JP2000313702A - Cellulose-containing complex and its production, sugar compound and its production, resource recovery of paper, recycling waste paper into resource, and formed article and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cellulose-containing complex capable of improving molding processability, excellent in mechanical strength or the like and useful for producing a formed article capable of expressing the function of biodegradability or the like by compounding cellulose with a specific compound. SOLUTION: The complex contains cellulose and a compound of formula I [R is a (substituted) alkylene or a (substituted) arylene; G is a monosaccharide residue or an oligo residue; n is 1-5,000] (e.g. a compound of formula II). The ratio of a compound of formula I in a cellulose-containing complex is preferably about 10-40 wt.%. The cellulose can be a bacterial cellulose. The complex is obtained by drying a solution prepared by homogeneously mixing cellulose with a compound of formula I. The compound of formula I is obtained by (i) preparing a saccharide residue (e.g. cellobiose) expressed by G in formula I by decomposing cellulose of paper and (ii) binding the saccharide residue to a dicarboxylic acid which contains the part expressed by R in formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite having improved properties of cellulose and a method for producing the same.

[0002]

2. Description of the Related Art Cellulose is a structural polysaccharide which is a main component of the cell wall of higher plants. It accounts for 1/3 to 1/2 of the plant body and is the most abundant organic compound on the earth.

[0003] Cellulose is a polymer compound having high crystallinity between main chains due to strong hydrogen bonds between hydroxyl groups and exhibiting no thermoplasticity. Cellulose includes plant-derived cellulose and microbial-derived bacterial cellulose. The processing has conventionally been performed as follows. Plant-derived cellulose is improved in solubility in a solvent by alkali treatment or by introducing a soluble substituent, and then the solution is put into a desired shape mold, and the solvent is removed to form a cellulose molded product. I was getting it. On the other hand, as a method for processing bacterial cellulose, there has been reported a method of controlling the crystal structure of bacterial cellulose by adding xanthan gum to a medium of a cellulose-producing bacterium (see JP-A-6-206904). In addition, there has been reported a method for producing a sheet-like material having high mechanical strength by applying pressure and heat treatment to a bacterial cellulose film made of ribbon-shaped microfibrils produced by a cellulose-producing bacterium (Japanese Patent Publication No. Heiho-Hei). 8-32798). In addition, a method of applying pressure and heat treatment to finely powdered cellulose, that is, a so-called powder molding treatment is also known.

[0004] In recent years, along with the worsening of environmental problems and resource problems, cellulose has regained attention as a biodegradable and reproducible resource in nature. However, cellulose was insoluble in general solvents and unsuitable for the solvent method. In addition, when cellulose is dissolved in a special solvent such as a copper ammonia solution, a molded product such as a film can be obtained by a solvent method, but the molded product obtained by this method is poor in flexibility and practically usable. The quality was not good enough. Furthermore, since cellulose does not exhibit thermoplasticity, it has been extremely difficult to prepare a thermoformed article by the heat compression method.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above technical background, and is intended to improve the processability of cellulose while maintaining the original biodegradability of cellulose. It is an object to provide a containing complex. It is another object of the present invention to provide a method for producing a cellulose-containing composite in which the processability of cellulose is improved without impairing the inherent biodegradability of cellulose.

[0006]

Means for Solving the Problems A cellulose-containing composite which can achieve the above object is characterized by containing cellulose and a compound represented by the following formula (I).

[0007]

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

[0008] One embodiment of a method for producing a cellulose-containing composite that can achieve the above object is a method for producing a composite comprising cellulose and a compound represented by the following formula (I): A step of heating and drying a solution obtained by uniformly mixing the cellulose and the compound represented by the following formula (I).

[0009]

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

Another embodiment of a method for producing a cellulose-containing composite which can achieve the above object is a method for producing a composite comprising cellulose and a compound represented by the following formula (I). A step of culturing a cellulose-producing bacterium in a medium containing a compound represented by the following formula (I) to produce cellulose.

[0011]

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

That is, as described above, the present inventors have found that the poor processability of cellulose is due to the high crystallinity due to strong hydrogen bonds between the main chains derived from the microfibril structure of cellulose. Of the structure of the monosaccharide derivative or the oligosaccharide derivative represented by the structural formula (I) and cellulose, the results of various investigations revealed that the compound represented by the structural formula (I) A complex which has a good binding property (affinity) to the cellulose and mixes the two and causes an intermolecular interaction can greatly improve the poor processability of cellulose. It has been found that a molded article produced by using the method has excellent strength and flexibility, and the present invention has been accomplished.

It is not clear why the complex of the present invention exhibits the above-mentioned various effects. However, the sugar moiety (G) of the compound represented by the above formula (I) has a similar structure to cellulose and has a hydroxyl group. However, the dicarboxylic acid moiety is an aliphatic hydrocarbon chain or an aromatic hydrocarbon chain. Thus, it is considered that the crystallinity in the cellulose is lowered because the appropriate ratio of the portion where the aggregate is easily formed by the hydrogen bond and the portion where the aggregate is not formed are in an appropriate ratio.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A composite according to one embodiment of the present invention contains cellulose and a compound represented by the following structural formula (I).

