JP2000129000A - Recording medium having ink receiving layer containing sugar chain polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording medium having an ink receiving layer for recording media, excellent in ink recording suitability and having such excellent characteristics that waste matter subjected to disposal treatment after using has not an undesirable influence upon environment. SOLUTION: This recording medium has at least a substrate and an ink receiving layer. In the recording medium, the ink receiving layer comprises a sugar chain polymer constituting a main chain together with other components or a sugar chain polymer obtained by crosslinking a molecular chain having at least one kind of recurring unit with sugar. In the sugar chain polymer, the sugar is preferably bonded to other components by ester bond, urethane bond or amide bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium having an ink receiving layer, and more particularly to a recording medium having excellent ink absorbency, water resistance, curling resistance, scratch resistance and the like, and having high image quality. It relates to a recording medium having an ink receiving layer that can be obtained. In particular, the present invention relates to a recording medium suitable as a recording medium in a recording method using an aqueous ink, such as a color inkjet method and an aqueous color printer plotter, and a color recorded matter recorded using the recording medium.

[0002]

2. Description of the Related Art In recent years, an ink jet recording method has attracted attention as a recording method capable of performing high-speed printing and color printing with little noise, and has been widely used. As a recording medium used in the ink jet recording method, a recording medium in which a porous ink receiving layer is provided on a base material which is conventionally referred to as ordinary paper, an ink jet recording paper, or an overhead projector ( OHP)
Transmissive recording media have been used. In particular, when it comes to OHP recording media, these constituent materials, mainly the materials constituting the base material, include polyester resins, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, and polyvinyl chloride. Resin,
A film such as a polyimide resin is used.

On the other hand, the amount of synthetic plastic materials used in various industrial fields tends to increase year by year, and accordingly, the amount of synthetic plastic waste also increases, and the treatment thereof has become a major social problem worldwide. I have. Some of these waste plastics are collected and incinerated, while others are disposed of in landfills. Generally, when synthetic plastics are incinerated, they generate a large amount of heat, which may cause damage to the incinerator. Further, many synthetic plastics generate harmful gases when incinerated. Further, in the case of landfill disposal, the problem of securing a disposal site and the problem of adverse effects on the natural environment cannot be ignored.

[0004] Under such circumstances, with regard to consumables used in an ink jet recording apparatus, disposal of consumables after use has become important due to environmental problems and the like with the spread of the apparatus. I have. In particular, as for the OHP recording medium, as described above, since the base material is made of synthetic plastic, sufficient consideration must be given to disposal treatment after use. However, in the conventional OHP film for inkjet,
Since no consideration is given to waste treatment as described above, there is a concern that a large amount of waste will adversely affect the environment. In consideration of this problem, JP-A-6-239014 and JP-A-9-39379 disclose that a biodegradable plastic sheet is used as a base material, and a synthetic polymer ink receiving surface is provided on the base material surface. A recording medium provided with a layer has been proposed.

In Japanese Patent Application Laid-Open No. Hei 8-20657,
There has been proposed a recording sheet provided with an ink receiving layer formed of a mixture of a natural polymer (protein or polysaccharide) and a synthetic polymer.

[0006]

However, the above-mentioned recording medium is a recording medium which is excellent in ink-jet recording suitability and suppresses adverse effects on the environment. There is a problem that the polymer material remains without being decomposed due to the use of the polymer material.

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink receiving layer for a recording medium which has excellent suitability for ink jet recording and has excellent characteristics such that a waste product upon disposal after use does not adversely affect the environment. Another object of the present invention is to provide a recyclable recording medium capable of effectively utilizing waste.

[0008]

The above object is achieved by the present invention described below.

1. In a recording medium having at least a base material and an ink receiving layer, the ink receiving layer may be a sugar chain polymer compound in which a sugar forms a main chain together with other components, or a sugar chain comprising at least one type of repeating unit. A recording medium comprising a sugar chain polymer compound cross-linked with the above.

[0010] 2. 2. The recording medium according to the above item 1, wherein the sugar chain polymer compound has a sugar bonded to another component through an ester bond, a urethane bond, or an amide bond.

3. 3. The recording medium according to the above item 1 or 2, wherein the sugar is a sugar chain polymer compound that is a sugar containing only a glucopyranose ring.

4. 4. The recording medium according to any one of the above items 1 to 3, wherein the saccharide is an oligosaccharide.

5. The oligosaccharide is maltose, cellobiose, lactose, isomaltose, chitobiose, nigerose, trehalose, melibiose, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose, maltotetraose, cellopentaose, maltopentaose, chito Pentaose,
5. The recording medium according to any one of the above items 1 to 4, wherein the recording medium is at least one of cellohexaose, maltohexaose, chitohexaose, and acetylated products thereof.

6. 4. The recording medium according to any one of the above items 1 to 3, wherein the saccharide is a polysaccharide.

[0015] 7. The recording medium according to claim 6, wherein the polysaccharide is at least one of cellulose, starch, glycogen, galactan, mannan, chitin, chitosan, alginic acid, polyglucosamine, pullulan, and hyaluronic acid.

