JP3323836B2 - Thermoformed body, manufacturing method thereof, toner cartridge, recording medium, and recycling method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoformed article containing a sugar chain polymer compound, a method for producing the same, a toner cartridge ,
The present invention relates to a recording medium and a recycling method , particularly, a thermoformed article having biodegradability and recyclability, and excellent in bending strength and tensile strength, a method for manufacturing the same, a toner cartridge , and a recording medium.
It relates to recording media and recycling methods .

[0002]

2. Description of the Related Art Global environmental pollution has become evident, and it has become necessary to consider not only industrial waste but also household waste as well as the environment. Under such circumstances, with respect to plastic resins as industrial materials, treatments with reduced environmental load are required, or new materials capable of processing with less environmental load are required.

[0003] A conventional method of treating waste plastic is a method of incinerating or reclaiming low-molecular-weight materials by, for example, thermal decomposition or chemical decomposition. However, incineration involves emission of carbon dioxide, which is one of the causes of global warming. If the resin contains a halogen, sulfur, or nitrogen element, it may cause air pollution by harmful gas. In addition, when landfilled, most of the resins currently in practical use remain in a state of being left for a long time. During this period, additives and the like in the resin flow out and become one of the causes of soil contamination.

[0004] In response to this problem, biodegradable polymer compounds are being actively developed as polymer compounds that do not adversely affect the global environment when they are finally disposed of. (For example, JP-A-5-287043). Biodegradable resins are roughly classified into three types: microbial products, plant-derived natural products, and chemically synthesized products. Examples of microbial products include:
Alkaline Genes Eutroprus
Nestroplus) is a commercially available polyester of D-3-hydroxybutyrate and 3-hydroxyvalerate under the trade name "Biopol". It is biodegraded by microorganisms.

[0005] Natural products include collagen, gelatin,
There are starch, cellulose, chitosan and the like. These are themselves biodegradable. Further, a mixture of starch and modified polyvinyl alcohol, a cellulose ester obtained by chemically modifying cellulose, a complex of cellulose and chitosan, and the like are also known. Among the chemically synthesized products, water-soluble polymers such as polyvinyl alcohol and polyethylene glycol, and aliphatic polyesters such as polyethylene adipate and polycaprolactone exhibit biodegradability.

[0006] On the other hand, from the viewpoint of effective use of resources, there is known an example in which waste plastics obtained by reducing the molecular weight are reused as raw materials for polymer compounds. For example, polystyrene is recovered as a styrene monomer or dimer by catalytic cracking using a solid base catalyst, and is supplied as a repolymerization raw material, a methanolysis method using methanol, a glycosis method using ethylene glycol, an acid or a base. Examples of the method include decomposing polyethylene terephthalate into dimethyl phthalate, ethylene glycol, terephthalic acid, and the like by a hydrolysis method using dimethyl phthalate, and using these as a raw material of polyethylene terephthalate and other chemicals. However, in order to extract a reusable component in these examples, it is necessary to separate and purify the decomposition product in many steps. As a biodegradable polymer capable of solving such problems, the present applicant has disclosed in European Patent Publication No. 814093 a saccharide capable of being biodegraded, particularly enzymatically decomposed, and capable of efficiently reusing decomposition products. A chain polymer compound has been disclosed.

Also, Kurita et al. (Journal of P)
Polymer Science: Polymer Ch
emistly Edition, 18,365-37
01980) describes a copolymer of cellobiose with adipic acid and phthalic acid.

[0008]

By the way, although these biodegradable plastics have been developed from the viewpoint of biodegradability, the present inventors have developed such biodegradable plastics. In order to spread as a substitute for conventional plastics, based on the prediction that ease of thermoforming and the strength of the thermoformed body will be required,
When evaluating the thermoforming properties of the copolymer of cellobiose and adipic acid disclosed by Kurita et al., The effect of adipic acid on internal plasticity was small, or the point of softening to a temperature lower than the decomposition point. It does not show thermoplasticity without it, and also about the copolymer of cellobiose and phthalic acid, if there is an aromatic ring such as phthalic acid, the interaction between the main chains of the polymer will be strong, or only at the decomposition point It did not show thermoplasticity.

[0009] The present inventors have further studied and as a result, thermoforming into a biodegradable sugar chain polymer compound described in the above-mentioned European Patent Publication No. (EP 814093A2). It has been found that it contains a substance which is easy to perform and has excellent strength of the thermoformed article.

The present invention has been made based on such findings, and an object of the present invention is to provide a biodegradable thermoformed article having excellent strength. It is another object of the present invention to provide a method for producing a thermoformed article having excellent strength from a biodegradable polymer. It is still another object of the present invention to provide a toner cartridge and a recording medium which are excellent in strength and can be disposed of with little load on the global environment. Further, the present invention relates to the above-mentioned thermoforming.
Body, toner cartridge and recording medium recycling
It is another object to provide a method.

[0011]

Thermoformed article according to an embodiment of the SUMMARY OF THE INVENTION The present invention provides viewing contains a sugar polymer represented by the following general formula (I), molded using thermal molding Body
It is an Ranaru this and features.

[0012]

Embedded image

(Wherein G is a residue of a monosaccharide, oligosaccharide or polysaccharide, and R is a group having 4 carbon atoms when G is a residue of a monosaccharide.)
The above linear or branched alkylene group,
When G is an oligosaccharide or polysaccharide residue, it has 6 carbon atoms.
The above straight-chain or branched alkylene group,
n is an integer of 1 to 5000. )

That is, the present inventors have conducted various studies on a polymer compound containing a saccharide, and as a result, have found that the compound represented by the above general formula (I) has excellent thermoplasticity. It has been reached. In addition, since the sugar chain polymer compound represented by the general formula (I) has a softening point at a temperature lower than the decomposition point, it has become possible to produce an excellent thermoformed product.

In the above formula (I), G represents a monosaccharide, oligosaccharide or polysaccharide residue. When G is a monosaccharide residue, R has 4 or more carbon atoms, particularly 4 carbon atoms.
To 14, more preferably a linear or branched alkylene group having 4 to 10 carbon atoms. When G is a residue of an oligosaccharide or a polysaccharide, R is a linear or branched alkylene having 6 or more carbon atoms, particularly 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Groups are preferred. These alkylene groups may be substituted with, for example, a methyl group, an ethyl group, or the like.