[0015]

Embedded image

(Monosaccharide Derivative or Oligosaccharide Derivative) As described above, the compound used in the complex according to the present embodiment has an intermolecular interaction with cellulose and has strong crystallinity of cellulose. A structure that can be relaxed is suitably used.

Examples of the site capable of forming a hydrogen bond with cellulose include a hydroxyl group of a saccharide residue of a monosaccharide derivative or an oligosaccharide derivative, and an oxygen atom in a ring. Further, when the sugar moiety of the monosaccharide derivative or oligosaccharide derivative is substituted with an ester group such as an acetyl group, a hydrogen bond can be formed between a carbonyl group contained in the acetyl group and a hydroxyl group of cellulose.

The compound satisfying such structural requirements includes, for example, a monosaccharide derivative or an oligosaccharide derivative, specifically, a compound having a structure represented by the following formula (I).

[0019]

Embedded image

In the general formula (I), R is an alkylene group having 1 or more carbon atoms or an arylene group. G represents a monosaccharide residue or an oligosaccharide residue. The alkylene group preferably has 1 to 20 carbon atoms. When G is an oligosaccharide residue, the alkylene group has 6 or more and 1 carbon atoms.
When the compound having a carbon number of 4 or less is used, or when the alkylene group having a carbon number of 4 or more and 14 or less is used when G is a monosaccharide residue, the resulting composite has excellent thermoplasticity. This is particularly preferable since thermoformability can be imparted to the composite. The alkylene group and the arylene group each have one or two or more hydrogen atoms,
It may be substituted by other groups, examples of the substituent include
For example, a linear or branched alkyl group having about 1 to 6 carbon atoms may be mentioned.

G may be disubstituted or more. N represents the degree of polymerization, and is 1 to 5000, preferably 2
It is an integer of 0 to 3000.

The monosaccharide derivative or oligosaccharide derivative represented by the general formula (I) is, for example, a monosaccharide or oligosaccharide containing the monosaccharide residue or oligosaccharide residue “G” and “R” in the molecule. Is reacted with the hydroxyl group of the sugar and the COOH group or COCl group of the dicarboxylic acid to form an ester bond, or by transesterification of the dicarboxylic acid ester with a monosaccharide or oligosaccharide, and It can be synthesized by bonding using a reaction or the like.

(Monosaccharide or oligosaccharide) Examples of the monosaccharide or oligosaccharide which can be used herein include cellobiose, maltose, lactose, isomaltose, nigerose, trehalose, melibiose, cellotriose, maltotriose, cellotetraose, maltotetraose. Oligosaccharides such as aose, cellopentaose, maltopentaose, cellohexaose, and maltohexaose, and monosaccharides such as glucopyranose, mannopyranose, and galactopyranose are included. Further, these monosaccharides and oligosaccharides may be substituted with an ester group such as an acetyl group.

In the synthesis of the derivative of the above general formula (I), one selected from the group consisting of these monosaccharides and oligosaccharides,
Alternatively, more than one sugar can be used.

It is particularly preferable to use, for example, those obtained by decomposing paper (such as waste paper) from the viewpoint of effective use of resources.

That is, in recent years, with the rapid spread of copiers and printers, paper dust tends to increase more and more. From the past, systems that reuse newsprint and corrugated paper as recycled paper have been established. However, there is a limit to the demand for recycled paper, and it is estimated that the limit of waste paper in the raw material is 66.1% ("Eco-Material Dictionary" Science Forum). In addition, recent recycling initiatives have only accelerated the recovery process, ironically contributing to an increase in excess waste paper.

Further, paper having a large amount of printing, paper having a coat layer, paper having a large amount of additives, etc., cannot be converted into recycled paper in many cases due to the large amount of impurities mixed therein.

However, cellulose, which is a main component of paper, is chemically modified to be decomposed into sugar, and the above-mentioned sugar derivative is used, so that the low-quality waste paper described above can be used for purposes other than recycled paper. It can be used effectively. As a method for producing the above-mentioned sugar from paper, for example, a β1 → 4 bond of a cellulose fiber constituting paper is cleaved with an acid such as sulfuric acid or hydrochloric acid or an enzyme such as cellulase to prepare glucose (monosaccharide) and cellooligosaccharide. (2 to 10 sugars).

(Dicarboxylic acid) Examples of dicarboxylic acids containing "R" in the molecule include aliphatic dicarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, Dodecanedioic acid, etc.), aromatic dicarboxylic acids (phthalic acid, isophthalic acid,
Terephthalic acid).

(Cellulose) As the cellulose, cellulose derived from plants or bacterial cellulose derived from bacteria can be used. In the case of bacterial cellulose, fine fibrous cellulose having higher purity than plant-derived cellulose can be obtained. Further, as described later, there is an advantage that the complex according to the present invention can be produced during the culture of the cellulose-producing bacterium. Use of the cellulose derived from the above-mentioned paper (used paper or the like) as the cellulose is also a preferred embodiment from the viewpoint of effective use of resources. Specifically, cellulose fibers in the paper can be extracted by loosening the paper in a weak alkaline aqueous solution. Cellulose fibers as a residue generated in the process of decomposing paper into sugars described above can also be used as the cellulose in this embodiment. The cellulose fibers may be further eluted with an organic solvent such as a mixed solvent of dimethylacetamide and lithium chloride.

