JPH06508866A - Biodegradable composition composed of starch derivatives - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Biodegradable composition composed of starch derivatives The present invention is capable of forming articles with substantial dimensional stability through heat and pressure. The present invention relates to a biodegradable polymer composition. The present invention particularly focuses on starch derivatives, plasticizers and homogeneous Alkenol homos combined under conditions sufficient to ensure melt formation At least one selected from polymers and/or alkenol copolymers The present invention relates to a biodegradable composition. Such compositions can be used inter alia for injection molding, film Suitable for use in forming and forming foam packaging materials.

Background of the invention It is known that natural starches present in plant products form melts when processed at high temperatures. It is being

Such melts preferably maintain the starch material at temperatures above the glass transition and melting temperatures of its components. It can be produced by an endothermic rearrangement reaction by heating to a high temperature. Preferably starchy substances contains a limited amount of water, and melt formation occurs at elevated temperatures in a closed volume. Therefore, it is carried out under high pressure.

However, starch in the substantial absence of water may also be used with other suitable plasticizers, e.g. Melting in the presence of a liquid with a boiling point higher than the glass transition temperature and melting temperature of starch It is possible to

Different degrees of melt formation are possible, which can be measured in different ways. one This method involves measuring the amount of granular structure remaining in the starch melt using a microscope, for example. That is. The starch is structurally modified, i.e. the properties of the melt are substantially uniform. be substantially free of grain structure under approximately 500x magnification using an optical microscope. shows a decrease, such that the molten starch exhibits little or no birefringence. The starch crystals in the melt are substantially reduced or Preferably not.

The advantage of this invention is that compositions can be made from starch that exhibits a relatively low degree of structural change. This is an advantage of brightness.

Ind, Eng, Ches, Prod, Res, Dev, (194: 23. Pages 594-595) is water-soluble polyvinyl alcohol diluted with starch. describes the extrusion of According to this disclosure, the melt flow rate of such extrudates is The index decreases with increasing starch concentration and increases with low molecular weight (20,000) 1:1 ratio of vinyl alcohol and low molecular weight (30,000) corn starch The composition has a melt flow index of 0.53. such a low Melt Flow Index compositions are unsuitable for injection molding articles therefrom. , in which case a melt flow index of about 7 or higher is typically required. required. Compositions of the invention containing relatively high concentrations of starch derivatives can be easily injection molded. It's amazing what you can do.

The melt flow index of this composition is when a force of 0.2160 grams is applied. Amount of thermoplastic that can pass through a 2.0665 mm orifice in 10 minutes (Durham).

Moreover, thermoplastic resin forming technology requires that its main components have high molecular weight. and preferably the molecular weights of such components are of similar size. It has become.

Articles with excellent physical properties and dimensional stability are formed from the compositions of the present invention. Among them, the starch derivative component of the composition has a low molecular weight compared to the molecular weight of the starch derivative component. It is surprising that polyvinyl alcohol exists in high concentrations relative to starch derivatives. This is something that should be done.

Summary of the invention In accordance with the present invention, the plasticizer is assembled under conditions sufficient to ensure the formation of a homogeneous melt. from alkenol homopolymers and/or alkenol copolymers that are combined A starch derivative comprising at least one selected from the group consisting of at least one starch derivative. Biodegradable compositions obtained from melts are provided.

Plasticizers are incorporated into raw materials to increase the flexibility, processability, or extensibility of articles, or to Can reduce viscosity, lower second-order transition temperature, or lower elastic modulus means substance. The plasticizer referred to herein includes solvent plasticizers and internal plasticizers. preferred A good plasticizer is water.

The starch derivative can be selected from the group consisting of starch esters and starch ethers; The degree of substitution of the starch derivative may be from about 0.1 to about 3.0.

The degree of substitution of said derivative is at least 0.8, and more preferably this degree of substitution is about 0.8 to about 2.1.

In one embodiment of the composition, the starch derivative is about 95% by weight of the composition. with an amylose content of up to.

The lower limit of amylose content is about 10 to about 15% by weight based on the weight of the starch derivative. is preferable.

The starch derivative preferably has an equilibrium moisture content of about 7% or less and a relative humidity of about 50% at 25°C. have a degree.

A component consisting of at least one of the above is present in the composition per 100 parts of dry starch derivative. It can be present in a concentration of 10 to 200 parts.

The alkenol homopolymer is preferably pre-prepared with a polyhydric alcohol such as glycerol. Polyvinyl alcohol that can be plasticized. polyvinyl alcohol is preferably about 45 to about 100% hydrolyzed, and preferably about having a number average molecular weight of 15.000 to about 250.000, and more preferably It has a number average molecular weight of 15.000 to 150.000.

This composition is prepared by melting it into polyvinyl alcohol and substantially in the melt. A preconditioning method obtained by applying sufficient energy to remove crystallinity beforehand. Particular preference is given to containing processed polyvinyl alcohol in the form of a melt. Like that Particularly preferred is substantially complete absence of crystallinity. Such a polyviny Pretreatment of alcohols is disclosed in EP-0415357.

The alkenol copolymers mentioned above are preferably vinyl esters, preferably vinyl acetate. monomers preferably ethylene, propylene, isobutylene and/or styrene. vinyl, such as those obtained by copolymerization with vinyl and subsequent hydrolysis of the vinyl ester groups. It is a synthetic copolymer containing alcohol units as well as aliphatic chain units.

Such copolymers are known and described in the rEn-cyclopedia o f　Polymer　5science and　TechnologyJ(In ter-science Publ, Vol. 14.1971) ing.

The composition further comprises one or more water-soluble and/or water-swellable polymers. contains more compounds and one or more substantially water-insoluble hydrophobic thermoplastics. It can include a plastic polymer.

The composition may also contain extenders, fillers, lubricants, mold release agents, other plasticizers, stabilizers, etc. , colorants, nucleating agents, flame retardants, boron-containing compounds and alkali and alkaline earth metals. It can contain at least one kind selected from the group consisting of salts of the genus.

The concentration of the components in the composition, particularly the coloring agent, can be determined as desired by master patching. It will be understood that this can be done.

The invention further provides for assembly with a plasticizer under conditions sufficient to ensure the formation of a homogeneous melt. alkenol homopolymers and/or alkenol copolymers that can be combined a starch derivative; and a starch derivative. Concerning compositions in the form of melts.

The invention furthermore includes granules or pellets containing said composition or melt. Concerning molded articles.

The molten composition can be further processed by injection molding, compression molding, film forming, blow molding, and vacuum forming. , thermoforming, extrusion, coextrusion, foam forming and combinations thereof. It can be processed into molded articles by various methods.

The present invention further provides a) Starch derivative, plasticizer and alkenol homopolymer and/or alkenol copolymer A starting composition consisting of at least one selected from polymers is prepared, b) processing or During plasticization, the plasticizer content of the composition is adjusted to between about 0.5% and about 40% by weight of the total composition. and C) the composition thus prepared in a closed volume at a temperature of 100-220°C; and melting of at least the composition at this temperature and at a pressure corresponding to at least the water vapor pressure. heated long enough to form a thing, d) Moisture content of about 5% to about 20%, with all excess moisture removed before the extrusion die. and e) thereby extruding the heated composition. The present invention relates to a method for producing the composition of the present invention.

The invention further includes melts as obtained by this method.

The invention will further be apparent from the following description of the following embodiments and from the appended claims. It will become clear.

specific description The invention is defined by the claims appended hereto. In particular, the present invention is a plasticizer and a homogeneous alkenol groups that are combined under conditions sufficient to ensure the formation of a melt. At least one selected from monopolymers and/or alkenol copolymers A biodegradable composition obtained from a melt characterized by containing a starch derivative It is something that provides something.

