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Description  |
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The invention relates to a highly transparent, single-phase, biodegradable
starch mixture consisting of selected polyamides and a starch molding
composition. Preferably, the composition contains one or more emulsifiers,
urea, and/or derivatives thereof, as well as chemically modified starch
and plasticizer. The invention also relates to a process for producing
this highly transparent starch mixture. The invention is used for making
thermoplastically shaped parts, in particular films, especially by
injection molding, extrusion, co-extrusion, blow molding, injection
stamping, and thermo forming.
BACKGROUND OF THE INVENTION
As starch is a vegetable carbohydrate, there have been attempts to use it
as a "natural" plastic material in a wide variety of areas, employing
known plastics processing methods. However, owing to their granular
structure, native starches first have to be destructured before they can
become thermoplastically processible.
To impart the good properties known and desired of plastics materials to an
opaque basic starch molding composition of this type, it is necessary to
process it further. When this is done, it often loses its
biodegradability.
EP 344 118 A2 relates to a polymer blend material consisting of a melt of
at least one water-containing destructured hydrophilic polymer and at
least one synthetic, substantially water-insoluble thermoplastic polymer.
The dimensional stability of the material is improved by the addition of
the water-insoluble polymer; this is demonstrated by examples of blends
based on gelatins, as well as cellulose derivatives, and polyethylene,
polystyrene, polyvinylether, polyoxymethylene, and ethylene acrylic acid
copolymers. The patent's reference to possible biodegradability, namely
the loss of this additional stability after several days, is considered to
be a disadvantage for the products shaped from the blends; no comment is
made as to the biodegradability of the blend.
EP-OS 327 505 A2 describes a melt-mixed polymer blend consisting of
destructurized but chemically unmodified starch and at least one
water-insoluble synthetic thermoplastic polymer. Similarly, polymer blend
compositions consisting of chemically unmodified destructurized starch and
a functionalized polymer are known from the laid open and EP Applications
409 789 A2, 409 788 A2, 409 783 A2, 409 782 A2, 409 781 A1, 408 503 A2,
408 502 A2, 408 501 A2, 407 350 A2, 404 728 A2, 404 723 A2, and 404 727
A2. These compositions may each additionally contain a further
water-insoluble thermoplastic polymer. In that case, the functionalized
polymer acts as a compatibilizer between the chemically unmodified starch
and the additional third thermoplastic polymer.
German Patent Application DE 41 19 915.4 describes starch polymer mixtures
consisting of a starch molding composition and selected linear polymers.
Their specific disadvantage, as well as that of all starch materials
disclosed in the above-mentioned specifications, is their typical yellow
tinge as well as their non-transparency. Opaque material can be used only
to a limited extent, in particular in the packaging field, as transparency
of the plastic materials is usually required.
BRIEF DESCRIPTION OF THE INVENTION
It is, therefore, an object of the invention to provide a highly
transparent, biodegradable, single-phase starch mixture for thermoplastic
processing which has no yellow tinge and contains no polymeric
compatibilizers, and to provide a process for producing this mixture.
Furthermore, this starch mixture is to be stable when stored as a
granulate, i.e. it must be insensitive to moisture under normal storage
conditions, and suitable for the production of highly transparent
thermoplastically formed shapes. Of special interest are highly expandable
films which are resistant to cold water and have a particularly smooth
surface. This starch mixture has application in the production of
co-extruded films with further polymers without the addition of adhesives.
DETAILED DESCRIPTION OF THE INVENTION
Surprisingly, it has been found that a highly transparent, single-phase,
biodegradable starch mixture may be produced from a starch molding
composition which contains chemically modified starch and a selected
biodegradable polyamide, without the necessity of a polymeric
compatibilizer for thermoplastic processing.
