JP3363246B2 - Biodegradable cellulose derivative molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to processability and various
Cellulose with excellent physical properties and good biodegradabilityAcetate
GIt relates to a molded product. [0002] 2. Description of the Related Art Internally in cellulose derivatives
Alternatively, external plasticization is performed to enhance moldability and facilitate processing.
Conventionally, various methods have been proposed. [0003] For example, an unsaturated monomer is added to a cellulose derivative.
Radical polymerization and ionization of
Graft polymerization by ring-opening polymerization
Therefore, a cellulose derivative that is easier to process
(Japanese Patent Laid-Open No. 50-48032,
"Editing Committee for Polymer Science, Molecular Society of Japan"
Volume Polymer Reaction '' (Kyoritsu Shuppan, 1978) p.147-p.192
etc). However, the reaction in these methods is
Is mainly polymerized by addition polymerization of radical polymerization and ionic polymerization
Generally, grafting with a cellulose derivative
Very low yield of polymer or block copolymer
Often. In addition, the graft weight on cellulose itself
Many publications have been published, and the above book "Polymer Experiment
Vol.6 Polymer Reaction ”p.147-p.192
Shin Kawahara, "Lecture on Polymerization Reaction (10) Chemical Reaction of Polymers"
(Above) "(published by Kagaku Doujin in 1972).
Have been. However, these documents do not
Cell for graft polymerization to cellulose itself
As in the case of the loin derivative, mainly the polymerizable monomer is
Polymerization by addition polymerization (radical polymerization, ionic polymerization, etc.)
Compound, and other examples are slightly cellulose
Ethylene oxide, ethylene imine or
There are several examples of reacting β-propiolactone etc.
Not just. Further, a cellulose derivative having excellent solubility is used.
Some research has been conducted with the aim of obtaining
It is found in JP-A-59-86621. Here, the cell
Ring-opening polymerization of cyclic ester in the presence of
To produce a new graft polymer with a high graft ratio
And the graft polymer is transparent.
To be a new polymer material with good properties, film forming properties and solubility
I have found it. However, even in this case, the graft reaction
Time is quite long, 14-20 hours (reaction temperature 140-170 ° C)
This is a problem as an industrial manufacturing method. Also,
In the above reaction, a large amount of solvent such as xylene is used.
These are considered to be problems from a practical point of view. [0006] Recently, from the viewpoint of environmental impact,
So-called biodegradable plastics are attracting attention.
And aliphatic polyesters (for example, synthetic polyesters).
"Bionore" (Showa High Polymer Co., Ltd.) attracts attention
I am collecting. This polyester is processable, biodegradable and
And physical properties are excellent, but there are difficulties in price and practical
Poor sex. In addition, polymer materials derived from natural polymers
What is noticed in the food is poly milk derived from starch
Acid, which also has excellent biodegradability, processability and physical properties
But there is a disadvantage in price. Best biodegradable polymer materials
Most applications are packaging used in supermarkets, etc.
Disposable plastic products such as trays and shopping bags
It is considered as low cost performance as possible
It is desirable to use a fee. [0007] In addition, biodegradable plastics
In recent years, cellulose acetate with a substitution degree of up to 2.5
Biodegradability under conditions close to the natural environment such as in activated sludge
(C. M. Buchanan et al.,
 J. Appl. Polym. Sci.,47, 1709 (1993); ibid.,50, 173
9 (1993); Ji-Dong Gu et al., J. Environ. Polym. Degr
adation,1(2), 143 (1993)]. However, this cell
Loose acetate has relatively good cost performance
However, it is not yet satisfactory in terms of biodegradability.
Plastic material that is more biodegradable
One of the objects of the present invention is to obtain efficiently from a loin derivative.
One. [0008] Means for Solving the Problems The present inventors have identified the above problems.
Has not been replaced as a result of intensive studies to resolve
Cellulose having hydroxyl groupacetateIn the presence of polysalt
Base acid or its anhydride, monoepoxide compound or polyvalent
Esterification reaction with alcohol, twin-screw extruder, etc.
And preferably kneading at 60 to 250 ° C for about 5 to 40 minutes.
Molding processability and various physical properties
Excellent thermoplastic celluloseacetateEfficient composition
And a molded article formed from the composition is non-
The present inventors have found that they always show excellent biodegradability, and reached the present invention.