This melt is preferably thermoplastic in nature.

Such derivatives are at least one starch selected from the group consisting of starches of plant origin. Produced by a known method, this starch is made from potatoes, rice, tapioca, corn, Obtained from beans, rye, oats and wheat.

The starch derivative can be selected from the group consisting of starch esters and starch ethers; and can have a degree of substitution of about 0.1 to about 3.0.

Preferably, the degree of substitution of said derivative is at least 0.8, and more preferably The degree of substitution is from about 0.8 to about 2.1.

This derivative contains acetate, propionate, butyrate and C6-Cat fatty acids. The starch ester may be selected from starch esters of.

This derivative has a degree of substitution of about 0.5 to about 1.8, more preferably a starch content of about 0.5 to about 1.8. 7 to about 1.8, and most preferably the degree of substitution is about 0. ．． 8 to about 1.5 starch acetate.

When the derivative is starch propionate, the degree of substitution is from about 0.5 to about 1.6, and More preferably, it is about 0.7 to about 1.4.

Derivatives include alkyl ethers, hydroxyalkyl ethers, and hydroxyalkyl ethers. and mixtures thereof.

Preferred starch ethers are methyl ether, ethyl ether, propyl ether, Butyl ether, hydroxymethyl ether, hydroxyethyl ether, hydride Roxypropyl ether, hydroxyethyl methyl ether and hydroxypropyl ether Includes pyl methyl ether and derivatives thereof.

In one embodiment of the composition, the starch derivative is about 95% by weight based on the weight of starch. with an amylose content of up to.

In other embodiments of the composition, the derivative comprises up to about 85% by weight based on the weight of starch. Has amylose content.

In yet another embodiment of the composition, the derivative is about 75% by weight based on the weight of starch. with an amylose content of up to.

In yet another embodiment of the composition, the derivative is about 65% by weight of starch. With an amylose content of up to % by weight.

In yet another embodiment of the composition, the derivative is about 45% by weight of starch. With an amylose content of up to % by weight.

In yet another embodiment of the composition, the derivative is about 30% by weight of starch. It has an amylose content of ~35% by weight.

The lower limit of amylose content is preferably about 10% to about 1001% by weight of starch. Delicious.

Starch derivatives can have an equilibrium moisture content of less than about 7% and a relative humidity of about 50% at 25°C. and more preferably an equilibrium moisture content of about 5% or less and about 50% at 25°C. with a relative humidity of

The component consisting of one of the above is present in the composition in an amount of 10 to 200 parts per 100 parts of dry starch. can be present at a concentration of

The composition contains from about 10 to about 120 parts of the polyester per 100 parts by weight of dry starch derivative. polymers and/or copolymers, and in preferred embodiments The composition contains from about 10 to about 100 parts of said polymer or copolymer per 100 parts of starch derivative. Including Rimmer.

The composition contains 10 to 65 parts and especially 20 to 40 parts per 100 parts of starch derivative. of polymer or copolymer content.

The alkenol homopolymer preferably has a number average molecular weight of at least about 15,000 (which corresponds to a degree of polymerization of at least 340) (PVA).

More preferably the PVA has a number average molecular weight of about 50.000 to 250.000. and most preferably it is about go, oo.

It has a number average molecular weight of ~120.000. If the composition is in the form of a foam, The number average molecular weight of the alcohol is preferably about 160,000 to 250,000. , and 160.000 to 200.000 are more preferred.

Polyvinyl alcohol (PVA) is generally produced by hydrolysis of polyvinyl acetate or alcohol. It is created by decomposition of a metal. To obtain polyvinyl alcohol used in the present invention The degree of hydrolysis of is preferably about 75 to about 99.9 mol%, and more preferably The content is 80 to 99.9 mol%. The degree of hydrolysis is about 87-99,9 mol% is most preferable.

Such polyvinyl alcohols are known and available from Air Product Airvol 540S from And Chemical Inc. Solubility 87-89%, molecular weight approximately 106-110.000), Airvol 205 S (degree of hydrolysis 87-89%, molecular weight approximately 110-31, QQQ), Elva nol 9O-50 (degree of hydrolysis 99.0-99.8%, molecular weight approximately 35-80. 000) and Airvol 107 (degree of hydrolysis 98.0-98.8%, molecular 11,000 to 31,000).

EP by Air Products and Chemical Inc. Ao 415357 is extrudable polyvinyl alcohol compositions and their production. It describes the construction method. The method of EP-^0415357 is polyvinyl alcohol with enough energy to melt it and essentially eliminate the crystallinity in the melt. and simultaneously at a rate sufficient to avoid decomposition of polyvinyl alcohol from the melt. It consists of removing energy.

Therefore, the present invention relates to polyvinyl alcohol pretreated according to the disclosure of EP-0415357. Cole is intended for use in the compositions of the present invention. Therefore, the composition of the present invention The thing is to pre-melt it in polyvinyl alcohol and essentially in the melt. Add enough energy to remove the crystallinity and simultaneously remove polyvinyl alcohol from the melt. melting obtained by removing energy at a rate sufficient to avoid decomposition of the Contains pretreated polyvinyl alcohol in the form of a product.

The pretreated polyvinyl alcohol is mixed with 2 to 30% by weight of polyvinyl alcohol. % of polyhydric alcohol plasticizers. pre-treated The added polyvinyl alcohol is added in an amount of 2 to 20% by weight of the polyvinyl alcohol. Preferably, plasticization is carried out by adding a polyhydric alcohol plasticizer. Pretreated polyvinyl vinyl The alcohol may further contain sodium acetate and phosphoric acid in a molar ratio of about 2:1. I can do it. Sodium acetate is a byproduct of its manufacturing process in polyvinyl alcohol and under conditions of melt formation such sodium acetate Acts as a catalyst for the decomposition of alcohol. thus neutralizing the sodium acetate To make a pretreated polyvinyl alcohol melt, the polyvinyl alcohol Phosphoric acid may be added to the roll composition in a ratio of 1 mole acid per 2 moles acetate. Book Low ash polyvinyl alcohol, which is qualitatively free of sodium acetate, is Does not require addition of acid.

The pretreated melt of polyvinyl alcohol was measured by differential scanning calorimetry and at least about 5° C. below the maximum melting temperature of the corresponding untreated polyvinyl alcohol; Preferably at least about 10°C lower than that of untreated polyvinyl alcohol. and particularly preferably at least about 15°C below that of untreated polyvinyl alcohol. Exhibits low maximum melting temperature.

The formation of such a polyvinyl alcohol pretreatment melt involves the use of polyvinyl alcohol. requires a specific energy of at least about 0.27 kWh/&9, and typically Generally, about 0.3 to about 0.6 kvh/hg of such energy is required. .

The actual upper limit of energy is about Q, 9 to 5kWh, but this is More energy than is required to melt the alcohol and remove the crystallinity should be removed as “waste energy”, and pretreated polyvinyl alcohol This is because the formation efficiency is reduced.

Optimally, polyvinyl alcohol melts it and substantially reduces the crystallinity of the melt. About 0.35 to about 0.45 kfh/kg is required to remove the

Such alkenol copolymers contain vinyl alcohol units and aliphatic chain units. and vinyl acetate, ethylene and/or propylene, preferably can be obtained by copolymerization with ethylene and subsequent hydrolysis of vinyl acetate groups. Wear. The degree of hydrolysis of such copolymers may vary.

