JP2527523C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   The present invention provides satisfactory physical and physical properties by the usual methods of treating thermoplastics.
Starch suitable for producing a substantially biodegradable article having mechanical and mechanical properties
And a polymer composition comprising a synthetic thermoplastic polymer.   Thermoplastic compositions of the type described above are known and available on the market, for example in Europe
Patent Publication Nos. 0032802 and 0327505, International Publication 90/1067
No. 1, European Patent Publication Nos. 400532, 0404723, and 4047
27, EP 0404728, WO 91/02024, and
And No. 91/02025.   Typically, these compositions, under conditions typical of extrusion cooking,
Limited water or plasticizer (typically 5 to 40 based on starch-water system)
(% By weight), sufficient to break the starch crystallinity and obtain a thermoplastic melt.
Mix starch-based and synthetic thermoplastic components at different temperatures and pressures
It is obtained by doing. Ingredients based on starch by such a method
And a thermoplastic material interpenetrated or at least partially interpenetrated
The thermoplastic blend that forms is obtained.   The object of the present invention is to compare the corresponding properties of known starch-based compositions.
High biodegradation rate, improved mechanical properties, and / or improved water
With improved resistance and improved low permeability to water vapor
It is to provide a novel polymer composition of the type.   A further object of the present invention is to improve the processability of known biodegradable polymers, thereby
Made of such polymers, biodegradable and end products, especially sheets, films and
New filaments and filaments suitable for easier processing
That is.   The above objective is accomplished by a polymer composition of the above type, wherein the composition comprises:
The synthetic thermoplastic polymer component is a) aliphatic hydroxy acids having 2 to 24 carbon atoms, the corresponding lactones or
Lactide homopolymer; b) aliphatic hydroxy acids having 2 to 24 carbon atoms, the corresponding lactones or
Lactide and having 2 to 24 carbon atoms other than those making up the first monomer
Aliphatic hydroxy acids, corresponding lactones or lactides, aromatic hydroxy acids
And a monomer selected from the group consisting of aliphatic or aromatic isocyanates.
Polymer; c) the homopolymer and copolymer a) or b), one or more of the following components:   i) cellulose or cellulose acetate, carboxymethyl cellulose;
Modified cellulose;   ii) amylose, amylopectin, native or modified starch;   iii) diols (ethylene glycol, propylene glycol, butylene glyco
, Polyoxyethylene glycol, polyoxypropylene glycol, neo
Pentyl glycol, 1,4-butanediol, cyclohexanediol, sol
Polyester prepolymers with diol end groups (such as bitol dianhydride)
Or a polymer,   -Fragrant or aliphatic difunctional isocyanates,   -Aromatic or aliphatic bifunctional epoxides,   -Aliphatic dicarboxylic acids (malonic, succinic, maleic, fumaric, italic)
Conic, glutaric, adipic, pimelic, suberic, azelaic,
(Like vinatic acid)   Dicarboxylic acid cycloaliphatic acids (cyclohexanedicarboxylic acid, 2,2,2
-Like bicyclooctanedicarboxylic acid)   -Aromatic acids or anhydrides (such as phthalic acid)   Macromolecules derived from the reaction with;   iv) Polyamides from polyurethanes, diisocyanates and amino alcohols
Polyester from dourethane, polyamide, dicarboxylic acid and amino alcohol
Polyesters from diesters of ster-amides, amino acids and glycols Ester urea;   v) polyhydroxylated polymers (such as polyvinyl alcohol), ethylene
-Vinyl alcohol copolymer (wholly or partially hydrolyzed), and
Polysaccharides up to   vi) polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer,
Triethyloxazoline;   vii) ionomer-like polyacrylates and polymethacrylates
Remar;   Block or graft copolymers with; d) isocyanates, epoxides, phenyl esters and aliphatic carbonates
Monomers or como as defined above in a) and b) modified with a chain extender such as
Polyesters obtained from nomers; e) Multifunctional acids such as trimellitic acid, pyromellitic acid, polyisocyanates,
And moieties partially crosslinked by polyepoxides as defined in a) and b) above.
Polyesters obtained from nomers and comonomers; Comprising one or more macromolecules selected from the group consisting of:   ε-hydroxy acids, especially 6-hydroxycaproic acid, 6-hydroxyoctane
Acid, 3,7-dimethyl-6-hydroxyoctanoic acid and the corresponding lactone
Homopolymers and copolymers are preferred.   As monomers of aliphatic hydroxy acids having 2 to 24 carbon atoms, the following acids
And the corresponding lactide or lactone are specifically contemplated: Α-hydroxy acids such as lactic acid and the corresponding lactide, glycolic acid and
The corresponding glycolide; -Of hydroxypropionic acid, hydroxypivalic acid, hydroxypelargonic acid
Such β-hydroxy acids and the corresponding lactones; -Γ-hydroxy acids such as hydroxybutyric acid and the corresponding lactones; Δ-hydroxy acids such as hydroxyvalerate and the corresponding lactones; -Ε-hydroxy acids as described above; It has a hydroxy group located at more than 6 positions such as -10-hydroxydecanoic acid.
Hydroxy acids; savininic acid (12-hydroxydodecanoic acid) and unipelin
Natural source products such as acid (16-hydroxyhexadecanoic acid);
Such as unsaturated hydroxy acids; such as myristic acid, palmitic acid, stearic acid
Acids derived from α-hydroxylation of various fatty acids; oleic acid, ricinoleic acid,
Derived from hydroxylation of unsaturated aliphatics such as linolenic and erucic acids
Acid; Rings such as cyclohexane and hydroxy acids of 2,2,2-bicyclooctane
Aliphatic hydroxy acids.   As a copolymer of an aliphatic hydroxy acid and an isocyanate, ε-caprolact
4,4'-diphenylmethane-diisocyanate (MDI)
Cyanate (TD1), isophorone diisocyanate or hexamethylene diiso
Copolymers with cyanates are preferred.   Copolymerization of aliphatic hydroxy acids and corresponding lactones with aromatic hydroxy acids
Copolymerization of ε-caprolactone with β-phenyllactic acid or mandelic acid
The body is preferred.   The crystalline macromolecules a) to e) used within the framework of the invention are typically between 40 and 175 ° C.
