JP2000089498A - Recording material which can be recycled - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material having enough image removing performance by incorporating a water-swellable resin component and a specified proportion of fine particle component into the surface layer. SOLUTION: This recording material which can be recycled consists of at least a base body layer 1 and surface layer 3. The surface layer 3 contains at least a water-swellable resin component and fine particle component, and the fine particle component is incorporated by 1 to 50 pts.wt. to 100 pts.wt. of the water-swellable resin. In this case, the base layer 1 has water proof property (strength), and a transparent plastic film or a plastic film converted into opaque by addition of inorg. fine particles is preferably used. The surface layer 3 formed on the base body layer 1 consists of a water-swellable resin and fine particles, and the water-swellable property means that the resin is swollen with water or aq. solvent but does not dissolve. The water-swellable resin is prepared by crosslinking a water soluble resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material capable of removing a printing material adhered to the recording material by forming an image with a copying machine, a printer or the like from the recording material, and reusing the recording material repeatedly. In particular, the present invention relates to a recording material suitable for a removing means by physical rubbing force such as a brushing method using an aqueous solvent such as water.

[0002]

2. Description of the Related Art Today, electrophotographic copying (so-called copying) techniques using toner have become widespread, and recording materials such as paper and OHP sheets have been used in large quantities.

The printing material printed or copied on such a recording material cannot be easily removed, and since such a technique has not been put to practical use, a large amount of printed matter generated in an office is unnecessary. The fact is that it is discarded as it is.

It is obvious that this is not preferable for environmental protection and resource protection. For this reason, techniques for reproducing or recycling the recording material to be discarded are being actively studied. For example, in JP-A-7-31523 or JP-A-6-222604, a swelling layer that swells with water is formed on the surface of a recording material, and the swelling layer is swelled by wetting with water. Discloses a method for removing an image recorded on a recording material.

[0005] Such recyclable recording materials are:
Reusability is a necessary function of the number, but at the same time, performance as a recording material is also required. Therefore, it is necessary to enable repeated use without lowering this performance. In order to achieve this requirement, it is necessary to adjust various physical properties.

For example, in Japanese Unexamined Patent Publication No. Hei 7-31523, the surface roughness of the surface layer is reduced to 1 to 30 μm by adding fine particles to the resin component in an amount equal to about twice the amount of the resin component.
A technique for adjusting the peeling characteristic by adjusting the range of m is known.

The water-swellable resin used for the above-mentioned recording material has a high tackiness, and the adhesion between the recording materials becomes remarkable especially at a high humidity of 80% or more. For this reason, if the recording materials are left in a high humidity environment with the recording materials stacked, stickiness occurs between the recording materials, causing problems such as deterioration in handling properties, characteristics, and peeling of the surface layer. It is known that the problem caused by the adhesion of the recording materials can be improved by adding fine particles as described above, which reduces the adhesion between the recording materials and can be left in a high-humidity environment. It is known that a recording material can be used.

However, Japanese Patent Application Laid-Open No. 7-31152 discloses
As described in JP-A No. 3 (1993) -305, when a large amount of fine particles are added, the effect of removing a recorded image, which is a basic function as a recyclable recording material, is impaired.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is intended to provide a recyclable recording material from which a printing material such as toner can be removed to obtain a sufficient image removing performance. It is an object of the present invention to provide a recordable material. Another object of the present invention is to provide a recording material that does not cause adhesion between recording materials even when stored in a high-humidity environment and does not cause the various problems described above.

[0010]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, it is effective to add a specific amount of fine particles in advance to the water-swellable surface layer in order to achieve the above object. The present inventors have found that the present invention has been made.

That is, the present invention is a recyclable recording material comprising at least a base layer and a surface layer, wherein the surface layer contains at least a water-swellable resin component and a fine particle component, and the fine particle component is a water-swellable resin. 1 for 100 parts by weight
The present invention relates to a recyclable recording material characterized by being contained in a proportion of about 50 parts by weight.

[0012]

FIG. 1 is a schematic sectional view of a recording medium according to an embodiment of the present invention. As shown in FIG. 1, this recording material is obtained by laminating a surface layer 3 on a base material layer 1. FIG. 1 shows a state where the printing material 4 is printed on the surface of the surface layer 3. Although FIG. 1 shows a configuration in which a surface layer is formed on one surface of the base material layer 1, a configuration in which a surface layer 3 is formed on both surfaces of the base material layer 1 may be used.