Preferred are ethylene/vinyl alcohol polymers (EVOII) and propylene vinyl/vinyl alcohol polymer. Most preferred is ethylene/vinyl It is an alcohol polymer. The molar ratio of vinyl alcohol units to alkylene units is Preferably from about 40:60 to about 90:10, and more preferably about 45 : 55 to about 70:30. The most preferred EVOII has an ethylene content of 4 It is 4%.

The starch derivatives present in this composition consist of chemically modified starches of vegetable origin. At least one starch selected from the group, and this starch is made from potato, rice, tapioca, and chili pepper. Physically modified starch, irradiated starch obtained from sorghum, beans, rye, oats, wheat , by removing some or all of the monovalent or divalent ions related to phosphate groups therein. partially or by different divalent ions or - or multivalent ions as the case may be. Oxidation characterized by totally replaced starch, preextruded starch and a specific endothermic transition and starch heated to undergo thermal decomposition.

The starch component of the compositions of the invention is free of added water but may contain other plasticizers such as glycerol. Contains starch that melts in the presence of water. However, the preferred plasticizer is water.

Preferably, starch is present in the composition of the invention and in the starting composition based on its total weight. and then formed into a melt in the presence of water, which may be present at about 0.5% to about 4.0% by weight. be done.

Accordingly, the water content of the compositions of the present invention is approximately 1 0 to about 20% by weight, and preferably about 14 to about 18% by weight, and especially about 17% by weight. It may be % by weight.

The starch derivative may be combined with a polymer or copolymer and optionally other additives mentioned below. They can also be mixed with additives in any desired order. For example, this derivative mix with all intended additives, including polymers or copolymers to form a blend. This blend can then be heated to form a homogeneous solution that is generally thermoplastic. A melt can be formed.

However, if the starch derivative is mixed with any additives and this derivative is The copolymer, e.g. polyvinyl alcohol, can be melted and granulated before addition. and the mixture can then be further processed.

However, preferably the derivative is combined with additives and with polymers or copolymers. can be mixed with polyvinyl alcohol to form a free-flowing powder useful in continuous processes. The solid composition of the present invention may be dried, melted, and granulated or directly extruded into the solid composition of the present invention.

The composition optionally includes at least a starch derivative and a pretreated alkenol homozygote. It may consist of a combination of one selected from polymers and copolymers. this Such pre-treatment is necessary for the production of granules under conditions sufficient to obtain a homogeneous melt formation of the ingredients. May include grain or pellet preparation.

Alternatively or additionally, e.g. polyhydric alcohols e.g. glycerol The alganol homopolymers and copolymers were preplasticized using a It's okay.

The starch derivative present in the composition is present in the presence of 15-40% by weight of water and It may be pre-melted at temperatures and pressures within the ranges mentioned.

Optionally, the composition contains extenders, fillers, lubricants, mold release agents, plasticizers, stabilizers, colorants, and a flame retardant.

The composition may further contain up to 60%, preferably up to 35% by weight of the total composition. and most preferably in an amount of up to 25% by weight of one or more substantially water-insoluble species. It can contain many hydrophobic thermoplastic polymers. Such polymers are When soaked in water at a ratio of less than 25y per 10h dry polymer, and More preferably soluble in water at a ratio of less than 159 parts per 1009 parts dry polymer It is something to do.

Examples of hydrophobic thermoplastic polymers are polyolefins such as polyethylene (PE), Polyisobutylene, polypropylene, vinyl polymers such as poly(vinyl chloride) (PvC), poly(vinyl acetate), polystyrene: polyacrylonitrile (P AN), polyvinylcarbazole (PVI); substantially water-insoluble poly(A acrylic acid) ester or poly(methacrylic acid) ester; polyacetal (Po ll), polycondensates such as polyamide (P^), thermoplastic polyester, polycarbonate -bonate, polyurethane, poly(alkylene terephthalate): boaryl Ether: Thermoplastic polyimide: Poly(hydroxybutyrate) (P I'lB) and high molar mass substantially water-insoluble poly(alkylene oxide) examples For example, polymers of ethylene oxide and propylene oxide and their copolymers. Also includes mar.

Further different types of known hydrophobic thermoplastic copolymers such as ethylene/vinyl acetate Copolymer (EVA); Ethylene/vinyl alcohol copolymer (EVO) ll) ; Ethylene/acrylic acid copolymer (EAA): Ethylene/acrylic acid copolymer (EAA) Ethyl acrylate copolymer (EEA); ethylene/methyl acrylate copolymer - (EAA): to BS-copolymer: styrene/acrylonitrile-copolymer (SAN): and mixtures thereof.

Bulking agents include water-soluble and/or water-swellable polymers, such as known thermoplastic polymers. For example, gelatin, vegetable gelatin, acrylated proteins: Water-soluble polysaccharides: For example, hydroxyalkyl cellulose, hydroxyalkyl cellulose and hydroxyalkyl cellulose Killed cellulose: e.g. methylcellulose, hydroxymethylcellulose, hyde Roxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose Chylcellulose, Hydroxypropylmethylcellulose, Hydroxybutylmethythyl cellulose, cellulose esters and hydroxyalkyl cellulose esters For example, cellulose acetylphthalate droxypropyl methylcellulose ([ IPMCP), carboxyalkylcellulose, carboxyalkyl-alkyl cellulose, carboxyalkyl cellulose esters: e.g. cellulose and their alkali metal salts: all the cellulose derivatives mentioned above and Similar starch derivatives: water-soluble synthetic polymers such as poly(acrylic acid) and salts and essentially water-soluble poly(acrylic acid) esters, poly(methacrylic acid) ) and their salts and essentially water-soluble poly(methacrylic acid) esters, essentially Water-soluble poly(vinyl acetate), poly(vinyl acetate phthalate) (PVAP) , poly(vinylpyrrolidone), poly(crotonic acid): e.g. containing a group such as a diethylaminoethyl group which can be optionally quaternized. cation-converted acrylates and methacrylates; and mixtures of such polymers. Including compounds.

The term "water-soluble or water-swellable polymer" refers to a dry polymer that is immersed in water at room temperature. A polymer that absorbs or adsorbs a small amount of water (both 30% by weight) based on its weight. Taste.

Suitable fillers include, for example, raw materials obtained from wood and magnesium, aluminum. oxides of silicon and titanium. Fillers are based on the total weight of the composition. and then at a concentration of up to about 20% by weight, and preferably from about 3.0 to about 10% by weight. present in the product.

Lubricants include aluminum, calcium, magnesium and tin stearates, and free acids and magnesium silicates, silicones and lecithins, and mono- and di- Included are materials that function similarly for purposes of this invention, such as glycerides. Appropriate As a lubricant, unsaturated fatty acid amides, preferably C1, to C24 unsaturated fats are further used. Amides of acids, such as the amide of cis-13-tocosenoic acid (erucamide) and C1 1 to (,24 amides of carboxylic acids, e.g. amides of tocosanoic acid (behenamides) is included. A particularly preferred lubricant is stearic acid, which contains starch in the composition. Amounts up to 10 parts per 100 parts of derivative, preferably 1 part per 100 parts of derivative present in an amount of ~3 parts and most preferably per 100 parts of derivative in the composition. It is present in an amount of 1 part.

The compositions of the present invention may include nucleating agents with particle sizes of 0.01 to 5 microns (particularly ), this includes silica, titania, alumina, oxidized Liumium, magnesium oxide, sodium chloride, potassium bromide, barium phosphate , barium sulfate, aluminum sulfate, boron nitrate and magnesium silicate, or The nucleating agent selected from the group consisting of mixtures thereof is inter alia silica, titanium A, alumina, barium oxide, magnesium oxide, sodium chloride, and silicic acid Preferably it is chosen from magnesium or mixtures thereof.

