JP7009942B2 - Image-forming substance removing agent, laminate and image-forming substance removing method - Google Patents

Description

The present invention relates to an image forming substance removing agent, and more specifically, contains a thermoplastic resin formed on the surface of a recording material such as a resin film by a method such as an electrophotographic method, a thermal transfer method, or an inkjet method. An image forming substance that can remove characters and images due to toner and / or an image forming substance from the surface of the material to be recorded extremely easily, reliably and neatly, and can be peeled off by an excellent method in terms of cost. The present invention relates to a removing agent and a method for removing a laminate and an image forming substance using this image forming substance removing agent.

Currently, with the increasing performance of copiers and printing printers, these devices are used for various purposes and forms such as printing and copying documents, printing photos and videos, and issuing forms and slips. The consumption of copy paper and printer paper in companies and homes is increasing.

In contrast to the large consumption of paper including copy paper and printer paper, increasing the import volume of wood chips, which are the raw material for paper, is not desirable from the viewpoint of curbing deforestation. Recycled paper that has been separated into recycled pulp and recycled has been used.

Recycled paper is used paper recovered from its main raw materials, but in order to make recycled paper from the recovered used paper, a certain amount of new wood resources are also required, so it is tentatively recycled paper. Even if the utilization rate of paper increases, wood resources will still be consumed, and the use of recycled paper will not be a drastic solution to protect the forest environment.
In addition, the quality of recycled paper is still inferior to that of high-quality paper, and even when color printing is performed using copy paper of high-quality paper, the toner tends to soak into the paper and the color becomes lighter. When a copy paper made of recycled paper is used, the whiteness of the paper is lowered and the color is grayish, so that the degree of color development at the time of printing is further lowered and the image quality tends to be deteriorated.
Further, recycled paper has a problem that it is expensive to manufacture and tends to be more expensive than high-quality paper, so that the actual situation is that the use as a substitute for high-quality paper has not been established.

Instead of such recycled paper, a technique has been proposed in which once used paper can be reused by peeling and removing an image formed on the surface of the paper by an electrophotographic method such as a copying machine. For example, a peeling member having adhesive strength is superposed on the surface of an image formed on paper with an image forming substance of a toner containing a thermoplastic resin, and the image forming substance is made into a peeling member by appropriately heating and pressurizing in that state. A method of transferring and removing is known (see, for example, Patent Document 1).

However, in the method using such a peeling member, it is necessary to heat the image-forming substance on which the peeling member is superposed to a temperature at which cohesive failure occurs, and it is difficult to adjust the heating temperature. The image removal device for implementation has a complicated and large structure incorporating heating means and a mechanism for adjusting the heating temperature, and the running cost has to be high, so the image forming substance is removed and the paper is removed. There is a problem that the cost of regeneration cannot be kept low.

Further, a method is known in which a heat-meltable image formed on a resin film is peeled off and removed from the sheet surface by heating the image surface with a heat-meltable release body interposed therebetween (see, for example, Patent Document 2). ). However, in this method, since both the heat-meltable stripper and the image-forming substance contain the heat-meltable resin, the heat-meltable resin is compatible with each other by heating and pressurizing the sheet surface, and the interface is not formed. There is a problem that it is difficult to cleanly remove the image-forming substance transferred from the sheet surface to the release member.

Japanese Unexamined Patent Publication No. 2007-279619 Japanese Unexamined Patent Publication No. 1-297294

The present invention has been made in view of the above circumstances, and the problem to be solved thereof is a toner containing a thermoplastic resin formed on the surface of the material to be recorded by a method such as an electrophotographic method, a thermal transfer method, or an inkjet method. And / or the image-forming substance removal that can remove characters and images due to the image-forming substance from the surface of the recorded material extremely easily, reliably and neatly, and can be peeled off by an excellent method in terms of cost. It is an object of the present invention to provide an agent and a method for removing a laminate and an image-forming substance using the image-forming substance removing agent.

As a result of diligent studies in view of the above circumstances, the present inventors have found that the above-mentioned problems can be easily solved by an image-forming substance removing agent having a specific constitution, and have completed the present invention.

That is, the gist of the present invention is the following [1] to [5].