It has a melting point. However, both crystalline and amorphous polymers may be used. 40,
Homopolymers and copolymers having a molecular weight of 000 or more are preferred.   Aliphatic polyesters with low melting points or low glass transition temperatures are
Addition by conventional techniques for thermoplastics such as extrusion and blow molding.
It is known that it is difficult to work. Poly-ε-caprolact with low melting point
With particular reference to tons and their copolymers, the films made therefrom are extruded.
Has a low melt strength at 130 ° C. and above;
Because the crystallization rate of the product is low, the crystallization process proceeds a long time after
Undesirable changes in properties occur with this. Mixing the polymers a) to e) with starch causes the force
Has been found to improve their processability without compromising their chemical properties and biodegradability
The improvement is particularly effective for polymers having a low melting temperature of 40-100 ° C. It is a target.   The ratio between the starch component and the polymer component is the final
It changes in a wide range depending on the way. Typically 1: 9 to 9: 1, preferably 1: 4 to
A ratio of 4: 1, more preferably 1.5: 1 to 1: 1.5 is used.   In a preferred embodiment, the polymer component has a molecular weight of preferably 40,000 or more.
Poly-ε-caprolactone or copolymer estane (registered trademark, BF Goodley)
Of ε-caprolactone and an aliphatic or aromatic isocyanate such as
From a polymer or a mixture thereof, preferably having a weight ratio of 5: 1 to 1: 1
A blend comprising:   According to another aspect of the present invention, the synthetic polymer component is a polymer or a polymer listed in a) to e).
Is a component A consisting of a mixture thereof, and preferably hydroxyl or carboxy.
, Carboxyalkyl, alkylcarboxyl, pyrrolidyl and acetal
(Alkyl is preferably C₁~ C_FourAt least one of
From ethylenically unsaturated monomers having repeating units with two functional polar groups
Component B comprising one or more derived polymers or copolymers.   The polymer of the component B has a melting point of 80 to 130 ° C., and about 50% by weight or more of ethylene.
Ethylene-acrylic acid, ethylene-vinyl alcohol,
Ethylene copolymers such as tylene-vinyl acetate copolymers and mixtures thereof
Comprising. However, the corresponding polyvinyl acetate, ethylene-vinyl acetate,
Polyvinyl alcohol produced by hydrolysis at a degree of hydrolysis of 50 to 100%
-Vinyl alcohol having an ethylene content of 10 to 44% by weight
High-melting polymers, such as copolymers of toluene, are particularly preferred.   Blends of starch and ethylene-vinyl alcohol copolymer are part of this specification.
Which is described in European Patent Publication No. 0400532.   The alcohol groups of the above polymers have been partially or completely modified to produce:
You may. 1) ethers formed by reaction with: -Ethylene oxide -C₂₀Ethylene oxide substituted with an alkyl group or an aromatic group Acrylotrile (Ce²⁺(Initiator) -Acrylamide -Arylalkyl halide -Chloroacetic acid -Methylchloromethyl ether -Silane. 2) sulfate, nitrate, phosphate, arsenate, xanthate,
Inorganic and organic esters such as rubamate, urethane, borate, titanate
. 3) The reaction of fatty acids or aromatic acids, especially fatty acids or anhydrides with chloroacyl
Organic ester formed by reaction. 4) Acetal or ketal produced by reaction with: Aliphatic aldehydes having up to 22 carbon atoms Unsaturated unsaturated aldehydes having up to 22 carbon atoms -Chloroacetaldehyde -Glyoxal -Aromatic aldehydes -Cycloaliphatic aldehydes -Aliphatic ketones -Aryl alkyl ketone -Alkyl cyclic alkyl ketones.   The reaction to make ethers, organic and inorganic esters and acetal described above,
Chapter 9 and quotes of "Polyvinyl Alcohol" edited by CA Finch
As described in the published literature.   Polyfunctional poly (vinyl alcohol) and ethylene-vinyl alcohol
(Containing up to 40% by weight of ethylene and having a degree of hydrolysis of acetate of 100 to 5%)
0%) can also be used. Ethylene-vinyl alcohol copolymer
In which up to 50% of the ethylene is: Propylene, isobutene, styrene, vinyl chloride, 1,1-dichloroethene, formula
CH_Two= CR-OR '(wherein R is hydrogen or a methyl group and R' is 1-18
An alkyl group having a carbon atom, a cycloalkyl group or a polyether)
Vinyl ether, acrylonitrile, methacrylonitrile, formula CH_Two= CR-
CO-CH_Two-R '(wherein R is hydrogen or a methyl group, and R' is hydrogen or C₁
~ C₆Vinyl ketone of the formula CH)_Two= CR-COOR '(where R
Is hydrogen or a methyl group, and R ′ is hydrogen or C₁~ C₆Alkylalkyl group
Acrylic acid or methacrylic acid and their esters, of these acids
Alkali metal or alkaline earth metal salts, formula CH_Two= CR-OCOR '(wherein R
Is hydrogen or a methyl group; R 'is hydrogen, a methyl group, chloro- or fluoro
A methyl group mono-, bee, or trisubstituted by_Two~ C₆Alkyl group
Is a vinyl derivative of the formula CH_Two= CR-CONR'R "(where R is hydrogen or
R ′ and R ″ are the same or different and are hydrogen or C₁~ C_ThreeArchi
Vinyl carbamate, maleic anhydride, fumaric anhydride, vinyl
Lolidone, vinylpyridine or 1-vinylimidazole, May be substituted by a comonomer selected from the group consisting of:   The copolymerization is called “Encyclopedia of Polymer Science and E.
Engineering ”(Encyclopedia of Polymer Science and Engineering)
Chapter 17, "Methods of Polymerizing Vinyl Esters," and page 406 and beyond
Hydrogen peroxide, peroxysulfate, as described in the references cited below
And using a radical initiator such as benzoyl peroxide.   Preferred compositions according to the invention comprise, as component A, poly-ε-caprolactone or
Or a copolymer thereof, preferably an isocyanate copolymer, polyhydroxybutylene.