A particularly preferred nucleating agent is magnesium silicate (microtalcum), which It is present in the composition in an amount of up to 10 parts per 100 parts of derivative. Preferably this nucleus The agent is present in the composition in an amount of 1 to 3 parts per 100 parts of derivative, and most preferably is present in an amount of 2 parts per 100 parts of derivative.

Plasticizers include urea and low molecular weight poly(alkylene oxides) such as poly(ethylene oxide). ethylene glycol), poly(propylene glycol), poly(ethylene-propylene) glycol), low molar mass organic plasticizers, e.g. glycerol: pentaeryth Litol: Glycerol monoacetate, diacetate or triacetate: Ropylene glycol: Sorbitol: Sodium diethyl sulfosuccinate: Triethyl citrate and tributyl citrate and other substances that function similarly included.

Such plasticizers are preferably present in the composition by weight of all ingredients (including water therein). from about 0.5 to about 40% by weight, and more preferably from about 0.5 to about Present at a concentration of 5% by weight.

Preferably the total plasticizer (including water present as plasticizer) content of the composition is not more than about 25% by weight, based on the total weight of the article, and most preferably about 20% by weight, based on the total weight of the article. Not exceeding % by weight.

Antioxidants such as thiobisphenol and alkylidene bisphenol are used as stabilizers. secondary aromatic amines; stabilizers against photodegradation, such as UV absorbers and quenchers (quencher>; :A hydrogen oxide decomposer: free radical remover and antibacterial agent included.

Colorants include known azo dyes, organic or inorganic pigments, or colorants of natural origin.

Inorganic pigments are preferred, for example oxides of iron or titanium, these oxides being from about 0.01 to about 10% by weight, based on the total weight of the composition, and preferably about 0.0% It is present in the composition at a concentration of 5 to about 3% by weight.

More preferably, the colorant comprises about 0.03% to about 0.07% by weight of the total composition. present in the composition in an amount. 0.05% by weight of iron oxide based on the total composition.

The composition further includes flame retardants, such as phosphorus, sulfur and halogens or including mixtures thereof.

Suitable phosphorus-containing flame retardants include diethyl-N,N-bis(2-hydroxyethyl ) Aminomethylphosphonate: Dimethylmethylphosphonate: Methyl phosphonic acid Polymer of fluorine, dimethyl ester, oxirane and phosphorus oxide: aliphatic phosphene Salt: Phosphonate oligomer m: Tributyl phosphate: Triphenylphosph ate: tricresyl phosphate; 2-ethylhexyl diphenyl phosphate and tributoxyethyl phosphate. These flame retardants are Akz o Chea+1cals Inc.

Yet another suitable phosphorus-containing flame retardant is FMC Corporation's Chemical Co., Ltd. Bis(hydroxypropyl) sec, which can be obtained from the product group Tylphosphine oxyto: and ^lbright and lilson, The following compounds are available from Americas Inc.; Xylated dibutyl pyrophosphate: Methyl-1(5-ethyl-2-methyl) phosphonic acid -1,3,2-dioxaphosphorinan-5-yl)methylethyl ester, P -Methyl-, bis[(5-ethyl-2-methyl-1, 3,2-dioxaphosphorinan-5-yl)methyl]ester, Amgard A mixture of P, P'-dioxide sold under the trade name V19: polyphosphoric acid Ammonium: ethylene diamine polyphosphate, melamine diphosphate; dimelamine phosphate : and microencapsulated red phosphorus.

Ammonium polyphosphate and ethylenediamine polyphosphate are used as flame retardants. If they are used, they are less corrosive to the equipment used to process compositions containing them. Preferably, they are buffered with disodium orthophosphate so that

Yet another suitable phosphorus-containing flame retardant is guanidinium phosphate, which is Che +sie Rinz GsbH.

Suitable halogen-containing flame retardants include 0cidental Chemical Cor Chlorinated paraffin available from poration; Great It can be obtained from Lakes Chemical Corporation. tetrabromophthalic anhydride and venter, octa- and decabromodife Nyl oxide: and can be obtained from ^1bright and Wilson. Brominated chlorinated paraffin, brominated epoxy resin, brominated polystyrene, and Lis(2-chloropropyl)phosphate and tetrakishydroxymethylphosphate There is Honium Chloride.

Yet another suitable halogen-containing compound is from ^meriBro Inc. Dibromoneopentyl glycol and tribromoneopene available Chil alcohols are included.

Suitable sulfur-containing flame retardants include ammonium sulfate: ammonium sulfamate; and tetrakis(hydroxymethyl) phosphonium sulfate. These are all handmade by ^merican Cyanamid Company. can be done. Gua sulfate available from Chesie Lintz Nidinium can also be used as a flame retardant.

The flame retardants mentioned above are present in the starch-containing composition in an amount of 0.1 to 10%, preferably 1 to 6%, and is most preferably present in an amount of 2-4%, all percentages refer to the derivative of the composition. By weight relative to the weight of the ingredients.

Other suitable flame retardants that may be present in the compositions of the invention include aluminum Hydrate: aluminum acetylacetonate, aluminum acetate; sodium Magnesium Aluminum Hydroxycarbonate: Magnesium Aluminum Hydroxycarbonate Sicarbonate, antimony oxide: molybdenum oxide: ammonium octamolybdate Zinc: Zinc molybdate; Magnesium hydroxide; Zinc borate - Ammonium pentaborate Contains sodium diborate and sodium tetraborate. These flame retardants are generally are available, and in particular borax compounds are available from United 5tates Bo It can be obtained from rax and Chemical Corporation. can.

These latter flame retardants are present in amounts of 1 to 90% by weight relative to the starch derivative component of the composition. may be present in the composition, and preferably 20-80% and at most Preferably it is present in the composition in an amount of 40-75% by weight.

Particularly preferred flame retardants are guanidinium phosphate, ammonium polyphosphate and/or is ethylenediamine polyphosphate (with or without disodium orthophosphate) ) and guanidinium sulfate or ammonium sulfate.

Further substances that can be added to the composition include animal or vegetable fats. , preferably in their hydrogenated form, especially those that are solid at room temperature. such fat The fat preferably has a melting point of at least 50°C, preferably C++-1C+4-1C +S- and C+S- fatty acid triglycerides.

This fat can be added to a material consisting solely of a thermoplastic melt without fillers or plasticizers, or or diglycerides or phospholipids, said phospholipids are Chin is preferred. Said mono- and diglycerides are preferably said animal or vegetable fats. derived from.

The total concentration of said fats, mono- and diglycerides and phospholipids is based on the total weight of the composition. The content can be up to 5% by weight.

Further compounds that may be added or present in the composition include boron-containing There are compounds that are necessary, especially when the composition is to be formed into films, sheets or fibers. be.

The presence of such compounds in the composition improves transparency, Young's modulus and tear An article with improved toughness is obtained. Preferred boron-containing compounds are boric acid, meth Boric acid, alkali and alkaline earth metal salts, borax and their derivatives.

Said compound is present in the composition in an amount of 0.002 to 0.4% by weight relative to the weight of the composition. may be present, and preferably also in a concentration of about 0.01-0.3% by weight can exist in

Inorganic salts of alkali or alkaline earth metals, in particular LiCl and NaC/, may additionally be may be present in the composition in an amount of 0.1 to 5% by weight relative to the weight of the total composition. Ru. The presence of such salts in a composition increases the Young's modulus of articles made from the composition. , further improving transparency and tear strength.

