JP3367750B2 - Thermoplastic cellulose derivative composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulose derivative composition having improved thermoplasticity. More specifically, a molded article obtained by using the composition has sufficient mechanical strength, smoothness and coating property. The present invention relates to a thermoplastic cellulose derivative composition which is excellent in water resistance and has a melt viscosity and a melt property at the time of molding which are generally within a range capable of being molded.

[0002]

2. Description of the Related Art In the molding of cellulose derivatives, the proportion by wet processing is extremely high,
Molding by dry molding using heat and force is not so much done. Cellulose derivatives with high thermoplasticity and plasticity include cellulose diacetate, ethyl cellulose, and nitrocellulose among industrial products, but compared to general-purpose polymers such as polystyrene and polypropylene, they have higher plasticity and heat fluidity. It is inferior, and it is necessary to add a large amount of plasticizer for dry molding. For example, in the case of cellulose diacetate, diethyl phthalate is used as a plasticizer at 22-
38% is mixed and mixed for several hours to obtain the required moldability.

Conventionally, biodegradation of cellulose acetate and the like
Most of the studies on cellulase
And cellulose acetate with a degree of substitution of 1 or more is a raw material.
It was thought to not be understood. However, recently
Cellulosics in an environment where various microorganisms survive, such as in sludge
Source acetates with acetyl substitution up to about 2.5
Was found to show a clear biodegradation
(C. M. Buchanan et al., J. Appl. Polym. Sci.,Four
7, 1709 (1993); ibid.,50, 1739 (1993); Ji-Dong Gue
t al., J. Environ. Polym. Degradation,1(2), 143 (1
993)). This result shows that in an experimental system involving activated sludge,
Lulose acetate is biodegradable and is a traditional stereotype
It can be said that it defeats. Thus cellulose
With regard to acetate as well, its biodegradability should be fully taken into consideration
It has become important to achieve
See the development status of the biodegradable polymeric materials based on the loose derivative
And satisfy both physical properties and cost performance
It can be said that things have not appeared yet.

In view of the above problems, the object of the present invention is to provide the cellulose derivative with sufficient heat fluidity and moldability, and further to impart good biodegradability.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors under the above-mentioned idea, as a reaction agent (plasticizer) for plasticizing a cellulose derivative, an unsaturated carvone derived from a natural product is used. A modified unsaturated fatty acid or an ester thereof modified with an acid or a modified α-olefin modified with an unsaturated carboxylic acid derived from a natural product can effectively plasticize a cellulose derivative, and at the same time, the biodegradability of a plasticized composition. The present invention has been completed and the present invention has been completed. As a result of various studies on the relationship between the chemical structure of the plasticizer and the susceptibility of the cellulose diacetate to plasticization, it was found that the combined use of a polymer or starch of lactone or occlusion is effective.

That is, the present invention relates to a cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified unsaturated fatty acid or its derivative. Cellulose in which an α-olefin (B) and a modified unsaturated fatty acid or an ester thereof modified with an unsaturated carboxylic acid or a derivative thereof or a modified α-olefin modified with an unsaturated carboxylic acid or a derivative thereof is introduced by an ester bond. Derivative (C)
The present invention provides a thermoplastic cellulose derivative composition containing:

The present invention is also modified with a cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or an unsaturated carboxylic acid or its derivative. Modified α-olefin (B), lactone or polymer (D) thereof and modified unsaturated fatty acid or ester thereof modified with unsaturated carboxylic acid or derivative thereof, modified α-modified with unsaturated carboxylic acid or derivative thereof Provided is a thermoplastic cellulose derivative composition containing a cellulose derivative (E) in which an olefin or lactone or a polymer thereof is introduced by an ester bond.

The present invention further relates to a cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified derivative with an unsaturated carboxylic acid or its derivative. α-olefin (B), starch (F), modified unsaturated fatty acid or its ester modified with unsaturated carboxylic acid or its derivative, or modified α-olefin modified with unsaturated carboxylic acid or its derivative is an ester bond. The cellulose derivative (C) and the unsaturated unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative or the modified α-olefin modified with an unsaturated carboxylic acid or its derivative are introduced by an ester bond. Starch derivative (G There is provided a thermoplastic cellulose derivative composition containing.