8. 8. The recording medium according to any one of the above 1 to 7, wherein the other component is a dicarboxylic acid.

9. 2. The recording medium according to the above 1, wherein the molecular chain having the repeating unit is synthesized from a compound selected from dicarboxylic acid, diol, diamine, diisocyanate, and polyvinyl alcohol.

10. 10. The recording medium according to the above 1 or 9, wherein the crosslinked chains are crosslinked by a sugar moiety in the chain.

11. 10. The recording medium according to the above 1 or 9, wherein the crosslinked chains are crosslinked at a portion other than the sugar in the chain.

[12] 2. The recording medium according to the above item 1, wherein the repeating unit is derived from a compound having a vinyl group or derived from a sugar.

13. 13. The recording medium according to any one of the above items 1 to 12, wherein all the constituent components are made of a biodegradable polymer substance.

The sugar chain polymer compound according to the present invention is capable of selectively decomposing a hydrolyzable bond (an ester bond, a urethane bond, an amide bond, etc.) between the sugar and another component, and forms a bond between the sugar and the sugar. By selectively decomposing glycosidic bonds, it has a recyclability that allows the substance generated by the decomposition to be easily reused as a raw material and a biodegradability in soil and compost.

The recording medium according to the structure of the present invention has good ink jet suitability and is excellent as a recording medium such as OHP and paper. The ink receiving layer has a hydrophilic sugar portion and a hydrophobic dicarboxylic acid portion, so that the ink receiving layer becomes amphiphilic, and when used as an OHP recording medium, has excellent adhesion to a polymer substrate and absorbs ink. It has the effect of suppressing bleeding. When paper is used as the base material, the glossiness after ink application is excellent.

Further, in the recording medium of the present invention, since the ink receiving layer has biodegradability and is recyclable, it is possible to suppress adverse effects on the environment when disposed. Furthermore, if both the base material and the ink receiving layer are made of a biodegradable and recyclable polymer compound, a recording medium having excellent properties such that waste when disposed after use does not adversely affect the environment is obtained.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION As the ink receiving layer used in the recording medium of the present invention, a sugar chain polymer compound in which sugar forms a main chain together with other components, or a molecular chain having at least one type of repeating unit Any one can be used as long as it is composed of a sugar chain polymer compound obtained by cross-linking with a sugar.

As a preferred example of such a sugar chain polymer substance, in a sugar chain polymer compound in which a sugar containing only a glucopyranose ring forms a main chain together with other components, the sugar is combined with other components. It is preferable that they are linked by an enzyme-decomposable bond (ester bond, urethane bond, amide bond, etc.).

The sugar is an oligosaccharide, and the oligosaccharide is cellobiose, lectose, maltose, isomaltose, chitobiose, nigerose, trehalose, melibiose, hyaluronic acid, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose. , Maltotetraose, cellopentaose, chitopentaose, maltopentaose, cellohexaose, chitohexaose, maltohexaose, and at least one of these acetylated products. Preferably, the sugar is an oligosaccharide and the other component is a dicarboxylic acid.

Further, the saccharide is a polysaccharide, and the polysaccharide is preferably at least one of chitosan, alginic acid, cellulose, starch, glycogen, galactan, mannan, polyglucosamine and pullulan. Preferably, the sugar is a polysaccharide and the other component is a dicarboxylic acid.

In the crosslinked sugar chain polymer compound, the crosslinkable chains are preferably crosslinked with a bifunctional or higher-functional aliphatic organic compound. And the aliphatic organic compound
It is preferably a compound selected from dicarboxylic acids, diols, diamines, and disissocyanates. Preferably, the aliphatic organic compound is polyvinyl alcohol.

Crosslinking can be carried out at the sugar chain in the chain or at a site other than the sugar. Also, at least one
In a sugar chain polymer compound in which a molecular chain having a kind of repeating unit is crosslinked with a sugar containing only a glucopyranos ring,
Preferably, the repeating unit is derived from a compound having a vinyl group.

Preferably, the repeating unit is derived from a sugar containing only a glucopyranose ring.

It is preferred that the saccharide is linked to a site other than the saccharide in the repeating unit or the saccharide in the repeating unit to crosslink the molecular chain.

Hereinafter, the present invention will be described in detail with reference to the drawings.

The first aspect Figure 1 is a schematic diagram showing a sugar chain polymer compounds and their decomposition method according to an embodiment of the present invention. FIG. 1A is a conceptual diagram for explaining a linear sugar chain polymer compound, and FIG.
(B) is a conceptual diagram showing a state where a sugar chain polymer is decomposed. 1 represents a sugar moiety, and 2 represents another component which binds to the sugar moiety 1 to form a sugar chain polymer. The sugar moiety 1 and the other moiety 2 are linked by, for example, an ester bond 3.

Here, the oligosaccharides are disaccharides to decasaccharides, and both homo-oligosaccharides and hetero-oligosaccharides can be used as the material of the above-mentioned oligosaccharide portion. However, homooligosaccharides are more preferable because they can be decomposed with a single enzyme and are easily separated and purified for reuse.