All parts and percentages throughout the specification and claims are by
weight unless otherwise stated. The starch mixture according to the
invention comprises
(a) 10 to 99 parts of at least one starch molding composition which
comprises
(i) 96 to 46 parts of at least one chemically modified starch,
(ii) 4 to 40 parts of at least one plasticizer, and
(iii) 0 to 4 parts of at least one additive, in particular selected from
urea, urea derivatives, emulsifiers, and mixtures thereof,
wherein (i), (ii), and (iii) total 100 parts, and
(b) 90 to 1 parts of at least one selected polyamide,
wherein components (a) and (b) total 100 parts and
(c) 0 to 20 parts of additives.
The chemically modified starch has a natural water content of 5% to 16%,
preferably 5% to 12%, most preferably 6% to 8%. This generally results in
a final water content in the highly transparent starch mixture of 2% to
8%, preferably 2% to 5%.
The preferred starch molding composition is produced by a process described
in German Patent Application DE 41 17 628.6, wherein a mixture of
chemically modified starch having a natural water content, at least one
plasticizer, urea and/or urea derivatives, and at least one emulsifier are
destructurized at elevated temperatures and pressures in an extruder and
are extruded as a melt. Typical emulsifiers are metal stearates, glycerol
monostearate, polyoxyethylene(20)-sorbitan monolaurate,
polyoxyethylene(20)-sorbitan monopalmitate, polyoxyethylene(40)-stearate,
polyoxyethylene(100)-stearate, and mixtures thereof.
One form of the process comprises:
a) introduction of a chemically modified starch into the intake region of
an extruder and conveyance thereof in a downstream direction,
b) addition of a pre-homogenized mixture of liquid anhydrous plasticizer,
emulsifier, and any desired additives, mixing thereof with the starch
while continuing to convey the combined starch and mixture downstream,
c) destructurization of the starch granules without addition of extraneous
water, and complete plasticization of the mixture to form a homogeneous,
thermoplastically processible melt, and conveying the melt downstream to a
degasification chamber,
d) degasification of the melt and further conveyance thereof to an
extrusion chamber,
e) extrusion of the melt through a die.
The material being processed is exposed to elevated temperatures in b) to
e), reduced pressure in d), and elevated pressure in e).
As a modification of the foregoing process, the chemically modified starch
and plasticizer are separately introduced into the intake region of the
extruder. They are mixed and conveyed to the next chamber into which a
pre-homogenized mixture of the emulsifier and the additives is introduced.
All of the ingredients are blended to form the mixture of starch,
plasticizer, emulsifier, and additives. The remainder of the process is
the same as that described above.
The chemically modified starch is produced by reaction of the OH groups of
the original starch with alkylene oxides or other ether-, ester-,
urethane-, and/or carbamate-forming substances. Hydroxy alkyl of 2 to 6
carbon atoms, acetyl, and carbamate starches or mixtures thereof are
preferred. The degree of substitution of the chemically modified starch is
0.01 to 0.2 and the amylose content is 20% to 100% by weight, particularly
preferably 50% to 100% by weight.
The plasticizer is an organic compound containing at least 1 hydroxyl
group, preferably a polyol, most preferably sorbitol, mannitol, D-glucose,
ethylene glycol, polyethylene glycol, propylene glycol, or mixtures
thereof. It is used in amounts of 4 to 40 parts, preferably 9 to 40 parts,
most preferably 10 to 30 parts, per 100 parts of the modified starch
molding composition. One or more additives are introduced totaling 0 to 4
parts per 100 parts of starch molding composition. Urea, urea derivatives,
and/or emulsifiers are preferred. The urea or urea derivatives, if used,
are present in amounts of 0.1 to 2 parts, preferably 0.1 to 1 part, most
preferably about 1 part, per 100 parts of starch molding composition.
The emulsifier has a hydrophilic-lipophilic balance of 0 to 20, preferably
10 to 20 and, if used, is in amounts of 0.1 to 1 parts, preferably about
0.2 parts, per 100 parts of starch molding composition. Suitable
emulsifiers include metal stearates, glycerol monostearates,
polyoxyethylene(20)-sorbitane monolaurate, polyoxyethylene(20)-sorbitane
monopalmitate, polyoxyethylene(40)-stearate, and/or
polyoxyethylene(100)-stearate.
