JPH06507929A - Degradable cellulose polymer - Google Patents

Abstract

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

Description

[Detailed description of the invention] Degradable cellulose polymer Director of Seito Kamitachi Ushiri The present invention relates to the formation of thermoplastic polymeric materials that have good degradability upon contact with moisture. The present invention relates to a cellulose ester composition that can be used for. This composition has a polymer composition In the presence of moisture, polymeric materials leach after being disposed of in the environment. Both contain one decomposition accelerator. In certain embodiments, the present invention provides Contains lulose, cellulose acetate plasticizer and hydrophilic decomposition accelerator. Concerning thermoplastic cellulose acetate polymer compositions having good degradability on contact It is something that

Kogoryu! east Current products such as polyethylene, polypropylene, polyvinyl chloride and polystyrene Disposal of used packaging resins has become a very serious problem. coming. Therefore, significant technological efforts are required to produce biodegradable polymer compositions. Power is being expended. Typical characteristics involved in the production of biodegradable polymer compositions See U.S. Pat. No. 3,950,282 to Gilbert et al. and Tiller et al. U.S. Pat. No. 4,048,410 by Tiller, U.S. Pat. No. 4,038,228 by Tiller. , U.S. Patent No. 40'51306 to Tobias et al., U.S. Patent No. 40'51306 to Tiller No. 4,056,499, and U.S. Pat. No. 3,907,726 to Tomiyama. All of these are related to the production method of degradable bo, wa, mer materials and their composition. relating to things.

The first polymer species developed for commercial use was based on cellulose. It is something that These include regenerated cellulose (rayon) and various cellulose Esters, such as cellulose acetate, cellulose butyrate, cellulose propionate and mixed cellulose esters (acetate, acetate butyrate, and Acetate propionate).

Regenerated cellulose materials such as cellophane and rayon degrade at a very slow rate in the environment. , can be decomposed. However, cellulose in the form of melt-extruded film High levels of plasticizer are required to provide stellability. Possible like this The plastic agent is a cellulose ester compound that can form a thermoplastic film using a melt manufacturing method. used to provide products. Cellulose acetate is pressed into its pure form. If it is melt-manufactured by a method such as melting, it is not thermoplastic. this With high levels of thermoplastics such as A very stable, flexible ff1l material was produced that did not decompose even at low temperatures. fermentation Essentially hydrolyzes and dissolves cellulose and pure cellulose esters. A variety of microorganisms and soils known to be able to intermediate It does not react with cellulose ester that has been plasticized. Needless to say, Films and flexible films made from cellulose esters such as cellulose acetate Sible sheet plastic packing material is a small amount of cellulose acetate produced. Highly desirable in that it is one of the least expensive plastic films available. has been done. In addition, cellulose esters that are degradable under normal atmospheric conditions It would be highly desirable to provide a knocking material. The standard used here ``Atmospheric environmental conditions'' refers to the conditions at which most waste materials are stored, such as in landfills or garbage dumps. It includes the environment in which it is placed during disposal.

The main objective of the present invention is that by contacting with moisture in normal atmospheric environmental conditions, An object of the present invention is to provide a degradable cellulose ester composition.

Brother sucking Entsuji Contains decomposition accelerator. This degradation accelerator is used to degrade the polymer composition into one final product. After conversion, it becomes water-soluble in the presence of moisture and can be leached from the final polymer product. or hydrolyzed in the presence of moisture and leached from the final polymer product. It forms possible water-soluble by-products. Decomposition accelerators also act as catalysts. The mixture of cellulose and acetic acid I It is something to be rubbed. Cellulose is then broken down into more biodegradable saccharides. It is solvable. Degradation accelerator also functions as a plasticizer for cellulose ester polymers Yes, and can be used in combination with other known plasticizers.