The base material layer 1 is preferably a water-resistant (strength), transparent plastic film or an opaque plastic film by adding inorganic fine particles. The material of the plastic film is not particularly limited,
Considering heat resistance and the like, polyester, polycarbonate, polyimide, polymethyl methacrylate and the like are preferable. Further, in consideration of versatility, price, heat resistance, durability and the like, polyester, particularly polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the like are desirable. It is also possible to use various sheets available as OHP. In addition, so-called synthetic paper such as paper made of plastic fiber such as PET fiber or paper based on plastic is also commercially available, and such synthetic paper is also useful as a base material. Besides this,
Metal foil, paper having improved water resistance, and composite materials such as resin, paper, and metal can also be used. In addition, flatness can be maintained through printing and removal of printing material,
Any material having water resistance and appropriate mechanical strength can be used.

The surface layer formed on the base layer is composed of a water-swellable resin and fine particles. By including fine particles in the surface layer, it is possible to obtain a recording material having sufficient durability at high humidity while maintaining sufficient image removal performance.

The term "water swelling" means that the substance swells but does not dissolve in water or an aqueous solvent. Water-swellable resins are made by crosslinking water-soluble resins. Further, by adding a water-insoluble component to the water-soluble resin, a property of absorbing a solvent such as water and swelling but not dissolving in the solvent may be imparted.

As the water-soluble resin, a water-soluble resin having a functional group having an active hydrogen such as a hydroxyl group, an amino group, an amide group, a thiol group, a carboxyl group, a sulfonic acid group in a molecule,
For example, polyvinyl alcohol, methyl cellulose, polyacrylic acid, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, diacetone acrylamide and the like can be used.
Preferably polyvinyl alcohol, methyl cellulose,
Polyacrylic acid is used, and among them, polyvinyl alcohol having many hydroxyl groups is preferable, and the degree of polymerization is 300 to 300.
0, preferably 500-2000, more preferably 50
It is preferably 0 to 1700. It is appropriate that such a water-soluble resin is used after being dissolved in 2 to 30 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the aqueous medium.

In order to crosslink a water-soluble resin, a crosslinking agent and, if necessary, additives may be added to an aqueous solution of the resin.
Any crosslinking agent may be used as long as it has reactivity with a functional group such as a hydroxyl group, an amide group or a carboxyl group present in the water-soluble resin molecule and can crosslink the water-soluble resin. Examples include epoxy compounds, isocyanate compounds, glyoxals, methylol compounds, melamine resins, dicarboxylic acids, aziridine, dihydrazide and compounds having a double bond, such as diacrylate compounds and dimethacrylate compounds.

When the above compound is added as a cross-linking agent, it is added in an amount of 0.1 to 100 parts by weight of the water-soluble resin.
100 parts by weight, preferably 1 to 50 parts by weight are added. If the amount is too small, the film strength may be insufficient at the time of swelling, or the film may be dissolved. If the amount is too large, the crosslinking agent becomes a bulk component, which causes a problem in the strength of the surface layer and the like.

As the fine particles added to the surface layer, inorganic fine particles and resin fine particles can be used. As inorganic fine particles, silica, titanium oxide, alumina, zinc oxide,
Examples include, but are not limited to, calcium carbonate. Silica is preferably used because it is easily dispersed.

The resin fine particles include polymethyl methacrylate, polystyrene, benzoguanamine, phenol,
Examples include fine particles of an epoxy resin and the like, but are not limited thereto.

The fine particles added to the surface layer are suitably those having a secondary particle size of at least 5 μm and a large secondary particle size of at most 50 μm. If the particle size is too small, the effect of improving adhesion and adhesion between recording materials at high humidity is small. On the other hand, if the particle size is too large, the unevenness of the surface layer becomes large, causing a problem in writability and the like. The secondary particle size means a particle size when an aggregate formed by aggregating individual particles is regarded as one particle. The secondary particle size can be measured by microscopic observation or the like.