N is 1 to 5000, preferably 50
It is an integer of ２０００2000. G represents a sugar residue, and G may be three or more substituted.

In the case where the sugar residue is a sugar comprising only a hydroxyl group, it is preferable to form an ester bond, and in the case of a sugar containing an amino group, it is preferable to form an amide bond and / or an ester bond. Preferably, the sugar residue is a monosaccharide, oligosaccharide or polysaccharide consisting of only a pyranose ring.

Preferably, the monosaccharide is at least one of glucose, mannose, galactose and glucosamine.

The oligosaccharide is maltose, cellobiose, lactose, isomaltose, chitobiose, nigerose, trehalose, melibiose, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose, maltotetraose, cellopentaose, malto Pentaose, chitopentaose,
It is preferably at least one of cellohexaose, maltohexaose, and chitohexaose.

It is preferable that the polysaccharide is at least one of cellulose, starch, glycogen, galactan, mannan, chitin, chitosan and pullulan.

The sugar chain polymer compound according to the present invention is a compound of the general formula (I) which selectively decomposes a hydrolyzable bond (ester bond, amide bond, etc.) between G and R. By selectively decomposing the glycosidic bonds between them (however, except for monosaccharides), it is possible to easily recycle the substances generated by the decomposition as raw materials and to improve the biodegradability in soil and compost. Have. Furthermore, this novel sugar chain polymer has a softening point at a temperature below the decomposition point and has thermoplasticity,
Hot press molding becomes possible. It can be a material suitable for mass production.

Further, by utilizing the thermoplasticity of the sugar chain polymer compound of the present invention and performing hot melting and press molding, a thermoformed body which is improved in workability and can be produced at lower cost can be obtained.

The above object can be achieved.
The method for producing a thermoformed article according to one embodiment of the present invention comprises the steps of: adding a sugar chain polymer compound represented by the general formula (I) to a polymer compound having a softening point or higher and lower than a thermal decomposition temperature; The method is characterized by a method for producing a thermoformed body, which comprises a step of forming by applying the above temperature.

[0024]

Embedded image

Wherein G is a residue of a monosaccharide, an oligosaccharide or a polysaccharide, and R is a group having 4 carbon atoms when G is a residue of a monosaccharide.
The above linear or branched alkylene group,
When G is an oligosaccharide or polysaccharide residue, it has 6 carbon atoms.
The above straight-chain or branched alkylene group,
n is an integer of 1 to 5000. )

Further, a toner cartridge which can achieve the above-mentioned object is characterized by including, for example, a thermoformed product containing a sugar chain polymer compound represented by the above general formula (I). Still further, a recording medium capable of achieving the above object is characterized by including, for example, a thermoformed article containing the sugar chain polymer compound represented by the general formula (I). Furthermore, the present invention provides the above thermoformed body,
It is characterized by a method of recycling a toner cartridge and a recording medium. That is, look containing a sugar polymer represented by the following general formula (I), is molded using heat
And a method of recycling thermoformable body, (i) Step of depolymerizing at least a portion of the sugar chain polymer compound; using heat depolymerization products obtained by the and (ii) said step (i) re polymerization allowed to step in a method for recycling heat molded by utilizing the heat molded product characterized by having a city.

Embedded image Wherein G is the residue of a monosaccharide, oligosaccharide or polysaccharide;
R is a linear or branched alkylene group having 4 or more carbon atoms when G is a monosaccharide residue, and a straight-chain or branched alkylene group having 4 or more carbon atoms when G is an oligosaccharide or polysaccharide residue. A squamous or branched alkylene group, wherein n is 1 to 50;
It is an integer of 00. The above method for recycling a toner cartridge, further comprising: (i) a step of depolymerizing at least a part of the sugar chain polymer compound represented by the general formula (I); and (ii) the step (i). Re-polymerizing the depolymerized product obtained by the above method. The method for recycling a recording medium according to the above, further comprising: (i) a step of depolymerizing at least a part of the sugar chain polymer compound represented by the general formula (I); and (ii) the step (i). Re-polymerizing the depolymerized product obtained by the above method. Next, preferred embodiments of the recycling method of the present invention will be described. Preferably, the step (ii) is a step of repolymerizing the depolymerized product obtained in the step (i) without purification. The depolymerization in the step (i) is preferably a reaction for cleaving an ester bond or an amide bond of the sugar chain polymer compound represented by the general formula (I). It is preferable to use a base for the depolymerization. Preferably, the base is sodium hydroxide.
The depolymerization in the step (i) is preferably a step of decomposing the sugar residue G of the sugar chain polymer compound represented by the general formula (I). The sugar residue G contains an oligosaccharide or a polysaccharide, and the step of decomposing the sugar residue G preferably includes the step of decomposing a glycosidic bond connecting the monosaccharide molecules. It is preferable to use an enzyme for the depolymerization.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION (Sugar chain polymer compound) A sugar chain polymer compound and a thermoformed article using the same will be described in detail. A thermoformed product according to one embodiment of the present invention contains a sugar chain polymer compound represented by the following general formula (I).

[0028]

Embedded image

In the formula, G represents a monosaccharide, oligosaccharide or polysaccharide residue. And when G is a monosaccharide residue,
Is preferably a linear or branched alkylene group having 4 or more carbon atoms, particularly 4 to 14, and more preferably 4 to 10 carbon atoms. When G is a residue of an oligosaccharide or a polysaccharide, R has 6 or more carbon atoms, particularly 6 to 6 carbon atoms.
14, and more preferably a linear or branched alkylene group having 6 to 10 carbon atoms. These alkylene groups may be substituted with, for example, a methyl group, an ethyl group, or the like.

Further, n is 1 to 5000, preferably 50.
It is an integer of ２０００2000. G represents a sugar residue, and G may be three or more substituted.

For example, a sugar chain polymer obtained by reacting an oligosaccharide or polysaccharide with a dicarboxylic acid having a small number of carbon atoms such as adipic acid (carbon number = 4) has no softening point below the decomposition point. When reacted with a long dicarboxylic acid having 6 or more carbon atoms, such as sebacic acid (carbon number = 8), the softening point is lower than the decomposition point, probably because the dicarboxylic acid portion contributes to internal plasticity. Will have.