, Polyhydroxybutyrate / valerate, or lactic acid polymer or
Poly-ethylene-vinyl alcohol as component B, optionally containing
The polyvinyl alcohol or poly-ethylene-acryl modified as described above
Or phosphoric acid or poly-ethylene-vinyl acetate or mixtures thereof.   According to a further aspect, the present invention provides a method as described above wherein the synthetic polymeric component is as component A. Polymers a) to e) and polyethylene and polybutylene adipate or sebacate
And polymers obtained by polymerization of dicarboxylic acids and aliphatic diols.
Containing the same polyester as described in the previous paragraph as Component B
Includes blends containing children.   Biodegradable polymer set containing starch and ethylene-vinyl alcohol copolymer
The product is known and has outstanding mechanical properties and fairly good resistance to water
Provide a film. However, such compositions suffer from loss of mechanical properties due to humidity changes.
It has some disadvantages with respect to loss. Especially at 10 ° C or lower and low humidity,
There is an unfavorable increase and loss of impact strength, which is an article for packaging and similar applications
Constitute limitations in relation to their use in manufacturing. On the other hand, as mentioned earlier
In general, polymers a) to e) with good biodegradability are difficult to process,
Due to its low melting point, it is used only in a limited range of temperatures.   According to the present invention, adding a starch component to polymer A and adding a polymer component B to polymer A
The addition improves mechanical properties and lowers water vapor and liquid permeability to water.
It has been found suitable to achieve. Especially for starch and polymer B component
Addition to polymer A has a nucleating effect and the polymer under the processing conditions of the blends of the invention
This results in a substantial increase in the crystallization rate of A. Its advantages are inflation, extrusion
, Melt-spinning, blow molding and injection molding
Lament, as well as molded articles, are particularly effective.   A blend comprising starch, polymer B and a plasticizer is a trademark of Novamont
Available commercially under the name Mater Bi, such blends are available as starch and
And the blend of the present invention is used as a raw material for B and B polymers.   The weight ratio of components A and B of the synthetic polymer component is preferably 1: 6 to 6: 1, more preferably.
Preferably it is 1: 4 to 4: 1.   Preferred compositions particularly adapted for injection molding are From about 20 to about 60% by weight of the starch component; About 10 to about 80% by weight, especially about 10 to about 50% by weight of component A, From 0 to about 45% by weight, especially about 2 to about 30% by weight of component B; (Percentages are based on the sum of starch and all synthetic ingredients).   For compositions adapted for the production of films, sheets, etc., preferred compositions are
, From about 5 to about 60% by weight of the starch component From about 40 to about 80% by weight of component A 0 to about 35% by weight, especially about 5 to about 30% by weight of component B (Percentages are based on the sum of starch and all synthetic ingredients).   A product that can be used as a raw material for starch and B-type polymers.
(Mont®), the preferred weight of A-type polymer and matterby
The ratio is between 80:20 and 30:70.   The starch used in the polymer composition is preferably potato, rice, tapioca,
It is a natural starch extracted from vegetables such as corn and cereals. Any
In some cases, the term “starch” includes physically and chemically modified starch.
Intend.   With a starch component containing at least 78% by weight of amylopectin, extrusion blowing
The film can be obtained by injection molding, and the cross section is a scanning electron microscope.
When observed with a microscope (2,000x magnification), many linear polymer microphases and
Alternating starch microphases where the starch crystal structure can no longer be identified
Figure 3 shows a layered or lamellar structure made by: The fact that such a layered structure was made
And gas and liquid films and sheets obtained from polymer blends such as
Substantially increase the barrier properties to   In this regard, 90% by weight or more, more preferably 95% by weight or more of amylopecti
Starch components having starch are preferred. Starch that meets the above requirements is the only
Using waxy starch (amicropectin content 95% by weight) as starch material
Or amylopectin, waxy starch and / or
Normal amylopectin-low protein such as mais starch and potato starch
Obtained by using a mixture of starches.   On the other hand, less than about 78% by weight of amylopectin and correspondingly more than about 22% by weight of amylopectin.
Starch components with a loin content are used under processing conditions for extrusion and inflation. It appears to promote the interpenetration of the starch component with the synthetic polymer component.   Boric acid, borax, metaboric acid, aluminum hydroxide, alkali metal salts, especially salts
Can reduce the complexing power of amylose, such as
Or a substance that can interact with starch through hydrophilic interactions
Has a lower amylopectin content, about 70% or more by weight
By using a starch component, the above-mentioned lamellar or lamellar structure is obtained. This eye
An effective amount of such a substance for targeting is 0.01 to 10 based on the starch component.
% By weight, preferably 0.05 to 5% by weight.   Added boron containing compounds to improve the clarity of starch / polymer blends
Is described in U.S. Patent Application No. 744,492, filed June 23, 1991.
And that patent is incorporated herein by reference.   The polymer composition is based on the weight of the total composition of starch and polymer components
, 1 to 50% by weight, preferably 5 to 40%, more preferably 5 to 25% by weight.
Including plasticizer. Using a polyol selected from the following as a plasticizer: a) 1 to 20 repeating hydroxylated units, each unit containing 2 to 6 carbon atoms
A) a polyol formed by b) 1 to 20 repeating hydroxylated units, each unit containing 2 to 6 carbon atoms
Ethers, thioethers, inorganic and organic ethers of the polyols
Steles, acetal and amino derivatives, c) 1 to 20 repeating hydroxylated units (each unit containing 2 to 6 carbon atoms)
Reaction product of a polyol having d) 1 to 20 repeating hydroxylated units (each unit containing 2 to 6 carbon atoms)
The oxidation product of a polyol having at least one aldehyde or
Contains carboxyl functional groups or mixtures thereof.   A water-soluble compound having a vapor pressure equal to or lower than the vapor pressure of glycerin at normal temperature (25 ° C.)