[1] Contains one or more (meth) acrylates selected from the group consisting of hydroxyalkyl-based (meth) acrylates, aromatic (meth) acrylates, and alkyl glycol-based (meth) acrylates, and a photopolymerization initiator. An image-forming substance remover comprising an active energy ray-curable resin composition having a viscosity at 25 ° C. of 200 mPa · s or less.

[2] A laminate in which the image-forming substance removing agent according to [1] is laminated on a recording material or an image-forming substance.

[3] The laminate according to [2], wherein the recorded material is a resin film.

[4] The laminate according to [3], wherein the resin film contains polyester and a polymer incompatible with polyester.

[5] Removal of the image-forming substance removing agent and the image-forming substance that removes the image-forming substance removing agent and the image-forming substance from the recorded material after irradiating the laminate according to any one of [2] to [4] with active energy rays. Method.

According to the image-forming substance removing agent of the present invention, a toner and / or an image containing a thermoplastic resin formed on the surface of a material to be recorded such as a resin film by a method such as an electrophotographic method, a thermal transfer method, or an inkjet method. A resin layer made of this image-forming substance removing agent is formed on characters and images made of a forming substance, and is rapidly cured by irradiation with ultraviolet rays, electron beams, visible light, etc., and is formed on the surface of the material to be recorded during curing. By transferring and holding the characters and images on the resin layer side and separating them from the surface of the material to be recorded, the characters and images can be transferred from the surface of the material to be recorded extremely easily, reliably, cleanly, and cost-effectively. It can be removed by the above method. Therefore, a recording material such as a resin film from which an image forming substance has been removed can be repeatedly used as a recording material for copying paper or printer paper, and its industrial value is high.

Hereinafter, embodiments of the present invention will be described in detail.

If the use of resin film as a general-purpose material for copy paper and printer paper becomes widespread, resin film can be manufactured without using wood resources, which is extremely effective in protecting the forest environment. Further, even when color printing is performed, toner penetration does not occur, and it is possible to print an image with high quality and reduce the amount of toner used without degrading the image quality.

In addition, copy paper and printer paper made from paper should not be torn or jammed in the copier or printer, and may be wrinkled or curled by absorbing moisture, or may be heated or pressed during toner fixing. It has a certain thickness so that it will not be torn and that show-through will not occur on both sides, especially when the entire surface is printed. However, if a resin film is used instead of paper made of paper, the resin film is thinner than paper and can be printed / printed by a copier or a printer without show-through, and the thickness is also high. Being able to make the paper thinner makes transportation and delivery efficiency more efficient than paper made of paper, contributes to the reduction of CO ₂ generated in the distribution process, and reduces the volume and storage space when printing and printed matter are made into files. There are many practical merits such as reduction of the work load when carrying a large amount of printed matter and printed matter, excellent water resistance, and long-term storage.

However, if a resin film is used instead of paper or recycled paper as a recording material to be printed or printed by a copying machine or a printer, there are many advantages as described above, but this can be printed only once on the resin film. Or, if it is discarded by printing, it will be a waste of petroleum resources.

Therefore, the present inventors have studied so that the same sheet can be repeatedly used as a recording material for copying or a printer by removing the image printed or printed on the surface of the resin film. Was carried out.
Furthermore, from the viewpoint of maintaining confidential information of documents, for example, for copy paper and printer paper used in offices of public institutions and companies, from the viewpoint of maintaining confidential information, processing of confidential documents outsourced is being transported. In order to contribute to the risk of information leakage and the reduction of CO ₂ generated in the transportation process, we conducted a study so that it would be possible to easily remove image-forming substances in-house and process confidential documents.

In order to satisfy these performances, a method for peeling and removing characters and images formed on the surface of the recorded material of the resin film by a toner containing a thermoplastic resin and / or an image forming substance from the surface of the recorded material is investigated. As a result, the method of peeling and removing the active energy ray-curable resin composition using the image-forming substance removing agent is extremely easy and cost effective without causing deterioration of the recorded material due to heating. It was found that the material to be recorded can be repeatedly peeled off and removed by the method, and the material to be recorded after removing the image-forming substance can be repeatedly used as the material to be recorded on copy paper or printer paper.
Furthermore, as a result of studies by the present inventors, an active energy ray-curable resin composition that can be suitably used when peeling and removing using this active energy ray-curable resin composition as an image-forming substance removing agent. I found out the physical characteristics of.