In the present invention, as the component (A), a cellulose derivative having a non-substituted residual hydroxyl group is used. Specifically, cellulose diacetate, cellulose acetate such as cellulose monoacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose ester such as cellulose acetate phthalate and cellulose nitrate, or ethyl cellulose, methyl cellulose, benzyl cellulose,
Examples thereof include cellulose ethers such as cyanoethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like. Further, as raw material cellulose, it can be sufficiently used even if its purity and degree of purification are lower than those of conventional wet processing (processing of forming it into a solution and then molding). Lignocelluloses such as fibers may also be used.

The component (B) in the present invention is a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified α-olefin modified with an unsaturated carboxylic acid or its derivative.

Any unsaturated fatty acid may be used as a raw material for the above-mentioned modified unsaturated fatty acid or modified unsaturated fatty acid ester, and examples thereof include oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid and undecylen. Acid, isocrotonic acid, crotonic acid and the like, sorbic acid containing two or more unsaturated groups, linoleic acid,
Linolenic acid, arachidonic acid, propiolic acid, etc. may also be mentioned. Furthermore, stearic acid containing a triple bond can also be used with the proviso that care is taken not to act as a crosslinking agent. As these unsaturated fatty acids, those derived from natural products are suitable.

Examples of the unsaturated carboxylic acid for modifying the above unsaturated fatty acid include maleic acid, nadic acid anhydride,
Itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, sorbic acid, acrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and the like are preferable, and maleic anhydride is particularly preferable. Further, as the derivatives of these unsaturated carboxylic acids, the metal salts, amides, imides, esters and the like of the above unsaturated carboxylic acids can be used. These unsaturated carboxylic acids and their derivatives may be used either individually or in combination of two or more.

The modified unsaturated fatty acid ester may be produced, for example, in a pressure-resistant reaction vessel in which the unsaturated fatty acid ester and the unsaturated carboxylic acid or its derivative, particularly unsaturated carboxylic acid anhydride, are mixed in an amount of 1.5 mol and 1 mol, respectively. Weigh it in, and replace it with nitrogen while heating to about 60 ° C.
After reacting at 220 ° C. for 12 hours, the latter can be radically added to the former to give an unsaturated carboxylic acid anhydride-added unsaturated fatty acid ester. In addition, subsequently, for example, in the case of the synthesis of anhydrous maleated fatty acid ester, 15 to 20 mm
After heating unreacted maleic anhydride (representative compound of unsaturated carboxylic acid anhydride) by heating at about 80 ° C under reduced pressure of Hg, the objective compound was distilled under reduced pressure at 6 mmHg and 260 ° C. The modified unsaturated fatty acid ester can be obtained by an operation such as obtaining a compound.

Needless to say, the unsaturated fatty acid ester is an ester formed from unsaturated fatty acid and alcohol, but examples of the alcohol include methanol, ethanol, propanol, butanol, allyl alcohol, benzyl alcohol and the like. However, inexpensive and easy-to-handle methanol and ethanol are particularly suitable.

Next, the α-olefin modified with an unsaturated carboxylic acid or its derivative will be described. α-Olefin is a general term for unsaturated aliphatic hydrocarbon compounds having a double bond (unsaturated group) at the end. These can be obtained by thermal decomposition of naphtha, natural gas, and refinery gas, and also by dimerization or multimerization of propylene.

The α-olefin modified with an unsaturated carboxylic acid or its derivative is synthesized as follows when the modifying species is, for example, maleic anhydride. That is, 1 mol of maleic anhydride and 1.5 mol of α-olefin were weighed in a pressure resistant reactor, and after nitrogen substitution at 60 ° C, the mixture was reacted at 220 ° C for 12 hours, and maleic anhydride radically added to α-olefin. Thus, maleic anhydride α-olefin is obtained. As described above, maleic anhydride is recovered from the crude reaction product, and then the product is separated by distillation under reduced pressure.

Examples of the modified α-olefin include octenyl succinic anhydride, dodecenyl succinic anhydride, tetradodecenyl succinic anhydride and hexadecenyl succinic anhydride. Examples of the unsaturated carboxylic acid or its derivative used for modification include those used for modification of the unsaturated fatty acid described above. Among these, dodecenyl succinic anhydride is preferable, and the amount thereof is preferably 30 to 40 parts by weight in 100 parts by weight of the total amount of the components (A) and (B).