The concentration of ingredients in the composition, particularly the concentration of colorants and borax-containing compounds, can be adjusted as desired. It can be obtained by the tarpatching method.

The composition described above forms a thermoplastic melt when heated under conditions of controlled temperature and pressure. Form. Such melts can be processed by any conventional forming method. When used in shaping the compositions or melts of the present invention, the present invention covers such Also related to method. Such melts can therefore be used in conventional thermoplastic materials. Methods such as injection molding, blow molding, extrusion, coextrusion, compression molding, vacuum forming and can be processed by thermoforming to produce shaped articles. Such articles include Containers, cartons, trays, cups (especially for candles if the composition contains flame retardants) ), dishes, sheets, and seed fill variety (loose fill) There are various packaging materials including Includes pellets and granules that can be made into powders for use in the manufacture of products. Ru. Particularly preferred articles are in foam, injection molded or extruded form. .

Suitable pressures and temperatures for injection molding, film forming, foam forming and extrusion The range of is shown below.

injection molding of compositions To melt starch according to the present invention, the temperature must be sufficient to allow homogeneous melt formation. Heat for sufficient time at ℃.

The composition is formed in a closed volume, such as a closed container, or by the confining action of unmolten feedstock. Preferably, the heating is carried out in a limited volume in which the It is clearly seen in the screw and barrel of the shaped device.

Said screw and barrel are therefore to be understood as closed volumes. such a capacity The pressure built up during loading is compatible with the vapor pressure of the plasticizer (usually water) at the temperature used. I guess. As is known to be used in the screw and barrel It will be appreciated that pressures may be used or generated.

The preferred pressures used and/or generated are those that occur during injection molding or extrusion. is essentially within the known pressure range, approximately 150X 10SN/m ”, preferably up to about 75X10'N/genus 2 and most preferably 50X It is up to 105N/true 2.

The temperature used for injection molding the composition preferably ranges from 100°C to 220°C, more Preferably in the range of 160-200°C, and most preferably in the range of 160-180°C ℃, and the appropriate temperature depends on the type and nature of the derivative used.

It is preferable to use potato or cornstarch derivatives because they are easy to process. Delicious.

The molten composition thus obtained is granulated and subjected to selected mixing and processing procedures. The molten lees is mixed with other ingredients and fed to the screw barrel by Preparations are now made to obtain a granular mixture of powder starting materials.

Film formation of the composition The composition is preferably heated to temperatures below those normally used during injection molding and extrusion of the composition. as described above, except that the heating is typically about 10 to about 20 degrees Celsius higher. plasticize.

Foaming of the composition A method of forming a foam from the composition of the present invention includes a) a starch derivative, a plasticizer and A small amount selected from alkenol homopolymers and/or alkenol copolymers b) processing or processing the plasticizer content of the composition; C) is adjusted to between about 15 and about 40% by weight of the composition during plasticization; The composition was prepared at a temperature of 100-220°C and a homogeneous melt of the composition was prepared. heat for sufficient time to form; d) Excess water is removed before the extruder die to a moisture content of about 10% to about 20%. ,and e) The extrudate thereby passes the heated composition through the cross section of the exit orifice of the die of the extruder. Extrude under conditions that result in a larger cross section Consists of things.

The plasticizer is water, and the water content of the composition before extrusion is reduced to 14-2% of the total composition. 0% by weight, more preferably 16-18% by weight and most preferably 17% by weight and maintain the composition at a temperature of about 60°C to about 200°C and preferably about at a temperature of from 80°C to about 200°C and at least equivalent to the water vapor pressure at said temperature. Preferably, the heating is carried out at a pressure of at least 30 seconds.

After its extrusion, this composition can be shaped using known thermoforming methods. Ru.

The present invention will be further clarified by the following examples. Describes the formation of cantorca whelk from extrusion blends of kohl and starch derivatives. Ru.

Hydroxypropylated corn starch or hydroxypropylated high amylose Starch (National 5tarch and Chemical Corpo power (tlyLon ■ and hydro xypropylation + 1ylon ■), Boeson VP (Boehring er Ingelheis), and lecithin (Lucas Meyer) (sold as Metarin P) in a ratio of 100:2+1, respectively. Prepare a mixture.

13.6JZ9 of this mixture in a horizontal cylindrical barrel with simultaneously rotating screws and A twin screw screw with an outlet guide attached to the discharge end of the extruder and its inlet on the opposite side. to the inlet of a micro extruder (Leistritz LSll type 34).

This mixture contains 4409 glycerol, a number average of about 15.000 to 45.000. Preplasticized polyvinyl alcohol with molecular weight and hydrolytic freshness of 88-99% Add 5.2 kq of water and enough water to properly mix the blended mixture.

The amount of water added is largely controlled by the nature of the derivative and is readily determined by those skilled in the art. determined.

The composition is then heated to a temperature of about 175°C, as necessary to avoid water vapor formation at this temperature. Heat under appropriate pressure for 30-120 seconds.

It is added to the starch composition by dissolving ammonium sulfate in water and heating and pressurizing it. Added before extrusion from the exit die of the extruder.

Ammonium sulfate depends on its final concentration in the cooled extrudate due to the weight of its starch derivative component. It is added in an amount of 3.5% by weight based on the amount.

The molten composition is extruded through the exit die of the extruder and the extrudate is cooled. Cool and pelletize.

Pellets of the preblended mixture obtained above (■20 content is preferably about 1 1%) through a hopper and then fitted with a mold suitable for manufacturing candle cups. Feed to a molding machine (Arburg 320).

Candle cups made in this way have excellent physical properties and substantial dimensional stability. and is sufficiently flame retardant to meet DIN 75200 flame retardant standards. It is extracted from the composition.

Example 2 Example 1 was repeated except that the composition of the candle cup was changed. vinegar. The modified compositions each contain hydrocarbons present in a ratio of 100:2+1. Xypropylated nylon ■ (National 5tarch and C (available from Chemical Corporation), Bo eson VP (sold by Boehringer Ingelheim) and From Shichin (sold as 11etarin P by Lucas Meyer) Ru.

10 hq of this mixture was transferred to a horizontal cylindrical barrel using a screw and an extruder that rotated simultaneously. Two-wheel screw extrusion with an exit die installed at the discharge end and its inlet on the opposite side (Leistritz LSM type 34).

Add to this mixture 440 g of glycerol, a number average of about 11.000 to 31.000. polyvinyl alcohol 3 & 9 with a molecular weight and degree of hydrolysis of 98-98.8%, and enough water to properly mix the combined mixture.

The starch composition is then heated at a temperature where the composition melts as necessary to avoid the formation of water vapor. melt at the required pressure (approximately 1200 bar).

Ammonium sulfate is dissolved in water and it is pressed into the heated and pressurized composition. It is added before being extruded from the outlet die of the extruder.

Ammonium sulfate depends on its final concentration in the cooled extrudate due to the weight of its starch derivative component. It is added in an amount of 3.5% by weight based on the amount.

The molten composition is extruded through the exit die of the extruder and the extrudate is cooled. Cool and pelletize.

Pellet of the preblended mixture obtained above 1. (H20 content is preferably about 11%) is passed through a hopper and then installed with a mold suitable for manufacturing candle cups. Supply to the extrusion molding machine (^rburg 320).

Candle cups made in this way have excellent physical properties and substantial dimensional stability. fully flame retardant to meet DIN 75200 flame retardant standards. The flame retardant used in the composition is polyethylene diamine phosphate, which is Example except that it is present in an amount of 4% by weight relative to the weight of the starch derivative component. Repeat step 1.