Bleeding or mixing of plasticizer from the final product obtained from the composition of the present invention
It is preferable to reduce the etching phenomenon.   Aliphatic polyols of type a) include ethylene glycol, glycerol, erythr Litol, arabitol, adonitol, xylitol, mannitol, idi
Formulas like toll, galactitol, sorbitol and allitol:   OH-CH_Two-(CHOH) n-CH_TwoOH (I) Wherein n is 0-4, and propylene glycol, polyglycol
, Trimethylolpropane, pentaerythritol, 3-20 repetitions
Polyvinyl alcohol with units, and 2 to 10, preferably 2 to 5
Polyglycerol formed by monomer units (mixture of various oligomers
And polyols not within the above formula.   The aliphatic polyol derivative of paragraph b) is the same as the polio mentioned in the previous paragraph.
At least one alcohol officer of the polyol in question, preferably selected from
Noki has the following: -O- (CH_Two) n-H (where n = 1 to 18, preferably 1 to 4), -O-CH = CH-R₁(Where R₁= H or -CH_Three), -O- (CH_Two-CHR₁-O) n-H (wherein R₁= H or CH_Three, N = 1-20),
-O- (CH_Two) n-Ar (where Ar is a simple, substituted or heterocyclic aromatic
Group group, n = 0-4), -O-CO-H, -OCO-CR₁R_TwoR_Three(Where R₁, R_TwoAnd R_ThreeThe groups are the same or different, H,
Cl, and F), -OCO- (CH_Two) n-H (wherein n = 2-18, preferably 2-5), -ONO_Two, -OPO_ThreeM_Two(Where M is H, ammonium, alkali metal, alkaline earth,
Or organic cations, especially trimethylammonium, pyridinium or picoli
), -SO_Three-Ar (where Ar is benzene or toluene), -OCO-CH (SO_ThreeM) -COOM (wherein M is the same or different, H,
Limetals, alkaline earth metals, ammonium, and organic cations, especially pyridini
Um, picoline, or methylammonium), -O-CO-B-COOM (where B is (CH_Two) n (where n is 1-6) or -CH
= CH-, and M is H, an alkali metal, an alkaline earth metal or-(CH_Two) nH
(Where n = 1 to 6) or an aryl group), -OCONH-R₁(Where R₁Is -H or an aliphatic or aromatic group), -O- (CH_Two) n-COOM (where n = 1 to 6, M is H, alkali metal, alkali
Earth metal, ammonium or organic cations, especially pyridinium, trimethyl
Ammonium or picoline), -O- (CH_Two) n-COOR₁(Where n = 1 to 6, R₁= H (CH_Two) m- (where m = 1
~ 6)), -NR₁R_Two(Where R₁And R_Two= H, CH_Three-, CH_ThreeCH_Two-, -CH_TwoCH_TwoO
H or a salified amino group), -O- (CH_Two) n-NR₁R_Two(Where n = 1 to 4, R₁And R_Two= H, CH_Three-, C
H_ThreeCH_Two-Or CH_Two-CH_TwoOH, the amino group may be a salt),-O-CH_Two-CHOH-CH_Two-NR₁R_Two(Where R₁And R_TwoAre the same or phases
Different, H, and H (CH_Two) n (where n = 1-6), wherein the amino group is a salt
May be present), -O-CH_Two-CHOH-CH_Two-R₁ ⁺Cl^-(Where R₁ ⁺Is a trialkyl ammonium
, Pyridinium, or picoline groups), -O- (CH_Two) nR₁ ⁺Cl^-(Where n = 1 to 6, R₁ ⁺Is a trialkyl ammonium,
Pyridinium or picoline group), -O- (CH_Two) n-CN (where n = 1-6), -O- (CH_Two) n-CONH_Two(Where n = 1 to 6), -O- (CH_Two) m-SO_Two− (CH_Two) nH (where m and n = 1 to 4), -SCSNH_Two, -OSiX_ThreeAnd -O-SiOX_Three(Where X is an aliphatic or aromatic group) Structural formulas obtained by substitution with a functional group selected from
I do.   Mono- and di-ethers of the polyols of formula (I) and mono- and di-
Esters are particularly preferred, especially sorbitol monoethoxylate and monopropoate.
Xylates and monoacetate derivatives are most preferred.   The compound of paragraph c) may comprise two or more polyol molecules, especially dicarboxylic acids,
Resulting from conjugation by chain extenders such as aldehydes and isocyanates.   Preferred compounds have the formula:   R-CH_Two-(CHR) n-CH_Two-OAO-CH_Two-(CHR) m-CH_Two-R Wherein n and m are the same or different, have a value of 1 to 6, and the R groups are the same or different.
A is a hydroxyl group or has the meaning described above, wherein A is: -CHR₁(Where R₁= H or H- (CH_Two) n- (where n = 1 to 5)   (Acetal), − (CH_Two) n- (where n = 1-6), − (CH_Two-O-CH_Two) n (where n = 1 to 20), − (CH_TwoCH_Two-O) n-CH_TwoCH_Two-(Where n = 1 to 20), -OC- (CH_Two) n-CO (where n = 0 to 6), -OC-Ar-CO- (where Ar is an aromatic group which is also a heterocyclic), -PO_Two− -CONH- (CH_Two) nNHCO- Selected from the group consisting of And has the formula:   R-CH_Two-(CHR) n-CH_Two-A-CH_Two-(CHR) m-CH_Two-R Wherein n and m are the same or different and are the total number of 1 to 6, and the R groups are the same or different.
Are different and have a hydroxy group or the meaning indicated above, wherein A is NH-, and -NH
− (CH_Two-CH_Two-NH) n- (wherein n is a total number of 1 to 6)
] Is a compound of   Of the above compounds, only one of the R groups forms an ether or ester Preferred are compounds which are groups of the formula   The term "polyol" refers to mono- and polysac-rides having up to 20 monosaccharide units.