Next, the component (C) in the present invention is one, two, or even three kinds of the above-mentioned modified unsaturated fatty acid or its ester or modified α-olefin, which is a chemical bond mainly having an ester bond. It is the introduced cellulose derivative. This type of chemically modified product can be obtained by various production methods, but generally, by kneading both components (A) and (B) under heating (60 to 250 ° C.),
(B) the residual hydroxyl group of the cellulose derivative in the component (A)
It is obtained by a condensation reaction by ester bond with the carboxyl group of the modified unsaturated fatty acid ester, modified unsaturated fatty acid or modified α-olefin as a component.

Therefore, one kind of the thermoplastic cellulose derivative composition of the present invention uses only the above-mentioned components (A) and (B) as raw materials, and kneads them to obtain (A), (B) and It may be composed of the three components (C), or may be diluted by further adding only the component (A), especially an unmodified cellulose derivative.
Further, as the raw materials, the components (A) and (B) may be added with the component (C) produced by various production methods.

In any case, in the first thermoplasticized cellulose derivative composition of the present invention, (A) itself
It only has to be composed of three components (B) and (C), and its raw material and manufacturing method are not limited. However, it is preferable that only the components (A) and (B) are used as raw materials, and the mixture is kneaded to produce. Hereinafter, a method for kneading the component (A) and the component (B) to obtain the composition of the present invention will be described. In this case, the mixing ratio of the components (A) and (B) is 40 to 98 parts by weight, preferably 50 to 95 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
Parts by weight, 60 to 2 parts by weight of component (B), preferably 50 to 5 parts by weight. Here, if the proportion of the component (A) exceeds 98 parts by weight, the thermoplasticity is greatly reduced, which is not preferable. On the other hand, if the ratio of the component (A) is less than 40 parts by weight, the plasticizer is largely deposited on the surface of the molded product, and the strength, glossiness and transparency of the molded product are deteriorated, which is not preferable.

Further, in producing a composition only with the components (A) and (B), when the component (A) is to be plasticized, if the content of the component (B) is, for example, 30% or more, the melt viscosity is Is certainly equivalent to polypropylene for injection molding and has a good condition, but in some cases, a phenomenon may occur in which the plasticizer floats on the surface over time. In such a case, it is desirable to carry out the kneading and kneading reaction by further coexisting the lactone or the polymer (D) thereof with the components (A) and (B). The presence of the component (D) solves the problem of the plasticizer floating and provides a composition having better physical properties. By adding the component (D), a modified unsaturated fatty acid or ester thereof modified by an unsaturated carboxylic acid or a derivative thereof, a modified α-olefin or lactone modified by an unsaturated carboxylic acid or a derivative thereof, or a polymer thereof can be obtained. A thermoplastic cellulose derivative composition containing a cellulose derivative (E) introduced by an ester bond is obtained, and the composition containing the components (A) to (C) has better physical properties.

The lactone (cyclic ester) as the component (D) may be one which is polymerized by ring-opening reaction by a known method, for example, propiolactone, β-butyrolactone,
α, α′-bischloromethylpropiolactone, α,
α'-Dimethyl-β-propiolactone, δ-valerolactone, β-ethyl-δ-valerolactone, 3,4,5
-Trimethoxy-δ-valerolactone, 1,4-dioxan-2-one, glycolide, trimethyl carbonate, neopentyl carbonate, ethylene oxalate, propylene oxalate, ε-caprolactone, α
-Methyl-ε-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, 4-methyl-7-isopropyl-ε-caprolactone, 3,
3,5-trimethyl-ε-caprolactone, cis-disalicylide, trisalicylide and the like can be mentioned. Among these environmental esters, it is advantageous to use ε-caprolactone, which is industrially available, easy to handle, and easy to liquefy lignocellulose. However, it may be used in combination with other lactone. (D) component is (A) and (B)
When the total amount of the components is 100 parts by weight, it is appropriate to add them in the range of 1 to 30 parts by weight.