(Bacterial Cellulose Producing Bacteria) Bacteria producing bacterial cellulose are not particularly limited. For example, Acetobacter aceti subsp. Xylinum (Acetobacter aceti subsp.)
-Xylinum) ATCCl0821; A. pasteurianus ATCCl0
821, the same license (A. lancens), Sarsina ventricul
i), Bacterium xyloides (Bacteriu)
xyloides), Pseudomonas genus bacteria, Agrobacterium genus bacteria, etc., which produce bacterial cellulose can be used alone or in combination.

The method for producing bacterial cellulose by these fungi may be performed according to known bacterial culture conditions. That is, by inoculating the microorganism into a normal nutrient medium containing a carbon source, a nitrogen source, inorganic salts, and other organic trace nutrients such as amino acids and vitamins as necessary, and allowing the mixture to stand or gently aerated, the fungus Produces bacterial cellulose.

As the carbon source, glucose, sucrose, maltose, starch hydrolyzate, molasses and the like can be used.
Ethanol, acetic acid, citric acid and the like can be used alone or in combination with the above-mentioned sugars. As the nitrogen source, an organic or inorganic nitrogen source such as ammonium salts such as ammonium sulfate, ammonium chloride and ammonium phosphate, nitrates, urea and peptone can be used. As inorganic salts, phosphates, magnesium salts, calcium salts,
Iron salts, manganese salts and the like can be used. As organic micronutrients, amino acids, vitamins, fatty acids, nucleic acids, as well as peptones, casamino acids, yeast extracts containing these nutrients,
When a soybean protein hydrolyzate or the like can be used and an auxotrophic mutant that requires an amino acid or the like for growth is used, the required nutrients must be further supplemented. Culture conditions may be normal, and culture may be performed for 1 to 30 days while controlling the pH to 5 to 9 and the temperature to 20 to 40 ° C.

(Production Method) Next, the method for producing the above-mentioned cellulose-containing complex of the present invention is not particularly limited. For example, a condition in which a chemical interaction between cellulose and a monosaccharide derivative or an oligosaccharide derivative occurs. Is preferably formed. Specifically, for example, cellulose in the form of fine fibers and / or fine powder and a monosaccharide or oligosaccharide derivative are mixed in a solvent in which the monosaccharide or oligosaccharide derivative dissolves or swells. Is heated and dried to obtain the composite of the present invention. Such a solvent cannot be unambiguously specified because the solubility of the monosaccharide or oligosaccharide derivative changes depending on its molecular weight or the like. For example, water, acetone, alcohol (methanol, ethanol, etc.), ether (tetrahydrofuran, etc.) ) Or a mixed solvent thereof. It is also possible to subject cellulose to a surface treatment with a surfactant or the like before mixing.

When cellulose derived from paper is used as the cellulose, a solution obtained by dissolving the cellulose in dimethylacetamide, lithium chloride or the like and a solvent containing a monosaccharide or oligosaccharide derivative in a dissolved or swollen state as described above are used. Can also yield a complex in which a chemical interaction has occurred between cellulose and a monosaccharide or oligosaccharide derivative.

On the other hand, in the case of bacterial cellulose,
The complex according to the present invention can be easily produced by adding a sugar derivative to the culture medium of a cellulose-producing bacterium and culturing the cellulose-producing bacterium under conditions capable of producing cellulose to produce cellulose. It is.

By such a treatment, the number of hydrogen bonds existing in the cellulose molecule can be reduced, and as a result, a composite having better processability than cellulose can be obtained.
This will be described with reference to FIGS.

FIG. 1 schematically shows an example of a complex composed of cellulose and a cellobiose derivative (compound of the formula (I) in which “G” is a residue derived from cellobiose). FIG.
, A circle indicates a glucopyranose residue, and a broken line indicates a hydrogen bond acting between glucopyranose residues. 11 indicates a cellobiose derivative molecule, and 1la indicates a non-saccharide residue constituting the derivative. Reference numerals 12 and 13 denote cellulose molecules (construed as schematically comprising eight glucopyranose residues). Assume that these three molecules are on the same plane. Cellobiose residues constituting the cellobiose derivative 11 form hydrogen bonds with the cellulose molecules 12 and 13.

On the other hand, a system composed of three cellulose molecules (supposed to be composed of eight glucose residues) is schematically shown in FIG. 21, 22, and 23 are coplanar 3
Two cellulose molecules, in which hydrogen bonds are formed between glucopyranose residues. As is apparent from a comparison between FIG. 1 and FIG. 2, in the complex according to the present invention, the hydrogen bond formed between the cellulose molecules is blocked by the sugar derivative (the compound of the formula (I)). For this reason, the number of hydrogen bonds formed between the cellulose molecules in the composite has been reduced. As a result, the composite according to the present invention can be given the following properties.

First, even if the complex is subjected to pulverization at room temperature without freezing, there are regions in the cellulose molecules on the powder surface which are shielded by the sugar derivative (compound of the formula (I)). . For this reason, recombination of powders during pulverization can be considerably prevented. Secondly, it is possible to obtain a molded article having more flexibility than a film composed of cellulose alone, probably because a strong hydrogen bond between cellulose molecules is relaxed by the sugar derivative. Third, the sugar derivative (compound of formula (I)) exhibiting thermoplasticity and the cellulose have thermoplasticity due to the interaction, and can be thermoformed.