Kori n Seitan-kai departure Cellulose is a polysaccharide formed from anhydroglucose units. each an The hydroglucose unit consists of three free hydrogen molecules that can react to form esters. It has a roxy group. The limit at which acid substitution occurs is known as the degree of substitution. , of the three hydroxyl groups in the substituted anhydroglucose unit, Expressed as the average number of hydroxyl groups. Cellulose ester useful in the present invention Ter has a degree of substitution of about 2.0 to about 2.6. In other words, the book Cellulose acetate useful in the invention ranges from about 39% to about 39% based on acetyl equivalents. It has an ester content of about 42.5%. Substitution degree below 3, i.e. from 2.0 In the preparation of cellulose esters with a degree of substitution in the range of 2.6, the desired Producing products with good homogeneity by esterifying to a high degree of substitution is possible. This is due to the topochemical nature of the reaction. haracter). Esterification is done on the outside of cellulose fibers Proceeding from the surface inward, the uniformity is until the product is completely dissolved in the mixture. It is not in good condition. Such complete dissolution approaches the )-reester stage. It happens when To prepare a homogeneous product with a degree of substitution of 2.0-2.6 , forming the triester and hydrolyzing the triester in solution to the desired degree of substitution. It is necessary to

Therefore, previously, ``cellulose thousand-styrene was utilized for triester formation.'' there was. However, cellulose triesters are difficult to mold, and Many attempts have been made to improve the moldability of cellulose triesters and their composition. It was about things. For example, U.S. Patent No. 2,067,310 by Open is a low molding temperature of 120℃ to 180℃ and a forming temperature of 2000 to 3000psi. A method of forming a molded article that can use mold pressure is disclosed. In addition, 1. This molding temperature and pressure is lower than normal for cellulose acetate. be.

Open's patented method combines cellulose triacetate with lactide and maleic acid. , consists of. By adding lactide and anhydride in combination with plasticizer, A moldable cellulose triacetate composition was prepared.

U.S. Pat. No. 2,805,171 to William also describes a moldable triacetate cell. Discloses a method for producing a loin composition, which contains 52.5% to 53.5% (% acetic acid and Cellulose triacetate containing acetyl (calculated as It's stealth. The cellulose esters useful in the present invention are about 39% and about 42.5% William's as having an acetyl content between and being soluble in acetone It is characterized in the patent.

The degradable thermoplastic cellulose ester composition of the present invention is based on acetylene. and an ester content of between about 39% and about 425% and between about 2.0 and about 2.0%. with a mixture of cellulose esters, plasticizers, and degradation accelerators with a degree of substitution of 6. be. The degradable functionality of the compositions of the invention is at least partially due to the polymer promoted by water and hydrolysis of the polymer at the acetyl group and acetal bond. It is thought that this will be advanced.

The decomposition accelerator of the present invention is a hydrophilic material. The decomposition accelerator is a cyclic internal monoester , a cyclic internal double ester, and an oligomer of an acid having from 2 to 50 acid parts. Ru. Monoesters have one oxygen molecule in the ring and are alpha-hydroxy acids. It can be prepared from a variety of hydroxy acids except . In the present invention, as a decomposition accelerator The diester lactones useful in biochemistry are typically prepared from hydroxy acids. annular dub esters can be prepared from a-hydroxy acids. Cyclic internal esters are common Generally called lactone. Cyclic double 6-membered ring esters are often dioxanedi It is called on.

The cyclic internal esters of this invention can be prepared from suitable hydroxy acids, but other Chemical methods of preparation may also be used. γ- and δ-lactones are usually γ- or δ-lactones. converts unsaturated acids into hydrobromic acid or by either distillation or hydrolysis of δ-haloacids. or by treatment with sulfuric acid or by partial reduction of cyclic acid anhydrides. be done. β-lactones can be produced by reacting ketene with aldehydes or ketones. More can be obtained. The reaction between ketene and formaldehyde is shown below.

Hexacyclic lactones can be prepared by oxidizing cyclic ketones with caro acids: That is, one caprolactone is obtained from cyclohexanone. Lactone' is , can be prepared by reacting a dicarboxylic acid with a polyhydric alcohol, e.g. Obtained by reacting malonic acid and ethylene glycol.