When the G moiety in the general formula (I) is a monosaccharide residue, the dicarboxylic acid moiety has an aliphatic hydrocarbon chain length of 4 or more, and the G moiety is an oligosaccharide or polysaccharide residue. If the aliphatic hydrocarbon chain length of the dicarboxylic acid moiety is 6 or more, the sugar chain polymer compound has thermoplasticity (softening point) and is a thermoformable biodegradable polymer compound Can be.

On the other hand, the carbon number of the dicarboxylic acid is 14 or less,
Particularly, it is preferably 10 or less. That is, within this range, the softening point does not become too low, and a biodegradable polymer compound having excellent heat resistance can be obtained. Examples of dicarboxylic acids that can be used only when G is a monosaccharide include adipic acid and pimelic acid.
Examples of dicarboxylic acids that can be used when G is an oligosaccharide or polysaccharide include, specifically, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, Examples thereof include aliphatic dicarboxylic acids such as pentadecandioic acid and hexadecandioic acid, and derivatives thereof (salts, acid chlorides, esters, acid anhydrides, and the like). In any of these, the aliphatic hydrocarbon moiety may be substituted with a linear or branched alkyl group having about 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, etc.). More specifically, for example, 2-methylazeleic acid and the like can be mentioned.

Next, in the above general formula (I), G represents a sugar residue and is a monosaccharide, polysaccharide or oligosaccharide. These saccharide moieties preferably contain a saccharide containing only a pyranose ring from the viewpoint of heat resistance.

Representative monosaccharides containing only the pyranose ring include glucose (glucopyranose), mannose (mannopyranose), galactose (galactopyranose), glucosamine and the like.

Representative oligosaccharides containing the pyranose ring include cellobiose, lactose, maltose,
Isomaltose, chitobiose, nigerose, trehalose, melibiose and other disaccharides, cellotriose, chitotriose, maltotriose and other trisaccharides, tetrasaccharides and more as cellotetraose, chitotetraose,
Examples include maltotetraose, cellopentaose, chitopentaose, maltopentaose, cellohexaose, chitohexaose, and maltohexaose.

Representative polysaccharides containing the pyranose ring include chitin, chitosan, cellulose, starch, glycogen, galactan, mannan, pullulan and the like. These sugars may be sugar derivatives in which the OH group contained in the molecule is substituted with, for example, an acetyl group or a benzyl group.

These sugars have a glycosidic bond, for example, an α bond and a β bond. The bonds to reducing sugars are (1 → 2) bond, (1 → 3) bond,
The (1 → 4) bond, the (1 → 6) bond, and the bond with a non-reducing sugar include a (1⇔2) bond and a (1⇔1) bond.

In the present invention, the bond between the sugar and the aliphatic dicarboxylic acid for constituting the repeating unit of the sugar chain polymer compound may be an ester bond when the sugar moiety is only a hydroxyl group (for example, cellobiose). When the moiety contains an amino group (eg, chitobiose), an amide bond is desirable.

The method for producing a sugar chain polymer compound is, for example, a method in which a hydroxyl group or an amino group of a sugar as described above is condensed with a dicarboxylic acid, dicarboxylic acid chloride, or dicarboxylic acid ester to form a polymer through an ester bond or an amide bond. To form the main chain.

Furthermore, in order to obtain a sugar chain polymer compound, the number of ester bond and amide bond sites of G is two or more (disubstitution). In the case of disubstitution, a more linear main chain is formed, and in the case of trisubstitution or more, a branched polymer compound can be obtained. It is desirable to control the degree of substitution of the sugar chain polymer compound depending on the use of the molded article.

The ester bond is an ester bond obtained by reacting the dicarboxylic acid of the other component with any one of the -OH groups at positions 1, 2, 3, 4, and 6 of the sugar. n shows the degree of polymerization and is an integer of 1 to 5000. More preferably, it is 50 to 2000.

(Thermoformed product) The sugar chain polymer compound described above has thermoplasticity and can be formed into a desired shape by heating or heating and pressing. Specifically, for example, the sugar chain polymer compound powder, particles, pellets,
After forming into a shape such as flakes, various molded products can be manufactured by appropriately thermoforming into a desired shape by a method such as pressure molding, film molding, extrusion molding, or injection molding.

The sugar chain polymer compound according to the present invention is practically sufficiently molded by thermoforming in a temperature range from its softening point to less than the thermal decomposition temperature, specifically, for example, in a temperature range of about 100 to 180 ° C. A thermoformed article having a high strength can be obtained. Specifically, the flexural strength is 1.0 to 6.0 kg.
/ Mm ² , and a thermoformed body having a tensile strength of about ²⁰ to 700 kg / cm ² . This has the same strength as, for example, conventional general-purpose polyesters, and opens the way for biodegradable plastics to replace general-purpose plastics.

By the way, in order to obtain a thermoformed product, a flame retardant, a stabilizer, an ultraviolet absorber, an antioxidant, a plasticizer, a lubricant, and the like, as long as the biodegradability and recyclability of the sugar chain polymer compound are not hindered. Alternatively, various additives such as a decomposition deterioration accelerator, a face dye, and other components may be appropriately compounded. For example, an aliphatic dibasic acid ester or the like can be added as a plasticizer.

The kneading of such other components into the sugar chain polymer compound can be carried out by a conventionally known method, for example, using 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 to be used, and the like. For example, when using a kneader or a Banbury mixer, the temperature is set to 60 to 250 ° C, preferably 70 to 230 ° C, and it is appropriate to knead at this temperature for 1 to 40 minutes, preferably 2 to 20 minutes.

(Biodegradation of Thermoformed Body) Next, the biodegradation of the thermoformed body can be performed in the same manner as the biodegradation of the sugar chain polymer compound before thermoforming. This will be described with reference to FIG.
FIG. 1 (a) schematically shows the sugar chain polymer compound represented by the general formula (I), wherein 1 represents a sugar (G) moiety and 2 represents an alkylene group (R) moiety. For the thermoformed article containing such a sugar chain polymer compound, for example, the following two decomposition methods, decomposition method 1 and decomposition method 2, can be used.