The ratio of the compound in the cellulose-containing composite according to the present invention can be appropriately selected within a range that does not impair the cohesiveness, thermal properties, mechanical strength and other properties of the composite. For example, the ratio of the sugar derivative in the cellulose-containing composite is about 1 to 60%, preferably 1 to 60%.
It is about 0 to 40%.

(Molding Method) For the composite according to the present invention, a solvent method or a heat compression method, which is a conventionally known processing method, can be used. And this complex is acetone,
Since it shows relatively good solubility in solvents such as methanol and tetrahydrofuran, it can be molded by a solvent method without using a special solvent. When the solvent method is used, the synthesis of the composite and the molding may be performed simultaneously.

In the case of the heating compression method, for example,
A complex containing the compound of the formula (I) synthesized so as to have a monosaccharide residue as G using an aliphatic dicarboxylic acid having 14 or less, or an aliphatic dicarboxylic acid having 6 to 14 carbon atoms, In addition, the complex containing the compound of the formula (I) synthesized so as to have an oligosaccharide residue as G exhibits thermoplasticity, so that it can be molded by heating, and the strength of the molded product is also the same as that of conventional cellulose molding. Be better than your body.

[0044]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples. That is, it goes without saying that the present invention is not limited to the cellulose-containing composite used in the following examples.

Synthesis Example 1 First, a compound (oligosaccharide derivative) of the formula (I) represented by the following structural formula (a) and used in Examples and Comparative Examples was synthesized by the following method.

[0046]

Embedded image

That is, 50 g of cellobiose was placed in 400 ml of N, N-dimethylformamide (DMF), and 100 ml of pyridine was added. Heated to 70 ° C. under nitrogen atmosphere. Here, 40 ml of sebacic chloride was added to DMF10
What was diluted with 0 ml 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 (hereinafter, referred to as “Compound No. I-1”). Gel permeation chromatography (GP
C) By measurement, Compound No. The molecular weight of I-1 was Mw = 200,000. The measurement conditions are as follows.

Measurement device: Tosoh HLC8020 Column: Polymer Laboratories Mixed-B
* 2 eluents: DMF + 0.1% LiBr Column oven temperature: 50 ° C Standard: polysaccharide (made by Polymer Laboratories)

Also, according to IR measurement, C of 1743 cm was measured.
= O stretching peak, 175 pp from 13C-NMR measurement
m = C = O group, 24.8 ppm and 34. 1 ppm of methylene sebacate group was confirmed, and it was confirmed that the sugar ester copolymer was successfully synthesized.

Next, a compound of the formula (I) was synthesized in the same manner as described above, except that the combination of cellobiose and sebacic acid was changed to the combination shown in Table 1 below. Incidentally, the acetylation of the sugar residue “G” of the compound is carried out by a usual synthesis method, ie,
The compound was heated and stirred in sodium acetate-acetic anhydride at 130 ° C.

[0051]

[Table 1]

Example 1 Preparation of Molded Cellulose-Containing Composite by Solvent Method Compound No. 1 was added to a 30% by weight aqueous suspension of fine powdered cellulose (KC Floc 400G; manufactured by Nippon Paper Industries). I-
8 after adding 20% by weight of the maltotriose derivative,
The mixture was heated and stirred at ℃. Next, this water suspension was heated and dried at 95 ° C., and the obtained dried film was crushed at room temperature. As a result, the size (average particle size; hereinafter the same) was about 10 μm. A fine powder was obtained. This powder did not agglomerate. This powder was dissolved in methanol, and the methanol solution was cast on a Teflon sheet and dried to obtain a sheet-shaped molded body having a thickness of 0.5 mm.

Fine fibrous cellulose (Selish F
D100 (manufactured by Daicel Chemical Industries, Ltd.) in a 20% by weight aqueous suspension. After adding 10% by weight of the lactose derivative of I-23, the mixture was heated and stirred at 50 ° C. Next, this water suspension was dried by heating at 100 ° C., and the obtained dried film was crushed at room temperature. As a result, a fine powder having a size of about 10 μm was obtained. This powder did not agglomerate. This powder was dissolved in acetone, and the acetone solution was cast-molded on a Teflon sheet in the same manner as above to obtain a sheet-shaped molded body.

Compound N was added to a 20% by weight methanol suspension of fine fibrous cellulose (Avicel; manufactured by Asahi Kasei Corporation).
o. After adding 10% by weight of the cellotetraose derivative of I-10, the mixture was heated and stirred at 50 ° C. Thereafter, the methanol solution was cast-molded on a Teflon sheet in the same manner as described above to obtain a sheet-like molded body.

Hestrin-Schlum standard medium (glucose 2.0%, peptone 0.5%, yeast extract 0.5%, disodium phosphate 0.15%, citric acid 0.27%:% is weight Acetobacter xylinum (cell number ATCC 23767) was statically cultured at 28 ° C. in a medium to which 5% by weight of a glucopyranose derivative (Compound No. I-15) was added. 30 days later,
A gel-like film accumulated in the upper layer of the culture solution was obtained. After sufficiently washing this film with water, the water absorbed by the film was squeezed out using a press machine. Further, the pressed membrane is treated with 10
It was dried by heating at 5 ° C. The dried film was crushed at room temperature to obtain a fine powder having a size of about 10 μm. This powder did not agglomerate. This powder was dissolved in acetone, and the acetone solution was cast-molded on a Teflon sheet in the same manner as above to obtain a sheet-shaped molded body.