Hydroxy acids and compounds suitable for the preparation of lactones useful as decomposition promoters of the present invention Examples of dicarboxylic acids include 3-hydroxypropionic acid, 2-hydroxy, 1゜2 ．． 3 Propanetricarboxylic acid (citric acid), 3-hydroxybutyric acid, 4-hydro Xybutyric acid, 4-hydroxy-valeric acid, 5-hydroxyvaleric acid, 6-hydroxyvaleric acid Pronic acid, 2-hydroxyacetic acid (glycolic acid), 2-hydroxy-propion Acid (lactic acid), 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxycap rononic acid, 2-hydroxy-hebutanoic acid, 2-hydroxyoctanoic acid, 2-hydro xy-pelargonic acid, 2-hydroxyphenylacetic acid, ■-hydroxy-cyclohe Xan-1-carboxylic acid, oxalic acid and ethylene glycol, oxalic acid and propylene glycol, malonic acid and ethylene glycol, and malonic acid and propylene glycol One example is a recall.

Generally, lactones useful in the present invention have 3 to 6 carbon atoms and 1 or 2 carbon atoms in the ring. of oxygen atoms. Lactones prepared from hydroxy acids are: It has a structure corresponding to the formula: (+) (2) (3) Here, R is a hydrogen atom, C, -C,. AJ lekyl group, 1 again, benzene, na Phthalene, benzene substituted with C,-C4 alkyl group, and C,-C4 alkyl group An aryl group selected from naphthalene substituted with a kill group.

In formula 1, 3-hydroxypropionic acid is used to produce propiolactone. when 3-hydroxybutyric acid is butyrolactin, R1 and R2 are H; R1 is H, R, is methyl: 3-hydroxy When shisobutyric acid is used in the production of 2,3-dimethylpropiolactone, R, is methyl, R2 is methyl; 3-hydroxy 3-phenyl is 3-phenyl When used in the production of propiolactone, R1 is phenyl, R. teeth H; 3-hydroxy, 2-phenyl is 2-phenylpropiolactone When used in H. R2 is phenyl.

In formula 2, when 4-hydroxybutyric acid is used to produce valerolactone, is R1, R2 and R, are H: 4-hydroxyvaleric acid is 4-methylvaleric acid. When used in the production of rolactone, R1 is methyl, R2 and R, are H. be.

In formula 3, 6-hydroxycaproic acid is used to produce C-caprolactone. R1 to R5 are H; when 6-hydroxyheptinoic acid is When used in the production of luca-caprolactone, R1 is methyl and R2-R is It is H.

In formula 4, when glycolic acid is used for the production of glycolide, R1 or R, are H; when lactic acid is used for the production of lactide, R1 and R , is methyl, R2 and R4 are H; phenyl-2 hydroacetic acid is 2,5- R when used in the production of diphenyl-dioxane-3,6-dione.

and R3 is phenyl, R'2 and R4 are ten thousand; 2-hydroxyoctane When the acid is used in the production of 2,5-dimoxyldioxane-3,6-sion , R1 and R3 are hexyl, and R1 and R4 are H.

In formula 5, oxalic acid and ethylene glycol are 1,4-dioxane-2.

When used in the production of 3-diones, R1 and R2 are H; oxalic acid and propylene glycol of 5-methyl-1,4-dioxane-2,3-dione. When used in manufacturing, R, is methyl and R2 is H.

In 26, malonic acid ester and ethylene glycol are 1,4-diopin- When used in the production of 5-ph,dione, R, -R4 is H: malonic acid Ester and propylene glycol to produce 2-methyl-1,4-dioxevin When used, R is methyl, R, -R4 is H, and methylmalonate ester Teru and ethylene glycol are used in the production of 6-methyl-1,4-dioxevin. If R, -R3 is H. R4 is methyl.

In formula 7, 5-hydroxyvaleric acid is R, -R, is H; 5-hydroxycaproic acid (5-methyl When used in the production of ru-valerolactone, R1 is methyl, R2-R, l It's yoH.

Oligomers with hydroxy acids that can be used to form lactones can also be used as a decomposition promoter in combination with other lactones. 2ka・ra Oligomers of lactic acid with 50 lactic acid moieties are particularly preferred). Preferably ν) Acceleration of decomposition Ill, lactones from lactic acid or hydroxycaproic acid and lactic acid or hydrogen A mixture of oligomers of droxycaproic acid containing from about 10% to about 9% lactone. It has 5%.