Preferably, the sugar moiety 1 contains a sugar containing only a glucopyranose ring. That is, the heat resistance of the polymer can be improved by introducing a sugar containing only a glucopyranose ring into the sugar moiety. Representative oligosaccharides containing the glucopyranose ring include disaccharides such as cellobiose, lactose, maltose, isomaltose, chitobiose, nigerose, trehalose, and melibiose; trisaccharides such as cellotriose, chitotriose, and maltotriose; and tetrasaccharides. Examples of the above include cellotetraose, chitotetraose, maltotetraose, cellopentaose, chitopentaose, maltopentaose, cellohexaose, chitohexaose, and maltohexaose.

Representative polysaccharides containing the glucopyranose ring include chitosan, alginic acid, cellulose, starch, glycogen, galactan, mannan, polyglucosamine, pullulan, hyaluronic acid and the like. These sugars may be sugar derivatives in which the OH group contained in the molecule is substituted with a non-polymerizable atomic group such as an acetyl group or a benzyl group.

The other component portion 2 includes, for example, dicarboxylic acid capable of forming an ester bond 3 by reacting with the OH group of the sugar as described above. Examples of saturated dicarboxylic acids include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecandioic acid, octadecandioic acid, and unsaturated aliphatic dicarboxylic acids such as maleic acid. acid,
As aromatic dicarboxylic acids such as fumaric acid, phthalic acid,
Isophthalic acid, terephthalic acid and the like. Further, there may be mentioned salts and derivatives thereof.

In the present invention, in order to constitute a repeating unit of the resin composition, a sugar-chain-linked chain is a glycosidic bond 4, and a sugar-aliphatic or aromatic carboxylic acid-linked chain is an ester bond. Is desirable.

The glycosidic bond 4 includes, for example, an α bond and a β bond. The bonds to the reducing sugar are (1 → 2) bond, (1 → 3) bond, and (1 → 4) bond, respectively. , (1 → 6) bond, and a bond with a non-reducing sugar include (12) bond and (11) bond (the number in () indicates the position of the OH group).

As the ester bond, the dicarboxylic acid of the other component and -OH at any of the 1,2,3,4,6 positions of the sugar
This is an ester bond reacted with a group.

Further, a combination of a glycoside bond, an ether bond and an ester bond may be used.

The sugar chain polymer compound shown in FIG. 1 is, for example, a OH group of a sugar and a COOH of a carboxylic acid as described above.
A main chain polymerized by an ester bond can be formed by reacting a group or a COCl group, or it can be synthesized by transesterification between a dicarboxylic acid ester and an oligosaccharide.

Next, the decomposition of the sugar chain polymer having the structure shown in FIG. 1A will be described. Two kinds of decomposition methods, decomposition method 1 and decomposition method 2, can be applied to the sugar chain polymer compound shown in FIG. In the decomposition method 1, an enzyme that decomposes the ester bond 3 between the sugar moiety 1 and the other component 2 is acted on, for example, to decompose the sugar moiety 1 into the other component moiety 2 as shown in FIG. can do. Specifically, when an enzyme (eg, lipase, esterase) that catalyzes the hydrolysis of an ester bond is allowed to act on a sugar chain polymer compound having cellobiose and adipic acid as repeating units, the sugar chain polymer The ester bond of the compound is hydrolyzed, and as a result, cellobiose and adipic acid are obtained as decomposition products as shown in FIG. Since this is the same substance as the raw material, repolymerization is possible.

In the decomposition method 2, an enzyme for decomposing the glycosidic bond 4 between the saccharide of the saccharide moiety 1 and the saccharide is acted on.
For example, as shown in FIG. 1 (b), both ends can be decomposed into a unit (double-headed glycolipid) or a sugar having sugars. Specifically, for example, a cellulase that catalyzes hydrolysis of a β (1 → 4) bond with respect to a sugar chain polymer compound of cellobiose having a β (1 → 4) bond as an oligosaccharide and another component is used. When acted, the glycosidic bond of the sugar chain polymer compound is hydrolyzed, and as a result, as shown in FIG. 1 (b), double-headed lipid and glucose are obtained as decomposition products. Since the oligosaccharide or polysaccharide portion 1 and the other portion 2 of the sugar chain high molecular compound shown in FIG. Can be obtained with a uniform molecular weight.

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

In the above embodiment, the bond between the sugar and other components is not limited to only an ester bond, and specifically includes an amide bond and a urethane bond.

The above-mentioned sugar chain polymer compound may be added to various additives such as pigments, plasticizers and various fillers, and may be applied to various structural materials as a polymer compound having a predetermined strength. It is possible.

Second Embodiment FIG. 2 is a conceptual diagram of a sugar chain polymer according to a second embodiment. In FIG. 2, 1 indicates a sugar moiety, and 2 indicates a molecular chain as another component. The molecular chain of the other component 2 has a structure crosslinked by the sugar moiety 1.