It is intended to contain callide.   The following monosaccharides are of particular interest: formula: Wherein the R groups are the same or different and are hydroxyl groups or have the above meanings
Do) Pentose and its derivatives.   Examples of these compounds are arabinose, lyxose, ribose, and xylose.
And preferably their monoethers and monoesters. formula: Aldohexose and its derivatives of the formula: Wherein the R groups are the same or different and are hydroxyl groups or have the above meanings
Ketohexose and its derivatives.   Examples of these monosaccharides are glucose, fructose, mannose, allose, a Lutulose, galactose, growth, eyes, inositol, sorbose
And talitol.   Among their etherified or esterified derivatives, monoethoxylates and
Preferred are monopropoxylate derivatives and monoesters, especially acetic acid.   Polysaccharides have a molecular weight up to the molecular weight of dextrin, and have the formula (II), (III) or (
Compounds having up to 20 repeating units of IV) are included.   The R functional group may be, for example, “polyvinyl alcohol” edited by CA Finch.
And the known reactions described in Chapter 9 and in the cited references.
Into the basic structure of the   Preferred plasticizers are glycerin, polyglycerol, glycerol ethoxylate
Or ethylene or propylene glycol, ethylene or propylene diglycol
Coal, ethylene or propylene triglycol, polyethylene or polyp
Propylene glycol, 1,2-propanediol, 1,3-propanediol, 1
, 2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-
1,1,5-hexanediol, 1,2,6-, 1,3,5-hexanetriol,
Pentyl glycol, trimethylolpropane, pentaerythritol, sol
Bitol acetate, sorbitol diacetate, sorbitol monoethoxyle
Sorbitol dipropoxylate, sorbitol diethoxylate, sol
Bitol hexaethoxylate, aminosorbitol, trihydroxymethyla
Reaction of minomethane, glucose / PEG, and ethylene oxide with glucose
Adult, trimethylolpropane monoethoxylate, mannitol monoacetate
G, mannitol monoethoxylate, butyl glucoside, glucose monoeth
Xylate, α-methylglucoside, carboxymethylsorbitol sodium
Salt, polyglycerol monoethoxylate and mixtures thereof.   For example, polyvinyl alcohol, an ethylene having an ethylene content of 44% by weight or less
Synthetic polymer having a high melting point such as vinyl alcohol copolymer
When used, the described plasticizer is a composition having an interpenetrating structure (at least partially)
Plays an important role in the methods leading to the formation of The melting points of these polymers (160 〜200 ° C.), so that full interpenetration by the starch molecules is not possible. Den
Addition of a common plasticizer to the starch and polymer components lowers the melting point of the synthetic polymer,
Sometimes alters its rheological behavior.   The high molecular substances are urea, alkali metal or alkaline earth metal hydroxides, etc.
It may also contain chemicals that break hydrogen bonds, and may be 0.5 parts by weight based on the total weight of the entire composition.
Add ~ 20% to the mixture of starch and copolymer.   The addition of urea (preferably 5-20% by weight)
This is particularly advantageous for the production of a metal.   The compositions of the present invention include polyethylene, polypropylene and polystyrene.
May contain relatively small amounts of hydrophobic polymers; however, it does not impair its biodegradable nature.
To achieve this, the amount of such polymer should preferably exceed about 5% of the total composition.
I can't.   The polymer composition of the present invention may contain aldehydes, ketones, and glyoxal.
Crosslinkers, processing aids and release agents, fatty acids, fatty acid esters, higher alcohols
Usually added to molding or extrusion compositions such as polyethylene wax, LDPE
Lubricants, fungicides, flame retardants, herbicides, antioxidants, fertilizers, opacifiers and
An agent may also be included.   Further additives include polyvinylpyrrolidone, polyoxazoline, cellulose
Acetate and nitrate, regenerated cellulose, alkyl cellulose, cal
Boxymethylcellulose, casein-type protein and its salts, gum arabic,
Includes natural gums such as algin and alginates, chitin and chitosan.   The polymer composition is extruded by heating the above components to a maximum temperature of usually 100 to 220 ° C.
EP-A-413798 and EP-A-40 40, which form a part of this specification in-flight.
It is preferably prepared by mixing according to the method described in US Pat. Extruder
The composition supplied to the mixture depends on the specific water content of the starch used (9 to 15% by weight).
And water may be added moderately.   The composition according to the invention is 1.5 to 5% by weight when extruded before conditioning.
Preferably having an initial water content of the entire composition to an intermediate degassing It is obtained by reducing during extrusion more.   The pressure on the mixture during thermal processing can be reduced by extrusion in single or twin screw extruders.
This is a typical case. Processing is preferably carried out in an extruder, but with starch,
Synthetic polymers and plasticizers combine starch and polymers from a rheological point of view.
Mix by any device that guarantees suitable temperature and shear stress conditions for melting.
You may.   A method for preparing the composition of the present invention under preferred conditions comprises the following steps; The starch component and the synthetic polymer component are 80-180 with a plasticizer and optionally water;
Swell at ℃ to dynamically change the melting point and rheological properties of the composition
This effect is for example 2 to 50 seconds during the first stage of transporting the components to the extruder.
Achieved during the -Mix under shear conditions corresponding to similar viscosity values of plasticized starch and synthetic polymer components.
Put the compound, -Degas under pressure or under reduced pressure freely or in a controlled manner and
A melt having a liquid content such that, for example, no foam is formed at the exit of the extruder
At a temperature of 140-180 ° C, -Cool the final product in a water bath or in air.   Requires a pressure of 0.5 to 10 MPa, preferably 1 to 5 MPa in the whole method
.   As noted, the thermoplastic composition is preferably prepared by directly mixing the components.
The starch is 100-220 ° C. in the presence of a plasticizer and optionally added water.
The temperature may be adjusted in advance to produce a thermoplastic starch. This starch
The mixture is mixed with the synthetic polymer and an additional amount of plasticizer during the second stage. Polyvinyl
In the case of alcohol and ethylene-vinyl alcohol copolymer, all plasticizers
At the beginning of the mixing of the pretreated starch with the synthetic polymer. Because
Modifies the melting point and rheological properties of the polymer to make it compatible with starch.