Plasticizers useful in the polymer compositions of the present invention include thermoplastic cellulose esthetics compositions. A common plasticizer used in the formation of objects. 1, phthalate as a suitable plasticizer Diethyl acid, dimethyl phthalate, ethoxyethyl phthalate, methoxyethyl phthalate Dibutyl tartrate, Diethylene glycol-butyl ether, Diethylene glycol Recol mono-ethyl ether, triprobionin, benzoyl benzoate, Triphenyl phosphate, triacetin, cyamyl phthalate and organo Cresylvalartoluenesulfonate is mentioned.

Thermoplastic cellulose has an interstellar composition, commonly known as being useful in the formation of food products. Most plasticizers used in plasticizers are highly hydrophobic and affect the final polymer product. It is extremely resistant to moisture. Some plasticizer strength) C et al. It is relatively hydrophilic. The decomposition accelerator of the present invention is hydrophilic. Therefore, the present invention In some embodiments, the hydrophobic plasticizer HLB (hydrophilic l ip.

philic balance) of the present invention within the range of about 1075' to about 40. It is desirable to provide a decomposition accelerator.

Generally, the cellulose ester contains about 20% strength by weight in the compositions of the present invention. present at a level of about 80% by weight. All 7(-cents) used here ・Unless otherwise specified, weight percentages are given. Cellulose esters useful in the present invention include vinegar cellulose acid, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate and cellulose acetate-propionate. Cellulose S Tel has a molecular weight of at least about sooo, preferably about 5000 and about soooo It has a molecular weight between o. Cellulose acetate-butyrate preferably has a molecular weight of about 90 to about 9 It has 9% acetate and about 10 to about 1% butyrate. Acetic acid-propylene The cellulose onate preferably has a butyrate level of about 80 to about 99% and about 2 It has a propionate level of 0 to about 1%.

Plasticizers can be present in the polymer compositions of the present invention in amounts ranging from about 0% to about 50% by weight of the composition. Amount% present. The hydrophilic degradation accelerator preferably ranges from about 1% to about 60% by weight of the composition. present in the polymer composition at a level of % by weight. Use of plasticizers and hydrophilic decomposition accelerators The sum of all levels is from about 20% to about 80% by weight of the composition.

Some of the degradation accelerators useful in the present invention also function as plasticizers and Can be used without adding plasticizer. Decomposition accelerator that can be used without plasticizer contains oligomers of lactic acid and lactones formed from lactic acid and citric acid.

Degradation of the degradable cellulose ester formulations of the present invention is due to the relatively hydrophilic This occurs when the decomposition accelerator leaches out of the composition, and upon contact with water opens or A thank-you molecular lattice remains. Cellulose esters are highly plasticized during melt manufacturing If so, it exists in an amorphous state.

Once the cellulose ester comes into contact with water after leaching the decomposition accelerator, the conventional cellulose ester Uses hydrophobic plastic cellulose ester. The water has a higher concentration than if it were The mass action of accelerates hydrolysis. Acidic decomposition accelerators catalyze hydrolysis. It provides a source of bosu acid. Cellulose ester containing water sand in contact As a result of the lattice structure, enzymatic degradation is also possible. Hydrolysis is caused by the power of a decomposition accelerator. from the formation of acidic medium and its hydrolysis, and the hydrolysis of cellulose esters. Forms organic acid.

By using plasticized and degradable cellulose esters, cellulose The market for stealth could expand. The degradable cellulose ester of the present invention is , provides a low-cost plasticizing system and is particularly suitable for plasticizing systems used in general items such as trash cans. It offers biodegradability to an expanded market in biodegradable materials.

Although the following examples illustrate various features of the invention, the present invention The examples are not limited.

