JP3408907B2 - Printed material with transparent coating layer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed matter provided with a transparent coating layer that protects a printing ink film that constitutes visible information, and particularly to a printed matter that is adjacent to other printed matter and is stored under pressure for a long time. The present invention also relates to a printed matter with a transparent coating layer, which does not adhere to the other printed matter even when the printed matter is present, and thus both printed matter can be peeled off without damaging the surface thereof.

[0002]

2. Description of the Related Art In a printed matter in which a printing ink film is formed on a base material sheet such as paper, in order to protect the printing ink film from scratches and contamination, or for another reason, the printing surface containing the printing ink film is A printing technique in which substantially the entire surface is covered with a transparent coating layer is known.

Such a printing technique is used, for example, on the cover of a book. The cover of a book is generally exposed to the outside air and is often damaged or contaminated. Therefore, a transparent coating layer is provided on the surface of the cover to protect the cover.

The above printing technique is also used for printed matter such as maps and pamphlets. In these printed materials, the transparent coating layer has the purpose of not only protecting the printed surface from scratches and contamination, but also improving the glossiness of the printed surface and imparting a high-class feeling to the printed pattern.

As the transparent coating layer, generally, a soft polyvinyl chloride film or a polypropylene film which is inexpensive, has high transparency, and has a mirror-like surface and high gloss is used.
A transparent coating layer is formed by adhering the printed surface with an adhesive.

[0006]

By the way, the printing ink film in the above-mentioned printed matter generally constitutes visible information (for example, characters, symbols, etc.) that can be recognized as a concept-driven type. In such printed matter, its value depends exclusively on the visible information, and since the decorative effect of its structure and shape is of little value, by accumulating and storing these printed matters, Often saves storage space. For example, in books and the like, it is routinely stored in bookshelves or the like. Then, when accumulating and storing with other printed matter in this way, the printed matter is placed adjacent to the other printed matter (for example, another book), and its printing surfaces are pressed for a long period of time. It is stored (for example, for a year or more).

In such a case, the transparent coating layer may adhere to the other printed matter adjacent thereto due to the pressure, and it may be difficult to separate the two.

For example, when a soft polyvinyl chloride film is used as the transparent coating layer, the plasticizer contained in a large amount in this soft polyvinyl chloride film oozes to the surface with the passage of time, and the adjacent plasticizer The printed ink film applied to the surface of other printed matter is affected, and as a result, both printed matter adhere to each other in an indistinguishable manner. Then, if it is forcibly peeled off, the printing ink film on the surface of the other printed matter is peeled from the base sheet of the other printed matter, or the surface layer of the base sheet is destroyed and a part of the printed matter is printed. Transferred to the transparent coating layer side together with the ink film. As a result, the surface of both of the above-mentioned printed matters is damaged.

Further, the polypropylene film has a smaller plasticizer content as compared with the soft polyvinyl chloride film, and therefore the amount of the plasticizer leached out with time is also suppressed. However, even when a polypropylene film is used as the transparent coating layer, the printing ink film of other printed matter that is pressure-bonded to the polypropylene film contains a residual solvent, a plasticizer, and other organic low molecular weight substances. It is usually that, when stored for a long period of time adjacent to the other printed matter and under pressure, the solvent or organic low molecular weight substance oozes out from the printing ink film, affects the polypropylene film, and , Swell, and as a result, both are firmly fixed. And
If it is forcibly peeled off, the printing ink film on the surface of the other printed matter or the surface layer of the substrate sheet is transferred to the transparent coating layer side. As a result, as in the case where the soft polyvinyl chloride film is used as the transparent coating layer, both of the above-mentioned printed matters are damaged on the surface thereof.

The present invention has been made on the basis of such a technical background, and its object is to prevent scratching and contamination of a printing ink film on the surface of a printed matter, and
Even when the printed matter and the other printed matter are stored adjacent to each other for a long period of time in a state where their surfaces are pressed against each other, the printed matter and the other printed matter do not adhere to each other, and the surfaces of both printed matter are An object of the present invention is to provide a printed matter that can be easily separated from each other without damaging them.

[0011]

[Means for Solving the Problems] That is, the invention according to claim 1 is a base sheet, and printing that constitutes visual information that is provided on at least a part of the base sheet and is capable of concept-driven recognition. In a printed matter comprising an ink film and a transparent coating layer provided by covering a printing surface containing the printing ink film, the transparent coating layer contains a fluorine element.
The constitutional units and the other constitutional units are connected alternately with each other.
It is characterized in that it is a coating film containing a fluororesin using the alternating copolymer .

In the invention according to claim 1, the transparent coating layer for coating the printing surface including the printing ink film contains a fluorine-based resin, and even if an aqueous solvent such as water adheres to the surface, the fluorine-containing resin is used. The system resin repels the aqueous solvent to prevent contamination. For example, even if the ink of a fountain pen or the ink of a water-based pen adheres, the contamination can be almost completely removed by gently wiping it with a dry cloth.

Further, since the above-mentioned fluorine-based resin is difficult to be compatible with an oily solvent, it is possible to effectively reduce the adhesion of fingerprints or the like and the contamination by oily printing ink or the like.

Since the above-mentioned fluororesin is not easily compatible with organic low molecular weight substances such as plasticizers, even when this fluororesin is placed adjacent to other printed matter and stored under pressure, the other printed matter It is difficult for the residual solvent contained in the printing ink film on the surface to be exuded from the residual solvent, plasticizer, etc., and swelling deterioration of the transparent coating layer due to the exuded component is unlikely to occur. Therefore, the close contact between the printed matter according to the present invention and another printed matter is effectively suppressed. For this reason, the printed matter according to the present invention and the other printed matter are adjacent to each other, and
Even when stored for one year or for a long period of time in a state where the surfaces are pressed against each other, both the printed matter according to the present invention and the other printed matter arranged adjacent to the printed matter are It is possible to easily separate the two printed materials while maintaining a beautiful printed state without damaging the surface and the visible information.