Recycled paper for PPC (Canon Distributor, E
Used N-500, A4) (printed on one side with an NP copier) was cut into 5 mm squares, and 100 g of the cut was placed in 3 liters of the enzyme solution and stirred at 45 ° C. for 6 hours. The enzyme solution was prepared by adding 10 g of cellulase (Meitherase TP60, manufactured by Meiji Seika) to an aqueous solution of acetic acid / sodium acetate (pH 4.0).
5) A solution dissolved in 3 liters was used. After the reaction, 200 ml of methanol was added, the insoluble residue was separated by filtration, and further passed through an ion exchange resin column (Organo Inc., Amberlite IR-120B) 50 cm, and the solvent was distilled off to obtain 64 g of a slightly yellow powder.

From gel filtration chromatography and infrared absorption spectrum, it was confirmed that the mixture was a mixture containing glucose, cellobiose, and cellotriose as main components.
50 g of the sugar mixture obtained in this way was acetonitrile 400 m
and pyridine in 200 ml of a mixed solvent and heated to 80 ° C. under a nitrogen atmosphere. A solution obtained by diluting 40 ml of sebacic chloride into 200 ml of acetonitrile was added thereto, and the mixture was further stirred for 2 hours. After a part of the solvent was distilled off, the mixture was poured into water and stirred to form a precipitate. The precipitate was washed with acetone and dried to obtain 42 g of a pale yellow powder.
The weight average molecular weight was about 50,000. The sugar chain compound thus obtained was used as the above compound No. Except having replaced with I-8, it carried out similarly to the above and obtained the sheet-shaped molded object.

Recycled paper for PPC (manufactured by Canon Sales Co., Ltd.
EN-500) (printed on one side with a Coby machine) was cut into 2 mm squares, and 100 g of the used paper pieces were heated and refluxed in 1 liter of water for 5 hours, washed with methanol, and dried. This is added to 1 liter of dimethylacetamide containing 70 g of anhydrous lithium chloride,
Stirred for hours. Thereafter, the solution was filtered to obtain a cellulose solution. Compound No. 1 was added to the cellulose solution. 20 g of a cellobiose derivative of I-1 was added and stirred at room temperature. Next, this solution was cast-molded on a Teflon sheet and dried to obtain a sheet-shaped molded body having a thickness of 0.5 mm.

A strip-shaped test piece (width 1 cm × length 6 cm ×
(Thickness: 0.5 mm) was cut out, and its flexibility was evaluated using an autograph (manufactured by Instron). The measurement conditions were as follows: bending speed: 0.5 mm / min, distance between fulcrums: 30
mm, and when no cracks or the like were observed in the molded body, it was judged as ○, and when observed, it was judged as ×.
Table 2 shows the results.

After embedding the molded body prepared in (1) in the aged compost, after 6 months, the molded body is decomposed and does not retain the original shape. As x, biodegradability was also evaluated.

Comparative Example 1 A 2% by weight cuprammonium solution of fine powdered cellulose (KC Floc 400G; manufactured by Nippon Paper Industries) was cast-molded on a Teflon sheet in the same manner as above to obtain a sheet-like molded body. The flexibility and biodegradability of this molded article were evaluated in the same manner as the molded article obtained above. The results are shown in Table 2 below.

[0062]

[Table 2]

As shown in Table 2, the molded article made of the composite prepared in the above item was able to improve the brittleness of the film made of cellulose alone. Also, it was confirmed that the excellent property of cellulose such as biodegradability was maintained.

Example 2 Preparation of Molded Cellulose-Containing Composite by Heat Compression Method Compound N was added to a 20% by weight aqueous suspension of fine fibrous cellulose (Selish FD100; manufactured by Daicel Chemical Industries, Ltd.).
o. After adding 20% by weight of the cellobiose derivative of I-1, the mixture was heated and stirred at 50 ° C. Next, the aqueous suspension was added to 10
After heating and drying at 5 ° C., the obtained dried film was crushed at room temperature, and as a result, a fine powder having a size of about 10 μm was obtained. This powder did not agglomerate. A hot press for testing (product name: Mini Test Press-1)
0; manufactured by Toyo Seiki Co., Ltd.) at 140 ° C. and 25 k
A heat-compression treatment was performed at g / cm ² to obtain a plate-like molded body.

Surfactants (Neugen ET-149;
20 g of a 1% by weight methanol solution of Daiichi Kogyo Seiyaku Co., Ltd. (KC-Floc W-100;
Nippon Paper Industries Co., Ltd.) and add 1000 g with a homogenizer.
The mixture was stirred at 0 rpm for 5 minutes. After suction filtration and drying at 90 ° C. for 10 minutes with a circulating air dryer, surface treatment was performed. Compound 25 was added to 25 g of the surface-treated cellulose. After 15 g of the maltose derivative of I-3 was added, roller dispersion was performed for 24 hours. After 24 hours, a homogeneous powder was obtained, and the powder did not agglomerate. This powder was heated and compressed at 120 ° C. and 30 kgf / cm ² using a hot press for testing (trade name: Mini Test Press-10; manufactured by Toyo Seiki Co., Ltd.) to obtain a plate-like molded body. Was.