Shaking away and cold storm superior Table 1 shows conventional cellulose acetate-plasticizer mixtures containing conventional plasticizers and 2 shows an example of the invention containing a plasticizer that can be removed. Sample calligraphy number 2-2.2-3 ．． 2-4.3-3 and -8 are thermoplastic resins using non-leachable hydrophobic plasticizers. It may be considered as a falsified cellulose control. Non-leaching allows the composition to absorb moisture. It is not easily accessible and therefore essentially indegradable. present invention Each degradation accelerator used in the composition exhibits appreciable solubility in water. and/or easily hydrolyzed into water-soluble acid components. After hydrolysis , acids accelerate decomposition.

Adding inorganic or organic acids to conventional cellulose compositions produces similar results. cannot be obtained. Samples 2-5 containing 1% fumaric acid and 24% lactic acid. Containing sample 2-6 shows a considerable degree of weathering after being exposed to seawater for 6 months. It wasn't something. Sample 2-7, containing 1% phosphoric acid, was too degraded to be tested. The result was a composition that could not be struck. Inorganic acids put into a conventional hydrophobic plasticizer matrix When removed, it can be effectively insulated from moisture and achieve the purpose of promoting hydrolysis. It becomes. The organic acid combined with the leachable decomposition accelerator of the present invention inhibits hydrolysis. It can be promoted.

This leachable degradation accelerator is useful for accelerating hydrolysis, especially when it forms acids. It remains and functions well. For example, compare the results for -8 and -9 in Table 1.

Eighteen samples using a traditional plasticizer, diethyl phthalate, lasted for more than a year. Did not disassemble. Weathering and decomposition tests were carried out using Frock's seawater, Frock's beach breeze, and field panels in Ohio. Diethyl phthalate as a plasticizer and one containing cellulose acetate with lactide as the leachable component. Nine samples weathered quickly. In 21 days, a highly flexible, richly colored and transparent film However, it deteriorated so much that it became a white, opaque material.

Other examples of the present invention, -32, -36-3, -37, -42-2, -42-5 and and 43-1 were similarly leachable and weatherable. All of these compositions The decomposition accelerator forms a smooth, glossy, thin film without decomposition. It is an effective mixture that can produce transparent films that are easily melt-processed. Ru.

Tensile strength testing was performed according to ASTM D638. tensile stress Alternatively, stiffness measurements were varied with the amount of plasticizer and/or degradation accelerator. in general The total amount of plasticizer is added to the film to mimic the malleability and bendability of polyolefins. More than 40% by weight is necessary in order to obtain a silica film. Sample-37 and -42-5 were heated and molded into rigid, colorless and transparent salad cover shapes.

Sample-42-2 was molded into a trash box shape.

Oligomeric lactic acid and polyethyl lactate are commercially available, which also function as plasticizers. It is a readily available decomposition accelerator. These are easy methods using easy and economical precursors. It is prepared by the condensation of lactic acid and ethyl lactate. These raw materials are Both can be melted and dispersed using cellulose acetate, resulting in thermoplastics with good properties.

The cellulose acetate used had a weight average molecular weight of 85,000 by GPC. It was of commercial grade. If the molecular weight is higher, under stress, It gives higher elongation and better strength.

In the table, aCA-3983, Eastman Kodak Cellulose Diacetate B Commercial Industrially formulated Eastman Kodasoku 036A, molded gray using DEP. code cc-3782, no DEP d Hamakaze, Daidna, FL, Summer e　Seawater, Dydna, FL, summer, pH 7.2 7.4.27-29℃, 3゜6 % salinity f　Seawater, Dydna, FL, winter, pH 7.3 to 8.1.15-21℃, 3゜5 % salinity g Test started outdoors, OH1 winter, -9 to 7℃ h Test started outdoors Tempered, OH1 summer, 21 to 35℃ i Storage stability, 70C150%r, h , is 1 year” Estimated KEY: DEP=diethyl phthalate; FA=fumaric acid; LA=lactic acid; P A = phosphoric acid; LD = lactide; 0LA = oligomeric polylactic acid with 5 lactic acid moieties; Pc; propylene carbonate; Et L, A = ethyl lactoyllactate Tomotobu L The following examples demonstrate the use of 7-membered ring lactones as plasticizers.