In the decomposition method 1, an enzyme which decomposes the ester bond 3 between the saccharide moiety (G) 1 and the alkylene group (R) 2 is acted on, for example, as shown in FIG. And an alkylene group moiety 2. Specifically, enzymes (eg, lipase, esterase) that catalyze the hydrolysis of an ester bond to a sugar chain polymer compound having cellobiose and sebacic acid as repeating units
Is caused to hydrolyze the ester bond of the sugar chain polymer compound, and as a result, cellobiose and sebacic acid are obtained as decomposition products as shown in FIG. 1 (b). Since this is the same substance as the raw material, repolymerization is possible.

Degradation method 2 is applied to a system containing oligosaccharides or polysaccharides, and an enzyme which degrades the glycosidic bond 4 between the saccharides of the saccharide moiety 1 is acted on, for example, in FIG.
As shown in (c), it can be decomposed into a unit (double-headed glycolipid) having both ends sugars or a sugar. Specifically, for example, a cellulase that catalyzes hydrolysis of a β (1 → 4) bond is applied to a sugar chain polymer compound composed of cellobiose having a β (1 → 4) bond as an oligosaccharide and an alkylene group portion. When acted, the glycosidic bond of the sugar chain polymer compound is hydrolyzed, and as a result, as shown in FIG. 1 (c), double-headed lipid and glucose are obtained as decomposition products. Since the oligosaccharide or polysaccharide portion 1 and the alkylene group portion 2 are regularly arranged in the sugar chain polymer compound shown in FIG. Can be obtained with a uniform molecular weight.

Therefore, when these decomposed products are reused, no separation work and purification are required, or simple purification compared to the conventional method is sufficient, and the cost of reusing decomposition products can be significantly reduced. Can be planned.

Further, the thermoformed article according to the present invention exhibits excellent strength, and hardly causes coloring or the like even by thermoforming. Further, the thermoformed article shows excellent biodegradability and recyclability, and controlling the biodegradability and physical properties to a preferable one by a molded article aimed at the composition, molecular weight, and auxiliary material of the sugar chain polymer compound It is easy by adjusting the blending amount and the like.

(Mixing) By the way, the polymer compound according to the present invention may be mixed with another polymer compound as long as the original properties are not impaired.

The molded article produced by the above method can be in any shape such as a film, a sheet, a foam, etc., and can be used for packaging containers, disposable packaging containers (one-way containers), toys, sheets, furniture parts, building materials, automobiles, home appliances, It can be effectively used for members of OA equipment, interior materials, housings, and the like. Since such a molded article has good biodegradability and recyclability, it has little effect on the environment in terms of disposal and the like. More specifically, the use of a recording medium such as a toner cartridge of an electrophotographic image forming apparatus as shown in FIG. 7 or a recording medium such as an ink jet recording medium in the form of a film or a sheet is shown in FIG. Can be used for Such a recording medium is represented by the above-mentioned general formula (I)
The sugar chain polymer compound shown in (1) is formed into a powder or a pellet, and the resulting product is subjected to an inflation method, a T-die method, a calendar method, a casting method, or the like.
By applying a certain amount of heat and forming, a sheet- or film-shaped recording medium having sufficient strength can be obtained.

When applied to a recording medium, the molecular weight of the high molecular compound is from 10,000 to several million, more preferably from 10,000 to
Hundreds of thousands are desirable. Further, an additive such as a plasticizer or a filler may be further added as long as the recyclability is not hindered.

The thickness of the recording medium is not particularly limited, but is preferably about 25 to 300 μm for use in a general ink jet printer.

(Opacity) The recording medium is basically colorless and transparent and can be suitably used as an OHP light transmitting recording medium (transparency). It can also be used as synthetic paper for high-quality printing and the like.

As a method of opacity, there is a method of adding a known white or colored pigment. Further, there is a method in which white or colored printing is performed on the entire surface of the front surface or the back surface, or a white or colored film is laminated on the back surface.

(Addition of Ink Receiving Layer) The recording medium can be used alone as a recording medium.
That is, printing can be performed by an ink jet recording apparatus without separately providing an ink receiving layer on the surface of the recording medium. However, depending on the characteristics and needs of the ink to be used, an ink receiving layer may be provided on the surface of the recording medium in order to obtain better printing characteristics. If the amount of the material used for the ink receiving layer is about several percent of the amount of the base material, the problem of recycling does not substantially become a problem.

As a material for forming the ink receiving layer,
Any conventionally known material can be used.
Specifically, albumin, gelatin, casein, starch, cationic starch, gum arabic, polyvinylimidazole, agar, hydrophilic natural materials such as sodium alginate, dextrin, viscose, methylcellulose, ethylcellulose, carboxymethylcellulose,
Hydroxyethyl cellulose, cation-modified hydroxyethyl cellulose, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol (polyvinyl acetal), polyethylene glycol, polypropylene glycol, polyacrylic acid,
Water-soluble alkyd, polyvinyl ether, polyvinylpyrrolidone, quaternized polyvinylpyrrolidone, polyamide, polyacrylamide, poly (N-vinyl-3-methylpyrrolidone), polymaleic acid copolymer, polyethyleneimine, polyethylene oxide, polyvinylimidazole, polyallylamine, polyallylamine Examples thereof include water-soluble or hydrophilic synthetic resins such as hydrochloride, melamine resin, polyurethane, and polyester. If desired, two or more of these materials may be used.

In order to improve the physical properties of the recording medium, for example, beading resistance and blocking resistance, various additives, dispersants, lubricants, pH adjusters, fluorescent paints, preservatives and the like are used. The recording medium according to the present invention can be used as long as the performance of the medium is not deteriorated.

As a method for forming an ink receiving layer on the surface of the recording medium, a coating liquid composed of the above-mentioned material is coated with a conventionally known coating method, for example, a roll coating method, a lot bar coating method, a spray coating method or the like. It can be formed by coating by a coating method, an air knife coating method, a casting method, or the like. The thickness of the ink receiving layer is preferably from 1 to 50 μm, and more preferably from 2 to 30 μm.

(Recycling Method) The recovered recording medium after use is subjected to deinking treatment and the like, and then hydrolyzed in a basic aqueous solution or an aqueous enzyme solution to depolymerize into a saccharide compound and an organic acid or organic acid salt. . The water can be removed, or the components can be separated and purified as needed, or if necessary, subjected to reaction substitution if necessary, and used again for the synthesis of the polymer compound.