The fine particles are in a proportion of at least 1 part by weight, and at most 50 parts by weight, based on 100 parts by weight of the water-swellable resin, preferably at least 2 parts by weight, based on 100 parts by weight of the water-swellable resin. It is contained in a proportion of at most 30 parts by weight or less. When removing an image using a water-swellable resin, the image is removed using the shearing force at the interface between the recording material and the image, which is caused by the swelling. When added, the degree of swelling decreases because the ratio of the resin that is the swelling component decreases, and as a result, the shearing force at the interface also decreases, so that the effect of removing the image deteriorates. on the other hand,
If the addition amount is too small, a sufficient effect on the adhesion between the recording materials at high humidity cannot be obtained.

Further, an antistatic agent may be added to the surface layer, if necessary, in order to improve the paper passing property. The antistatic agent may be added to the material forming the surface layer, or after forming the surface layer, a material dissolved and dispersed in an appropriate solvent may be applied. Examples of the antistatic agent include a cationic surfactant such as a quaternary ammonium salt.

As a method for forming the surface layer, a solvent coating method can be used. Specifically, the above water-swellable resin material, that is, a water-soluble resin material and a crosslinking agent, or a water-soluble resin material and a monomer or an oligomer, and if necessary, other additives, water, a water / organic solvent mixture, Alternatively, by dissolving and dispersing in a suitable solvent such as an organic solvent, and applying on the substrate layer such that the film thickness after heating and drying is 0.5 to 30 μm, preferably 3 to 20 μm, and more preferably 5 to 20 μm. Good.
In the case where the surface layer is formed by application using an aqueous solvent, an effect that the application formation of the surface layer is facilitated when a surfactant is contained in the application solution is also obtained.

A surfactant may be added to the resin solution constituting the surface layer in order to improve the coating performance. The surfactant is not particularly limited, such as anionic, cationic and nonionic. The addition amount is preferably 0.1 to the resin.
% To 20%, more preferably 0.5% to 10%
The following are appropriate:

After coating, the surface layer is heated to 50 to 180 ° C, preferably 80 to 150 ° C. In the case of crosslinking with a compound having a double bond, the heating may be performed after or together with the irradiation.

An intermediate layer may be formed between the substrate layer and the surface layer. The intermediate layer is provided for the purpose of bonding the surface layer more firmly to the base material.

FIG. 2 is a schematic sectional view of a recording material having an intermediate layer according to another embodiment of the present invention. 1 is a substrate layer,
2 is an intermediate layer and 3 is a surface layer. FIG. 2 shows a configuration in which the printing material 4 is printed on the surface of the surface layer 3. Although FIG. 2 shows a configuration in which the intermediate layer 2 and the surface layer 3 are formed on one surface of the base material layer 1, a configuration in which the intermediate layer 2 and the surface layer 3 are formed on both surfaces may be used.

The intermediate layer 2 is made of a resin having a high adhesiveness. The intermediate layer contains a compound (reactive compound) 5 having a functional group capable of chemically bonding to the resin constituting the surface layer, if desired. . By doing so, it is possible to improve the adhesiveness and bonding property between the intermediate layer and the surface layer. Examples of the highly adhesive resin constituting the intermediate layer include acrylic resin, styrene resin, polyester resin, polycarbonate resin, vinyl acetate resin, vinyl chloride resin, urethane resin, etc., preferably, polymethyl methacrylate resin, polyester resin. , Polycarbonate resin, vinyl chloride resin and urethane resin. In particular, it is preferable to use a material having high adhesiveness to the base material layer.

The reactive compound optionally contained in the intermediate layer is not particularly limited as long as it has a functional group capable of chemically bonding to the resin constituting the surface layer. Examples thereof include a methylol compound, an isocyanate compound, an aldehyde compound and an epoxy compound. Compounds, aziridine compounds and the like can be used. When the resin constituting the surface layer is a resin having a hydroxyl group such as polyvinyl alcohol and methyl cellulose, a methylol compound, an isocyanate compound, an aldehyde compound, and an epoxy compound are preferable. When the resin constituting the surface layer is a resin having a carboxyl group such as polyacrylic acid, an isocyanate compound, an epoxy compound, and an aziridine compound are preferable. In addition, these compounds can be similarly used as a crosslinking agent for the water-soluble resin constituting the surface layer.

Examples of the methylol compound include methylolated melamine such as dimethylolmelamine and trimethylolmelamine, dimethylolated urea, and melamine-formaldehyde resin. In addition to these, various methylol compounds can be used, and those having a moderately high molecular weight and those having a moderately long molecular chain are preferable. From this viewpoint, among the methylol compounds exemplified above, melamine- Formaldehyde resins are preferred.