In a preferred embodiment, component (a) consists of 70 parts of
hydroxyethyl and/or hydroxypropyl starch (having a degree of substitution
of 0.06 and an amylose content of 50%), 15 parts of glycerol, 13.8 parts
of sorbitol, 1 part of urea, and 0.2 parts of magnesium stearate.
Aliphatic polyamides having melting or softening points of 50.degree. C. to
160.degree. C., and melt flow indices (MFI) of 100 to 5000 Pa.s (at
160.degree. C. and 21.2 N), are suitable as (b). Of particular interest
are homopolyamides and/or copolyamides of at least one of
.omega.-aminocaproic acid, .omega.-aminoenanthic acid,
.omega.-aminocaprylic acid, .omega.-aminopelargonic acid,
.omega.-aminocapric acid, .omega.-aminoundecylic acid, .omega.-aminolauric
acid, caprolactam, lactam-7, lactam-8, lactam-9, lactam-10, lactam-11, and
laurolactam have been found to be suitable. Also, worthy of special
mention are homo- and/or copolyamides of methylene diamine, dimethylene
diamine, trimethylene diamine, tetramethylene diamine; pentamethylene
diamine, and hexamethylene diamine with oxalic acid, malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic
acid, undecanedioic acid, and dodecanedioic acid. Polyamides based on
caprolactam, laurolactam, .omega.-aminolauric acid, .omega.-aminocaproic
acid, hexamethylene diamine with adipic acid, and mixtures thereof are
preferred.
Optical brighteners, stabilizers, antioxidants, flame proofing agents,
dyes, fillers, processing aids, and the like are also used as additives in
amounts of 0 to 20 parts per 100 parts of starch mixture. The additives
may be introduced either during the production of the starch mixture or
preferably to (a) and/or (b).
In another preferred embodiment, the single-phase starch mixture according
to the invention contains 50 to 95 parts of (a), 50 to 5 parts of (b); 70
to 95 parts of (a) and 30 to 5 parts of (b) are particular preferred. The
transparency of the starch mixture according to the invention is generally
proof that it is a single phase.
The process for producing the highly transparent starch mixture according
to the invention comprises fusion of (a) and (b) in a ratio of 10/90 to
99/1 in an extruder or an injection molding machine. The temperatures are
not higher than 10.degree. C. below the decomposition point of the starch
and not lower than 50.degree. C. above the melting or softening point of
the polyamide.
The starch mixture according to the invention can be further processed into
highly transparent, thermoplastically shaped parts. It is preferred that a
granulate first be produced; it is then used for the manufacture of shaped
articles. These may be formed by injection molding, blow molding,
extrusion, co-extrusion, injection stamping, or thermo-forming. The
production of mono- or co-extruded films as flat or blown films is
particularly preferred.
There are many advantages of the starch mixtures according to the invention
and shaped articles produced from it; they include
1. High transparency
2. Very smooth surfaces, free from exudation marks
3. Single phase compatibility without need of a polymeric compatibilizer
4. Biodegradability
5. Good tensile strength and elongation at break
6. Low moisture uptake from the air; therefore the granulates are stable in
storage
7. Simple processing into films and co-extruded films without a tendency to
block formation and tackiness.
8. Good adhesion of the co-extruded film layers without addition of an
adhesive
9. High expandability
10. Welding of the films using conventional heat sealing devices
11. Anti-static behavior
12. Printability using water soluble dyes
For the production of the co-extruded films consisting of layers of the
transparent starch mixture and layers of further polymers, these further
polymers should have a melting or softening point of 50.degree. C. to
160.degree. C. Polyamides, polyesters, polyolefins, and mixtures thereof
are suitable for this purpose. Polyolefins selected from polyethylene,
polypropylene, polybutylene, and derivatives thereof are preferred.
Polyethylene and its derivatives are particularly preferred.