As the basic aqueous solution used for the hydrolysis,
A 0.01 to 1N aqueous solution of sodium hydroxide or potassium hydroxide is suitable. As the enzyme, esterase, lipase, and peptide bond (and urethane bond) are reacted at an optimum pH and temperature, respectively, for enzymatic degradation according to the bond.

[0064]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.

Example 1 (Synthesis example: monosaccharide) 50 g of glucose, 200 ml of dimethylformamide,
100 ml of pyridine was stirred at room temperature under a nitrogen atmosphere. A solution prepared by diluting adipic acid chloride (20 ml) with dimethylformamide (100 ml) was added dropwise thereto for 1 hour.
Stirred . After 1 hour, 20 ml of adibic acid chloride was added dropwise and stirred for 1 hour. After the next one hour, 200 ml of dimethylformamide was added, and a solution obtained by diluting 20 ml of adipic acid chloride with 200 ml of dimethylformamide was added dropwise and stirred for one hour. After a part of the solvent was distilled off, the solution was poured into water and reprecipitated. The generated precipitate was washed with ethanol to obtain a colorless powder (Compound No. A-
1).

The molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. Measurement device: Tosoh, HLC8020 Column: Polymer Laboratories, Mixed-B (2) Eluent: DMF, 50 ° C Standard: Polysaccharide (Polymer Laboratories) conversion

The weight average molecular weight of the obtained polymer compound was 940,000, and the degree of polymerization was estimated to be about 3,200. An IR measurement confirmed a CＯO stretching peak at 1740 cm ⁻¹ , indicating that a sugar ester was successfully synthesized.

The sugar chain polymer compounds A-2 to A-6 shown in Table 1 below were synthesized according to the above synthesis examples.

[0069]

[Table 1]

Example 2 (Synthesis example: oligosaccharide) 100 g of cellobiose was added to N, N-
The mixture was placed in 800 ml of dimethylformamide (DMF), 400 ml of pyridine was added, and the mixture was heated to 70 ° C. under a nitrogen atmosphere. Here, 85 ml of sebacic chloride was added to DMF2
What was added to 00 ml and diluted was added dropwise and stirred for 3 hours. After completion of the reaction, a part of the solvent was distilled off, and then the reaction solution was poured into water and stirred. The purified precipitate was washed with methanol to obtain a white powder (Compound No. B-1). The weight average molecular weight of the obtained polymer compound was 900,000, and the degree of polymerization was estimated to be about 1800.

The IR measurement showed a CＣO stretching peak at 1743 cm ^-1 as shown in FIG. 2, and the 13C-NMR measurement showed a 175 ppm C ＝ O group and 2C as shown in FIG.
4.8 ppm and 34. A methylene sebacate group of 1 ppm was confirmed, and it was found that a sugar ester could be synthesized.

FIG. 5 shows a sugar chain polymer compound (Compound No. B).
-1) and FIG. 6 shows DSC data of the sugar chain polymer compound (Compound No. B-1). Hereinafter, sugar chain polymer compounds B-2 to B-2 shown in Table 2 below according to the above Synthesis Examples.
B-19 was synthesized.

[0073]

[Table 2]

(Synthesis of acetylated product) B-1 powder 5g, anhydrous sodium acetate 1.3
g was added to 100 ml of acetic anhydride and stirred at 120 ° C. for 2 hours. The reaction product was poured into 500 ml of ice water, and the precipitate was
Washed twice and dried to obtain a light brown powder (Compound No.
B-IA). By IR measurement, it was confirmed that the initial hydroxyl group was acetylated. In addition, it was confirmed by GPC measurement that there was almost no change in the initial molecular weight distribution. Compound No. An acetylated product was obtained in the same manner as for B-19 (Compound No. B-19A).

Example 3 (Synthesis example: polysaccharide) 5 g of cellulose was put in 80 ml of DMF and heated to 60 ° C. under a nitrogen atmosphere. Here, 1 ml of pyridine and 2 ml of azelaic acid chloride are added dropwise,
Stirred for hours. After the reaction is completed, the reaction solution is
Poured into the precipitate obtained. This precipitate was sequentially washed with ethanol and diethyl ether to obtain 3 g of a white powder (Compound No. C-1).

When the molecular weight was measured by GPC measurement, 1
It was 50,000. By IR measurement, as shown in FIG.
= O stretching peak and sugar ester could be synthesized. Table 3 shows examples of compounds synthesized according to the above synthesis examples.

[0077]

[Table 3]

Examples 4 to 8 and Comparative Examples 1 and 2 (Evaluation of Thermal Properties of Oligosaccharides) Compounds synthesized by the methods of Examples 1 and 2 (Nos. A-1, B-1, 18, 14, 1)
Regarding 9), the thermal characteristics of the softening point and the thermal decomposition temperature were measured.

The softening point was determined by DSC (Perkin-Elm).
er (Perkin-Elmer); trade name; DSC Robo). The measurement was performed under a nitrogen atmosphere at a heating rate of 10 ° C./min from 40 to 500 ° C., and an endothermic peak lower than the thermal decomposition temperature was defined as a softening point.

The decomposition point was determined by TG (thermal balance) (Perkin
-Elmer (Perkin-Elmer); trade name; D
SC7). The measurement conditions were as follows:
At a heating rate of 10 ° C./min, the temperature was measured from 30 to 500 ° C., and the thermal decomposition temperature was determined from the differential curve.

As Comparative Examples 1 and 2, compounds in which sebacic chloride was replaced with adipic chloride and terephthalic chloride were synthesized in the same manner as in Example 2. R-1 and R-2. Table 4 shows the thermal characteristics of each compound.

[0082]

[Table 4]

As shown in Table 4, the compounds R-1 and R-2 have a high thermal decomposition temperature and excellent heat resistance, but do not soften at a temperature lower than the decomposition temperature. Both compounds of R-1 and 2 turned brown (burned) without softening and decomposed when heating was continued.

Using a melting point measuring device, B-1 and R
The compound of No. -1 was sandwiched between cover glasses, and each softening temperature was pressed with a metallic spatula and visually observed. B-1
Compound softened around 140 ° C. However, R-1
Even when heated to 320 ° C., the compound had no softening point, gradually became dark brown, and was decomposed.