In Examples 1-3, the flame retardant was added at a later stage after blending the composition before its injection molding. and minimize retention of the composition (here consisting of a flame retardant) in the extruder. Keep it within limits.

Furthermore, the parts of the extruder that come into contact with the flame retardant-added starch composition are It can be used to reduce corrosion caused by corrosion.

Example 4 Cornstarch acetate with a degree of substitution of about 0.8 to 9, about 106,000 to 11 2 kg of polyvinyl alcohol with a number average molecular weight of 0,000 and a degree of hydrolysis of 87-89%. Nyl alcohol (^1rvoll 540S), 200g magnesium silicate and 100 g of stearic acid. The water content of the combined ingredients is then moistened with starch. The amount is adjusted to 25-30% by weight based on the mixture.

The starch adjusted in this way is simultaneously rotated in a horizontal cylindrical barrel and extruded. Twin screw with outlet die installed at the discharge end of the machine, its inlet on the opposite side Feed to the inlet of an extruder (Leistritz LSli type 34).

The starch composition is then heated to a temperature of 170°C, as necessary to avoid the evolution of water vapor at this temperature. Heat under appropriate pressure for about 70 seconds.

The starch thus molten is extruded through the exit die of the extruder, and the extrudate is cooled. and pelletize it.

The pelletized molten starch mixture was adjusted to a moisture content of approximately 17% and then - at the inlet of a single screw extruder with a length to diameter ratio in the range 25. supply

Extruders with a ratio of 10 to 30 can also be used in the process of the invention.

The mixture thus formed was heated at 190 °C for 20-60 seconds and then extruded. vinegar. Upon exiting the exit orifice of the extruder die, the extrudate is A foam material having a large cross section is formed which is suitable for use as a packaging material.

In this way, open and discontinuous cell foams are produced, which vary in density and range. It has excellent properties in terms of resilience and compression ratio.

The present invention is not intended to be limited only to the embodiments described above (although there may be many variations regarding these). Numerous changes and improvements may occur to those skilled in the art without departing from the scope of the appended claims. It will be recognized that this is possible.

international search report international search report Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), AU, BR, CA, C3, FI, HU, JP, KR, No, PL, RU (72) Inventor Zdrahara, Richard, New Chassis, USA 07045, Saintville. Cobblestone Terrace 35 (72) Inventor: Dreiprat, Adam, New Chassis, USA 78 Musiver Avenue, Randolph, 07869 (72) Inventor Radmar, Beter Day-7850 Lorach -7, Loraherstrasse 69

Claims (109)