Here, ε-caprolactone is selected as the component (D) in the coexistence of (A) and (B), but the addition amount of (B) is suppressed to about 20%, for example, 160 to 200.
When kneaded at a high temperature such as ℃, one of the fact that unsaturated carboxylic acid is present in the component (B), and also the action of the hydroxyl group possessed by the component (A), ε-caprolactone is ring-closing polymerized. And polymerizes itself to become a polyester oligomer (oligoester),
It is considered that it may react with the residual hydroxyl group of cellulose acetate or the maleloyl group of the plasticizer. As a result, the component (A) undergoes plasticization and the interaction with the plasticizer component also becomes high, so that a molded product having essentially good surface properties can be obtained.

The characteristics of the addition of ε-caprolactone are as follows.
The amount of the component (B) is suppressed to, for example, 20 parts by weight, and the amount of the component (A) is 80
When using parts by weight for plasticization, a composition having a too high melt viscosity was obtained. However, ε-caprolactone was added to the composition (for example, a total of 100 parts by weight of the component (A) and the component (B) was added). By contrast, about 20 parts by weight), it is possible to obtain a composition exhibiting processability equivalent to that of polypropylene for injection molding and at the same time excellent in surface properties of the molded product.

Although it has been described above that the lactone or its polymer (D) is added to the components (A) and (B), the component (B) is, for example, 40 parts by weight and the component (A) is 60 parts by weight. It is also known that a method in which the melt viscosity is made smaller than that of polypropylene (general-purpose plastic) as a weight part, and at the same time starch (F) is added as a material capable of effectively reacting with the component (B) is also effective. It was By thus adding the component (F), a modified unsaturated fatty acid or ester thereof modified by an unsaturated carboxylic acid or a derivative thereof or a modified α-olefin modified by an unsaturated carboxylic acid or a derivative thereof is added to the composition. However, there is a starch derivative (G) introduced by an ester bond.

Examples of the starch as the component (F) include ground starch such as corn starch, waxy corn starch and wheat starch, subterranean starch such as tapioca starch and potato starch, and starch rich in amylose or amylopectin. . In this case, the addition amount of the component (F) is appropriately in the range of 5 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). When the amount of the component (F) is 80 parts by weight or more, the matrix resin is deficient and forms a continuous phase, the sea-island structure in which starch is an island cannot be taken, and the transparency and gloss of the molded product are poor. Therefore, there is a problem in strength, which is not preferable. On the other hand, if the amount of the component (F) is 5 parts by weight or less, it is not possible to prevent the component (B), which is added in a large amount, from leaking to the surface, which is not preferable.

The thermoplastic cellulose derivative composition of the present invention comprises the above-mentioned components (A), (B) and (C), or (A), (B), (D) and (E). Component, or (A) component, (B) component, (C) component,
Although it contains the component (F) and the component (G), it is desirable that the respective components are uniformly mixed in the composition so that the required kneading reaction proceeds properly.

The kneading for obtaining the composition of the present invention can be carried out by a conventionally known method, for example, a mixer such as a Banbury mixer or a Henschel mixer, a kneader, or various extruders. The kneading conditions can be appropriately determined according to the type and amount of each component, the kneader used, and the like. For example, when a kneader or Banbury mixer is used, the temperature is 60 to 250 ° C., preferably 70 to 230 ° C., and it is suitable to knead at this temperature for 5 to 40 minutes, preferably 10 to 35 minutes.

In kneading, the order of adding the above-mentioned components is not particularly limited, but it is preferable that all the components are first mixed at room temperature and then added to the kneading machine in the amounts used as described above. preferable.

If desired, the resin molded product of the present invention contains a flame retardant, a stabilizer, an ultraviolet absorber, an antioxidant, a plasticizer,
Various additives such as lubricants or decomposition and deterioration accelerators, facial dyes and other components can be appropriately mixed.

The thermoplastic cellulose derivative composition of the present invention obtained as described above is usually formed into a shape of powder, particles, pellets, flakes or the like as a raw material for molding. The thermoplastic cellulose derivative composition of the present invention in the shape of flakes obtained in this manner is molded into a desired shape by a method such as pressure molding, film molding, extrusion molding, injection molding, etc. Molded articles can be manufactured.
However, in some cases, the composition of the present invention obtained by kneading can be directly molded into a desired molded product. Further, the thermoplastic cellulose derivative composition of the present invention shows not only good physical properties but also excellent biodegradability, and it is necessary to control the biodegradability and physical properties to be preferable depending on the molded article. It is easy by adjusting the compounding amount.

Specific embodiments of the above-described thermoplastic cellulose derivative composition of the present invention and a method for producing the same will be briefly described below.