The active energy ray-curable resin composition constituting the image-forming substance removing agent of the present invention (hereinafter, may be referred to as “active energy ray-curable resin composition of the present invention”) is hydroxyalkyl-based (meth). It contains one or more (meth) acrylates selected from the group consisting of acrylates, aromatic (meth) acrylates, and alkyl glycol-based (meth) acrylates, and a photopolymerization initiator, and has a viscosity of 200 mPa at 25 ° C. -It is characterized by being s or less.
In addition, "(meth) acrylate" refers to one or both of "acrylate" and "methacrylate".

Specific examples of the active energy ray-curable resin in the active energy ray-curable resin composition of the present invention include an ultraviolet curable resin, an electron beam curable resin, and a visible light curable resin. Above all, an ultraviolet curable resin is preferable in consideration of ease of handling and curability. An example of an active energy ray curable resin is a hard coat.

The (meth) acrylate contained in the active energy ray-curable resin composition of the present invention includes hydroxyalkyl-based (meth) acrylate, aromatic (meth) acrylate, and alkyl glycol-based (meth) acrylate (hereinafter referred to as “these”. It may be referred to as "the (meth) acrylate" of the present invention). Only one of these may be used, or two or more thereof may be mixed and used.

By including hydroxyalkyl-based, aromatic-based, and alkylglycol-based (meth) acrylates, the adhesion to image-forming substances such as toner is improved, and not only is it easy to peel off, but also the material to be recorded Damage is suppressed, and the recorded material can be reused after the image-forming substance is removed. On the other hand, if the (meth) acrylate does not contain the above component, the adhesion to the image-forming substance such as toner is lowered, and the image-forming substance such as toner may not be reliably removed.

Hydroxyalkyl-based (meth) acrylates include hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxybutyl (meth) acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates, and 1,4-cyclohexanedi. Examples thereof include methanol mono (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, and glycerol (meth) acrylate.
Examples of the aromatic (meth) acrylate include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxypropyl (meth) acrylate.
Examples of the alkyl glycol-based (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethyl propanetri (meth) acrylate, and polyethylene glycol di (meth). Examples thereof include meth) acrylate and polypropylene glycol di (meth) acrylate.

The active energy ray-curable resin composition of the present invention may contain a (meth) acrylate other than the above-mentioned (meth) acrylate of the present invention. However, in this case, in order to more effectively obtain the effect of using the (meth) acrylate of the present invention, the (meth) acrylate of the present invention contained in the active energy ray-curable resin composition of the present invention ( The proportion of the meta) acrylate is preferably 1% by mass or more, particularly preferably 1 to 100% by mass.
Further, the active energy ray-curable resin composition of the present invention preferably contains the (meth) acrylate of the present invention in an amount of 3% by mass or more, particularly 5% by mass or more.

The active energy ray-curable resin composition of the present invention can function as a reaction initiation aid in a curing reaction by containing a photopolymerization initiator.

Photopolymerization initiators are roughly classified into two types according to the radical generation mechanism: a cleavage-type photopolymerization initiator that can generate radicals by cleaving and decomposing a single bond of the photopolymerization initiator itself, and a photo-excited initiator. And the hydrogen donor in the system form an excitation complex, which is roughly classified into a hydrogen abstraction type photopolymerization initiator capable of transferring the hydrogen of the hydrogen donor.

Examples of the cleavage-type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1. -On, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- [4- {4- (2-hydroxy-) 2-Methyl-propionyl) benzyl} phenyl] -2-methyl-propane-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglioxy Methyl licate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -On, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -Phenylphosphin oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphinoxide, derivatives thereof and the like can be mentioned.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and 2-benzoyl benzoyl. Methyl benzoylate, methyl benzoylate, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone , 2-Chlorothioxanthone, 3-Methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and derivatives thereof.