Examples of the aldehyde compound include glyoxal and glutaraldehyde. In addition to these, various aldehyde compounds can be used.

Examples of the epoxy compound include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, and polyglycerol polyglycidyl ether.
In addition to these, various epoxy compounds can be used.

As the isocyanate compound, those having two or more isocyanate groups in one molecule can be used. By using a compound having a plurality of isocyanate groups, the substrate layer and the surface layer can be more firmly bonded.

Examples of the isocyanate include 4,4′-diphenylmethane diisocyanate,
4'-methylenebiscyclohexyl isocyanate, tris (p-isocyanatophenyl) thiophosphate, tris (p-isocyanatophenyl) methane, trimethylolpropane tolylene diisocyanate triadduct, aliphatic poly- yl having a hydrophilic group in the molecule Isocyanates and the like can be used.

The isocyanate used in the present embodiment, including these compounds, may be protected with phenol, sulfurous acid and the like.

As the aziridine compound, for example, diphenylmethane-bis-4,4'-N, N'-diethyl urea, 2,2-bishydroxymethylbutanol-tris- [3- (1-aziridinyl) propinate] is used. can do. Further, an oxazoline group-containing polymer can also be used.

The above-mentioned reactive compound is more preferably a solid or wax at room temperature or a viscous liquid at room temperature. When the reactive compound is a solid or waxy at room temperature or a viscous liquid at room temperature, it does not evaporate due to drying during coating formation of the intermediate layer,
Moreover, since the surface is not tacky after drying, there is an advantage that the application of the surface layer becomes easy. In addition, when a reactive compound that dissolves in water or has affinity for water is used, there is no need to use an organic solvent to apply and form the intermediate layer, and the organic solvent remains in the intermediate layer. Can be prevented.

To coat the intermediate layer 2 on the base material layer 1,
A resin and optionally the above reactive compound in a suitable solvent,
For example, it can be performed by a solvent coating method or a melt coating method of coating and drying a solution dissolved in tetrahydrofuran (THF), dioxane, acetone, ethyl acetate, methyl ethyl ketone (MEK) or the like. What dissolved or disperse | dissolved resin, such as water-soluble or hydrophilic polyurethane and polyester in water, can also be used. Such resin solutions and resin emulsions are commercially available, and using them has the advantage that a coating film can be formed without using an organic solvent, especially a non-aqueous organic solvent. For this reason, safety at the time of manufacture can be improved. Further, it is possible to suppress a problem such as generation of gas of a residual solvent from the inside due to heating of the recording material due to paper passing through a copying machine or the like. When an aqueous solvent is used, the addition of a surfactant makes it easier to apply the intermediate layer. If the intermediate layer and the surface layer are formed using an aqueous solvent, it is possible to manufacture a recording material without using a non-aqueous organic solvent, and to ensure the safety and residual non-aqueous organic solvent in the recording material. Problems can be prevented. By the solvent coating method or the melt coating method, the film thickness is about 0.5 μm to 20 μm, preferably about 0.5 to 10 μm, more preferably about 0.5 to 10 μm.
An intermediate adhesive layer is formed to have a thickness of about 6 μm. When the thickness is less than 0.5 μm, coating unevenness is likely to occur, and an uncoated portion tends to be formed. If it exceeds 20 μm, problems may occur in the strength, heat resistance and the like of the recording material.

If the reactive compound is a high molecular weight substance, which itself has a film-forming property and is excellent in adhesiveness to the base material layer, the reactive compound itself is dissolved in a solvent or the like, coated and dried. It is also possible to form. In the case of coating by adding to a resin solution, the addition amount of the reactive compound can be, for example, 5 to 50 parts by weight based on 100 parts by weight of the resin constituting the intermediate layer.

The intermediate layer may be subjected to a corona discharge treatment.

When a paper or fibrous base material is used, the base material is immersed in the coating solution for forming the intermediate layer, the coating solution is impregnated in the base material, and the intermediate layer material is interposed between the fibers constituting the base material. May be satisfied.

The recording material obtained as described above can be suitably used for a method of removing a recording material through a process of swelling the surface layer → physical rubbing by brushing or the like → drying process, and is recyclable.