The selected cellulose acetate has a weight average of 149,000 with an average degree of substitution of 2.5. GPC molecular weight, a polymer with a number average GPC molecular weight of 47,000 (Eastmanke Michals Company, “SAMS-E”). It does not contain plasticizers. First, it turns into charcoal before it melts.

55 parts by weight of cellulose acetate were combined with 45 parts by weight of C-caprolactone (pure liquid The mixture was quickly absorbed into the polymer by simple manual stirring. This mixture The items were placed in an open 20-lumen preheated to 350°F. counter The rotary mill was set airtight at about 10 rpm. Mixture is fully mixed within 5 minutes It becomes transparent to show that it has been done. The mixture was rolled out of the mill and sheeted.

The mixture melted easily with some caprolactone evaporating without dripping.

The above melt compounded formulation is compression molded at 300°F and approximately 8 to 10 m! 1 of A thin film was formed. They are completely colorless, transparent, and made of plastic. This shows that. The film is flexible, tear resistant and can be heated by hand That is, it could be easily stretched at about 37°C.

The film was tested using an Instron tester (Instron tester) for tensile properties according to ASTM 882. The results are shown in Table 2. Contains caprolactone The amount is estimated to be 22.7% by weight due to isothermal weight loss at 200°C by TGA. established. The tensile strength, tensile stress, and elongation cut values shown in Table 2 are Similar to materials found useful in packaging applications, high-density polyethylene and It is also similar to certain grades of polypropylene.

Stormtrooper l This example demonstrates the use of a 5-membered ring lactone. The method of Example 2 Using 4-valerolactone instead of prolactone, the same cellulose acetate This was done using a For example, 55 parts of cellulose acetate is mixed with 45 parts of 4-barrel. Mix by hand with rolactone and mill-roll for 5 minutes at 350°F to 8 to 1 It was compression molded into a 0ml film. It was completely transparent and had no color. This frame The film is tough, strong, elongated FTQ, and tear resistant. It was. The percent lactone content was 17.0% by TGA. Bow 1 Tension data is shown in Table 2. Properties are used to mold and package It is almost the same as crystalline polypropylene.

cold soil 55 parts by weight of cellulose acetate (powder) similar to that used in Example 2 were Stir with 5 parts of granular pure glycolide, 6-membered ring, cyclic dilactone. mixture Easily melted into mill rolls at 350°F and compression molded into clear, brown films. . The surface of the film becomes hazy during use, which is due to the presence of small amounts of glycolide on the surface. This shows that it appeared in powder form. By TGA, the percentage of glycolide is , 22.3%. The tensile properties are shown in Table 2. low density polyethylene It was almost the same as Ren.

Submission of translation of written amendment (Article 184-8 of the Patent Law) November J9, 1993

Claims (44)