However, the photopolymerization initiator used in the present invention is not limited to the substances listed above. Any one of the cleavage-type photopolymerization initiator and the hydrogen-extracted photopolymerization initiator listed above may be used, or two or more of them may be used in combination.

The content of the photopolymerization initiator of the active energy ray-curable resin composition of the present invention is not particularly limited, but is 0.1 to 10% by mass, particularly 0.3 to 5% by mass, and particularly 0.5. It is preferably contained in a proportion of up to 3% by mass.
By setting the content of the photopolymerization initiator in the above range, it is possible to obtain an appropriate reaction sensitivity to active energy rays.

Other components contained in the active energy ray-curable resin composition of the present invention are not particularly limited. Other components contained in the active energy ray-curable resin composition of the present invention include, for example, inorganic or organic fine particles, polymerization initiators other than photopolymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, and the like. Examples thereof include dispersants, surfactants, light stabilizers and leveling agents.

Further, in the case of drying after film formation in the wet coating method, an arbitrary amount of solvent may be added to the active energy ray-curable resin composition of the present invention.
However, in order to widen the range of application in offices and the like, it is preferable not to use a solvent in the active energy ray-curable resin composition as much as possible from the viewpoint of the environment. When the active energy ray-curable resin composition of the present invention contains a solvent, the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1. It is by mass or less, and most preferably does not contain a solvent (intentionally does not contain it).

Since the active energy ray-curable resin composition is applied as a thin film, the viscosity at 25 ° C. is 200 mPa · s or less, preferably 100 mPa · s or less, and more preferably 50 mPa · s or less. A viscosity smaller than 25 ° C. is preferred, and by setting the viscosity to 200 mPa · s / 25 ° C. or lower, the thickness is made uniform and thin in the coating step of the active energy ray-curable resin composition which is an image-forming substance removing agent. Can be applied.

Further, since the active energy ray-curable resin composition of the present invention is applied as a thin film, the viscosity is adjusted by adding an active energy ray-curable (meth) acrylate other than the (meth) acrylate of the present invention as necessary. It is also possible to do. The active energy ray-curable (meth) acrylate is not particularly limited, and examples thereof include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and polyfunctional (meth) acrylate.

In the present invention, the method for applying the active energy ray-curable resin composition of the present invention, which is an image-forming substance removing agent, is not particularly limited, and for example, "coating method" (Yuji Harasaki, Maki Shoten, 1979). (Published in 1979), reverse roll coater, gravure coater, rod coater, air doctor coater or roll coat method, general wet coat method such as die coat method, extrusion method, etc., and other methods. A coating device can also be used.

In the present invention, the active energy ray-curable resin composition as an image-forming substance removing agent reliably transfers a toner and / or an image-forming substance containing a thermoplastic resin formed on the surface of a material to be recorded, and runs. In order to reduce the cost, it is preferable to apply it to a thin film as much as possible. The film thickness of the coating layer with the image-forming substance removing agent of the present invention is preferably 20 μm or less, more preferably 15 μm or less, and further preferably 10 μm or less as the thickness of the resin layer after curing. By setting the film thickness to 20 μm or less, not only in terms of cost, heat is generated by radical reaction during curing, and damage such as wrinkles due to shrinkage of the recorded material is minimized, and an image forming substance removing agent and an image are used. The forming substance can be removed.
On the other hand, the lower limit of the film thickness of the cured resin layer is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more.

The active energy ray-curable resin composition of the present invention, which is an image-forming substance removing agent, is irradiated with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams as necessary, and a curing reaction is carried out to carry out a curing reaction to carry out a curing reaction. Can be formed. By performing the curing reaction, the image-forming substance can be easily removed from the recorded material together with the image-forming substance removing agent.

Among the active energy rays, it is preferable to use ultraviolet rays because an inexpensive device can be used. Examples of the light source when ultraviolet rays are used include ultra-high pressure, high pressure, medium pressure or low pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps and the like. Ultraviolet rays may be irradiated for a few seconds to a few minutes.