Has been reached. That is, the present invention has an unsubstituted hydroxyl group.
celluloseacetateIn the presence of polybasic acid or its
Water and monoepoxide compound or polyhydric alcohol
The biodegradable cell consisting of the composition obtained by the reaction
LuloseacetateIt relates to a molded product. The thermoplastic cellulose used in the present inventionA
AcetateUnsubstituted hydroxyl used as starting material for composition
Cellulose with groupsacetateAs the cellulose
Cellulose such as diacetate and cellulose monoacetate
Ace acetateIsNo. In particular, cellulose diase
TheIspreferable. To get better biodegradability
Low substitution celluloseacetateIs preferred, but with resin
It is necessary to determine the substitution degree in consideration of the physical properties of the material. Also, the thermoplastic cellulose used in the present invention
SourceacetatePolybasic anhydride used in the production of the composition
Products include maleic anhydride, itaconic anhydride,
Succinic acid, adipic anhydride, glutaconic anhydride, glue anhydride
Talic acid, diglycolic anhydride, citraconic anhydride, anhydrous
Diphenic acid, nitrophthalic anhydride, phthalic anhydride, anhydride
Phthalonic acid and the like, preferably maleic anhydride
Acid, succinic anhydride, itaconic anhydride, adipic anhydride
used. Also, the thermoplastic cellulose used in the present invention
SourceacetateMonoepoxy used in the manufacture of compositions
Compounds include allyl glycidyl ether, phenyl
Glycidyl ether, styrene oxide, butyl glyci
Zyl ether, alkylphenol glycidyl ether
, Cresyl glycidyl ether, polyfunctional glycidyl ether
-Ter, tertiary fatty acid monoglycidyl ether, glycidyl
Epoxy acrylates such as
Ricidyl ether acrylate, etc.
Lil glycidyl ether, phenyl glycidyl ether
Styrene oxide, glycidyl methacrylate, etc.
Is preferred. Further, the thermoplastic cellulose used in the present invention
SourceacetatePolyhydric alcohol used in the production of the composition
Ethylene glycol, 1,4-butanediol
1,6-hexanediol, glycerin, polyethylene
Glycol, polypropylene glycol, etc.
Especially ethylene glycol, glycerin, polyethylene.
Len glycol is preferred. The thermoplastic cellulose used in the present inventionA
AcetateThe composition may optionally include a flame retardant, stabilizer, ultraviolet
X-ray absorbers, antioxidants, oligoesters according to the present invention
Plasticizer other than the polyester, lubricant, or decomposition,
Suitable for various additives such as deterioration accelerators, face dyes and other components.
These optional components can be blended as described above.
Even if it is charged at the reaction stage of each essential component,
May be added. The thermoplastic cellulose used in the present inventionA
AcetateThe proportion of each component when producing the composition is particularly
Without limitation, manufactured thermoplastic cellulose
SacetateOf the molded product finally obtained using the composition
Thermofluid properties related to strength properties and moldability, or biodegradation
It is desirable to determine in consideration of the nature. General below
But it is of course limited to this
There is no. (1) Cellulose having unsubstituted hydroxyl groupacetate         100 parts by weight (2) Polybasic acid or its anhydride 3-60 parts by weight (3) Monoepoxide compound or polyhydric alcohol 3 to 60 parts by weight (4) Optional ingredients Required amount. The polybasic acid or its anhydride, monoepoxide
Regarding the amount of oxide compound and polyhydric alcohol used
If the amount is not particularly limited,
%, Each 3-60% by weight, preferably 5-40% by weight
A composition which is physically preferable to be used in the range is obtained.
You. In preparing the composition of the present invention, each component
There is no particular limitation on the method of compounding
-, Banbury mixer, extruder, high-speed rotary mixer, etc.
Melting, kneading, etc. are performed, but especially extrusion
It is a preferable method to carry out the operation with a piling machine. Each component is reserved
Before mixing and kneading with these devices.
Reactivity by diffusion of reagents by standing for ~ 12 hours
Improvement can be expected and is preferable. The biodegradable molded article of the present invention can be used as described above.
Thermoplastic cellulose produced byacetateComposition
By a conventional method, pressure molding, film molding, extrusion molding,
It can be molded into a desired shape by means such as injection molding.
Can be Specifically, the shape of a film, sheet, foam, etc.
Shape, packaging container, disposable packaging container (one way container
Utensils), toys, seats, furniture parts, building materials, automobiles, home appliances
Effective use for product parts, interior materials, housing, etc.
Can be. [0019] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these examples.
Not. Embodiment 1 Absolutely dry cellulose acetate (Daicel Chemical Industries, Ltd.)
Manufacture, LL-10; degree of acetylation 44.7%; degree of substitution 1.76) 100 parts by weight,
21.6 parts by weight of maleic anhydride and phenylglycidyl
Weigh 33.1 parts by weight of ether into beaker and mix gently
After being combined, Labo Plastomi adjusted to 120 ° C
Le (manufactured by Toyo Seiki Seisakusho, batch type kneader)
The kneading bread (rotor blade) is rotated at 30 rpm
For 5 minutes and then the bread rpm to 90rpm
Raise and knead under heating for 20 minutes to perform a kneading reaction
Was. This kneaded material was prepared by Toyo Seiki Seisakusho Co., Ltd.
Hot pressing (190 ° C; 2 minutes)
0-50kgf / cm^TwoAfter preheating under pressure, 150kgf for 5 minutes
/cm^TwoTo form a sheet with a thickness of 0.4mm.