In another specific embodiment, the highly transparent starch mixture forms
the middle layer and the further polymer(s) form the upper and lower
layers of the co-extruded film. The starch mixture layer may also appear
several times in the case of more than three film layers. In further
embodiments of the co-extruded film, the highly transparent starch mixture
may also form the upper and/or lower layer.
All films or sheets may be produced in a thickness of 20 to 500 .mu.m,
preferably 50 to 100 .mu.m. They are suitable, for example, for carrier
bags, sacks, refuse bags, agricultural films, diaper covering films, and
for biologically degradable films and sheets of any type. Furthermore, all
films may be subjected to thermoplastic forming processes such as deep
drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic view of an extruder for use in connection with the
present invention.
The following examples illustrate the invention without restricting it. All
percentages, unless otherwise stated, are based on the total mixture of
starting materials.
I. Production of the Starch Molding Composition [Component (a)]
Example 1a
A starch molding composition was produced from 70 parts of hydroxypropyl
cornstarch (having a degree of substitution of 0.06 and an amylose content
of 50%), 15 parts of glycerol, 12.8 parts of sorbitol, 2 parts of urea,
and 0.2 parts of magnesium stearate by the process described hereinafter,
and was subsequently granulated.
Extruder data:
a) Heating zones:
(1) Room temperature
(2) 130.degree. C.
(3) 130.degree. C.
(4) 100.degree. C.
(5) 100.degree. C.
(6) 150.degree. C.
b) Pressure zone (6): 30-40 bar
c) Torque: 70%
d) Vacuum: -0.4 bar
70 parts of hydroxypropyl cornstarch, having a degree of substitution of
0.06 and an amylose content of 50%, and 12.8 parts of sorbitol were
introduced separately at point 7 in FIG. 1 into the intake region (heating
zone 1) of a co-rotating, intermeshing, twin screw extruder; the extruder
(shown in FIG. 1) has a screw length to diameter ratio of 41. The starting
materials were simultaneously mixed and conveyed to heating zone 2. At a
temperature of 60.degree. C., 0.2 parts of magnesium stearate were
dissolved with 2 parts of urea in 15% by weight of glycerol. This
pre-homogenized mixture of plasticizer, emulsifier, and additives was
introduced into the extruder (heating zone 2) at point 8 in FIG. 1, and
simultaneously mixed and conveyed onto heating zone 3. After
destructurizing of the starch granules and complete plasticization of the
starch mixture in the kneading chamber 11 (see heating zones 2 and 3) to
form a homogeneous melt, the melt was degasified by application of a
vacuum at point 9 in FIG. 1 (heating zone 4). After passing through
heating zone 5, the homogeneous, thermoplastically processible starch melt
was extruded through a die in heating zone (6) as a strand having low
strand expansion (die: 3 mm, strand: 4 mm), cooled, and granulated.
Example 1b
The same procedure as in Example 1a was followed except for a urea content
of 1 part and a sorbitol content of 13.8 parts.
II. Production of the Biologically Degradable, Single-phase Highly
Transparent Starch Mixture
Comparison Examples 2 to 12 and Examples 13 to 24 According to the
Invention
The starch granulate from Example 1a or 1b was mixed with the granulate of
polyamide (b) and was introduced into the metering zone of a twin screw
extruder ZSK-30 (made by Werner & Pfleiderer) with 6 heating zones. Speed
and throughput were 100 rpm and 8 to 10 kg/h respectively. The production
parameters are set forth in Table 1 and the material properties of the
resultant starch mixtures are shown in Table 2.
The melt viscosities of the polyamides (b) were determined at 160.degree.
C. and 21.2 N in accordance with DIN 53 735. The melt viscosities of the
starch mixtures were measured at 160.degree. C. and 236.4 N by a modified
melt flow index method. The water content was determined by the
Karl-Fischer method in accordance with DIN 53 714, and the melting point
by differential calorimetry in the dry state at a heating rate of
20.degree. C./min in a Du Pont Thermal Analyzer, type 1091B. The
mechanical properties were determined in the dry state by means of
injection molded test rods according to DIN 53 457 (elongation modulus)
and DIN 53 455 (tensile strength and elongation at break). The resistance
to moisture was determined in cold water by measuring the swelling. For
this purpose, pieces of film measuring 100 cm.sup.2 were left in cold
water for one hour and their water uptake was then determined by weight
measurement. The dissolution of the starch mixtures in hot water is a
condition for their biological degradability.