In the present invention, for example, when the active energy ray is irradiated with ultraviolet rays, the active energy ray-curable resin composition of the present invention may cause curing inhibition due to the influence of oxygen in the air. Therefore, it is preferable to prevent oxygen (air) from being mixed into the coated surface of the active energy ray-curable resin composition as much as possible so as not to come into contact with oxygen. Further, since it is necessary to peel off the cured image-forming substance removing agent from the recorded material together with the image-forming substance formed on the recorded material, the surface of the recorded material coated with the image-forming substance removing agent is coated. It is preferable to provide the surface of the support to which the image forming substance removing agent is in close contact so as to be in close contact with the surface.

As described above, in the present invention, a laminated body is obtained by laminating and forming a coating layer made of the image-forming substance removing agent of the present invention on a recording material or an image-forming substance.

The material to be recorded is not particularly limited, but a resin film is preferable because the image-forming substance and the image-forming substance resin can be easily peeled off and removed.

The type of resin used in the resin film as the recording material is not particularly limited, but it is preferable to have a polyester resin layer containing at least polyester as a main component resin and a polymer incompatible with polyester.
Here, the "main component resin" means a resin having the highest content ratio among the resin components constituting the polyester resin layer. It can be assumed that the main component resin occupies 30% by mass or more, particularly 50% by mass or more, and 80% by mass or more (including 100% by mass) of the resin components constituting the polyester resin layer.

The polyester constituting the resin film refers to a polyester obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol, 1. , 4-Cyclohexanedimethanol and the like.

Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), polybutylene terephthalate and the like. The polyester may be a non-copolymerized homopolymer, and 20 mol% or less of the dicarboxylic acid component is a dicarboxylic acid component other than the main component, and / or 20 mol% or less of the diol component is other than the main component. It may be a copolymerized polyester which is a diol component. It may also be a mixture thereof.

Polyester can be obtained by a conventionally known method, for example, a method of directly obtaining polyester by a reaction of a dicarboxylic acid and a diol, or a method of reacting a lower alkyl ester of a dicarboxylic acid with a diol with a conventionally known transesterification catalyst, and then the presence of a polymerization catalyst. It can be obtained by a method of carrying out a polymerization reaction below. As the polymerization catalyst, known catalysts such as antimony compounds, germanium compounds, titanium compounds and aluminum compounds can be used.

By containing a polymer incompatible with polyester in the resin film, innumerable ultrafine cavities can be contained in the resin film stretched at least in the uniaxial direction. The ultrafine cavities allow the resin film to scatter light, resulting in white opacity and reducing the apparent density of the resin film. In addition, the image-forming substance containing a thermoplastic resin such as toner printed or printed on the surface of the resin film can be easily peeled off and removed.

By containing a polymer incompatible with polyester on the surface layer of the resin film, a thermoplastic resin such as toner printed or printed on the surface of the laminated white resin film when used as a recording material for copy paper or printer paper can be used. The contained image-forming substance can be easily peeled off and removed. Further, in order to ensure sufficient hiding power and weight reduction, the intermediate layer may contain a polymer incompatible with polyester, if necessary.

When the resin film has a laminated structure, the polymer incompatible with polyester may be contained in all layers of the resin film, or may be selectively contained in a specific layer. Specifically, the polymer incompatible with polyester may be contained in at least one surface layer of the resin film, or may be contained in an intermediate layer.

As the polymer incompatible with polyester, conventionally known polymers can be used, and examples thereof include polyolefins, polystyrenes, polyacrylic acids, polycarbonates and the like. Among them, polyolefins and polystyrenes are preferable, and polyolefins are particularly preferable. Further, among the polyolefins, polypropylene, polyethylene, poly-4-methylpentene-1, amorphous polyolefin and the like can be mentioned, and among them, polypropylene is preferable in consideration of the easiness of forming cavities and forming a film.

When polypropylene is used as a polymer incompatible with polyester, the content of propylene units in the polypropylene used is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. By reducing the content of the copolymer obtained by copolymerizing other than the propylene unit and using it within the above range, the formation of fine cavities can be sufficiently sufficient.

In the polyester resin layer, the content ratio of the polymer incompatible with the polyester with respect to the polyester is 1 to 70 parts by mass with respect to 100 parts by mass of the polyester. Of these, it is more preferably contained in a proportion of 2 to 50 parts by mass, particularly preferably in a proportion of 3 to 40 parts by mass, and most preferably in a proportion of 5 to 35 parts by mass.