This is because a plasticizer must be used.   The blends of the present invention are obtained by extruding starch and polymeric components A and B, preferably by conventional extrusion.
The components A polymers a) to e) are converted into starch and B polymers by direct mixing It is obtained by mixing with a previously obtained blend. Example 1   38 parts of Mais starch grab 03401 (Celestar, registered trademark,
Water content of 12% by weight), ethylene mole content of 44% and hydrolysis of acetate groups.
38 parts of ethylene-vinyl alcohol copolymer having a decomposition degree of 99.5%, 5 parts of urea,
0.3 parts of Lumide E, 12 parts of monoethoxylated sorbitol, glycerin
3.7 parts, 3 parts of water, 58mm, L / D = 36, 9 heating zones with degassing section
It was fed to the equipped twin screw extruder OMC. The following operating conditions are selected for the extrusion operation
did. Screw speed (rpm): 170 Depressurization (bar): 0.9. Deaeration location: 8th zone Thermal profile: cold zone / 90 ° C / 140 ° C / 180 ° C / 180 ° C / 180 ° C
/ 180 ° C / 175 ° C / 165 ° C Head temperature: 145 ° C (melting temperature 145 ° C) Head pressure (bar): 27 Absorption (A): 67-69   The extrudate, shaped like spaghetti, was cooled in a water bath and pelletized. Pe
The let had a water content of 3.5% by weight (hereinafter referred to as @let A1).   The following composition: 70 parts of poly-ε-caprolactone (PCL “Tone P-787”, registered trademark,
(Union Carbite) 30 parts of pellet A1 4 parts of glycerin Directly with four controlled temperature zones and no intermediate degassing
Feed into an OMC extruder with a diameter of 20 mm and a compression ratio of 1: 3 under the following conditions: Screw speed: 45rpm Thermal profile: 140/145/150/155 ° C Operated by   The extrudate shaped like spaghetti was pelletized (pellet A2). Peret
A2 is a HAAKE extruder (19 mm in diameter, L / D = 25, two blow heads)
At a speed of 45 rpm, heat profile 140 ° C / 145 ° C / 150 ° C /
Operating at 155 ° C., a film having a thickness of 30-50 μm was obtained. The resulting file
Table 1 shows the mechanical properties of LUM. Example 2   The following composition: 70 copies of PCL "TONE P-787" (Union Carbide) 30 copies of Peret A1 6 parts glycerin Was used in the preparation of pellet A2, and the operation of Example 1 was repeated. Mechanical properties and
Table 1 shows the properties and permeability. Example 3   The following composition: 60 parts PCL "Tone P787" (Union Carbide) 40 parts of pellet A1 Was used in the preparation of pellet A2, and the operation of Example 1 was repeated. Table of mechanical properties
It is shown in FIG. Example 4   The following composition: 50 copies of PCL "Tone P-787" (Union Carbide) 50 parts of pellet A1 Was used in the preparation of pellet A2, and the operation of Example 1 was repeated. Mechanical properties and
Table 1 shows the properties and permeability. Example 5   50 parts of pellet A1 and 50 parts of poly-ε-caprolactone P787 (U
Nion carbide) is the same as that used for producing pellet A1 without an intermediate degassing part. Feed to OMC extruder under the following conditions: Screw speed: 130rpm Thermal profile: first cold zone / 90 ° C / 130 ° C / 150 ° C / 155
° C / 160 ° C / 160 ° C / 160 ° C / 150 ° C Head temperature: 145 ° C Pressure: 32 bar Absorption: 105A Productivity: 60kg / hour Operated by   The pellet thus obtained has the following characteristics: Die diameter: 100mm Die gap: 0.5mm Dyland: 10 Blower with a diameter of 44 mm and L / D = 30 equipped with an inflation head having
Supplied.   The conditions of inflation were as follows. Screw speed: 65rpm Extruder thermal profile: 135 ° C / 140 ° C / 140 ° C / 140 ° C Neck thermal profile: 140 ° C Thermal profile of head: 135 ° C Stretching ratio: 3.1 Blow-up ratio: 3.2   A film having an average thickness of 50μ was obtained. Tensile of the film thus obtained
Table 2 shows the properties of the adhesive, the properties of tearing, and the permeability. Example 6   47.5% by weight of pellet A1, 50% by weight of poly
Supplying a composition comprising -ε-caprolactone and 2.5% by weight of polyethylene
And the procedure of Example 5 was repeated. The characteristics of the film thus obtained are shown in Table 2.
. Example 7   47.5% by weight of pellet A1, 50% by weight of poly
-Ε-caprolactone and 2.5% by weight of urea to provide a composition.
The procedure of Example 5 was repeated. Table 2 shows the characteristics of the film. Example 8   48.5% by weight of pellet A1 and 48.5% by weight of
Li-ε-caprolactone, obtained from 2.4% by weight of water, 0.6% by weight of glycerin.
The procedure of Example 5 was repeated, supplying the pellets. Characteristics of the film thus obtained
The characteristics are shown in Table 2. Examples 9 to 16   Poly-ε-caprolactone P-787 (Union Carbide)
Li-ε-caprolactone and ε-caprolactone produced by BF Goodrich
(Polyester / urethane)
Example 4 by using a 4: 1 (by weight) blend with (Estan®)
Steps 1 to 8 were repeated. The properties of the films thus obtained are according to Examples 1 to 8.
Comparable to the properties of the resulting film. Examples 17 to 23   A twin screw extruder APV having a diameter of 30 mm and L / D = 25 is shown in Table 3 below.