A fine fibrous cellulose (Avicel; manufactured by Asahi Kasei Corporation) was surface-treated with a surfactant in the same manner as described above. Compound No. 30 was added to 30 g of the surface-treated cellulose. I-
20 g of a cellohexaose derivative was added, and THF was added.
The mixture was heated and stirred at 50 ° C. This solution was dried by heating at 80 ° C. Next, the dried film was crushed at room temperature, and as a result, a fine powder having a size of about 1 μm was obtained. This powder did not agglomerate. This powder was used at 127 ° C. and 28 kgf / cm ² using a hot press for testing (trade name: Mini Test Press-10; manufactured by Toyo Seiki Co., Ltd.).
To obtain a plate-like molded body.

Compound 25 was added to a 25% by weight aqueous suspension of fine fibrous cellulose (KC-Floc W-300; manufactured by Nippon Paper Industries). After adding 15% by weight of a galactopyranose derivative of I-25, the mixture was heated and stirred at 55 ° C. Next, this water suspension was heated and dried at 100 ° C., and the obtained dried film was crushed at room temperature.
Was obtained. This powder did not agglomerate. The powder was subjected to hot pressing using a test hot press (trade name: Mini Test Press-10; manufactured by Toyo Seiki Co., Ltd.) to obtain 1
It was heated and compressed at 20 ° C. and 25 kgf / cm ² to obtain a plate-like molded body.

Compound No. 1 was added to the hestrin-schlum standard medium used in Example 1. Acetobacter xylinum was statically cultured at 28 ° C. in a medium to which 5% by weight of a cellohexaose derivative of I-13 was added. After 30 days, a gel-like film accumulated in the upper layer of the culture solution was obtained. After sufficiently washing this film with water, the water absorbed by the film was squeezed out using a press machine. Further, the pressed film was heated and dried at 105 ° C. Next, the dried film was crushed at room temperature to obtain a fine powder having a size of about 10 μm. This powder did not agglomerate. This powder is used as a hot press for testing (trade name: Mini Test Press-1)
0; manufactured by Toyo Seiki Co., Ltd.) at 125 ° C. and 28 k
It was heated and compressed at gf / cm ² to obtain a plate-like molded body.

The compound No. 1 was added to the standard medium of hestrin-schlum used in Example 1. Acetobacter xylinum was statically cultured at 28 ° C in a medium to which 5% by weight of a mannopyranose derivative of I-17 was added. After 30 days, a gel-like film accumulated in the upper layer of the culture solution was obtained. After sufficiently washing this film with water, the water absorbed by the film was squeezed out using a press machine. Further, the pressed film was heated and dried at 105 ° C. Next, the dried film was crushed at room temperature to obtain a fine powder having a size of about 10 μm. This powder did not agglomerate. This powder is used as a hot press for testing (trade name: Mini Test Press-1)
0; manufactured by Toyo Seiki Co., Ltd.) at 118 ° C. and 23 k
It was heated and compressed at gf / cm ² to obtain a plate-like molded body.

Compound No. of Example 2 I-1
Was replaced with a sugar chain compound synthesized in the same manner as in Example 1 to obtain a plate-like molded body in the same manner as in Example 2.

A plate-like molded body was obtained in the same manner as in Example 2 except that the 20% by weight aqueous suspension of fine fibrous cellulose of Example 2 was replaced with the cellulose solution of Example 1. Was.

A strip-shaped test piece (width 1 cm × length 6 cm × thickness 0.5 m) was obtained from each of the compacts prepared above.
m) was cut out and the tensile strength was evaluated using an autograph DSC-R-500 (manufactured by Shimadzu Corporation). The measurement conditions were a load cell: 50 kg, a crosshead speed: 50 mm / min, and a distance between chucks: 10 mm. As a control example, a comparative test was performed using a strip-shaped test piece of the same shape cut out from a molded article made of general-purpose polyester (PET). Compared with PET, those with excellent tensile strength were rated as ◎, those with equivalent tensile strength as ○, and those with poor tensile strength as x.
The results are shown in Table 3.

Further, the biodegradability of the eight types of molded articles produced in the same manner as in Example 2 was also evaluated. After burying in the aged compost, after 6 months, the molded product was evaluated as 分解 and the undecomposed one as ×. The results are shown in Table 3.

[0074]

[Table 3]

As shown in Table 3, the molded article made of the composite produced in the same manner as in Example 2 had a tensile strength sufficiently within a practical range and a biodegradable molded article. confirmed.

Comparative Example 2 A 20% by weight aqueous suspension of fine fibrous cellulose prepared in the same manner as in Example 2 was heated and stirred at 50 ° C., and the aqueous suspension was dried by heating at 105 ° C. . Next, the dried product was crushed at room temperature. However, Example 2
Therefore, a fine powder as obtained was not obtained, and its size exceeded 150 μm. Moreover, the powder was easy to agglomerate. Further, the powder was subjected to a heat compression treatment in the same manner as in Example 2. However, a plate-shaped molded body could not be obtained.