When polypropylene is used as a polymer incompatible with polyester, the melt flow index of polypropylene under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) is usually 0.5 ml / 10 minutes or more as a lower limit. It is preferably 1 ml / 10 minutes or more, more preferably 3 ml / 10 minutes or more, and further preferably 5 ml / 10 minutes or more. When it is equal to or more than the above lower limit, a sufficient cavity size can be generated, and it is possible to easily avoid breakage during stretching. On the other hand, the upper limit is usually 50 ml / 10 minutes or less, preferably 40 ml / 10 minutes or less, more preferably 30 ml / 10 minutes or less, still more preferably 25 ml / 10 minutes or less. When it is equal to or less than the above upper limit, it is possible to prevent the clip from coming off during lateral stretching, and it is possible to maintain productivity.

The lower limit of the content of the polymer incompatible with polyester in the resin film is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 8%. It is mass% or more. By using the film above the above lower limit, the amount of fine cavities formed in the film becomes sufficient, the concealing property of the film is improved, and the effect of reducing the apparent density, that is, the weight reduction is sufficient. In addition, the slipperiness of the film and the writability of pencils and the like are improved, which is advantageous for print transportability. Further, on the surface of the film, characters and images due to an image forming substance such as printed or printed toner can be easily peeled off and removed, and the film can be repeatedly used as a recording material for copying paper or printer paper.
On the other hand, the upper limit of the content of the polymer incompatible with polyester in the resin film is usually 70% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, particularly preferably. Is 30% by mass or less, most preferably 25% by mass or less. By using it below the upper limit, the amount of cavities generated is not too large, and it tends to be easy to suppress breakage during stretching.
When the resin film has a laminated structure, the above-mentioned content may mean the average content in all layers of the resin film, or may mean the content in a specific layer. Specifically, it may mean the content in at least one surface layer of the resin film, or may mean the content in the intermediate layer.

When the resin film has three or more layers, the intermediate layer is a recycled product such as a selvage portion, a master roll ear portion, and a master roll lower winding portion generated during film production, as long as the gist of the present invention is not impaired. It may be blended. By including these recycled products, the effects of cost reduction and environmental load reduction can be achieved. The content of the recycled product in the intermediate layer is preferably 95% by mass or less, more preferably 85% by mass or less with respect to the intermediate layer from the viewpoint of film formation stability due to the decrease in ultimate viscosity, in addition to the color tone regulation. It is more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 40% by mass or less.

Further, if necessary, conventionally known inorganic or organic particles, antioxidants, heat stabilizers, lubricants, antistatic agents, fluorescent whitening agents, dyes, pigments and the like may be added to the material to be recorded. can. Further, depending on the application, an ultraviolet absorber, particularly a benzoxazinone-based ultraviolet absorber or the like may be contained.

The thickness of the resin film as the material to be recorded is not particularly limited, but it is usually about 10 to 1000 μm, which is preferable in terms of both mechanical strength and thin film property as the material to be recorded.

In the method for removing an image-forming substance of the present invention, at least characters, images, etc. made of the image-forming substance are obtained from a printed matter in which characters, images, etc. are formed by the image-forming substance on a recorded material made of the above-mentioned resin film or the like. After applying the active energy ray-curable resin composition of the present invention, which is the image-forming substance removing agent of the present invention, so as to cover the surface, the cured layer of the image-forming substance removing agent is irradiated with active energy rays such as ultraviolet rays. At the same time, the image forming substance is removed.

In the above-mentioned Patent Document 1, a thermoplastic resin is used as a cleaning material and the image-forming substance is removed by heating. However, in the case of heating, the material to be recorded is damaged, which may make it difficult to recycle. There was sex.
According to the present invention, by using the active energy ray-curable resin composition, the image-forming substance can be removed after being cured by irradiation with active energy rays such as ultraviolet rays, and the recorded material is damaged. The image-forming substance can be reliably removed, and the recorded material can be regenerated.

Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Measurement / evaluation method]
The measurement method and evaluation method used in the following Examples and Comparative Examples are as follows.