A method for removing a printing material from a recording material having a printing material such as a toner printed on the surface thereof will be described below. The method includes a step of supplying a recording material on which a printing material is printed to a solvent capable of swelling the surface layer, and scraping the recording material from the swollen recording material surface with a physical force. Hereinafter, a more detailed description will be given with reference to the drawings.

FIG. 3 is a process flow chart for explaining an example of a printing material removing method. In FIG. 3, the recording material 1
00 has an intermediate layer and a surface layer formed on both sides thereof,
The intermediate layer and the surface layer are collectively shown as 12. A printing material 4 such as toner is printed on the surface of the recording material. As a printing material, a toner used for electrophotography is preferably used. In addition, a recording material used for an ink-jet method, a thermal transfer method, a printing method, and the like using a hot melt ink, and other oil-based paint agents For example, a type that forms a film-like image by adhering to the surface of a recording material such as a recording medium can be used. The recording material is conveyed from right to left in the drawing.

The recording material on which the printing material 4 is printed is first supplied with a surface swelling solvent from the solvent supply device 11 to the surface layer. The solvent capable of swelling the surface layer is an aqueous solvent, that is, water, a mixed solvent of water and a water-soluble organic solvent,
Alternatively, various types such as an aqueous organic solvent can be used. Also, a desired additive such as a surfactant may be added. As described above, the present embodiment has a great advantage in that the printing material can be removed using water. In the following description, the case where water is used will be described.

As shown in FIG. 3, the water may be supplied by showering water from the shower device 11 onto the surface layer, or immersed in water (not shown). In order for water to penetrate into the surface layer of the recording material, it is preferable to contact the recording material for about 15 to 150 seconds. The longer the contact time, the more water can be permeated, but the longer the treatment. When water penetrates into the surface of the recording material, the surface swells (the swollen surface is shown as 13), and the adhesive force between the printing material 4 and the surface decreases. At this time, the water temperature is 15 ° C
~ 45 ° C is appropriate. If the temperature is too high, the evaporation of water increases, and if the temperature is too low, a sufficient cleaning effect may not be obtained.

After the water has sufficiently penetrated into the surface layer of the recording material, the recording material is further conveyed to the printing material removing area, where the brush 14
To The brush 14 is rotating, and the printing material 4 on the recording material 100 is removed by the brush.
In addition to the brush, a means of applying a physical or mechanical force to the surface to rub or scrape the surface, such as a blade or a cloth, may be employed. In FIG. 3, the brush 14 is disposed outside the liquid, but may be disposed in the liquid. The length of the bristles of the brush 14 can be about 5 to 20 mm, and the thickness can be about 10 to 60 μm. The material is not particularly limited, but nylon or the like is suitable.

The paper passing speed, that is, the recording material is the brush 14
May be determined in consideration of the balance between the processing time and the cleaning performance, for example, 0.5 cm /
Seconds to 5 cm / sec. The rotation speed of the brush is preferably 5 times or more, more preferably 10 times or more the transport speed.

After the printing material 4 is removed, the recording material is conveyed to a shower area, and a cleaning shower 15 is applied to the surface of the recording material to wash away the printing material remaining on the surface of the recording material. As the liquid used for the shower 15, the same aqueous solvent as used for swelling the surface layer can be used. The same solvent used to swell the surface layer may be used. It is particularly preferred to use water.

After the shower 15 is applied, the recording material is further conveyed to a drying area and dried by the dryer 16.
The drying method may be a contact type such as a heat roller or a non-contact type such as a far-infrared lamp. The heating temperature is suitably about 70 to 150 ° C.

FIG. 4 is a view showing an embodiment of a cleaning apparatus to which the above-described cleaning method can be applied.
The apparatus shown in FIG. 4 includes a cleaning tank 22 for storing a liquid 30 for swelling a recording material in a casing 23. The cleaning tank 22 is connected to a pump 20 having a filter for removing printing material in the liquid in the tank, and the pump 20 is further provided with a swelling shower 11 and a rinsing shower 15 via a pipe 31. It is connected.

The liquid in the cleaning tank 22 is supplied to the pump 20.
After being purified by the internal filter, it is sent to showers 11 and 15 through a pipe 31, and is used as a liquid for swelling the recording material in the shower 11 and as a rinsing liquid in the shower 15.