[Claims] 1. Combined with plasticizer under conditions sufficient to ensure the formation of a homogeneous melt. selected from alkenol homopolymers and/or alkenol copolymers obtained from a melt characterized by comprising at least one starch derivative and containing a starch derivative. composition. 2. A claim in which the starch derivative is selected from the group consisting of starch esters and starch ethers. 1. The composition according to item 1. 3. 3. The composition of claim 2, wherein the degree of substitution of the starch derivative is from about 0.1 to about 3.0. 4. 4. A composition according to claim 3, wherein the degree of substitution of the derivative is at least 0.8. 5. 5. The composition of claim 4, wherein the degree of substitution is from about 0.8 to about 2.1. 6. Derivatives include acetate, propionate, butyrate and C5-C12 fatty acids The composition according to claim 3, which is a starch ester selected from the group consisting of starch esters of thing. 7. 7. The derivative of claim 6, wherein the derivative is starch acetate having a degree of substitution of about 0.5 to about 1.8. Composition. 8. Claims 1 to 7, wherein the derivative is starch acetate with a degree of substitution of about 0.7 to about 1.8. Any of the compositions described. 9. Claims 1 to 8, wherein the derivative is starch acetate with a degree of substitution of about 0.8 to about 1.5. Any of the compositions described. 10. Claim that the derivative is starch propionate with a degree of substitution of about 0.5 to about 1.6. The composition according to item 6. 11. Claim that the derivative is starch propionate with a degree of substitution of about 0.7 to about 1.4. Item 11. The composition according to any one of Items 1 to 10. 12. Derivatives include alkyl ethers, hydroxyalkyl ethers, hydroxy Claim 3 selected from the group consisting of alkyl alkyl ethers and mixtures thereof. Compositions as described. 13. Ether derivatives include methyl ether, ethyl ether, propyl ether, Butyl ether, hydroxymethyl ether, hydroxyethyl ether, hydride Roxypropyl ether, hydroxyethyl methyl ether and hydroxypropyl ether Claims 1 to 12 selected from the group consisting of pyl methyl ether and derivatives thereof. A composition according to any one of the above. 14. The derivative has an amylose content of up to about 95% by weight relative to the weight of starch. The composition according to claim 1. 15. The derivative has an amylose content of up to about 85% by weight relative to the weight of starch. 15. The composition according to any one of claims 1 to 14. 16. The derivative has an amylose content of up to about 75% by weight relative to the starch weight. The composition according to any one of claims 1 to 15. 17. The inducer may have an amylose content of up to about 65% by weight relative to the weight of starch. 17. The composition according to any one of claims 1 to 16. 18. The derivative has an amylose content of up to about 45% by weight relative to the weight of starch. 18. The composition according to any one of claims 1 to 17. 19. The derivative has an amylose content of about 30 to about 35% by weight based on the weight of starch. A composition according to any one of claims 1 to 18. 20. The derivative has an amylose content of about 10 to about 15% by weight based on the weight of starch. 15. The composition according to claim 14. 21. The starch derivative has an equilibrium moisture content of less than about 7% at 25°C and a relative humidity of about 50%. The composition according to claim 1. 22. The starch derivative has an equilibrium moisture content of less than about 5% at 25°C and a relative humidity of about 50%. The composition according to any one of claims 1 to 21. 23. The starch derivative has an equilibrium moisture content of less than about 2% at 25°C and a relative humidity of about 50%. The composition according to claim 1. 24. The component consisting of one of the above is present in the composition in an amount of 10 to 2 per 100 parts of dry starch. A composition according to claim 1, wherein the composition is present in a concentration of 0.00 parts. 25. 1 to 1 component per 100 parts of dry starch in the composition. A composition according to claim 1, wherein the composition is present in a concentration of 20 parts. 26. The composition comprises from about 10 to about 100 parts of said polymer per 100 parts of starch. A composition according to claim 1. 27. The composition may contain from about 10 to about 85 parts of said polymer per 100 parts of starch. The composition according to claim 1. 28. The composition may contain from about 20 to about 40 parts of said polymer per 100 parts of starch. The composition according to claim 1. 29. Claim 1, wherein the alkenol homopolymer is polyvinyl alcohol. Composition. 30. Claim 29, wherein the polyvinyl alcohol is substantially completely hydrolyzed. composition. 31. Polyvinyl alcohol is hydrolyzed to a degree of about 75 to about 100% A composition according to claim 29. 32. Ensure that polyvinyl alcohol is hydrolyzed to a degree of about 85 to about 99%. The composition according to claim 29. 33. Polyvinyl alcohol is hydrolyzed to a degree of about 87 to about 99.9%. The composition according to claim 29. 34. Polyvinyl alcohol has a number average molecular weight of 15,000 to 250,000. 30. The composition of claim 29. 35. Polyvinyl alcohol has a number average molecular weight of 15,000 to 150,000. 35. The composition of claim 34. 36. Polyvinyl alcohol has a number average molecular weight of 160,000 to 250,000 36. The composition of claim 35. 37. The polyvinyl alcohol has a degree of hydrolysis of at least about 97% and about The composition of claim 1 having a number average molecular weight of 15,000 to about 150,000. 38. The polyvinyl alcohol has a degree of hydrolysis of at least about 97% and about 37. The composition of claim 36 having a number average molecular weight of 50,000 to about 150,000. . 39. The polyvinyl alcohol has a degree of hydrolysis of at least about 97% and about 37. The composition of claim 36 having a number average molecular weight of 70,000 to about 150,000. . 40. The polyvinyl alcohol has a degree of hydrolysis of at least about 97% and about 37. The composition of claim 36 having a number average molecular weight of 100,000 to about 150,000. thing. 41. Alkenol homopolymer or copolymer is mixed with polyvinyl alcohol. and add sufficient energy to melt and substantially eliminate crystallinity in the melt. , while at the same time sufficiently fast to avoid its decomposition from the polyvinyl alcohol melt. From a melt of polyvinyl alcohol formed by removing energy at A composition according to claim 1 which is the pretreated polyvinyl alcohol obtained. 42. The polyvinyl alcohol further contains sodium acetate and phosphoric acid in a ratio of about 2:1. 42. The composition of claim 41, comprising: 43. The pretreated polyvinyl alcohol is compatible as measured by differential scanning calorimetry. has a maximum melting temperature of at least about 5°C lower than the corresponding untreated polyvinyl alcohol. 43. The composition according to claim 42. 44. Furthermore, copolymerization of vinyl acetate with ethylene and/or propylene and subsequent vinyl alcohol units and fatty acids such as those obtained by hydrolysis of the pre-acid vinyl groups of 2. The composition of claim 1, comprising an alkenol copolymer containing group chain units. 45. Any of claims 1 to 44, wherein the copolymer comprises ethylene/vinyl alcohol. A composition according to. 46. The molar ratio of vinyl alcohol units to alkylene units is approximately 40; 60. 45. The composition of claim 44, wherein the composition has a molecular weight of up to about 90;10. 47. 47. The molar ratio of claims 1-46, wherein said molar ratio is from about 45;55 to about 70;30. Any of the compositions described. 48. 48. The ethylene vinyl alcohol has an ethylene content of 44%. Composition of. 49. The composition may further contain extenders, fillers, lubricants, mold release agents, plasticizers, stabilizers, and colorants. , flame retardants, alkali or alkaline earth metal salts and boron-containing compounds. The composition according to claim 1, comprising at least one selected from the following. 50. The composition may further contain polyolefins, polyisobutylene, polypropylene, vinyl Polymer, polystyrene; polyacrylonitrile (PAN); polyvinyl carbon Rubazol (PVK); a substantially water-insoluble poly(acrylic acid) ester or poly(methacrylic acid) ester; polyacetal (POM); polycondensate, thermoplastic Polyester, polycarbonate, polyurethane, poly(alkylene terephthalate) Polyaryl ether; Thermoplastic polyimide; Poly(hydroxybutylene) (PHB) and high molar mass substantially water-insoluble poly(alkylene oxide) ); ethylene/vinyl acetate copolymer (EVA); ethylene/vinyl alcohol -copolymer (EVOH); ethylene/acrylic acid-copolymer (EAA); Ethylene/ethyl acrylate copolymer (EEA); ethylene/methyl acrylate - copolymer (EMA); ABS-copolymer; styrene/acrylonitrile - copolymer (SAN); and a mixture thereof; or Containing more hydrophobic thermoplastic polymers in amounts up to 60% by weight of the total composition The composition according to claim 1. 51. The filler is present in the composition at a concentration of up to about 20% by weight based on the weight of the composition. 50. The composition of claim 49, wherein the composition is present in 52. A plasticizer is present in the composition from about 0.5% to about 15% by weight, based on the weight of the composition. 50. The composition of claim 49, wherein the composition is present in a concentration of % by weight. 53. A plasticizer is present in the composition in an amount of about 0.5% to about 5% by weight based on the weight of the composition. 53. The composition of claim 52, wherein the composition is present in a concentration of %. 54. The total plasticizer and water content of the composition is about 25 parts by weight based on the weight of the composition. 50. A composition according to claim 49, in which the amount does not exceed %. 55. The total plasticizer and water content of the composition is about 20 parts by weight based on the weight of the composition. 55. A composition according to any one of claims 1 to 54, in which the amount does not exceed %. 56. A coloring agent is present in the composition in an amount of from about 0.01 to about 10 by weight based on the weight of the composition. 50. The composition of claim 49, wherein the composition is present in a concentration of %. 57. The lubricant is from the group consisting of mono- or diglycerides, lecithin and stearic acid. 50. The composition of claim 49, which is selected. 58. 58. The composition of claim 57, wherein the lubricant is stearic acid. 59. Claims that the lubricant is present in the composition at a concentration of up to 10 parts per 100 parts of starch Item 59. The composition according to any one of Items 1 to 58. 60. Claims in which the lubricant is present in the composition at a concentration of 1 to 3 parts per 100 parts of starch. 60. The composition according to any one of 1 to 59. 61. 59. The lubricant is present in the composition at a concentration of 1 part per 100 parts of starch. Compositions as described. 