Comparative Example 3 Bacterial cellulose obtained when the sugar derivative was not added to the culture solution described in Example 2 was treated in the same manner as in Example 2. However, a fine powder as obtained in Example 2 was not obtained, and its size was 100 μm.
Was over. Moreover, the powder was easy to agglomerate. Furthermore,
This powder was heated and compressed in the same manner as in Example 2. However, a plate-shaped molded body could not be obtained.

Example 3 A composite powder prepared in the same manner as in Example 1
The mixture was stirred at 40 ° C. for 7 days in the esterase enzyme (Boehringer Mannheim) prepared at 8.6. The reaction mixture was filtered to filter the cellulose. Next, pour the filtrate
0 to be H5. After adjustment with 1N hydrochloric acid, the resulting insolubles were filtered off. The filtrate was passed through an ion-exchange resin (Amberlite IR-120B, manufactured by Organo Corporation).
Allowed to dry. As a result of measuring an infrared spectrum, it was confirmed that the insoluble content was adipic acid and the soluble content was maltotriose.

Further, the fractionated maltotriose and adipic acid were used as raw materials for repolymerization, wherein adipic acid was converted to adipic chloride using thionyl chloride. From the recovered maltotriose and adipic acid chloride, a sugar derivative (compound No. I) was obtained in the same manner as in the synthesis example.
-8) was synthesized. Also, using the resynthesized sugar derivative (Compound No. I-8) and the recovered cellulose, it was confirmed that a complex could be prepared again by the method described in Example 1 and recycling was possible. did.

Similarly, each molded article prepared in the same manner as in Example 1 and Example 2 was separated into saccharides, dicarboxylic acids, and cellulose in the same manner as in the above-mentioned hydrolysis with the enzyme. The saccharide and dicarboxylic acid were used as raw materials to resynthesize the corresponding saccharide derivative. In addition, it was confirmed that a molded article could be produced using the resynthesized sugar derivative and the recovered cellulose, and that recycling was possible.

[0081]

As described above, according to the present invention, the following effects can be obtained. A cellulose-containing complex comprising cellulose and a monosaccharide derivative or an oligosaccharide derivative can be finely powdered by inhibiting hydrogen bonds between cellulose molecules. In addition, the molding processability of cellulose can be improved by containing a sugar derivative having thermoplasticity.

A molded article of a cellulose-containing composite comprising cellulose and a monosaccharide derivative or an oligosaccharide derivative has better mechanical strength than general-purpose polyester (PET). Further, since the molded product of the cellulose-containing composite uses a natural product such as cellulose, monosaccharide or oligosaccharide, it is excellent in safety and can exhibit functions such as biodegradability and recyclability.

Further, according to the present invention, a saccharide polymer having high recyclability can be obtained by utilizing paper such as waste paper as a raw material and chemically modifying cellulose or a saccharide compound derived from cellulose as its main component. Compounds and compositions can be obtained, which can contribute to waste reduction and effective use of resources.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating the structure of a cellulose-containing composite comprising cellulose and a cellobiose derivative according to the present invention.

FIG. 2 is a schematic diagram illustrating the structure of cellulose.

[Explanation of symbols]

 11 Cellobiose derivatives 1la Non-sugar residues 12, 13, 21, 22, 23 Cellulose molecules

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 14, 2000 (2006.1.
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Cellulose-containing composite and method for producing the same, saccharide compound and method for producing the same, method for recycling paper, method for recycling used paper, and molded article and method for producing the same

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

14. The method of claim 13, wherein the solution process according to claim 11, wherein a solution of a mixture of compounds represented by the above mixed solvent of dimethylacetamide and lithium chloride anhydrous obtained by dissolving the cellulose (1).

15. mixed solvent of dimethylacetamide and lithium chloride anhydrous obtained by dissolving the cellulose is a mixed solvent of dimethylacetamide and lithium chloride anhydrous of steps and the cellulose fibers to cellulose fibers to loosen paper in alkaline solution 15. The production method according to claim 14, which is produced through a step of dissolving cellulose in the mixed solvent in addition to the above.

17. A method for producing a complex comprising cellulose and a compound represented by the following formula (I), wherein a cellulose-producing bacterium is cultured in a medium containing the compound represented by the following formula (I). A method for producing a cellulose-containing composite, comprising a step of producing cellulose.

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
Is an integer of 5000)

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
5000 is an integer).

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
Is an integer of 5000)

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
Is an integer of 5000)

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
Is an integer of 5000)

Embedded image (Wherein R is a substituted or unsubstituted alkylene group or
G is a substituted or unsubstituted arylene group;
Represents a group or an oligosaccharide residue, and n is a degree of polymerization,
Is an integer of 5000)

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

The present invention relates to a cell having improved characteristics of cellulose.
Loose-containing complex, method for producing the same, saccharide compound and production thereof
Manufacturing method, paper recycling method, waste paper recycling method, and
The present invention relates to a form and a method for producing the form .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

The present invention has been made in view of the above technical background, and provides a cellulose-containing composite that can further improve the processability of cellulose while maintaining the inherent biodegradability of cellulose. The purpose is to do so. It is another object of the present invention to provide a method for producing a cellulose-containing composite in which the processability of cellulose is improved without impairing the inherent biodegradability of cellulose. Further, the present invention relates to a method for recycling paper,
Paper recycling method and molded article of cellulose-containing composite
And its purpose is to provide a method for its manufacture.
is there.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] One embodiment of a method for producing a cellulose-containing composite that can achieve the above object is a method for producing a composite comprising cellulose and a compound represented by the following formula (I): A step of drying a solution obtained by uniformly mixing the cellulose and a compound represented by the following formula (I).