In the sugar chain polymer compound having such a structure, the sugar moiety 1 may be an oligosaccharide or a polysaccharide which can be used for forming the sugar moiety 1 of the sugar chain polymer compound of the first embodiment.

In this embodiment, as in the first embodiment, it is particularly preferable that the sugar moiety 1 contains only a glucopyranose ring in order to improve the heat resistance of the sugar chain compound.

The other component 2 includes, for example, at least 1
A molecular chain having a kind of repeating unit, specifically, a molecular chain having a repeating unit derived from a compound containing a vinyl group, and further having a plurality of sites capable of reacting with an OH group of a sugar in the molecular chain. Such a molecular chain is preferably used. Specific examples include a molecular chain made of polyacrylic acid. And cellobiose as sugar,
When polymerization is performed using polyacrylic acid as a material constituting the other component, a sugar chain polymer compound in which the other component 2 and the sugar moiety 1 are linked by an ester bond can be obtained. Here, the bond with the sugar moiety 1 is not limited to an ester bond, but may be an amide bond or a urethane bond.

FIG. 3 differs from the configuration of FIG. 2 in that the molecular chain of the other component part 2 in FIG. 2 is changed to a molecular chain containing sugar. In the sugar chain polymer compound shown in FIG. 3, as the molecular chain 5 containing a sugar, for example, a sugar chain polymer compound that can be synthesized by the method described in the first embodiment can be used. However, it is preferable to use a material having a functional group for enabling crosslinking by the sugar moiety 1 as a material constituting the other component moiety 2. Specifically, for example, tricarboxylic acid (for example, aconitic acid or a salt thereof)
And the like. When tricarboxylic acid is used as a material constituting the other component portion 2 and an oligosaccharide such as cellobiose is used as a material constituting the sugar portion in the molecular chain 5 and the sugar portion 1 which crosslinks the molecular chain, the molecular chain A sugar chain polymer compound is obtained in which all the bonds between the sugar portion and other component portions and the bonds between the sugar portion 1 and the molecular chain 5 that crosslink the molecular chain are ester bonds. Here, the bond between the molecular chain 5 and the sugar moiety 1 for crosslinking is not limited to an ester bond, but may be an amide bond or a urethane bond.

FIG. 4 is different from the polymer compound shown in FIG. 3 in that the molecular chains 5 are cross-linked with each other at the sugar portion 1 of the molecular chain 5 by sugar. The sugar chain polymer compound of FIG. 4 has two reactive sites capable of polymerizing with the other portion 2 as a sugar moiety, and further has one reactive site with a crosslinking agent, for example, two monosaccharides are bonded. The reacted oligosaccharide (eg, cellobiose, maltose, etc.) reacts with a material (eg, dicarboxylic acid, etc.) constituting another component to form a linear polymer compound (molecular chain 5) composed of the sugar portion and other components. It can be synthesized and then cross-linked at a site of a hydroxyl group or a carboxyl group of a saccharide moiety in the main chain using a saccharide having two or more monosaccharides bonded as a cross-linking agent. In addition, the bond between the molecular chain 5 and the sugar moiety 1 for crosslinking is not limited to an ester bond, but may be an amide bond or a urethane bond.

The sugar chain polymer compound shown in FIGS.
Similar to FIG. 1, it can be decomposed by two types of decomposition methods 1 and 2. Then, at least one of the decomposition products can be repolymerized in a small number of purification steps.

The weight average molecular weight of the sugar chain polymer compound used in the ink receiving layer is from 300 to 300,000, preferably from 500 to 3 from the viewpoint of ease of coating.
About 0000 is appropriate.

Further, in order to improve the suitability for ink jet recording, specifically, the beading resistance and the blocking resistance, a water-soluble low-molecular-weight organic compound and a water-insoluble compound can be used as needed in addition to the above-mentioned materials. is there.

As the water-soluble low molecular weight organic compound, ethylene glycol, polyethylene glycol, poly (ethylene glycol-propylene glycol) copolymer, D-
Polyhydric alcohols having a molecular weight of 5000 or less, such as sorbitol and sucrose, may be mentioned.

Examples of the water-insoluble organic compound include acrylic resin represented by polymethyl methacrylate, nylon resin represented by 6,6 nylon, polystyrene, phenol resin, epoxy resin, polyvinyl chloride, polyester resin, polyurethane resin and the like. Other examples include a condensate of D-sorbitol and an aromatic aldehyde, and a diacetate compound.

In addition to the materials constituting the ink receiving layer described above, it is also possible to include other additive materials in the ink receiving layer for the purpose of improving various ink jet recording suitability.

For example, when an acidic dye or a direct dye is used in the aqueous ink, a cationic resin can be used to prevent bleeding and elution of the dye after recording. Materials that can be used for this purpose include cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, and cationic monomer-containing acrylic resins.

In order to improve blocking resistance, it is also possible to add inorganic fine particles or the like to the ink receiving layer in an amount of about 0.01 to 1.0 g / m ² .

Similarly, a pH adjuster, a fluorescent dye, a dispersant,
Conventionally known additives such as a lubricant, a preservative and an antifoaming agent can be included in the ink receiving layer.

