabenen Veroffentlichungen 10 Veratfentlichung, die den ailgemeinan Stand der Technik Spaitere Veroffentlichung, die nach daem internatianalen An- definiart. aber nicht als besonders bedeuxsam anzusehen ist maidediatumn odor dam Prioritatsdatum verbffentlicht warden iltres okuentdesjeclch rst m oer nch em itera- st und mit dot Anmeidlung nicht koilidiort. sandern nur zumn ltees okuent da Jeach m a odr nch am nteria Verstandnis des der Erfindlung zugrundoliogondaen Prinzips tianalen Anmeldedatum veroffentlicht warden Ist oder der ihr zugrundeliegenden Theorie angegoben ist Verbffentlichung, die gefIgnet ist, amen PrioritAtsanspruch ""Vrfetihn o eadrrBduug i enpuh zweifeihaft erscheinen zu lassen, oder durch die das Verbf- te VErffeinung annnhal bsneu r alufug driedeahar Tcti fontlichungsdatum einer andaren im Recherchenb~ericht ge- ket Eruhelnd boanncht arnede u ridrshrTtg narriten Wrftentlichung baiegt warden soil oder die aus eir etbuhdbtace wdn anderen besonderen Grund angogeben ist We ausgefi~hrt) Veroffentlichung van besandarer Bedeutung: die beanspruch- erdfanlicung diesic au ele mndlihe ffebarng, to Erfindlung kann nicht als auf erfinderischer Tbtigkeit be- e Vedentung, ine Asich au iner ndce Offenbarn ruhend betrachtet warden, wonn die Voroffentlichung mit eiehBtz eieAstlunidradreMnamn aer oder mehreren andaron Veratfentlichungen dliesor Kate. bezog goe in Verbindlung gebracht wird und diese Verbindlung fur Verdffentlichung, die var demn Internationalen Anmeidoeda- einen Fachmann naheliegend ist turv% abor nach dem beanspruchten TiaritAtsdatumn veroffont- Verbffentlichung, die Migiled derseiben Patentfamilie Ist licht warden ist IV. BESCHEINIGULNG Datum des Abschlusses der interruationalen Recherche Absendadlatumn des internationalan Recherchenberlchis 17. Januar 1990 12. Qi Internationale Rechetchenbehorde Unterschrift des bevallmachtigten Bedlionstamnr- Europiisches Patentamt r-0. v.d. Wiet Formblatt PCT/lSA/21O0 (Blatt 21 (Januar 1985) ANHANG ZUM INTERNATIONALEN RECHERCHENI3ERICHT UDBER DIE INTERNATIONALE PATENTANMELDUNG NR. CH 8900185 SA 31872 In diesem Anhang sind die Mitgfieder der Patentfamilien der im obengenannten internationalen Recherchenbericht angerdhrten Pnatentdokumcnte angegebcn, Die Angabcn fiber die Familienmitglieder entsprechen dem Stand der Datei des Europliischcn Patentamts am 05/02/90 Diesc Angaben dienen nur zur Lnterrichtung und erfolgcn ohne Gewlihr. Im Recherchenbericht Datum der Mitglied(er) der Datum der angefllhrtcs Platentdokument VrfntchnPatentfanilie Verbffentlichung GB-A- 1014801 Keine US-A- 4076846 28-02-78 JP-A- 51070834 18-06-76 JP-A- 51061648 28-05-76 JP-A- 51070835 18-06-76 JP-A- 51069562 16-06-76 JP-A- 51073143 24-06-76 JP-A- 51077651 06-07-76 AU-A- 8677275 07-04-77 CA-A- 1061163 28-08-79 DE-A- 2552126 26-05-76 FR-A,B 2292005 18-06-76 GB-A- 1532783 22-11-78 NL-A- 7513527 25-05-76 BE-A- 654605 20-04-65 DE-A- 1470792 27-02-69 FR-A- 1413334 LU-A- 47186 21-12-64 NL-A- 6412198 26-04-65 US-A- 3243308 US-A- 2788546 Keine Fdr nihere Einzrlheiten zu diesem Anhang :siehe Anitsblatt des Europiischen Patentanits, Nr.12/82