From the above results, it was found that the compound of the present invention is a sugar chain polymer compound which softens at a temperature lower by about 120 to 160 ° C. than the decomposition point and has thermoplasticity. Further, the fact that the decomposition point and the softening point were far from each other revealed that the polymer compound was excellent in thermoformability.

Examples 9 to 14 and Comparative Example 3 (Preparation of thermoformed body) Example 1 was carried out using a test hot press (Mini Test Press-10) manufactured by Toyo Seiki Co., Ltd.
The compounds synthesized by the methods of (1) to (3) were thermoformed. Table 5 shows the results together with the heating temperature and the pressurizing conditions. Comparative Example 1
A molded body was prepared from the compound used in the same manner as above,
Comparative Example 3 was used.

[0087]

[Table 5]

As shown in Table 5, it was found that molding was possible at 200 ° C. or lower and a transparent molded article was obtained.

Examples 15 to 18 (Evaluation of thermoformed article characteristics) Strip-shaped test pieces were cut out from the compacts produced in Examples 9, 10, 12, and 13, and were manufactured by Shimadzu Corporation, Autograph DSC-R. Mechanical properties (tensile strength, elongation) were measured using a Model -500. Also,
The same strip-shaped test piece was embedded in aged compost, and the biodegradability was also evaluated. After 6 months, it was observed whether or not biodegradation had progressed. A sample in which degradability was observed was rated as Δ, and a sample in which no degradability was recognized was rated as ×. The results are shown in Table 6.

[0090]

[Table 6]

As shown in Table 6, it was clarified that the molded article had a sufficiently high tensile mechanical property and a biodegradability.

Example 19 (Evaluation of recyclability of thermoformed article 1) A thermoformed article (Compound No. B-2) prepared in the same manner as in Example 10 was pulverized with a pulverizer, and 1 g of the pulverized powder was used. And an esterase enzyme (Boehringer Mannheim) were placed in a pH 7.5 buffer solution and stirred at 45 ° C. One week later, the reaction supernatant was subjected to a high performance liquid chromatography system (HPL) manufactured by Tosoh Corporation.
C): LC-8020, column: SH1011 (manufactured by Showa Denko), eluent: When measured with water, new peaks corresponding to low-molecular-weight sugars and organic acids were newly observed. These gradually increased in strength over time. Each peak showing the peak was collected, and the infrared absorption spectrum was measured to confirm that it was an oligosaccharide and a fatty acid. Furthermore, the fatty acid part was confirmed to be suberic acid by NMR.

[0093] These sugars and fatty acids could also be separated by enzymatically decomposing the sugars by extracting the sugars with water and the fatty acids with diethyl ether. Suberic acid chloride was newly added to the separated sugar, and reacted as in Synthesis Example 1,
It was found that it could be repolymerized and recyclable.

Example 20 (Evaluation of recyclability of thermoformed article 2) A thermoformed article (compound No. B-7) prepared in the same manner as in Example 10 was pulverized with a pulverizer, and 1 g of the pulverized powder was used. And 2 mg of lactase enzyme (manufactured by Sigma) in 3 ml of pH 4.4 buffer,
When the reaction was carried out at 25 ° C., a low molecular weight product was gradually obtained.

After 10 days, the decomposed compound was measured by GPC and found to have a weight average molecular weight of about 6,000. Also,
To 3 g of this decomposition product, 1 g of azelaic acid was added, and
After heating at 0 ° C. for 20 minutes, repolymerization was performed by melt polymerization. The polymer was purified by washing with ethanol and ether. When the molecular weight was measured by GPC, the resin composition was 50,000, and it was confirmed that the resin composition was repolymerized.

Example 21 (Preparation of Toner Replenishing Container) Compound No. 1 synthesized by the method of Example 2 was prepared. The powder of B-1 was compression molded under the same conditions as in Example 10 and processed into a toner supply container which is a component of the toner cartridge for a copying machine shown in FIG. FIG. 7 is a schematic perspective view of the toner supply container according to the present embodiment, and constitutes a so-called stationary (built-in type) toner cartridge which is stationary in a copying machine and gradually supplies toner to the developing mechanism until the toner is used up. Part of a part. In FIG. 7, reference numeral 71 denotes a toner supply container, which is made of the biodegradable polymer according to the present embodiment.
Reference numeral 72 denotes a flange attached to the end of the toner supply container 71, and reference numeral 73 denotes a grip portion serving as a grip when the toner cartridge is attached to and detached from the copying machine.

Example 22 (Evaluation of recyclability of toner replenishing container) The toner replenishing container prepared in Example 21 was collected and crushed into a pellet. The pellet was subjected to enzymatic degradation. The decomposition was carried out by placing the pellet in a buffer containing an enzyme (esterase) (pH = 8, liquid temperature 40 ° C.). In this solution, oligosaccharides, sebacic acid, and ester compounds having cellobiose residues at the terminals were confirmed as raw materials of the degradable plastic. Confirmation of the decomposition product was performed by NMR and IR evaluation of the decomposition product collected by GPC. These decomposition products could be converted into sugar chain polymer compounds again in the same manner as in Example 17.

Example 23 (Evaluation of biodegradability of toner replenishing container) The toner replenishing container prepared in Example 21 was left in soil for 6 months, and it was confirmed that the toner replenishing container collapsed and partially disappeared.

Example 24 (Synthesis of polymer compound) 50 parts by weight of cellobiose was added to dimethylformamide 400
The suspension was added to 200 parts by weight of pyridine, and heated to 80 ° C. under a nitrogen atmosphere. A solution prepared by diluting 40 parts by weight of sebacic acid chloride into 200 parts by weight of dimethylformamide was added thereto, and the mixture was stirred for 2 hours. After a part of the solvent was distilled off, the mixture was poured into water and stirred, and the formed precipitate was washed with methanol. The weight average molecular weight of the obtained polymer compound was about 200,000.

Examples 25 to 29 (Synthesis of polymer compound) In the same manner as in Example 24, polymer compounds were synthesized from the starting materials shown in Table 7 below. However, only in the case of Example 25, after 2 hours of reaction time, 100 parts by weight of methanol was added and refluxed for 2 hours.