The recording material is introduced into the apparatus by the paper feed roller 21 and sprayed with a swelling liquid by the shower 11, and then passes through the guide 26 and the transport roller 24 and is immersed in the liquid 30 in the cleaning tank 22. You. And
After standing still for a predetermined time, the conveying roller 24 and the guide 28
Is sent to the opposite portion of the brush 14 to remove the printing material.

Thereafter, the recording material passes through the guide 29, the transport roller 25, and the guide 27, and is sprayed with a rinsing liquid by the shower 15, and finally dried by the drying roller 17 and discharged out of the apparatus.

FIG. 5 is a view showing another embodiment of the cleaning device. In the apparatus shown in FIG.
The recording material introduced by 1 is transported by the transport rollers 32, 3
By being transported directly to the cleaning tank 22 and immersed in the liquid 30 by the guide 3 and the guide 26, water permeates the surface layer of the recording material before brushing. After passing through the opposite portion of the brush 14, the liquid 3
After passing through the inside of the roller, the rinsing effect is obtained by reaching the drying roller 17. FIG.
The same components as those described above are denoted by the same reference numerals, and detailed description is omitted.

FIG. 6 is a view showing another embodiment of the cleaning device. The apparatus includes a swelling liquid tank 43 for storing the liquid 30 for swelling the recording material, and a rinsing liquid tank 42 for storing a liquid for cleaning the recording material after the surface is rubbed with the brush 14. It has the structure which has each independently. The liquid 30 stored in the swelling liquid tank 43 is pumped up by the pump 20 equipped with a filter, sent to the shower 11 through the pipe 31, and sprayed onto the recording material 100 introduced by the paper feed roller 21 for a predetermined time or a predetermined amount. . The recording material passes through the guide 26 and the transport rollers 24 and 25 and is sent to the brush 14. The swelling liquid sprayed on the recording material 100 in the shower 11 drops, returns to the swelling liquid tank 43 located below the shower 11, and is circulated.

The recording material 100 from which the printing material has been removed by the brush 14 is sent to a shower 15 where a cleaning shower 15 is applied to the surface of the recording material. In the cleaning shower, the rinsing liquid 50 stored in the rinsing liquid tank 42 is pumped up by the pump 40 equipped with a filter.
It is supplied to the shower area through a pipe 41. The printing material scraped off by the brush and the printing material washed away by the rinsing liquid are supplied to a filter 45 provided at the top of the rinsing liquid tank.
The ink is filtered together with the cleaning shower liquid that has fallen from the shower area and falls from the shower area, the printing material is filtered, and the rinsing liquid is returned to the tank 42 and used for circulation. The recording material that has passed through the shower area passes through a guide 27, is finally dried by a drying roller 17 having a built-in heater, and is discharged outside the apparatus.

[0059]

Example 1 Base material layer: A 100 μm thick polyethylene terephthalate (PET) sheet was used as the base material layer. Intermediate layer: A resin solution was prepared by dissolving 14 g of a polycarbonate resin in 86 g of 1,4-dioxane. 1 g of a melamine-formaldehyde resin (Sumirez Resin 613: manufactured by Sumitomo Chemical Co., Ltd.) was added to the resin solution and stirred. The obtained solution was applied to the substrate layer with a bar coater,
Heated for 3 minutes, and then subjected to corona discharge treatment to a thickness of 3μ.
m was obtained. Surface layer: polyvinyl alcohol CM- as water-soluble resin
16 g of 318 (manufactured by Kuraray) was dissolved in 184 g of water to prepare a resin solution. Melamine-formaldehyde resin (Sumirez Resin 613: Sumitomo Chemical Co., Ltd.) is added to the resin solution.
0.5 g, ammonium chloride 0.6 g, polyoxyethylene nonyl phenyl ether 0.2 as a surfactant
g and silica fine particles (Sylysia 45
0; manufactured by Fuji Silysia Ltd.) and stirred for 15 minutes. The obtained liquid is applied on the intermediate layer with a bar coater,
Heating was performed at 20 ° C. for 2 hours to obtain a surface layer having a thickness of 9 μm.