The following commercial products were used in the Examples and Comparison
Examples:
Grilon CF 62 BSE is a copolyamide based on the monomers of polyamide 6 and
polyamide 6.9 made by EMS-CHEMIE and having a melting point of about
136.degree. C.
Grilon CR 9 is a copolyamide based on the monomers of polyamide 6 and
polyamide 12 made by EMS-CHEMIE and having a melting point of about
200.degree. C.
Grilon CA 6E is a copolyamide based on the monomers of polyamide 6 and
polyamide 12 made by EMS-CHEMIE and having a melting point of about
130.degree. C.
Grilamid ELY 60 is a copolyamide made by EMS-CHEMIE, based on lactam-12,
polyether diamine, and dimerized fatty acid, and having a melting point of
about 160.degree. C.
Griltex 1 is a copolyamide made by EMS-CHEMIE, based on the monomers of
polyamide 6, polyamide 12, and polyamide 6.6, having a melting point of
about 110.degree. C. and a melt viscosity (DIN 53 735) of about 600 Pa.s
(21.2 N/160.degree. C.).
Griltex 2 is a copolyamide made by EMS-CHEMIE, based on the monomers of
polyamide 6, polyamide 12, and polyamide 6.6, having a melting point of
about 125.degree. C. and a melt viscosity (DIN 53 735) of about 400 Pa.s
(21.2 N/160.degree. C.).
Griltex 3 is a copolyamide made by EMS-CHEMIE, based on the monomers of
polyamide 6, polyamide 12, and polyamide 6.6, having a melting point of
about 110.degree. C. and a melt viscosity (DIN 53 735) of about 500 Pa.s
(21.1 N/160.degree. C.).
Griltex 4 is a copolyamide made by EMS-CHEMIE, based on the monomers of
polyamide 6, polyamide 12, and polyamide 6.6, and having a melting point
of about 110.degree. C. and a melt viscosity (DIN 53 735) of about 100
Pa.s (21.2 N/160.degree. C.).
Griltex 5 is a copolyamide made by EMS-CHEMIE, based on the monomers of
polyamide 6, polyamide 12, polyamide 6.6, polyamide 6.9, and polyamide 11,
having a melting point of about 80.degree. C. and a melt viscosity (DIN 53
735) of about 150 Pa.s (21.2 N/160.degree. C.).
TABLE 1
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Production parameters for the highly transparent starch mixtures
according to the invention and comparison
examples
Polyamide
Content
Melting.sup.1
Melt (Parts
Starch
Point Viscosity.sup.2
by Type T1 T2 T3 T4 T5 T6 Tm.sup.3
Example
Type (.degree.C.)
(Pa .multidot. s)
weight)
Example
(.degree.C.)
(.degree.C.)
(.degree.C.)
(.degree.C.)
(.degree.C.)
(.degree.C.)
(.degree.C.)