Was. Cut out strip-shaped test pieces from these sheets, and
Tensile force using Shimadzu Autograph DSC-R500
Physical properties were measured. In addition, Float manufactured by Shimadzu Corporation
Die size 1 under 50 kgf load using Star CFT-5000
Heat flow temperature and melt viscosity under the condition of using × 2mm
Was measured. As a result, the tensile strength was 66.1 MPa and the elongation at break
16.6%, Young's modulus 1520 MPa, heat pour point 174.9 ° C and melting
Excellent viscosity with a melt viscosity of 66630 poise
It showed chemical properties and remarkably large melt viscosity. Embodiment 2 A sheet was formed with the composition shown in Table 1 in the same manner as in Example 1, and the sheet was formed.
Degradation was measured as a biodegradability test for each.
Was. Degradation degree is ASTMD 5209-91It measured according to. Immediately
Test sample concentration 100ppm (100 mesh pass), under city
30 ppm of activated sludge in water treatment plant, consumed at 25 ± 1 ℃ for 4 weeks
Quantitative oxygen consumption is calculated to reduce the theoretical oxygen consumption required for complete decomposition.
The percent value obtained was defined as the degree of resolution. [0024] [Table 1]In Table 1, L-40 is Daicel Chemical Industries
It is a cellulose acetate manufactured by
It is an acetylated product. SA is maleic anhydride and AGE is
Allyl glycidyl ether, PGE is phenyl glycidyl
It is ether. Any sample of the present invention ~ control
Untreated cellulose acetate (L) which is a substance (comparative product)
L-10) Shows biodegradability as above, up to 67% after 4 weeks
Shows the resolution. As mentioned earlier, the substitution degree up to 2.5
Lulose acetate is degraded by microorganisms in activated sludge
It is already known that
Is the thermoplastic cellulose used in the present invention.acetatecomposition
Molded product is a material showing better biodegradability
It can be said that there is something. Embodiment 3 As a control sample, a non-biodegradable polypropylene
(PP), polycaprola, which is said to be biodegradable
Two types shown in Table 2 as the product of the present invention using Kuton (PCL)
Oligoesterified cellulose acetate (LL-10 / MA
/ PGE and L-40 / MA / PGE) from the same sheet as in Example 1.
Molded at a constant temperature of 30 ° C and a humidity of 80% RH.
Culture soil / humus / permiculite (8:
1: 1 (volume ratio) in soil for 1 month
I went there for another three months. Measure the total dry weight before and after the test,
The biodegradability was determined by the weight loss rate of the sample. Table 2 shows the results
Shown in [0027] [Table 2] As is clear from the results in Table 2, burial in the soil
Up to three months later, there was almost no change in PP, and
PCL, which is said to be biodegradable, loses 3% weight
The cellulosic material that constitutes the product of the present invention
Oligoesterified plasticized cellulose acetate is
When using LL-10 with a degree of substitution of 1.7,
Even when using L-40 with a degree of conversion of 2.4, it is considerably greater than PCL
Weight loss was observed. They also have a sheet shape
Markedly changed, deterioration was clearly visible from the appearance
Was. From these results, the thermoplastic cellulose constituting the present invention is also considered.
SourceacetateIf the composition is a sufficiently biodegradable material
The molded article of the present invention exhibits extremely excellent biodegradability.
I understand. Embodiment 4 Absolutely dry cellulose acetate (Daicel Chemical Industries, Ltd.)
Manufactured, LL-10; degree of acetylation 44.7%; degree of substitution 1.76) 100 parts by weight,
21.7 parts by weight of maleic anhydride and 11.7 parts by weight of glycerin
And the kneading and kneading reaction was carried out in the same manner as in Example 1.
A sheet was prepared. The physical properties of this sheet were evaluated in the same manner as in Example 1.
As a result, tensile strength 30 MPa, elongation at break 10%, Young's modulus
 950 MPa, heat pour point 185.5 ° C and melt viscosity 71300 poise
Was obtained. The biodegradability of this sheet was compared with that of Example 3.
As a result of the same evaluation, the weight loss rate after one month was 8.1%,
The weight loss rate after 3 months is 18.2%, indicating good biodegradability
Admitted. [0032]Comparative Example 1 Ethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., degree of substitution 2.4
 ) 100 parts by weight, 5.5 parts by weight of succinic anhydride and phenyl
Example 1 using 16.9 parts by weight of luglycidyl ether
A kneading-kneading reaction was carried out in the same manner as in the above to prepare a sheet. The physical properties of this sheet were evaluated in the same manner as in Example 1.
As a result, tensile strength 15 MPa, elongation at break 16.5%, Young
Rate 780 MPa, heat pour point 171.7 ° C and melt viscosity 65220 poi
The value se was obtained. The biodegradability of this sheet was compared with that of Example 3.
As a result of the same evaluation, the weight loss rate after one month was 5.8%,
The weight loss rate after 3 months is 16.9%, indicating good biodegradability
Admitted. 3 months after burial in the ground
Upon observation, erosion by microorganisms was observed.

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Claims (1)

(57) [Claim 1] Cellulose acetyl having an unsubstituted hydroxyl group
In the presence of lactate, polybasic acid or its anhydride, monoepoxide compound or polyhydric an alcohol comprising the composition obtained by reacting a biodegradable cellulose Asete
Sheet moldings.