Example 2 Base material layer: A polyethylene naphthalate (PEN) sheet having a thickness of 80 μm was used as the base material layer. Surface layer: polyvinyl alcohol CM- as water-soluble resin
318 (manufactured by Kuraray) was dissolved in 188 g of water to prepare a resin solution. To the resin solution, 4 g of an aliphatic polyisocyanate (SBU0772; manufactured by Sumitomo Bayer) as a crosslinking agent, 1 g of sodium polyoxyethylene lauryl ether sulfate as a surfactant, and 3 g of alumina fine particles (A11; manufactured by Nippon Light Metal Co., Ltd.) as fine particles are added. And stirred for 5 minutes. The obtained liquid was applied on a base material layer using a bar coater, and heated at 140 ° C. for 60 minutes to obtain a surface layer having a thickness of 8 μm.

Example 3 Substrate layer: A white PET sheet having a thickness of 100 μm was used as the substrate layer. Intermediate layer; water-dispersible urethane resin solution (HUX-23
2. To 100 g of Asahi Denka Co., Ltd., 5 g of a melamine-formaldehyde resin (Sumirase 613, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 g of polyoxyethylene octyl phenyl ether (Octapol 100, manufactured by Sanyo Chemical Co., Ltd.) are added.
The composition was applied to the base material layer using a bar coater and dried at 120 ° C. for 5 minutes to form an intermediate layer having a thickness of 5 μm. Surface layer: polyvinyl alcohol KL- as a water-soluble resin
16 g of 318 (manufactured by Kuraray) was dissolved in 184 g of water to prepare a resin solution. An epoxy-based crosslinking agent (Denacol EX-313, manufactured by Nagase Chemical Co., Ltd.) as a crosslinking agent in the resin solution.
1.6 g, 0.8 g of polyoxyethylene dodecylphenyl ether and 0.4 g of benzoguanamine resin (Eposter L15, manufactured by Nippon Shokubai Co., Ltd.) were added as fine particles, and the mixture was stirred for 5 minutes. The obtained liquid was applied on the intermediate layer with a bar coater and heated at 140 ° C. for 30 minutes to obtain a surface layer having a thickness of 7 μm.

Example 4 Base material layer: A white PET sheet having a thickness of 75 μm was used as the base material layer. Intermediate layer; water-dispersible urethane resin solution (HUX-26
0, 100 g of Asahi Denka Co., Ltd.), 5 g of melamine-formaldehyde resin (SUMIREZE 613, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 g of polyoxyethylene octylphenyl ether (Octapol 100, manufactured by Sanyo Chemical Co., Ltd.), and after stirring,
The composition was applied to the base material layer with a bar coater and dried at 120 ° C. for 5 minutes to form an intermediate layer having a thickness of 3 μm. Surface layer: polyvinyl alcohol KM- as a water-soluble resin
618 (manufactured by Kuraray) was dissolved in 184 g of water to prepare a resin solution. An epoxy-based crosslinking agent (Denacol EX-313, manufactured by Nagase Chemical Co., Ltd.) as a crosslinking agent in the resin solution.
1.6 g, polyoxyethylene dodecyl phenyl ether 0.8 g and alumina fine particles (A-31,
1.5 g (Nippon Light Metal Co., Ltd.) was added and stirred for 5 minutes.
The obtained liquid was applied on the intermediate layer with a bar coater,
C. for 40 minutes to obtain a surface layer having a thickness of 7 .mu.m.

Comparative Example 1 Base material layer: A PET sheet having a thickness of 150 μm was used as the base material layer. Intermediate layer: A resin solution was prepared by dissolving 14 g of a polycarbonate resin in 186 g of tetrahydrofuran. 4 g of isocyanate (Desmodur RFE: manufactured by Sumitomo Bayer) was added to the resin solution and stirred. The obtained solution was applied on the base material layer with a bar coater and heated at 80 ° C. for 3 minutes to obtain an intermediate layer having a thickness of 2 μm. Surface layer: polyvinyl alcohol CM- as water-soluble resin
16 g of 318 (manufactured by Kuraray) was dissolved in 184 g of water to prepare a resin solution. To the resin solution were added 0.5 g of a melamine-formaldehyde resin and 0.6 g of ammonium chloride as a cross-linking agent, followed by stirring for 5 minutes. The obtained liquid was applied on the above-mentioned intermediate layer with a bar coater, and heated at 120 ° C. for 2 hours to obtain a surface layer having a thickness of 8 μm.