(1) Method for measuring the ultimate viscosity of polyester 1 g of polyester from which a polymer and particles incompatible with polyester have been removed is precisely weighed, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (mass ratio) is added and dissolved. , Measured at 30 ° C.

(2) Method for measuring viscosity of active energy ray-curable resin composition Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured under the conditions of a rotation speed of 1.0 rpm and 25 ° C.

(3) Method for measuring the thickness of the active energy ray-curable resin composition An active energy ray-curable resin composition is applied onto a recording material (resin film) to be described later on which a toner image is not printed, and the resin composition is applied thereto. A laminated polyester film (manufactured by Mitsubishi Chemical Co., Ltd.) having a coating layer having excellent adhesion to the active energy ray-curable resin composition on both sides of the film and measuring the thickness of the film using THICKNESS GAGE (manufactured by Mitsutoyo Co., Ltd.). Diafoil T910E50 WM19-, thickness: 50 μm) is layered, and the active energy ray-curable resin composition is uniformly spread by a roller. Was irradiated to cure the active energy ray-curable resin composition.
Next, the laminated polyester film to which the cured resin layer adhered was peeled off from the recorded material, the film thickness was measured using THICKNESS GAGE (manufactured by Mitutoyo Co., Ltd.), and the measured thickness of the laminated polyester was subtracted. It was calculated as the thickness of the active energy ray-curable resin.

(4) Evaluation method of image removability Using a color electrophotographic image forming apparatus (Ricoh imagio MC C5001it, manufactured by Ricoh Co., Ltd.) for the recording material (resin film) described later, secondary color and monochromatic solid images and character images A full color pattern with was printed.
The active energy ray-curable resin composition is applied onto the material to be recorded on which the toner image is printed.
A laminated polyester film (manufactured by Mitsubishi Chemical Co., Ltd., Diafoil T910E50 WM19-, thickness: 50 μm) having a coating layer having excellent adhesion to the active energy ray-curable resin composition is layered on the film, and the active energy is activated by a roller. The ray-curable resin composition was uniformly stretched, and the active energy ray-curable resin composition of the laminated polyester film was irradiated with ultraviolet rays from the surface side on which the active energy ray-curable resin composition was not superposed to cure the active energy ray-curable resin composition. .. Next, the laminated polyester film to which the cured resin layer was adhered was peeled off from the recorded material, and the situation where the toner image was peeled off from the recorded material was confirmed.
Observe the peeled surface, and if the toner image can be completely removed, "◎", and if the toner image remains slightly, "○" if the level is 1 to 2 mm in size and partially remains. , If the remaining toner image is slightly visible, but the rest of the toner image can be seen as a whole, "△", if the toner image cannot be clearly removed and remains, "×" did.

[Manufacturing method of recorded material (resin film)]
The recorded material (resin film) used in Examples and Comparative Examples was manufactured as follows.

<Manufacturing method of polyester (A)>
Using 100 parts by mass of dimethyl terephthalate, 60 parts by mass of ethylene glycol, 30 ppm of ethyl acid phosphate for the produced polyester, and 100 ppm of magnesium acetate / tetrahydrate for the produced polyester as a catalyst, 260 ° C. under a nitrogen atmosphere. The esterification reaction was carried out in. Subsequently, 50 ppm of tetrabutyl titanate was added to the produced polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to an absolute pressure of 0.3 kPa, and the mixture was further polycondensed for 80 minutes to obtain the ultimate viscosity. Obtained a polyester (A) of 0.63 dl / g.

<Manufacturing method of polyester (B)>
Polyester (B) was obtained by using the same method as that for producing polyester (A) except that 3.5 parts by mass of silica particles having an average particle size of 3.5 μm were added before melt polymerization.

<Manufacturing method of polyester (C)>
Polyester (C) was obtained by the same method as that for producing polyester (A) except that 50 parts by mass of titanium oxide particles having an average particle size of 0.31 μm were added before melt polymerization.