The composition was fed directly. In some cases, indicated by asterisks in Table 3,
Li-ε-caprolactone polymer is an ethylene-vinyl alcohol copolymer (ethylene
And the degree of hydrolysis was 99.5%). AP
The V extruder was operated under the following conditions: Screw speed: 170rpm Productivity: 13.1kg / hour Thermal profile: 1st cold zone / 60 ° C / 160 ° C / 165 ° C / 170 ° C
/ 170 ° C / 170 ° C / 170 ° C / 160 ° C / 150 ° C Head temperature: 140 ° C   Extrudate shaped like spaghetti is pelletized and injection molded To Sandretto to make dumbbell specimens (ASTM638)
Was tested to determine its mechanical properties. The mechanical properties are shown in Table 3. Examples 24 to 25: Blow molding   The following compositions were processed directly by blow molding to make plastic bottles.  The above composition was provided with a constant taper screw (compression ratio of 1: 3) and a diameter of 30 mm.
, L / D = 25, supplied to an AEMME blow molding machine under the following operating conditions: Mold type: cylindrical bottle, diameter 50mm Cooling system: water 17 ℃ Air pressure: 6-7 bar   No difficulties found in the production of bottles by blow molding under the above conditions
Was. Comparison performed under the same conditions using only poly-ε-caprolactone P787
The test creates difficulties such as the need to substantially increase blow time and sticking problems
Was. Examples 26 to 27   A wax having an amylopectin content of about 95% by weight and an inherent water content of 12% by weight.
Using starch-like starch (Snowflake 04201 Starch, registered trademark)
The procedure of Example 1 for the preparation of the cut A1 was repeated.   The pellet thus obtained was subjected to poly-ε-caprolactone P-787 (Union
(Carbide) and inflation equipment Ghioldi under the following conditions
, Weight ratio (pellet / poly-caprolactone) 50/50 (Example 26), 60/4
Direct mixing at 0 (Example 27) (by weight). Giorgi device: diameter 40mm, L / D30 Screw: constant taper, compression ratio 1: 2.8 Shape: spiral Die diameter: 100mm Die gap: 0.5mm Dyland: 10 Inflation conditions: Screw speed: 65rpm Extruder heat profile: 135/135/140/140 ° C (melting temperature: 152
° C) Neck thermal profile: 140-140 ° C (melting temperature 152 ° C) Thermal profile of head: 135-135 ° C (melting temperature 140 ° C) Neck pressure: 274 bar Die pressure: 73 bar Stretch ratio: 3 Blow-up ratio: 3   Mechanical properties, water vapor permeability (39 ° C, humidity 90% according to the method of Lissy)
), Water permeability (the part that does not come in contact with water at 20 ° C and 10% or less humidity) Show.   The biodegradability test performed on the product obtained from the above example was compared with the known composition.
It shows substantial improvement. Starch, poly-E, especially under composting conditions
A composition comprising tylene-vinyl alcohol and poly-ε-caprolactone is known as
After only 10 days, up to 80% biodegradability was obtained.   Injection molding, extrusion, blow molding, blow molding, thermoforming and processing thermoplastic materials
A film prepared from a composition described herein by a similar conventional method.
Systems, sheets, laminated films and sheets, filaments, fibers and injection
Shaped articles, such as shaped articles, are within the scope of the present invention.   Specific applications include films for absorbent articles such as diapers, mulch and general
Packaging film, protective coating film, or biodegradable and non-biodegradable
There is a film coextruded with a hydrophilic polymer.   Absorbent article is U.S. Patent Application No. 91112942.7 (filed August 1, 1991)
And form a part of the present specification.   Laminated films are described in WO 92/02363,
Form a part of the book.   The composition of the present invention comprising Type A and Type B polymers comprises a "permselective membrane" European patent application entitled "and its uses" (priority IT T091A00032)
7, May 3, 1991) Production of selective membrane for pervaporation method
And that application is incorporated herein by reference.

Claims (1)

[Claims] 1. Rheology from melts containing starch and synthetic thermoplastic polymer components A homopolymer of an aliphatic hydroxyacid having 2 to 24 carbon atoms, the corresponding lactone or lactide, having a melting point in the range of 40 to 175 ° C ; b. A) an aliphatic hydroxy acid having 2 to 24 carbon atoms, the corresponding lactone or lactide, and an aliphatic hydroxy acid having 2 to 24 carbon atoms other than that making up the first monomer, the corresponding lactone or Lactide, aromatic hydroxy acids, copolymers with monomers selected from the group consisting of aliphatic or aromatic isocyanates; c) homopolymers and copolymers a) or b), one or more of the following components: i) cellulose, or modified cellulose such as cellulose acetate, carboxymethyl cellulose; ii) amylose, amylopectin, native or modified starch; iii) geo. , A polyester prepolymer, or a polymer having a diol end group;-an aromatic or aliphatic difunctional isocyanate;-an aromatic or aliphatic difunctional epoxide;-an aliphatic dicarboxylic acid;-a dicarboxylic acidic cycloaliphatic acid. -Polymers derived from the reaction with aromatic acids or anhydrides; iv) polyamides from polyurethanes, diisocyanates and amino alcohols-polyesters from urethanes, polyamides, dicarboxylic acids and amino alcohols-polyesters from amides, amino acids and glycols from diesters. Polyester ureasv) Polyhydroxylated polymers selected from the group consisting of polyvinyl alcohols, ethylene-vinyl alcohol copolymers (wholly or partially hydrolyzed), and polysaccharides up to destrin; vi) polyvinyl pyrrolides Block or graft copolymers with: polyvinylpyrrolidone-vinyl acetate copolymers, polyethyloxazolines; vii) ionomeric polymers selected from polyacrylates and polymethacrylates; d) isocyanates, epoxides, phenyl esters and aliphatics Polyesters obtained from monomers or comonomers as defined in a) and b) above, modified with a chain extender selected from the group consisting of carbonates; e) selected from the group consisting of trimellitic acid, pyromellitic acid A) and above partially crosslinked by polyfunctional acids, polyisocyanates and polyepoxides