[0101]

[Table 7]

Examples 30 to 35 (Preparation of Transparent Recording Medium) From a powder of the polymer compound synthesized in Examples 24 to 29, a T-die was extruded and successively biaxially stretched to prepare a recording medium having a thickness of 110 μm. did. The sugar chain polymer was heated to about 150 to 180 ° C. during the film formation. All of the recording media thus obtained are transparent and have a visible light range (400 to 80).
The average transmittance and haze at 0 nm) were as shown in Table 8.

[0103]

[Table 8]

Example 36 (Preparation of Opaque Recording Medium) Titanium oxide (R-580, manufactured by Ishihara Sangyo Co., Ltd.) was mixed at 10% by weight with the polymer compound powder synthesized in Example 24, and the same as above. 1 by the method of
A film recording medium having a thickness of 20 μm was produced. All of the obtained recording media were white and opaque and glossy.

Examples 37 to 43 (Printing Examples) An ink jet printer (BJC-6) was used for the recording medium manufactured in Examples 30 to 36.
00J (manufactured by Canon Inc.), an arbitrary text line and a solid portion were printed in cyan, yellow, and magenta, respectively. For comparison, the same printing was performed on a commercially available OHP film for color inkjet (CF-102, manufactured by Canon Inc.).

In general, in an OHP film for PPC without an aqueous ink receiving layer, there are disadvantages such as a drop of a liquid drop approaching the center of a printed portion or a flow of ink. In each case, clear printing could be performed. The drying speed and color development of the ink were almost the same as those of a commercially available OHP film for color inkjet.

Example 44 (Recording Medium with Ink-Receiving Layer) A coating liquid having the following composition was applied to a 110 μm-thick film of Example 30 (cellobiose = sebacic acid system) by a bar coater as an ink-receiving layer at a thickness of 5 μm. And dried at 80 ° C. In addition, it was confirmed that printing was possible by the above method.

Composition of coating liquid: 1% by weight of polyvinylpyrrolidone (PVP K-90, manufactured by GAF) 9% by weight of cation-modified polyvinyl alcohol (PVA-CM-318, manufactured by Kuraray Co., Ltd.) 90% by weight of water 50 (Recovery of Raw Materials) The recording medium films produced in Examples 30 to 35 were crushed, and 10 g of each of the crushed recording medium films was treated with 0.1 g of each. It was poured into 500 ml of 1N aqueous sodium hydroxide solution and stirred at 70 ° C. for 10 hours. By gel filtration chromatography, it was confirmed that the molecular weight had almost decreased to the value of the raw material saccharide compound. If any insolubles were present, they were filtered off. Then, the pH was adjusted to pH5. After adjustment with 1N hydrochloric acid, the resulting insolubles were filtered off. The remaining aqueous solution
After passing through an ion exchange resin (Amberlite IR-120B, manufactured by Organo Corporation), it was dried at 35 ° C. and 20 mmHg. Each fraction was identified as shown in Table 9 by infrared absorption spectrum. The recovery was 90% or more in each case.

[0109]

[Table 9]

Example 51 (Recovery of Raw Material by Enzyme) The recording medium films prepared in Examples 30 to 33 were crushed, and 10 g of the lipase powder and 40 g of lipase powder (Lipase Amano PF, manufactured by Amano Pharmaceutical Co., Ltd.) were each adjusted to pH 7.0. The solution was poured into 500 ml of a buffer solution (0.1mo1 / 1 potassium dihydrogen phosphate / sodium hydroxide) and stirred at 45 ° C for 2 days. Gel filtration chromatography confirmed an increase in components equal to the molecular weight of the starting saccharide compound. The solids containing the enzyme powder are filtered off and then 0. After adjustment with 1N hydrochloric acid, the resulting insolubles were filtered off. The remaining aqueous solution was passed through an ion-exchange resin (Amberlite IR-120B, manufactured by Organo Corporation) and then dried at 35 ° C. and 20 mmHg. From the infrared absorption spectrum, the insoluble matter (at pH 5) was identified as the fatty acid, and the soluble matter was identified as the saccharide compound. Recovery rate was 50-70%.

[0111]

As described above, according to the present invention,
It is possible to provide a novel sugar chain polymer compound having excellent thermoplasticity, recyclability and biodegradability. By utilizing the thermoplasticity of the novel sugar chain polymer compound, it is possible to produce a thermoformed article, and it is possible to provide a molded article having excellent recyclability, biodegradability, and mechanical properties.

Further, the toner cartridge according to the present invention can be returned to a plastic raw material again by disassembling after disposal. If this decomposition is performed in a container, the raw material of the decomposable plastic can be recovered. On the other hand, if the decomposition is performed in soil, the degradable plastic can be composted. Further, the recyclability of the polymer compound constituting the toner cartridge and the recording medium can contribute to waste disposal problems and effective use of resources. In addition, it is possible to provide an inkjet recording medium capable of performing recording without necessarily providing an ink receiving layer separately, for example, a transparency for OHP or a synthetic paper.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing decomposition of one embodiment of a sugar chain polymer compound of the present invention.

FIG. 2 shows a sugar chain polymer compound of the present invention (Compound No. B-
It is an infrared absorption spectrum figure of 1).

FIG. 3 shows a sugar chain polymer compound of the present invention (Compound No. B-
It is a figure which shows ¹³ C-NMR data of 1).

FIG. 4 shows a sugar chain polymer compound of the present invention (Compound No. C-
It is an infrared absorption spectrum figure of 1).

FIG. 5 shows a sugar chain polymer compound of the present invention (Compound No. B-
It is a figure which shows TG data of 1).

FIG. 6 shows a glycolytic polymer compound of the present invention (Compound No. B-
It is a figure which shows DSC data of 1).