<Manufacturing method of recorded material (resin film)>
Polyester (A), (B), (C), melt flow index (230 ° C, 2.16 kg load) 7.5 ml / 10 minutes polypropylene resin (manufactured by Japan Polypropylene Corporation: FL0007) 60% by mass, 10 respectively A mixed raw material mixed at a ratio of mass%, 15% by mass, and 15% by mass was used as a raw material for the surface layer. Further, polyester (A) and polypropylene resin (manufactured by Japan Polypropylene Corporation: FL0007) of 7.5 ml / 10 minutes of melt flow index (230 ° C., 2.16 kg load) are mixed at a ratio of 80% by mass and 20% by mass, respectively. The mixed raw material was used as the raw material for the intermediate layer. After supplying each raw material to two extruders and melting at 280 ° C., co-extruding with a laminated structure of two types and three layers (thickness ratio is surface layer / intermediate layer / surface layer = 1: 8: 1). , The unstretched sheet was obtained by cooling and solidifying on a cooling roll set at 30 ° C.
Next, using the difference in roll peripheral speed, the film was stretched 3.0 times in the mechanical direction (longitudinal direction) at a film temperature of 95 ° C., then guided to a tenter and stretched 4.0 times at 120 ° C. in the width direction (horizontal direction). After heat treatment at 200 ° C., the material was relaxed by 2% in the width direction (lateral direction) to obtain a recorded material (resin film) having a thickness of 75 μm.

[Compounds for image-forming substance removers]
The compounds constituting the active energy ray-curable resin composition which is an image-forming substance removing agent are as follows.
<(Meta) acrylate>
(I): Trimethylol Propane Triacrylate (II): Polyethylene Glycol # 200 Diacrylate (III): Polyethylene Glycol # 400 Diacrylate (IV): Dipropylene Glycol Diacrylate (V): Ethylene Glycol Dimethacrylate (VI): 2-Hydroxyethyl acrylate (VII): Phenoxyethyl acrylate (VIII): 2-Hydroxy-3-phenoxypropyl acrylate (IX): 1,4-Cyclohexanedimethanol Monoacrylate (X): Ethylated dipentaerythritol hexaacrylate (X) XI): 1,6-Hexanediol diacrylate (XII): Tetrahydrofurfuryl methacrylate <photopolymerization initiator>
Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide

[Examples 1 to 11, Comparative Examples 1 to 3]
Image-forming substance removing agents 1 to 14 comprising the active energy ray-curable resin compositions having the formulations shown in Table 1 below were prepared. The prepared image-forming substance removing agents 1 to 14 (active energy ray-curable resin composition) were measured in viscosity and film thickness by the above-mentioned method, and the image removing property was evaluated, and the results are shown in Table 2. rice field.

As is clear from Table 2, the image-forming substance removing agents of Examples 1 to 11 all had good peelability of the toner image. In addition, the film thickness of the resin layer of the image-forming substance removing agent was also good at 20 μm or less.
On the other hand, in Comparative Example 1, the peelability of the toner image was relatively good, but the film thickness of the resin layer was too thick at 28 μm due to the high viscosity of the image forming substance removing agent, and the recorded material was recorded. The result was that it caused damage to.
Further, in Comparative Examples 2 and 3 using the (meth) acrylate which does not correspond to the (meth) acrylate of the present invention, the peelability of the toner image was insufficient.

When the image-forming substance removing agent of the present invention is used, an image formed by an image-forming substance formed on the surface of a resin film used as a recording material, which is an information printing medium that replaces paper such as copy paper, can be easily, reliably and beautifully obtained. It can be peeled off and removed by an excellent method in terms of cost.

Claims (5)

With one or more (meth) acrylates selected from the group consisting of hydroxyalkyl (meth) acrylates, aromatic (meth) acrylates (excluding benzyl (meth) acrylates) , and alkyl glycol (meth) acrylates. An image-forming substance removing agent, which comprises a photopolymerization initiator and comprises an active energy ray-curable resin composition having a viscosity at 25 ° C. of 200 mPa · s or less. A laminate in which the image-forming substance removing agent according to claim 1 is laminated on an image-forming substance provided on a recording material. The laminate according to claim 2, wherein the recorded material is a resin film. The laminate according to claim 3, wherein the resin film contains polyester and a polymer incompatible with polyester. A method for removing an image-forming substance and an image-forming substance from the recorded material after irradiating the laminate according to any one of claims 2 to 4 with active energy rays.