a polymeric composition comprising at least one polymer or polymer mixture selected from the group consisting of: a polyester obtained from the monomers and comonomers defined in b). 2. A composition according to claim 1, wherein the starch-based component and the synthetic polymer component are in a weight ratio of 1: 9 to 9: 1, preferably 1: 4 to 4: 1. 3. Wherein the synthetic component comprises a polymer of an ε-hydroxy acid or a corresponding lactone selected from the group consisting of 6-hydroxycaproic acid, 6-hydroxyoctanoic acid and 3,7-dimethyl-6-hydroxyoctanoic acid. 2. The composition according to item 1, wherein 4. The composition according to claim 3, wherein the synthetic component is a copolymer of an ε-hydroxy acid and an isocyanate selected from the group consisting of 4,4-diphenylmethane-diisocyanate, toluylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. A composition as described. 5. The composition according to claim 1, wherein the synthetic component comprises poly-ε-caprolactone, a copolymer of ε-caprolactone and an aliphatic or aromatic isocyanate, or a mixture thereof. 6. The composition according to claim 5, wherein the synthetic component comprises poly-ε-caprolactone having a molecular weight of 40,000 or more. 7. 7. The composition according to claim 6, wherein the synthetic component comprises a mixture of poly-ε-caprolactone and a copolymer of ε-caprolactone with an aliphatic or aromatic isocyanate in a weight ratio of 5: 1 to 1: 1. The described method. 8. The synthetic polymer component comprises a component A selected from polymers a) to e) and mixtures thereof, and a component B comprising a polymer derived from an ethylenically unsaturated monomer, the polymer comprising The composition according to claim 1, having a repeating unit having at least one functional polar group selected from the group consisting of hydroxyl, carboxyl, carboxyalkyl, alkylcarboxyl, pyrrolidyl, and acetal. 9. Component B comprises a polymer selected from the group consisting of polyvinyl alcohol, ethylene-acrylic acid, ethylene-vinyl acetate, ethylene-vinyl alcohol, modified ethylene-vinyl alcohol, modified polyvinyl alcohol, and mixtures thereof. 9. The composition according to claim 8, comprising: 10. Component B is obtained by hydrolysis of the corresponding poly-ethylene-vinyl acetate, has an ethylene content of not more than 44% by weight and a degree of hydrolysis of the acetic acid groups of 50 to 100%.
10. The composition according to claim 9, comprising poly-ethylene-vinyl alcohol. 11. 9. The composition according to claim 8, wherein components A and B are present in a weight ratio of 1: 6 to 6: 1, preferably 1: 4 to 4: 1. 12. From about 20 to about 60% by weight of the starch component; from about 10 to about 80% by weight of component A; from 0 to about 45% by weight of component B (% amounts are based on the sum of starch and all synthetic components). 9. The composition according to claim 8, comprising a composition. 13. 13. The composition of claim 12, comprising about 10 to about 50% by weight of component A, and about 2 to about 30% by weight of component B. 14． -From about 5 to about 60% by weight of the starch component;-from about 40 to about 80% by weight of component A;-from 0 to about 35% by weight of component B (% amounts are based on the sum of starch and all synthetic components. 9. The composition according to claim 8, wherein the composition comprises: 15. 15. The composition of claim 14, comprising about 5 to about 30% by weight of component B. 16. Glycerin, polyglycerol, glycerol ethoxylate, ethylene or propylene glycol, ethylene or propylene diglycol, ethylene or propylene triglycol, polyethylene or polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2- 1,3-
1,4-butanediol, 1,5-pentanediol, 1,6-, 1,5-hexanediol, 1,2,6-, 1,3,5-hexanetriol, neopentyl glycol, trimethylolpropane Pentaerythritol, sorbitol acetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol dipropoxylate, sorbitol diethoxylate, sorbitol hexaethoxylate, aminosorbitol, trihydroxymethylaminomethane, glucose / PEG, ethylene oxide with glucose Reaction product, trimethylolpropane monoethoxylate, mannitol monoacetate, mannitol monoethoxylate, butyl glucoside, glucose monoethoxylate, α-
A plasticizer selected from the group consisting of methyl glucoside, sodium salt of carboxymethyl sorbitol, polyglycerol monoethoxylate and mixtures thereof, comprising from 1 to 50% by weight, based on the starch / synthetic polymer system. Item 9. The composition according to item 1 to item 8. 17． 17. The composition according to claim 16, wherein the plasticizer is present in an amount of 5 to 25% by weight, based on the total weight of the composition comprising starch and the polymer component. 18. 17. The composition according to claim 16, wherein the plasticizer is selected from glycerin, sorbitol ethoxylate and mixtures thereof. 19. 17. The composition according to claim 16, comprising 0.5 to 20% by weight of urea based on the weight of the whole composition. 20. A composition according to claims 1 to 8, comprising up to 5% by weight, based on the total composition, of a hydrophobic polymer selected from the group consisting of polyethylene, polypropylene and polystyrene. 21. 9. The composition according to claim 1, which has a water content of 1.5 to 5% by weight, based on the total composition. 22. Claims 1 to 5 wherein the starch component comprises at least 78% by weight of amylopectin.
Item 9. The composition according to Item 8. 23. Claims 1 to 8 comprising from 0.01 to 10% by weight, based on the weight of the starch component, of an additive selected from boric acid, borax, metaboric acid, aluminum hydroxide and alkali metal salts. A composition according to claim 1. 24. 24. The composition according to claim 23, wherein the starch component has an amicpectin content of 70% by weight or more. Comprising a polymer and / or polyvinyl alcohol and an aliphatic polyester, wherein the plasticizer is: a) 1 to 20 hydroxylated repeating units, each unit containing 2 to 6 carbon atoms B) ethers, thioethers, inorganic and organic esters, acetals of polyols formed by 1 to 20 hydroxylated repeating units, each unit containing 2 to 6 carbon atoms, and An amino derivative c) a reaction product of a polyol having from 1 to 20 hydroxylated repeating units, each unit containing 2 to 6 carbon atoms, with a chain extender; d) at least one aldehyde; Having 1 to 20 hydroxylated repeat units, each unit containing 2 to 6 carbon atoms, including a carboxyl function or a mixture thereof Oxidation products of polyols, compositions selected from the group consisting of. 26. Articles obtained by using the polymer composition according to claims 1 to 8,
Especially films, sheets, fibers and filaments.