The thickness of the ink receiving layer described above is as follows.
The thickness is preferably from 0.1 to 100 μm, and more preferably from 2 to 30 μm.

As a method of forming the ink receiving layer, a conventionally known method such as a roll coating method, a rod bar coating method, a spray coating method, an air knife coating method, and a dip coating method may be used.

As the base material for holding the ink receiving layer of the recording medium of the present invention, papers such as appropriately sized paper, non-size paper, resin-coated paper, sheet materials such as thermoplastic films, A fabric can be used, and there is no particular limitation.

In the case of a thermoplastic film, a transparent film such as polyester, polystyrene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polyethylene, polycarbonate, etc .; It is also possible to use a sheet that has been made opaque by various bubbles.

In terms of not adversely affecting the environment,
High strength, the same sugar chain compound of high molecular weight may be used,
Preferably, other biodegradable plastics are used. Examples of the biodegradable plastic include a) a chemically synthesized aliphatic polyester, b) a microbial biosynthetic polyester, c) a starch blend, and d) a natural polymer.

A) As a chemically synthesized aliphatic polyester, a random copolymer with poly-L-lactic acid (PLLA) or D-lactic acid (for example, trade name: Ecopre, manufactured by Cargill, trade name: Lacia Mitsui Toatsu) Chemical, trade name; Lacty, Shimadzu Corporation, etc.), poly-ε-caprolactone (PCL) (for example, trade name; Tone Union Carbide, trade name; Plaxel Daicel, etc.), polybutylene succinate (PBS) Alternatively, a random copolymer with butylene adipate (for example, trade name; manufactured by Bionore Showa Polymer, trade name; manufactured by Sky Green Syokyo, etc.) may be mentioned.

B) Microbial synthetic polyesters include:
Starch + PVA and others (eg, trade name; Matterby
Novamont / Nippon Synthetic Chemical), starch + aliphatic polyester, and the like (for example, trade name; Novon Novon International, etc.).

C) Starch blends include β-hydroxybutyric acid (HB) and 3-hydroxyvaleric acid (HV)
Random copolymer (for example, trade name; Biopol,
Monsanto), polysaccharides composed of β-1,3-glucan (trade name; Curdlan Takeda Pharmaceutical), and the like.

D) Natural polymers include benzylated wood (plasticized by subjecting cellulose or lignin of wood or the like to alkali treatment with caustic soda and reacting with a chemical substance having a benzyl group or acetyl group), higher fatty acids Esterified wood, wheat gluten with glycerin, glycol, emulsified silicone oil, urea, cellulose with chitosan, pullulan,
Alginic acid, chitin, chitosan, carrageenan, starch and the like.

These biodegradable plastics have no effect on the life cycle of the usage form of the plastic itself, and the decomposition is started only when the materials are placed in an environment where microorganisms are actively active, such as in soil or water. You.

The recording medium of the present invention does not need to have a transparent base material. When the substrate is opaque, a coloring material can be used to adjust the color tone of the entire recording medium. As the coloring material, conventionally known dyes and pigments can be used, but the compatibility with the base material to be used must be sufficiently taken into consideration.

The present invention can be used as an OHP recording film when the substrate is transparent. When used as an OHP film, the haze of the entire recording medium is preferably 50% or less, more preferably 20% or less.

In order to improve the adhesion between the substrate and the ink receiving layer, the substrate may be subjected to a surface treatment such as a corona treatment or a flame treatment, or an easy-adhesion layer may be provided as a subbing layer. Further, in order to prevent curling, a curling preventing layer such as a resin layer and a pigment layer and / or a layer having a brushability are provided on the back surface of the base body (the surface opposite to the surface on which the ink receiving layer is provided) or at a predetermined position. Can also.

In the recording medium of the present invention, when the sugar chain polymer of the present invention is used for the ink receiving layer and the same sugar chain polymer or biodegradable plastic as the present invention is used for the base material, , Biodegradable or recyclable.

In particular, in the case of recycling, hydrolysis using an acid, an alkali, or an enzyme may be used. The enzyme used for the hydrolysis can be selected depending on the bond to be decomposed, such as esterase, lipase, cellulase and β-glucosidase. Other enzymes include β-glucosidase, α-glucanase, α-galactosidase, β-galactosidase, β-amylase, mannosidase, β-glucanase, α-amylase, hyaluronidase, β-hexosaminidase, pullulanase, lysozyme, glucosidase Amylase, etc.
Either exo-type or endo-type enzymes may be used.

The hydrolysis is carried out with p
The reaction is performed under the conditions of H and temperature. For pH adjustment, a buffer (buffer) such as boric acid, ammonium acetate, ammonium hydrogen carbonate, N-ethylmorpholine-acetic acid, phosphoric acid, and tors-hydrochloric acid can be used.

Further, a microorganism producing the above-mentioned useful enzyme may be directly used for the biodegradation of the present invention, or may be buried in soil or compost.