The first aspect of the present invention is, maleic anhydride unsaturated fatty acid ester, maleic unsaturated fatty acid anhydride, or maleic α-olefin anhydride,
Further, in some cases, any mixture thereof and the cellulose derivative having an unsubstituted hydroxyl group are reacted by performing an appropriate reactive processing reaction such as a kneading reaction under heating at a temperature in the range of 60 to 250 ° C. to react with maleic anhydride. Unsaturated fatty acid ester or maleated unsaturated fatty acid anhydride, or maleic anhydride α-olefin, and in some cases, a part or almost all of a mixture thereof is introduced into the cellulose derivative through an ester bond to obtain a desired heat A cellulose derivative composition having plasticity and thermoplastic moldability is obtained.

In a second aspect of the present invention, the maleic anhydride unsaturated fatty acid ester or the maleic unsaturated fatty acid anhydride, or the maleic α-olefin anhydride, and, in some cases, any mixture thereof are treated with a lactone. (Cyclic ester) is also allowed to coexist with a cellulose derivative having an unsubstituted hydroxyl group, and a reactive reactive processing reaction such as a kneading reaction is performed under heating at a temperature in the range of 60 to 250 ° C to allow reaction with maleic anhydride. Unsaturated fatty acid ester or maleic anhydride unsaturated fatty acid, or part or almost all of maleic anhydride α-olefin, and further lactone and its polymer are chemically bonded to the cellulose derivative to obtain a desired heat as a whole. A cellulose derivative composition having plasticity and thermoplastic moldability is obtained.

The third aspect of the present invention further comprises a maleic unsaturated unsaturated fatty acid ester, or a maleic unsaturated unsaturated fatty acid, or alternatively a maleated α-olefin anhydride, and optionally any mixture thereof.
Under the condition that starch also coexists, the cellulose derivative having an unsubstituted hydroxyl group is subjected to an appropriate reactive processing reaction such as a kneading reaction under heating in the range of 60 to 250 ° C to cause a reaction, and then maleic anhydride unsaturated A fatty acid ester or maleic anhydride unsaturated fatty acid, or alternatively, a part or almost all of maleic anhydride α-olefin is introduced into the cellulose derivative and starch by a chemical bond,
A cellulose derivative having desired thermoplasticity and thermoplastic moldability as a whole is obtained.

[0036]

EFFECTS OF THE INVENTION The thermoplastic cellulose derivative composition of the present invention achieves effective plasticization, and while the conventional cellulose derivative is mainly formed by wet processing, the composition of the present invention is hot pressed. It becomes possible to highly utilize it as a material in the dry processing field by the action of. The conventional plasticization of cellulose diacetate using a general-purpose plasticizer such as diethyl phthalate requires a great deal of time for blending, and is a poorly efficient process. On the other hand, the plasticizing method of the present invention centering on internal plasticization by kneading is effective and enables blending in a short time.

Further, since the thermoplastic cellulose derivative composition of the present invention can be dry-processed, there is no reason to stick to the raw material quality of the cellulose derivative, and low-purity pulp or even lignocellulose can be used as a raw material. it is conceivable that. All of these lead to a reduction in the manufacturing cost of the thermoplastic cellulose derivative composition.

Further, the plasticizers used to obtain the thermoplastic cellulose derivative composition of the present invention include those derived from natural products, which makes it possible to enhance the biodegradability of cellulose diacetate. It was Neither the cellulose derivative nor the plasticizer of the composition of the present invention is considered to be harmful to human health.

Therefore, the thermoplastic cellulose derivative composition of the present invention is in the form of a film, sheet, foam or the like,
It can be effectively used for packaging containers, disposable packaging containers (one-way containers), toys, sheets, furniture parts, building materials and automobiles, home electric appliances, interior materials, housings and the like. Since such a molded product has a good biodegradability, it has little influence on the environment in terms of disposal processing and the like.

[0040]

The present invention will be described in more detail with reference to the following examples and reference examples, but the present invention is not limited to these examples.

Example 1 Cellulose diacetate having a substitution degree of 2.5 is said to have the highest thermoplasticity among cellulose acetates.
Nevertheless, even if it is hot pressed at 200 ° C, for example, a transparent film cannot be obtained, and it has much poorer heat and pressure fluidity than general-purpose plastics such as polypropylene, making it a material that is difficult to process. So some plasticization is needed.