[Claims] 1. A degradable thermoplastic consisting of a cellulose ester polymer and a hydrophilic decomposition accelerator. a plastic cellulose ester composition, and the decomposition accelerator The product is shaped into a thermoplastic material that can be used in low moisture indoor environments. After forming, the thermoplastic material slowly unravels in a relatively high moisture field environment. a degradable thermoplastic that is released into a degradable cellulose ester Cellulose ester composition. 2. The composition according to claim 1, further comprising a plasticizer. 3. The cellulose ester has a degree of ester substitution of about 2.0 to 2.6. , the composition of claim 1. 4. The cellulose esters include cellulose acetate, cellulose propionate, and cellulose butyrate. cellulose acetate, cellulose acetate-butyrate, and cellulose acetate-propionate The composition according to claim 1, selected from: 5. The decomposition accelerators include lactones prepared from hydroxy acids, dicarboxylic acids and and lactones prepared from polyhydric alcohols, and oligos of said hydroxy acids. 2. The composition of claim 1, wherein the composition is selected from the group consisting of mer. 6. the lactone has 3 to 6 carbon atoms and 1 or 2 oxygen atoms in the ring 6. The composition according to claim 5. 7. The lactones include 3-hydroxypropionic acid, 3-hydroxybutyric acid, and 4-hydroxybutyric acid. Hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxyvaleric acid Cicaproic acid, 2-hydroxyacetic acid (glycolic acid), 2-hydroxy-propylene onic acid (lactic acid), 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxy Caproic acid, 2-hydroxy-heptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy-heptanoic acid Droxy-pelargonic acid, 2-hydroxyphenylacetic acid, 1-hydroxy-sic Lohexane 1-carboxylic acid, oxalic acid and ethylene glycol, oxalic acid and propylene glycol lene glycol, malonic acid and ethylene glycol, and malonic acid and propylene 6. Prepared from a hydroxy acid selected from the group consisting of glycols. Compositions as described. 8. 6. The composition of claim 5, wherein the oligomer has from 2 to 50 acid moieties. 9. According to claim 5, the decomposition accelerator is a lactone prepared from lactic acid. Composition. 10. The decomposition accelerator is a mixture of lactone from lactic acid and oligomers of lactic acid. 6. The mixture of claim 5, wherein the mixture has from about 10% to about 95% of the lactone. composition. 11. The composition according to claim 5, wherein the decomposition accelerator is caprolactone. 12. The decomposition accelerator is a lactone from hydroxycaproic acid and a hydroxyl caproic acid. A mixture of oligomers of pronic acid, said mixture containing from about 10% to about 10% lactone. 6. The composition of claim 5, having 95%. 13. The decomposition accelerator contains about 10% to about 95% of lactone prepared from lactic acid. and about 5% to about 95% oligomers of lactic acid having 2 to 50 lactic acid moieties. , a composition according to claim 5. 14. The decomposition accelerator has the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)▲There are mathematical formulas, chemical formulas, tables, etc.▼( 2)▲There are mathematical formulas, chemical formulas, tables, etc.▼(3)▲There are mathematical formulas, chemical formulas, tables, etc. ▼(4)▲There are mathematical formulas, chemical formulas, tables, etc.▼(5)▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (7) Here, R is a hydrogen atom , C1-C10 alkyl group, or benzene, naphthalene, C1-C4 alkyl group benzene substituted with a C1-C4 alkyl group, and naphthalene substituted with a C1-C4 alkyl group. is a cyclic ester having a structure corresponding to an aryl group selected from , the composition of claim 1. 15. The decomposition accelerator includes diethyl phthalate, dimethyl phthalate, and ethyl phthalate. xyethyl, methoxyethyl phthalate, dibutyl tartrate, diethylene glycol -butyl ether, diethylene glycol mono-ethyl ether, tripropio Nin, benzoyl benzoate, triphenyl phosphate, triacetin, fluorine Group consisting of diamyl tartrate and ortho-cresylvalartoluenesulfonate 3. A composition according to claim 2, selected from: 16. 3. The composition of claim 2, having an HLB of about 10 to about 50. 17. the cellulose ester is present at a level of about 20% to about 80%; A composition according to claim 1. 18. The plasticizer is present at a level of about 1% to about 50%, and the degradation accelerator is present at a level of about 1% to about 50%. 3. The composition of claim 2, wherein the composition is present at a level of about 1% to about 60%. 19. The aggregate level of the plasticizer level and the degradation accelerator level is from about 20% to 16. The composition of claim 15, which is about 80%. 20. The cellulose ester has a molecular weight of about 5,000 to about 500,000. The composition according to claim 1. 21. The set of claim 1, wherein the cellulose ester is cellulose acetate. A product. 22. The set of claim 1, wherein the cellulose ester is cellulose butyrate. A product. 