Hereinafter, an ink-jet recording method used when producing the translucent color recorded matter of the present invention using the recording medium of the present invention having the above-described structure will be described. As the ink jet recording method used in the present invention, any conventionally known ink jet recording method in which small droplets of ink are ejected from nozzles using various driving principles to perform recording is applicable. As a typical example, in a method described in Japanese Patent Application Laid-Open No. 54-59936, the ink subjected to the action of thermal energy causes a sudden change in volume, and the ink is ejected from the nozzle by the action force due to this state change. Ink-jet system to be used.

[0082]

[Embodiment 1] Synthesis of Sugar Chain Polymer Compound This example describes a synthesis example of a sugar chain polymer compound used in the present invention. For convenience, the formula (I) when the sugar moiety and the other component are ester bonds, the formula (II) when the sugar moiety and the other component are an amide bond, and the formula (II) when the sugar moiety and the other component are a urethane bond. It is represented by the formula [III].

[0083]

Embedded image Wherein R, R ′ are sugar moieties, aliphatic or aromatic hydrocarbons,
n represents the degree of polymerization.

First, a synthesis example of the adiponyl cellobiose ester represented by the formula [I] will be described.

5 g of cellobiose was placed in 100 ml of N, N-dimethylformamide (DMF), and the solution was added under nitrogen atmosphere.
Heated to 0 ° C. To this, 2 ml of pyridine and 3 ml of adipic acid chloride were added dropwise and stirred for 2 hours. After the completion of the reaction, the reaction solution was poured into 400 ml of ethanol to obtain a precipitate. The precipitate was sequentially washed with ethanol and diethyl ether to obtain 2 g of a white powder. Gel permeation chromatography (GPC) measurement (Tosoh G
MPWXL * 2, eluent: water, column oven temperature;
40.degree. C.), and the weight average molecular weight (Mw.) Was 5,000 in terms of polysaccharide (manufactured by Polymer Laboratories). By IR measurement, 17
From a C = O stretching peak at 33 cm and 13C-NMR measurement, 175 ppm of C ＝ O groups and 24.8 ppm and 34.1 ppm of methylene adipate groups were confirmed, indicating that a sugar ester could be synthesized.

Adiponyl chitobiose and adiponyl maltose were similarly synthesized in place of the cellobiose sugar component chitobiose and maltose. In addition, sebacoyl cellobiose, phthaloyl cellobiose and the like were synthesized by replacing dicarboxylic acid partial adipic acid with sebacic acid, phthalic acid and the like.

Similarly, for the synthesis of an amide bond, a dicarboxylic acid chloride such as adipic acid chloride may be reacted with an aliphatic amine or an amino sugar.

The urethane bond can be similarly synthesized by replacing the dicarboxylic acid chloride moiety with diisocyanate (for example, hexamethylene isocyanate).

Tables 1 to 3 show examples of the compounds according to the above compound formula.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of a recording medium having an ink receiving layer of the present invention.

Embodiment 2 FIG. OHP recording medium 1 Transparent biodegradable plastic "Lacia" (trade name) made of a polylactic acid-based polymer material manufactured by Mitsui Toatsu Chemicals, Inc. Thickness 1
Using a 00 μm sheet as a substrate, a coating solution of the following composition A was applied by a bar coater method after drying to a weight of 100 g / m ^2, and then dried at 80 ° C. for 10 minutes to obtain a 10 μm thick sheet. Then, a recording medium of Example 2 was obtained.

Composition A: 10 parts by weight of compound III-7 90 parts by weight of water

A color image pattern was recorded on the recording medium using an ink jet printer BJC-600S (manufactured by Canon), the image quality was observed and evaluated with a loupe, and the ink absorbency was measured immediately after recording. Then, paper was rubbed on the recording portion, and the degree of ink transfer was determined as follows.

Image quality: ○: good dot shape and color, all poor; Δ: slightly poor; ×: dot flow, repelling,
There are bleeding and discoloration of the ink.

Ink absorption: ○ is good, Δ is slightly inferior, × is ink removed and not absorbed.

Image storability: Solid images (Y, M, and C, and secondary colors R, G, and B) recorded by inkjet recording were stored at room temperature for 20 days. The change in the image before and after storage was evaluated according to the following criteria. ○ indicates that the dot shape and color are all the same as before storage, Δ indicates that the sharpness is slightly inferior to that before storage, and × indicates that the ink is blurred compared to before storage and that the ink is discolored.

Biodegradability: After embedding the recording medium in aged compost, it is observed after 6 months whether biodegradation has progressed. Is indicated by x.

Table 4 shows the obtained evaluation results. The recording medium obtained in Example 2 has high transparency, is excellent in ink jet recording suitability, and is excellent in biodegradability, and is an excellent recording medium in consideration of the influence on the environment. Was.

[0102]

[Table 4]

Embodiment 3 FIG. Shimadzu polylactic acid-based polymer material (trade name: Lacty) as a recording medium substrate for OHP
A transparent biodegradable plastic having a thickness of 100 μm was used. In this example, a coating liquid of the following composition B was applied by a bar coater method to a weight of 100 g / m ² after drying, and then dried at 70 ° C. for 10 minutes to receive an ink having a thickness of 8 μm. By forming a layer, a recording medium of Example 3 was obtained.