First, the details of the plasticization of cellulose diacetate in the case where a large amount of maleic anhydride methyl oleate used as the central reactive plasticizer in this study is used will be described below.

Absolutely dried cellulose diacetate (manufactured by Daicel Chemical Industries, Ltd., L-40; degree of substitution 2.4 to 2.6, degree of acetylation 55)
%, Average degree of polymerization 160) 60 parts by weight and maleic anhydride methyl oleate 40 parts by weight were weighed in a beaker and mixed, and then the temperature was adjusted to 180 ° C. Labo Plastomill (Toyo Seiki Seisakusho Co., Ltd.) A kneading bread (rotary blade) was rapidly charged into a batch type kneader while being rotated at 50 rpm, and kneading was continued for 15 minutes to carry out a kneading reaction.

This kneaded product was thermocompressed using a 10-ton test bench hot press manufactured by Toyo Seiki Co., Ltd. (200 ° C .; the gauge pressure was increased to 50 kgf / cm ² over 2 minutes, and 30 seconds later, all at once. (Up to 200kgf / cm ² and keep that pressure for 30 seconds)
Then, a sheet with a thickness of 0.4 mm was created. A strip test was cut out from these sheets and the tensile mechanical properties were measured using an Autograph DSC-R-500 type manufactured by Shimadzu Corporation.
A flow tester CFT-5000 manufactured by Shimadzu Corporation was used to measure the heat flow temperature and melt viscosity under the condition of using a die size of 1 × 2 mm under a load of 50 kgf. As a result, the tensile strength was 29.05 MPa, the elongation at fracture was 52.41%, the Young's modulus was 749 MPa, the heat flow temperature was 179.4 ° C, and the melt viscosity was 8210 pois.
A value of e was obtained, and it became clear that a thermoplasticized cellulose acetate composition which could be easily molded and had a physical property sufficiently within a practical range could be produced.

COMPARATIVE EXAMPLE 1 Except that the anhydrous maleated methyl oleate was replaced by a simple maleic anhydride-free methyl oleate.
A kneading reaction sample was obtained by the same operation as in Example 1.
An attempt was made to form this kneaded material into a film having a thickness of 0.4 mm in the same manner as in Example 1, but no heat flow occurred even when hot pressed,
It could not be formed into a film.

From the results of Example 1 and Comparative Example 1, it was clarified that the anhydrous maleloyl group is indispensable for plasticizing cellulose diacetate, and therefore the purpose can be reached only after the internal plasticization is performed. That is, it means that methyl oleate itself does not have a plasticizing ability for cellulose diacetate, and it can be plasticized only when it is maleated and reacts with the residual hydroxyl group of cellulose diacetate in the kneading reaction.

Example 2 Maleic anhydride oleic acid not in the form of ester of fatty acid was used in place of the anhydrous maleated methyl oleate, the kneading temperature was 140 ° C., and the kneading and kneading reaction time was 15 minutes. In the same manner as in Example 1, a kneading reaction sample was obtained. This kneaded product was treated in the same manner as in Example 1.
Having obtained a 0.4mm thick film, this film is homogeneous,
It was almost transparent and showed the same physical properties as the film of Example 1 and was satisfactory in practical use.

Examples 3 to 7 Maleic anhydride methyl oleate and dodecenylsuccinic anhydride were selected as reactive plasticizers, and the kneading reaction conditions using them were examined. An example of the results is shown in Tables 1 and 2.

[0049]

[Table 1]

[0050]

[Table 2]

As the amount of both plasticizers increased, the tensile strength of the film decreased and the breaking elongation increased. Further, the heat flow temperature and the apparent viscosity of the kneaded product both become low as the amount of the plasticizer added increases.

Mixing 20% or more of methyl oleate maleic anhydride gives a kneaded product that can be molded.