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011]

Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. The present invention also relates to a saccharide compound represented by the above formula (I).
The monosaccharide residue or oligosaccharide residue in the formula (I) is represented by
Saccharide compounds, wherein G is derived from paper
It is. Further, the present invention provides a saccharide represented by the above formula (I)
A method for producing a compound, comprising: (i) decomposing cellulose;
And the monosaccharide residue or oligosaccharide represented by G in the above formula (I)
Obtaining a residue; and (ii) the monosaccharide residue or oligo.
Converting a sugar residue into a dica containing a moiety represented by R in the above formula (I);
Bonding with rubonic acid.
This is a method for producing a saccharide compound. The present invention also relates to a paper
A resource recycling method, wherein (i) extracting cellulose from paper
And (ii) the cellulose and formula (I)
And dry the solution containing the compound
Cellulose containing loin and a compound represented by the above formula (I)
And a step of producing a source-containing composite.
This is a paper recycling method. In addition, the present invention provides the paper
(I) A method of recycling the saccharide compound represented by the formula
(I) extracting cellulose from the paper; (ii)
A monosaccharide residue represented by G in the above formula (I) from the cellulose;
Or a step of obtaining an oligosaccharide residue; and (iii)
A dicarboxylic acid containing a sugar residue or an oligosaccharide residue with R;
Recycling paper characterized by having a step of bonding
Is the way. The present invention also relates to a method for recycling used paper.
(I) extracting cellulose from the paper;
(Ii) the cellulose and the compound represented by the above formula (I)
And the uniformly mixed solution is dried to dry the cellulose and the above
(I) Cellulose-containing composite containing a compound represented by the formula
Manufacturing a body, and
It is a recycling method. In addition, the present invention relates to the use of waste paper
(I) a method for recycling the saccharide compound represented by the formula
(I) extracting cellulose from paper;
i) a monosaccharide represented by G in the above formula (I) from the cellulose
Obtaining a residue or an oligosaccharide residue; and (iii)
Dicarboxylic acid containing the monosaccharide residue or oligosaccharide residue as R
Binding to an acid.
It is a recycling method. The present invention also relates to the above cellulosic composition.
It is a molded product characterized by containing a composite containing a metal. Ma
In addition, the present invention provides a method of heating and compressing the above-mentioned cellulose-containing composite.
It is a manufacturing method of a molded object including the step of performing.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tomoe Mihara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshihiko Kikuchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon In-house F term (reference) 4B064 AF12 CA02 CA21 CC03 CD07 CD09 CD11 CD19 DA16 4C090 AA03 AA07 BA24 BA52 BA74 BA91 BB72 BB97 BC20 BC21 BC24 BD24 BD35 BD41 CA04 CA06 CA07 CA19 CA42 CA46 DA21

Claims (15)

[Claims] 1. A cellulose-containing composite comprising cellulose and a compound represented by the following formula (I). Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. ) 2. The complex according to claim 1, wherein the sugar residue G is at least one of glucopyranose, cellooligosaccharide, maltooligosaccharide, and lactose. 3. The complex according to claim 2, wherein the sugar residue G is cellobiose. 4. The complex according to claim 2, wherein the sugar residue G is maltose. 5. The conjugate according to claim 2, wherein said sugar residue G is lactose. 6. The complex according to claim 2, wherein the sugar residue G is glucopyranose. 7. The conjugate according to claim 1, wherein the saccharide residue G is a saccharide residue derived from paper. 8. The composite according to claim 1, wherein the cellulose is a plant-derived cellulose. 9. The composite of claim 1, wherein said cellulose is bacterial cellulose. 10. The composite according to claim 1, wherein the cellulose is paper-derived cellulose. 11. A method for producing a composite comprising cellulose and a compound represented by the following formula (I), wherein a solution obtained by uniformly mixing the cellulose and a compound represented by the following formula (I) is heated. A method for producing a cellulose-containing composite, comprising a step of drying. Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. ) 12. The method according to claim 11, wherein the solution is a solution obtained by mixing the compound represented by the formula (1) with a suspension of fine fibrous cellulose. 13. The production method according to claim 11, wherein the solution is a solution obtained by mixing the compound represented by the formula (1) in a mixed solvent of dimethylacetamide and anhydrous lithium chloride obtained by dissolving cellulose. 14. A process in which a mixed solvent of dimethylacetamide and anhydrous lithium chloride obtained by dissolving the cellulose is used to loosen paper in an alkaline solution to form cellulose fibers, and a mixed solvent of dimethylacetamide and anhydrous lithium chloride in the cellulose fibers. 14. The production method according to claim 13, which is produced through a step of dissolving cellulose in the mixed solvent in addition to the above. 15. A method for producing a complex comprising cellulose and a compound represented by the following formula (I), wherein a cellulose-producing bacterium is cultured in a medium containing the compound represented by the following formula (I). A method for producing a cellulose-containing composite, comprising a step of producing cellulose. Embedded image (Wherein, R is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, G represents a monosaccharide residue or an oligosaccharide residue, n is a degree of polymerization,
It is an integer of 5000. )