Composition B: 10 parts by weight of compound II-1 90 parts by weight of water

As in the case of Example 2, the suitability for ink-jet recording and the biodegradability were evaluated. Table 4 shows the results. The recording medium of this example was an excellent recording medium having good OHP recording suitability and biodegradability.

Embodiment 4 FIG. OHP recording medium 3 A transparent biodegradable plastic sheet having a thickness of 100 μm was used as a base material of a cellulose-based polymer material (trade name: Cell Green) manufactured by Daicel Chemical. In this example, a coating liquid having the following composition C was applied by dipping so as to have a weight of 90 g / m ² after drying, and then dried at 70 ° C. for 10 minutes to form an ink receiving layer having a thickness of 8 μm. To create
A recording medium of Example 4 was obtained.

Composition C: 15 parts by weight of compound I-1 85 parts by weight of methanol

In the same manner as in Example 2, the suitability for ink-jet recording and the evaluation of biodegradability were evaluated. Table 4 shows the results. The recording medium of this example was an excellent recording medium having good OHP recording suitability and biodegradability.

Embodiment 5 FIG. Glossy paper recording medium 1 Aliphatic polyester-based biodegradable plastic (manufactured by Showa Polymer: Bionole # 3000) having a thickness of 100 as a base material
A μm transparent biodegradable plastic sheet was used. In this example, a coating liquid having the following composition D was dried and weighed 95 g.
/ M ² by dipping, and then dried at 70 ° C. for 10 minutes to form an ink receiving layer having a thickness of 9 μm. Thus, a recording medium of Example 5 was obtained.

Composition D 15 parts by weight of compound II-4 85 parts by weight of water

In the same manner as in Example 2, the suitability for ink-jet recording and the evaluation of biodegradability were evaluated. Table 4 shows the results. The recording medium of this example was an excellent recording medium having good OHP recording suitability and biodegradability.

Comparative Example 1 As a substrate, polyethylene terephthalate (PET)
Example 2 except that a sheet having the same thickness as that of Example 2 made of (trade name: Lumirror T-60, manufactured by Toray) was used.
In the same manner as in Example 1, a recording medium of Comparative Example 1 was obtained. The recording medium thus prepared was evaluated for ink jet recording suitability and biodegradability in the same manner as in Example 2. Table 4 shows the results. As is clear from Table 4, Comparative Example 1
Is a recording medium having good ink jet recording suitability as in Example 2, but having extremely poor biodegradability because the base material does not have biodegradability.

Comparative Example 2 A recording medium of Comparative Example 2 consisting of only the base material used in Example 2 was obtained. This recording medium was evaluated for ink jet recording suitability and biodegradability in the same manner as in Example 2. Table 4 shows the results. As is clear from Table 4, the recording medium of Comparative Example 2 has a biodegradability, but is extremely poor in ink-jet recording suitability, and has a poor storage stability of a recorded image, as compared with Example 2. there were.

Comparative Example 3 A sheet having the same composition and thickness as in Example 2 was used as a substrate, and a coating solution having the following composition E was dried to obtain a weight of 100 g / m ^2.
Is applied by a bar coater method so that
After drying at a temperature of 10 ° C. for 10 minutes, an ink receiving layer having a thickness of 8 μm was formed to obtain a recording medium of Comparative Example 3.

Composition E • Cation-modified polyvinyl alcohol (Kuraray, trade name: PVA-CM) 10 parts by weight • Water 90 parts by weight

This recording medium was evaluated for ink jet recording suitability and biodegradability in the same manner as in Example 2. Table 4 shows the results. As is clear from Table 4,
The recording medium of Comparative Example 3 had good ink jet recording suitability as compared with Example 2, but was poor in biodegradability.

Embodiment 6 FIG. Glossy paper recording medium 2 Color copy paper (Canon :) was used as a base material. In this example, a coating liquid having the same composition D as in Example 5 was applied by a bar coater method so as to have a weight of 90 g / m ² after drying, and then dried at room temperature for 10 minutes to form an ink receiving layer. Thus, a recording medium of Example 6 was obtained.

This recording medium exhibited excellent ink jet recording suitability and biodegradability as in Example 2. In addition, it was confirmed that after inkjet recording, the recording surface had glossiness and a high-quality image was obtained.

Embodiment 7 FIG. Evaluation of recyclability of recording medium for OHP The recording medium prepared in Example 4 was pulverized with a pulverizer, and 1 g of the pulverized powder and an esterase enzyme (manufactured by Boehringer Mannheim) were placed in a buffer solution having a pH of 7.5. With stirring. After 15 hours, the reaction supernatant was used for Tosoh high-performance liquid chromatography (HPLC); LC-802.
0, column: SH * 1011 (manufactured by Showa Denko), eluent:
When measured with water, a new low molecular weight sugar and a peak corresponding to an organic acid were newly observed. These gradually increased in strength over time. Each peak showing this peak was collected, and its 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 acetic acid and adipic acid from H-NMR and C-NMR.