Another study was conducted by comparing the apparent shear rate dependence of the apparent viscosity of the plasticized cellulose diacetate obtained by kneading 20 to 40% of dodecenyl succinic anhydride with that of polypropylene for injection molding. The product obtained by adding 20% of dodecenyl succinic anhydride and kneading the mixture has a melt viscosity far exceeding that of polypropylene, and is slightly inferior in processability. In addition, 30% of dodecenyl succinic anhydride has a melt viscosity slightly higher than that of polypropylene, but addition of 40% makes it rather low viscosity.
From these results, it is necessary to knead dodecenylsuccinic anhydride in an amount of 30 to 40% to obtain a thermoplastic resin that is easy to use. When the addition amount of dodecenyl succinic anhydride is 20%, there is some problem in processability, but there is no problem such as precipitation of plasticizer and it is sufficiently practical depending on the application.

Examples 8 to 17 From the results of Examples 3 to 7, it was found that by setting the amount of the reactive plasticizer to 20%, the precipitation of the plasticizer on the surface of the molded article can be avoided. In the examples, at the same time, as a measure to lower the apparent melt viscosity, a method of adding an appropriate amount of ε-caprolactone to a system in which the reactive plasticizer was suppressed to 20% was tried.

A system containing 80 parts by weight of cellulose diacetate and 20 parts by weight of maleic anhydride methyl oleate or dodecenyl succinic anhydride is added to 5 to 20 parts by weight of ε-.
Add caprolactone and mix well, then 180
Quickly add the kneading bread into the Lab-Plastomill that is adjusted to ℃ while rotating it at 50 rpm.
After kneading for a minute, a kneading reaction was performed.

The kneaded material thus obtained was treated in the same manner as in Example 1, and the tensile mechanical properties and the melting properties were measured. The results obtained are shown in Table 3.

[0057]

[Table 3]

Ε-caprolactone is used in this reaction system
It can be said that during the kneading reaction, it polymerizes itself to become an oligomer and also reacts with the residual hydroxyl group of the cellulose diacetate and the maleloyl group of the reactive plasticizer. for that reason,
It can be expected that this ε-caprolactone can be used as an effective plasticizer that is well compatible with the complex system.

From Table 3, it is known that the tensile strength decreases and the fracture elongation increases with the addition of ε-caprolactone. When 20 parts by weight of ε-caprolactone is added, the tensile strength is improved in the system using maleic anhydride methyl oleate.
29.04MPa, the system using dodecenyl succinic anhydride is 26.11MPa, the fracture elongation rate is 66.85%,
It has increased to 52.92%. It can be said that the cellulose derivative composition obtained by adding 20 parts by weight of ε-caprolactone is an attractive material as mechanical properties with reduced brittleness.

When 20 parts by weight of ε-caprolactone is added, the heat flow temperature at the same time is 195 ° C or 180 ° C (when ε-caprolactone is not added) to 160.0 ° C or 14 ° C.
It is known that the material has an apparent melt viscosity of 10 ⁴ order (when ε-caprolactone is not added) to 10 ³ or 10 ² order, and the material is easy to mold.

By using ε-caprolactone in combination with a reactive plasticizer, the strength is not extremely reduced, and
It can be said that it is possible to obtain a material that has attractive strength properties with large breaking elongation and at the same time has improved moldability.

Examples 18 to 41 When 30% or more of maleic anhydride methyl oleate or dodecenyl succinic anhydride is added to plasticize the cellulose acetate, the objective of plasticization is sufficiently achieved, but the time of 1 to 2 weeks is reached. When the time elapses, the plasticizer may exude to the surface. In order to prevent it and increase biodegradability, starch was added to produce a thermoplastic cellulose derivative composition.

0 to 60 parts by weight of corn starch was weighed in a system containing 60 parts by weight of cellulose diacetate (L-40) and 40 parts by weight of maleic anhydride methyl oleate or dodecenylsuccinic anhydride, and the whole was placed in a beaker. After mixing well, the kneading bread was quickly put into a Labo Plastomill controlled at 180 ° C while being rotated at 50 rpm, and kneading was continued for 15 minutes to carry out a kneading reaction (in Table 4). This is what is indicated in the reaction time column as 15 minutes).

On the other hand, cellulose diacetate L
-40 and the reactive plasticizer were first kneaded at 180 ° C for 10 minutes, and then a predetermined amount of cornstarch was added and further kneaded for 10 minutes to form a composite (10+ in the reaction time column in Table 4).
This is what is described as 10 minutes).

Each of the obtained kneaded products was treated in the same procedure as in Example 1, the tensile mechanical properties and the melting properties were measured, and the obtained results are shown in Table 4.