Comparative Example 2 Base layer: A white PET sheet having a thickness of 80 µm was used as the base layer. Intermediate layer; water-dispersible urethane resin solution (HUX-26
0, 100 g of Asahi Denka Co., Ltd.), 5 g of melamine-formaldehyde resin (SUMIREZE 613, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 g of polyoxyethylene octylphenyl ether (Octapol 100, manufactured by Sanyo Chemical Co., Ltd.), and after stirring,
The composition was applied to the base material layer with a bar coater and dried at 120 ° C. for 5 minutes to form an intermediate layer having a thickness of 3 μm. Surface layer: polyvinyl alcohol PVA as a water-soluble resin
12 g of -220 (manufactured by Kuraray) was dissolved in 188 g of water to prepare a resin solution. Melamine-formaldehyde resin (Sumireze resin 613:
Sumitomo Chemical Co., Ltd.) 0.5 g and ammonium chloride 0.6 g,
And silica fine particles (Sylysia 450;
10 g (Fuji Silysia) was added and stirred for 5 minutes.
The obtained liquid was applied on the intermediate layer with a bar coater,
C. for 2 hours to obtain a surface layer having a thickness of 8 .mu.m.

Evaluation Evaluation of Printing Material Removal Performance Images were formed on the recording materials obtained in Examples 1 to 4 and Comparative Examples 1 and 2 using a commercially available laser beam printer (LP-1700; manufactured by Epson Corporation). The recording material on which the image was formed was subjected to image removal (ink removal) using the apparatus shown in FIG. 4, and the removal of the printing material was evaluated. Furthermore, the performance of removing the printing material after repeating this process five times was evaluated. The above evaluations were ranked as follows, and the results are summarized in Table 1. ◎: 95% or more could be removed; ：: 80% or more could be removed; ×: Only less than 80% could be removed.

The operating conditions of the apparatus shown in FIG. 4 are as follows.・ Use a brush roller with a core diameter of 12 mm having nylon brush bristles with a hair length of 10 mm and a thickness of 30 μm ・ Water temperature in the tank 30 ° C. ・ Paper speed 1 cm / sec ・ Immersion time in water in the tank 2 minutes・ Brush rotation speed / paper passing speed = 30 ・ Heat roller temperature 110 ° C

Adhesion of Recording Materials Under High Humidity Conditions The surface layers of the recording materials obtained in Examples 1 to 4 and Comparative Example 1 were superposed on each other, and a weight of 10 kg was applied thereto from above. 3
It was stored for 1 week in an environment of 0 ° C. and 85%. The sample was evaluated as "O" when there was no adhesion between the recording materials after storage, and "X" when the adhesion was observed. The results are shown in Table 1 below.

[Table 1]

[0068]

According to the present invention, the recyclable recording material is as follows.
It has excellent image removal performance, and can be stably stored even in a high humidity environment without adhering to a recording material.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an embodiment of a recording material.

FIG. 2 is a schematic sectional view showing another embodiment of a recording material.

FIG. 3 is a process flow chart for explaining a method for removing a recording material.

FIG. 4 is a diagram illustrating an example of a cleaning device.

FIG. 5 is a diagram illustrating an example of a cleaning device.

FIG. 6 is a diagram illustrating an example of a cleaning device.

[Explanation of symbols]

1: base material layer 2: intermediate layer 3: surface layer 4: printing material 11: shower device 12: intermediate adhesive layer + surface layer 13: swollen surface layer 14: brush 15: cleaning shower 16: dryer 100: recording material

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA20 AK01A AK21A AK35 AK36 AK41 AK41B AK45 AT00A AT00B BA02 CA18 CA23A DE01A DE01H EJ55 GB90 JB10A JL16 YY00A YY00H

Claims (2)

[Claims] 1. A recyclable recording material comprising at least a base layer and a surface layer, wherein the surface layer contains at least a water-swellable resin component and a fine particle component, and the fine particle component is 100 parts by weight of the water-swellable resin. A recyclable recording material, characterized in that it is contained in an amount of 1 to 50 parts by weight with respect to the total weight of the recording material. 2. A recyclable recording material comprising at least a base material layer and a surface layer, wherein the surface layer contains at least a water swellable resin component and a fine particle component, and the fine particle component is 100 parts by weight of the water swellable resin. A recyclable recording material, characterized in that the recording material is contained in an amount of 2 to 30 parts by weight based on the weight of the recording material.