FIG. 7 is a schematic perspective view of a toner cartridge.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Sugar (G) part 2 Alkylene group (R) part 3 Ester bond 4 Glycoside bond 71 Toner supply container 72 Flange 73 Grasping part

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 11-31794 (32) Priority date February 9, 1999 (February 29, 1999) (33) Priority claim country Japan (JP) (72) Inventor Toshihiko Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-10-218903 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (30)

(57) [Claims] 1. A saw including a sugar polymer represented by the following general formula (I), heat moldings molded using heat. Embedded image Wherein G is the residue of a monosaccharide, oligosaccharide or polysaccharide;
R is a linear or branched alkylene group having 4 or more carbon atoms when G is a monosaccharide residue, and a straight-chain or branched alkylene group having 4 or more carbon atoms when G is an oligosaccharide or polysaccharide residue. A squamous or branched alkylene group, wherein n is 1 to 50;
It is an integer of 00. ) 2. The thermoformed product according to claim 1, wherein said G is a residue of a monosaccharide, and said R is a linear or branched alkylene group having 4 to 14 carbon atoms. 3. G is an oligosaccharide or polysaccharide residue,
The thermoformed article according to claim 1, wherein R is a linear or branched alkylene group having 6 to 14 carbon atoms. 4. The thermoformed article has a flexural strength of 1.0 kg / m.
m ² or more and 6.0 kg / mm ² or less, tensile strength 20 kg
/ Cm ² or more 700 kg / cm ² or less is claim 1 thermoformed article according. 5. The thermoformed article according to claim 1, wherein the sugar residue forms an ester bond when the sugar is only a hydroxyl group, and forms an amide bond and / or an ester bond when the sugar has an amino group. 6. The thermoformed article according to claim 1, wherein said sugar residue is a monosaccharide, oligosaccharide or polysaccharide consisting of only a pyranose ring. 7. The thermoformed product according to claim 1, wherein the monosaccharide is glucose, mannose, galactose, or glucosamine. 8. The oligosaccharide may be maltose, cellobiose, lactose, isomaltose, chitobiose, nigerose, trehalose, melibiose, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose, maltotetraose, cellopentaose. , Maltopentaose, chitopentaose,
7. The thermoformed article according to claim 1, which is at least one of cellohexaose, maltohexaose, and chitohexaose. 9. The method of claim 9, wherein the polysaccharide is cellulose, starch, glycogen, galactan, mannan, chitin, chitosan,
7. The thermoformed article according to claim 1, which is at least one of pullulan. 10. The thermoformed article according to claim 1, wherein R has 6 to 10 carbon atoms. 11. A method comprising applying a temperature to a polymer compound containing a sugar chain polymer compound represented by the following general formula (I), which temperature is equal to or higher than the softening point of the sugar chain polymer compound and lower than the thermal decomposition temperature, to mold the polymer. A method for producing a molded article. Embedded image Wherein G is the residue of a monosaccharide, oligosaccharide or polysaccharide;
R is a linear or branched alkylene group having 4 or more carbon atoms when G is a monosaccharide residue, and a straight-chain or branched alkylene group having 4 or more carbon atoms when G is an oligosaccharide or polysaccharide residue. A squamous or branched alkylene group, wherein n is 1 to 50;
It is an integer of 00. ) 12. A toner cartridge comprising the thermoformed product according to claim 1. 13. A recording medium comprising the thermoformed article according to claim 1. Description: 14. look including a sugar polymer represented by the following general formula (I), a method of recycling heat molded body formed using heat, (i) sugar chains polymeric compound (Ii) a step of repolymerizing the depolymerized product obtained in the step (i) using heat ; and (ii) a step of repolymerizing the depolymerized product obtained in the step (i) using heat. A method for recycling molded thermoformed articles. Embedded image Wherein G is the residue of a monosaccharide, oligosaccharide or polysaccharide;
R is a linear or branched alkylene group having 4 or more carbon atoms when G is a monosaccharide residue, and a straight-chain or branched alkylene group having 4 or more carbon atoms when G is an oligosaccharide or polysaccharide residue. A squamous or branched alkylene group, wherein n is 1 to 50;
It is an integer of 00. ) 15. The method according to claim 15, wherein the step (ii) is the same as the step (i).
The depolymerized product obtained by
The recycling according to claim 14, which is a step of polymerizing.
Method. 16. The depolymerization in the step (i) is carried out before
Esters of sugar chain polymer compounds represented by the general formula (I)
15. A reaction for cleaving a bond or an amide bond.
Or the recycling method according to 15. 17. The method according to claim 14, wherein a base is used for the depolymerization.
17. The recycling method according to any one of items 16 to 16. 18. The method according to claim 18, wherein said base is sodium hydroxide.
Item 18. The recycling method according to Item 17. 19. The depolymerization in the step (i) is carried out before
The sugar residue G of the sugar chain polymer compound represented by the general formula (I)
16. The method according to claim 14, wherein the step of
Cycle method. 20. The sugar residue G contains an oligosaccharide or a polysaccharide.
The step of decomposing the sugar residue G links the monosaccharide molecules to each other.
Dissolving the associated glycosidic bonds.
20. The recycling method according to 19. 21. The method according to claim 14, wherein an enzyme is used for the depolymerization.
Any of to 19 The recycling method described in the section. 22. The toner cartridge according to claim 12,
Recycling method, (I) the sugar chain polymer compound represented by the general formula (I)
Depolymerizing at least a portion thereof; and (Ii) the depolymerized product obtained by the step (i)
A step of repolymerizing the polymer.
Cycle method. 23. The recording medium according to claim 13, wherein
The cycle method, (I) the sugar chain polymer compound represented by the general formula (I)
Depolymerizing at least a portion thereof; and (Ii) the depolymerized product obtained by the step (i)
A step of repolymerizing the polymer.
Cycle method. 24. The method according to claim 24, wherein the step (ii) comprises the step (i).
The depolymerized product obtained by
The method according to claim 22 or 23, wherein the polymerization is performed.
Recycling method. 25. The depolymerization in the step (i) is carried out before
Esters of sugar chain polymer compounds represented by the general formula (I)
23. A reaction for cleaving a bond or an amide bond.
25. The recycling method according to any one of items 24 to 24. 26. The method according to claim 22, wherein a base is used for the depolymerization.
26. The recycling method according to any one of Items 25 to 25. 27. The method according to claim 27, wherein the base is sodium hydroxide.
Item 29. The recycling method according to Item 26. 28. The method according to claim 28, wherein the depolymerization in the step (i) is carried out before.
The sugar residue G of the sugar chain polymer compound represented by the general formula (I)
25. The method according to claim 22, wherein
The recycling method described in the section. 29. The sugar residue G contains an oligosaccharide or a polysaccharide.
The step of decomposing the sugar residue G links the monosaccharide molecules to each other.
Dissolving the associated glycosidic bonds.
29. The recycling method according to 28. 30. The method according to claim 22, wherein an enzyme is used for the depolymerization.
30. The recycling method according to any one of items 29 to 29.