[0066]

[Table 4]

From Table 4, the tensile strength and the elongation at break decrease with the addition amount of corn starch, but when the total amount of cellulose diacetate and the reactive plasticizer is 100 parts by weight, 60 parts by weight of corn starch is added. It can be seen that even at the stage, the tensile strength of 12 to 15 MPa is maintained.

Although there is some variation in the heat flow temperature, it can be said that the value generally decreases with the starch content. The melt viscosity obviously decreased with the increase of the starch content, and it can be said that it became easier to process.

The effects on the physical properties when starch is added have been described above. In all compositions, the precipitation of plasticizer and bleeding on the surface are clearly improved by the addition of starch, which is remarkable. It is an effect.

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Claims (14)

(57) [Claims] 1. A cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified α-olefin modified with an unsaturated carboxylic acid or its derivative. Cellulose derivative (C) in which (B) and a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative or a modified α-olefin modified with an unsaturated carboxylic acid or its derivative are introduced by an ester bond (C). ) Containing a thermoplastic cellulose derivative composition. 2. A cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified α-olefin modified with an unsaturated carboxylic acid or its derivative. (B), lactone or polymer (D) thereof, and modified unsaturated fatty acid or ester thereof modified with unsaturated carboxylic acid or derivative thereof, modified α-olefin or lactone modified with unsaturated carboxylic acid or derivative thereof, or The polymer is
A thermoplastic cellulose derivative composition containing a cellulose derivative (E) introduced by an ester bond. 3. A cellulose derivative (A) having an unsubstituted hydroxyl group, a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified α-olefin modified with an unsaturated carboxylic acid or its derivative. (B), starch (F), modified unsaturated fatty acid or its ester modified with unsaturated carboxylic acid or its derivative, or modified α-olefin modified with unsaturated carboxylic acid or its derivative is introduced by ester bond. Cellulose derivative (C)
And a modified unsaturated fatty acid or its ester modified with an unsaturated carboxylic acid or its derivative, or a modified α modified with an unsaturated carboxylic acid or its derivative
A thermoplastic cellulose derivative composition in which the olefin contains a starch derivative (G) introduced with an ester bond. 4. The component (A) is contained in an amount of 40 to 98 parts by weight, the component (B) in an amount of 60 to 2 parts by weight, and the total amount of the components (A) and (B) is 100 parts by weight. The thermoplastic cellulose derivative composition according to any one of 3 above. 5. The thermoplastic cellulose derivative composition according to claim 1, wherein the unsaturated carboxylic acid is maleic anhydride. 6. The thermoplastic cellulose derivative composition according to claim 1, wherein the component (B) is maleic anhydride oleic acid, maleic anhydride methyl oleate or dodecenylsuccinic anhydride. 7. The composition according to claim 2, wherein the component (D) is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). The thermoplastic cellulose derivative composition described. 8. The thermoplastic cellulose derivative composition according to any one of claims 2, 4, 5, 6, and 7, wherein the component (D) is ε-caprolactone. 9. The thermoplastic resin according to claim 3, wherein the component (F) is contained in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). Cellulose derivative composition. 10. The thermoplastic cellulose derivative composition according to claim 1, wherein the component (A) is cellulose acetate. 11. cellulose acetate, cellulose diacetate and / or cellulose Ah <br/> Ru at monoacetate 10. The thermoplastic cellulose derivative set composition. 12. Component (A) 40 to 98 parts by weight and component (B)
The method for producing a thermoplastic cellulose derivative composition according to claim 1, wherein 60 to 2 parts by weight is kneaded and kneaded to react under heating at 60 to 250 ° C. 13. Component (A) 40 to 98 parts by weight and component (B)
60 to 2 parts by weight and the total amount of component (A) and component (B) 100
1 to 30 parts by weight of component (D) is used in an amount of 60 to 250 parts by weight.
The method for producing a thermoplastic cellulose derivative composition according to claim 2, wherein the kneading and kneading reaction is carried out under heating at ° C. 14. Component (A) 40 to 98 parts by weight and component (B)
60 to 2 parts by weight and the total amount of component (A) and component (B) 100
5 to 80 parts by weight of component (F) to 60 to 250 parts by weight
The method for producing a thermoplastic cellulose derivative composition according to claim 3, wherein the kneading and kneading reaction is carried out under heating at 0 ° C.