Further, these sugars and fatty acids are obtained by converting sugars with water,
Fatty acids could also be fractionated by successive extraction with ethanol.

When adipic acid chloride was newly added to the fractionated saccharide and reacted as in Synthesis Example 1, it was found that repolymerization was possible and recycling was possible.

Embodiment 8 FIG. Evaluation of recyclability of recording medium for glossy paper The recording medium prepared in Example 5 was pulverized with a pulverizer, and 1 g of the pulverized powder and a lipase enzyme (Lipase Amano F, manufactured by Amano Pharmaceutical Co., Ltd.) were buffered at pH 7.0. 45 ℃
With stirring. After 15 hours as in Example 7, the reaction supernatant was measured by HPLC. Column; SH * 1011
When measured with water (manufactured by Showa Denko), eluent: water, a new peak corresponding to a low-molecular-weight sugar and an organic acid was newly observed.
These gradually increased in strength over time. Each peak showing this peak was collected, and its infrared absorption spectrum (IR) was measured to confirm that it was a chitooligosaccharide and a fatty acid. Further, the fatty acid moiety is H—N
From MR and C-NMR, it was confirmed that adipic acid was contained.

When these decomposed products are extracted with water,
A mixture of chitotriose and tetramethylenediol was obtained. Further, extraction with acetone allowed fractionation of adipic acid.

[0124] One mol of cellobiose was newly added to 1 mol of the fractionated adipic acid, and the mixture was heated and melted at 220 ° C for 30 minutes to polymerize adiponyl cellobiose.

According to GPC measurement, the molecular weight of the polymer was M
w. It was 12000. In addition, an ester bond was confirmed by IR measurement, and it was found that the adiponyl cellobiose sugar chain polymer compound could be polymerized and recyclable.

[0126]

As described above, according to the present invention,
A recording medium that has good inkjet recording suitability and biodegradability, and does not contribute to the environment when disposed, is provided. In addition, since it has recyclability, it is possible to provide a recording medium which is excellent in terms of effective use of resources.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a bond (a) and a decomposition (b) of an example of a linear sugar chain polymer compound used for an ink receiving layer of the present invention.

FIG. 2 shows a bond (a) and a decomposition (b) of an example of a sugar chain polymer compound having a crosslinked structure used in the ink receiving layer of the present invention.
FIG.

FIG. 3 is a schematic view showing different bonding modes of a sugar chain polymer compound having a crosslinked structure used in the ink receiving layer of the present invention.

FIG. 4 is a schematic view showing another bonding aspect of a sugar chain polymer compound having a crosslinked structure used in the ink receiving layer of the present invention.

Continued on front page F term (reference) 2H086 BA15 BA35 BA36 4F070 AA01 AA26 AC36 AC40 AC45 AC46 AC72 AE08 BB08 CA12 CA14

Claims (13)

[Claims] 1. A recording medium having at least a base material and an ink receiving layer, wherein the ink receiving layer contains a sugar chain polymer compound in which sugar forms a main chain together with other components, or at least one kind of repeating unit. What is claimed is: 1. A recording medium comprising a sugar chain polymer compound having a molecular chain crosslinked with sugar. 2. The recording medium according to claim 1, wherein the sugar chain polymer compound has a saccharide bonded to another component by an ester bond, a urethane bond, or an amide bond. 3. The recording medium according to claim 1, wherein the sugar is a sugar chain polymer compound that is a sugar containing only a glucopyranose ring. 4. The recording medium according to claim 1, wherein said saccharide is an oligosaccharide. 5. An oligosaccharide comprising maltose, cellobiose, lactose, isomaltose, chitobiose, nigerose, trehalose, melibiose, cellotriose, chitotriose, maltotriose, cellotetraose, chitotetraose, maltotetraose, cellopentaose, Maltopentaose, chitopentaose,
5. The recording medium according to claim 1, wherein the recording medium is at least one of cellohexaose, maltohexaose, chitohexaose, and acetylated products thereof. 6. The recording medium according to claim 1, wherein the saccharide is a polysaccharide. 7. The method of claim 7, wherein the polysaccharide is cellulose, starch, glycogen, galactan, mannan, chitin, chitosan,
7. It is at least one of alginic acid, polyglucosamine, pullulan and hyaluronic acid.
A recording medium according to claim 1. 8. The recording medium according to claim 1, wherein the other component is a dicarboxylic acid. 9. The recording medium according to claim 1, wherein the molecular chain having the repeating unit is synthesized from a compound selected from dicarboxylic acids, diols, diamines, diisocyanates, and polyvinyl alcohol. 10. The recording medium according to claim 1, wherein the crosslinked chains are crosslinked by a sugar moiety in the chain. 11. The recording medium according to claim 1, wherein the cross-linked chains are cross-linked at a portion other than the sugar in the chain. 12. The recording medium according to claim 1, wherein the repeating unit is derived from a compound having a vinyl group or derived from a sugar. 13. The recording medium according to claim 1, wherein all the constituent components are made of a polymer material having biodegradability.