23. Method for improving the decomposition rate of cellulose ester polymers by contacting them with moisture , which provides a cellulose ester polymer, and in which the mixture has a good Dispersing and dispersing an effective amount of decomposition accelerator to create a melt-formable thermoplastic material Accelerators can be slowly leached or hydrolyzed under relatively high moisture field conditions Enables degradation and slow hydrolysis of cellulose ester polymers How to make it effective. 24. 23. A plasticizer is further dispersed in the cellulose ester polymer. The method described in. 25. The cellulose ester has a degree of ester substitution of about 2.0 to 2.6. 24. The method of claim 23. 26. The cellulose esters include cellulose acetate, cellulose propionate, Cellulose butyrate, cellulose acetate-butyrate, and cellulose acetate-propionate 24. The method of claim 23, wherein the method is selected from: 27. The decomposition accelerator is a lactone prepared from a hydroxy acid, a dicarboxylic acid, and lactones prepared from polyhydric alcohols, and oligosaccharides of said hydroxy acids. 24. The method of claim 23, wherein the sesame is selected from the group consisting of sesame. 28. The lactone has 3 to 6 carbon atoms and 1 or 2 oxygen atoms in the ring. 28. The method of claim 27. 29. The lactones include 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4 -Hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydro Xicaproic acid, 2-hydroxyacetic acid (glycolic acid), 2-hydroxyproacid Pionic acid (lactic acid), 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxy Cicaproic acid, 2-hydroxy-heptanoic acid, 2-hydroxyoctanoic acid, 2- Hydroxy-pelargonic acid, 2-hydroxyphenylacetic acid, 1-hydroxy-sulfuric acid Clohexane-1-carboxylic acid, oxalic acid and ethylene glycol, oxalic acid and protein propylene glycol, malonic acid and ethylene glycol, and malonic acid and propylene glycol Prepared from a hydroxy acid selected from the group consisting of lene glycol. 27. The method described in 27. 30. 28. The method of claim 27, wherein the oligomer has from 2 to 50 acid moieties. 31. 28. The decomposition accelerator is a lactone prepared from lactic acid. How to put it on. 32. The decomposition accelerator is a mixture of lactone from lactic acid and oligomers of lactic acid. 28. The mixture of claim 27, wherein the mixture has from about 10% to about 95% of the lactone. Method described. 33. 28. The method according to claim 27, wherein the decomposition accelerator is caprolactone. 34. The decomposition accelerator is a lactone from hydroxycaproic acid and a hydroxyl caproic acid. A mixture of oligomers of pronic acid, said mixture containing from about 10% to about 10% lactone. 28. The method of claim 27, having 95%. 35. The decomposition accelerator contains about 10% to about 95% of lactone prepared from lactic acid. and about 5% to about 95% oligomers of lactic acid having 2 to 50 lactic acid moieties. 28. The method of claim 27. 36. The decomposition accelerator has the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)▲There are mathematical formulas, chemical formulas, tables, etc.▼( 2)▲There are mathematical formulas, chemical formulas, tables, etc.▼(3)▲There are mathematical formulas, chemical formulas, tables, etc. ▼(4)▲There are mathematical formulas, chemical formulas, tables, etc.▼(5)▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (7) Here, R is a hydrogen atom , C1-C10 alkyl group, or benzene, naphthalene, C1-C4 alkyl group benzene substituted with a C1-C4 alkyl group, and naphthalene substituted with a C1-C4 alkyl group. is a cyclic ester having a structure corresponding to an aryl group selected from 28. The method of claim 27. 37. The decomposition accelerator includes diethyl phthalate, dimethyl phthalate, and ethyl phthalate. xyethyl, methoxyethyl phthalate, dibutyl tartrate, diethylene glycol -butyl ether, diethylene glycol mono-ethyl ether, trilopioni Benzoyl benzoate, triphenyl phosphate, triacetin, lid The group consisting of diamyl acetate and orthocresylvalartoluenesulfonate 25. The method of claim 24, wherein the method is selected from: 38. 25. The method of claim 24, having an HLB of about 10 to about 40. 39. the cellulose ester is present at a level of about 20% to about 80%; 24. The method according to claim 23. 40. The plasticizer is present at a level of about 1% to about 50%, and the degradation accelerator is present at a level of about 1% to about 50%. 25. The method of claim 24, wherein the method is present at a level of about 1% to about 60%. 41. The aggregate level of the plasticizer level and the degradation accelerator level is from about 20% to 25. The method of claim 24, which is about 80%. 42. The cellulose ester has a molecular weight of about 5,000 to about 500,000. 24. The method of claim 23. 43. 24. The method according to claim 23, wherein the cellulose ester is cellulose acetate. Law. 44. 24. The method according to claim 23, wherein the cellulose ester is cellulose butyrate. Law.