62. The composition has a particle size of about 0.01 to about 5 microns and includes silica, titania, , alumina, barium oxide, magnesium oxide, sodium chloride, potassium bromide , magnesium phosphate, barium sulfate, aluminum sulfate, boron nitrate, and Claims containing a nucleating agent selected from the group consisting of magnesium olate, or mixtures thereof Item 1. The composition according to item 1. 63. Claims 1 to 62, wherein the nucleating agent is magnesium silicate (microtalcum). Any of the compositions described. 64. 63. The set of claim 62, wherein the composition comprises up to 10 parts of the agent per 100 parts of starch. A product. 65. 65. The composition of claim 64, wherein the composition comprises 1 to 3 parts of said agent per 100 parts of starch. Composition. 66. 66. The composition of claim 65, wherein the composition comprises 2 parts of said agent per 100 parts of starch. thing. 67. The flame retardant is guanidinium phosphate; diethyl-N,N-bis(2-hydroxy ethyl) aminoethylphosphonate; dimethylmethylphosphonate; phosphonate Methyl and dimethyl esters of acids, polymers of oxiranes and phosphorus oxide; aliphatic Phosphate/phosphonate oligomer; tributyl phosphate; triphenylate Tricresyl phosphate; 2-ethylhexyl diphenyl phosphate sphate; and tributoxyethyl phosphate; bis(hydroxypropyl )sec. Butylphosphine oxide; polyproboxylated dibutylpyrophosphate ; Methyl of phosphonic acid, (5-ethyl-2-methyl-1,3,2-dioxapho of sulfolinan-5-yl) methyl ethyl ester, P-oxide and phosphonic acid. Methyl-, bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorina (5-yl) methyl] ester, sold under the trade name Amgard V19. mixture of P,P'-dioxide; ammonium polyphosphate; ethyl polyphosphate Dimelamine; Melamine Phosphate; Dimelamine Phosphate; and Microencapsulated Red 50. The composition of claim 49, wherein the composition is selected from the group consisting of phosphorus. 68. If the flame retardant is ammonium polyphosphate or ethylenediamine polyphosphate or 68. The composition according to claim 67, which is a mixture thereof. 69. Ammonium polyphosphate or ethylenediamine polyphosphate is orthophosphoric acid 68. The composition of claim 67, wherein the composition is disodium buffered. 70. Flame retardants include guanidinium sulfate; ammonium sulfate; ammonium sulfamate and tetrakis(hydroxymethyl)phosphonium sulfate; 50. The composition according to claim 49, which is selected from the group consisting of: 71. The flame retardant is present in the composition in an amount of about 0.1 to about 10 weight based on the weight of the starch component of the composition. 50. The composition of claim 49, wherein the composition is present in an amount of %. 72. The flame retardant is present in the composition in an amount of about 1 to about 6% by weight based on the weight of the starch component of the composition. 71. The composition of claim 70, wherein the composition is present in an amount. 73. The flame retardant is present in the composition in an amount of about 2 to about 4% by weight based on the weight of the starch component of the composition. 73. The composition of claim 72, wherein the composition is present in an amount of 74. Boron-containing compounds include boric acid, metaboric acid, alkali and alkaline earth metals The composition according to claim 49, selected from the group consisting of salt, borax and derivatives thereof. . 75. The compound is present in the composition in an amount of 0.002 to 0.4% by weight based on the weight of the composition. 75. The composition of claim 74, wherein the composition is present in an amount of . 76. The compound is present in the composition in an amount of 0.001 to 0.3% by weight based on the weight of the composition. 76. The composition of claim 75, wherein the composition is present in an amount of 77. The amount of alkali or inorganic salt of alkaline metal is 0.1 to 0.1 to the weight of the composition. 5% by weight and selected from the group consisting of LiCl and NaCl. The composition according to claim 49. 78. The starch is at least selected from the group consisting of chemically modified starches of plant origin. is also one type of starch, and this starch can be found in potatoes, rice, tapioca, corn, beans, rye, Obtained from oat, wheat, physically modified starch, irradiated starch, related to phosphate groups in it. removing some or all of the associated monovalent or divalent ions, and optionally different divalent ions. Starch partially or completely replaced by ions or monovalent or polyvalent ions, reserves Extruded starch undergoes a specific endothermic transition characterized by a preference for oxidation and thermal decomposition 2. A composition according to claim 1, comprising starch heated so as to cause the starch to melt. 79. Selected from the group consisting of melts, foams, films, granules, pellets and powders. 79. A composition according to any one of claims 1 to 78, wherein the composition is in one form. 80. 80. The composition of claim 79 in the form of a foam. 81. 8. The bulk density of the composition is in the range of about 8.5 to about 30 kg/m3. The composition according to 0. 82. 81. The composition of claim 80, wherein the resilience of the composition is in the range of about 46-63%. A product. 83. 81. The composition of claim 80, wherein the degree of compaction of the composition is in the range of about 6-15%. 84. 80. The composition of claim 79 in the form of a melt. 85. Bottles, films, tubes, bars, laminated films, sacks, bags, granules, powders, Pellets, foam, containers, cartons, trays, cups, dishes, sheets, packaging materials , and claims for use in the manufacture of molded articles containing foam packaging materials containing loose fill. 79. The composition according to 79. 86. Foam forming, film forming, compression molding, injection molding, blow molding, vacuum forming selected from the group consisting of shaping, thermoforming, extrusion, coextrusion, and combinations thereof. 2. The composition according to claim 1, which is molded by a method according to claim 1. 87. The composition according to claim 1, formed by a film forming method. 88. 2. A composition according to claim 1, formed by a foam forming method. 89. A composition according to claim 1 which is injection molded. 90. A composition according to claim 1 which is extruded or coextruded. 91. From compression molding, blow molding, vacuum forming, thermoforming, and combinations thereof. The composition according to claim 1, which is molded by a method selected from the group consisting of: 92. a) Starch derivatives, plasticizers and alkenol homopolymers and/or alkenes preparing a starting composition consisting of at least one selected from alcohol copolymers, b ) Adjust the plasticizer content of the composition during processing or plasticization from about 0.5 to about 40 parts by weight of the total composition. c) the composition thus adjusted at a temperature of 100 to 220°C; at least a homogeneous composition at a pressure corresponding to at least the water vapor pressure at this temperature. heating for a sufficient time to form a melt; d) removing excess moisture before the extruder die to a moisture content of about 5% to about 20%; and e) extruding the heated composition. A method for producing the composition described above. 93. 93. A method according to any preceding claim, wherein the plasticizer is water. 94. Adjusting the plasticizer content in step b) to about 15 to about 40% by weight of the total composition. , in which case the moisture content obtained in step d) is from about 10% to about 20%, and The heated composition is optionally heated so that the extrudate is larger than the cross section of the exit orifice of the extruder die. 94. The method according to any one of claims 1 to 93, wherein the extrusion is carried out under conditions that result in a cross section. 95. 93. The method according to claim 92, wherein the one component comprises polyvinyl alcohol. Law. 96. The alkenol homopolymer and/or alkenol copolymer is heating the alcohol and applying enough energy to remove the crystallinity in the melt. while at the same time enough to avoid its decomposition from the polyvinyl alcohol melt. A pretreated product obtained from a melt formed by removing energy at a 96. A method according to any one of claims 1 to 95, wherein the alcohol is polyvinyl alcohol. 97. Claim: The composition further comprises sodium acetate and phosphoric acid in a ratio of about 1:2. 1-96. The method according to any one of 1 to 96. 98. Pretreated polyvinyl alcohol was measured by differential scanning calorimetry and has a maximum melting temperature of at least about 5°C lower than untreated polyvinyl alcohol. 97. The method of claim 96. 99. A specific energy of at least about 0,27 kwh/kg is applied to the polyvinyl vinyl during pretreatment. melt it in alcohol and substantially remove crystallinity from the melt. 97. The method of claim 96. 100. Claims 1 to 9 wherein the amount of specific energy is about 0.3 to 0.6 kwh/kg. 9. The method according to any one of 9. 101. Before extrusion, the moisture content of the composition is adjusted to 10-20% by weight of the total composition. , and the composition at a temperature of 100-200°C and at least at this temperature. 94. The method according to claim 93, wherein heating is carried out for 0.5 to 2 minutes at a pressure corresponding to water vapor pressure. 102. Before extrusion, the moisture content of the composition is adjusted to 15-18% by weight of the total composition. , and the composition at a temperature of 150-200°C and at least at this temperature. 94. The method according to claim 93, wherein heating is performed for 0.5 to 1 minute at a pressure corresponding to water vapor pressure. 103. Prior to extrusion, the moisture content of the composition was adjusted to 17% by weight of the total composition and the composition at a temperature of 180-200°C and at least water vapor at this temperature. 95. The method according to claim 94, wherein heating is performed for 0.5 to 1 minute at a pressure corresponding to pressure. 104. The composition is heated to a temperature above the melting and glass transition temperature of the starch raw material. The method according to claim 102. 105. The starting composition may optionally be prepared beforehand under conditions sufficient to form a melt. selected from at least starch and alkenol homopolymers and copolymers combined with 94. The method according to claim 93, comprising one type of. 106. Claims that the starting composition is melted in the presence of 15-40% water by weight of the composition 106. The method according to any one of Items 1 to 105. 107. Claims 1 to 106, wherein the starting composition is melted at a temperature of 100 to 200°C. Any method described. 108. Foam forming, film forming, compression molding, injection molding, blow molding, vacuum selected from the group consisting of molding, thermoforming, extrusion, coextrusion, and combinations thereof. A method of molding the composition according to claim 1. 109. Foam forming, film forming, compression molding, injection molding, blow molding, vacuum selected from the group consisting of molding, thermoforming, extrusion, coextrusion, and combinations thereof. 85. A method of forming a composition according to claim 84.