__________________________________________________________________________
2a + 2*
Grilon CF 62 BSE
136 3100 50 1a 0 140
145 145
145 150
167
3* Grilon CF 62 BSE
136 3100 40 1a 0 140
145 145
145 150
163
4* Grilon CF 62 BSE
136 3100 30 1a 0 140
145 145
145 150
161
5* Grilon CF 62 BSE
136 3100 20 1a 0 140
145 145
145 150
157
6* Grilon CF 62 BSE
136 3100 10 1a 0 140
145 145
145 150
165
7* Grilon CR 9
200 -- 50 1a 0 210
230 230
230 240
235
8* Grilon CA 6E
130 3600 50 1a 0 140
140 140
140 150
165
9* Grilamid ELY 60
160 -- 50 1a 0 150
170 150
150 170
179
10* Grilamid ELY 60
160 -- 30 1a 0 150
170 150
150 170
180
11* Grilamid ELY 60
160 -- 10 1a 0 150
170 150
150 170
178
12* Grilamid ELY 60
160 -- 5 1a 0 150
170 150
150 170
179
13 Griltex 1 110 600 50 1a 0 150
150 130
130 150
151
14 Griltex 1 110 600 40 1b 0 150
150 130
130 150
145
15 Griltex 1 110 600 30 1b 0 150
150 130
130 150
147
16 Griltex 1 110 600 20 1b 0 150
150 130
130 150
149
17 Griltex 1 110 600 50 1b 0 150
150 130
130 150
147
18 Griltex 1 110 600 10 1b 0 150
150 130
130 150
153
19 Griltex 1 110 600 5 1b 0 150
150 130
130 150
153
20 Griltex 2 125 400 50 1b 0 150
150 130
130 150
150
21 Griltex 2 125 400 20 1b 0 150
150 130
130 150
153
22 Griltex 3 110 500 50 1b 0 150
150 130
130 150
143
23 Griltex 4 110 100 50 1b 0 150
150 130
130 150
143
24 Griltex 5 80 150 50 1b 0 120
100 100
100 130
125
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*Comparison examples
.sup.1 Melting point according to DSC
.sup.2 Melt viscosity at 160.degree. C. and 21.2 N according to DIN 53 73
.sup.3 Tm = Melt temperature
TABLE 2
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Material properties of highly transparent starch mixtures according to
invention and comparison examples
Modulus.sup.4
Tensile.sup.5
Cold
Water.sup.1
Melting.sup.2
Melt.sup.3
of strength
Elongation.sup.6
water
(% by
Point Viscosity
Elasticity
at break
at break
swelling
Hot water
Trans-
Example
weight)
(.degree.C.)
(Pa .multidot. s)
(N/mm.sup.2)
(N/mm.sup.2)
(%) (%) dissolutn.
parency
Colour
__________________________________________________________________________
2a 11.6 -- 259 78 10.5 434 max. 10
Yes No +
2* 4.4 107 1867 254 21.1 404 max. 10
Yes No +
3* 2.2 111 4508 499 17.5 221 max. 10
Yes No +
4* 1.8 115 6500 1038 26.6 4 max. 10
Yes No 0
5* 1.6 113 8000 1393 30.4 3 max. 10
Yes No 0
6* -- -- -- -- -- -- Dissolutn.
Yes No 0
7* -- -- -- -- -- -- -- No -
8* -- -- -- -- -- -- -- No +
13 5.5 143 215 117 14.6 434 max. 10
Yes Good +
14 7.65 145 255 71 13.0 520 max. 10
Yes Good ++
15 7.57 147 275 110 9.6 355 max. 10
Yes Very
++od
16 8.11 149 271 89 6.4 220 10-20 Yes Very
++od
17 5.59 147 263 -- -- -- max. 10
Yes Good ++
18 4.60 165 2840 190 9.3 64 Dissolutn.
Yes Very
++od
19 4.43 163 3575 160 8.2 65 Dissolutn.
Yes Good 0
20 7.60 146 265 75 14.0 510 max. 10
Yes Very
++od
21 8.05 148 283 92 7.5 210 Dissolutn.
Yes Good ++
22 -- -- -- -- -- -- max. 10
Yes Good ++
23 -- -- -- -- -- -- max. 10
Yes No ++
24 -- -- -- -- -- -- max. 10
Yes No ++
__________________________________________________________________________
*Comparison examples
.sup.1 Final water content according to DIN 53 714
.sup.2 Melting point according to DSC
.sup.3 Melt viscosity at 160.degree. C. and 236.4 N
.sup.4 Elongation modulus according to DIN 53 457
.sup.5,6 according to DIN 53 455
While only a limited number of specific embodiments of the present
invention have been expressly disclosed, it is, nonetheless, to be broadly
construed, and not to be limited except by the character of the claims
appended hereto.
* * * * *
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