As the fluorine-based resin according to claim 1, for example, a solvent-insoluble fluorine-based resin such as polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyhexafluoropropylene resin, polyperfluoroalkoxy resin is used. it can. When these solvent-insoluble fluororesins are used, these fluororesins must be pulverized into fine particles, dispersed in a solvent, and applied. In this case, the transparent coating layer obtained by drying and removing the solvent component is one in which the fine particle fluorine-based resins are arranged in close contact with each other. Then, the transparent coating layer formed by arranging the fine particle fluorine-based resin in such a manner is adjacent to another printed matter, and if it is stored for a long period of time under pressure, the printing ink film on the surface of the other printed matter is removed. The leaching component such as residual solvent or plasticizer that oozes into the gap between the fine-particle fluororesin and the fine-particle fluororesin, and the printing ink film of the other printed matter is placed on the transparent coating layer side at the gap. There is a risk of transfer. Although such a fine and slight transfer does not damage the pattern of the printed matter as a whole, there is a risk of impairing the high-grade feeling of the printed pattern of the printed matter and degrading the print quality.

In order to avoid such a danger, the above-mentioned fluorine-based resin is solvent-soluble in the coating and film-forming process, and after the coating, it is crosslinked to secure the resistance to the solvent and the organic low molecular weight substance. It is desirable to apply the above.

The invention according to claim 2 is based on such a technical reason. That is, the invention according to claim 2 is based on the invention according to claim 1, wherein the transparent coating layer is formed by applying a coating solution containing a solvent-soluble fluororesin and then crosslinking the fluororesin. It is characterized by being obtained.

According to the second aspect of the invention, since the transparent coating layer is formed by applying a coating liquid containing a solvent-soluble fluororesin, the printed surface of the printed matter including the printing ink film is formed. It is possible to coat continuously with a transparent coating layer containing a fluororesin without gaps. Further, the fluorine-based resin contained in the continuous transparent coating layer contains a fluorine element and is cross-linked, and has a strong resistance to an organic low molecular weight substance such as an aqueous solvent, an oily solvent and a plasticizer. Therefore, even when it is stored for a long period of time in a state of being adjacent to other printed matter and under pressure, the residual solvent or organic low-molecular-weight substance contained in the printing ink film of the other printed matter remains on the transparent coating layer. Without sticking to
In addition, there is no risk of transfer of the printing ink film in the gap portion, which is a concern when using the fine particle fluorine resin.

For this reason, both prints are placed adjacent to each other and pressed while maintaining high quality and high print quality of both prints and without damaging the visible information formed by the printing ink film. In this state, for example, it can be stored for a long time in a bookshelf or the like.

The solvent-soluble and crosslinkable fluororesin according to claim 2 is, for example, a constitutional unit containing elemental fluorine, a constitutional unit ensuring solvent solubility, and a chemical bond to a crosslinking agent. A copolymer of three types of structural units having a substituent that can be formed can be used.

Here, as the constitutional unit containing elemental fluorine, for example, one represented by the following chemical formula (Formula 1) can be used.

[0022]

[Chemical 1]

(However, X is H, F, Cl, or CF
Shown are substituents selected from ₃ )

Specifically, for example, the following chemical formula (Formula 2)
Is a structural unit represented by.

[0025]

[Chemical 2]

As the constituent unit for ensuring the solvent solubility, there can be exemplified one constituted by binding a solvent-affinitive side chain to a main chain containing no fluorine element. Examples of such a side chain include an alkyl group and an alkoxy group. Further, the structural unit having such a side chain is, for example, a structural unit represented by the following chemical formula (Formula 3).

[0027]

[Chemical 3]

(However, R ₁ represents an alkyl group)

Specifically, for example, the following chemical formula (Formula 4)
It is a structural unit shown in.

[0030]

[Chemical 4]

Further, as the above-mentioned constitutional unit for ensuring solvent solubility, a constitutional unit represented by the following chemical formula (Formula 5) can be used. For example, it is a structural unit represented by the following chemical formulas (formula 6) to (formula 10).

[0032]

[Chemical 5]

(However, R ₂ and R ₃ represent an alkyl group)

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

Next, examples of the substituent capable of forming a chemical bond to the crosslinking agent include an OH group and a COOH group, and these substituents can form a chemical bond with the NCO group. And 2 or more of the above NCs as a crosslinking agent
By using a polyfunctional isocyanate compound having an O group, it is possible to crosslink the above substituents with each other.

Examples of the constitutional unit having an OH group include those represented by the following chemical formula (Formula 11).

[0041]

[Chemical 11]

As the above structural unit having an OH group, it is also possible to use one represented by the following chemical formula (Formula 12). Specific examples of such a constitutional unit include those represented by the chemical formula (Formula 13).

[0043]

[Chemical 12]

(However, R ₄ represents an alkylene group)

[0045]

[Chemical 13]

Next, examples of the above-mentioned structural unit having a COOH group include those represented by the following chemical formula (Formula 14).

[0047]

[Chemical 14]

Further, as the above-mentioned constitutional unit having a COOH group, it is also possible to use one represented by the following chemical formula (Formula 15). Specific examples of such a constitutional unit include those represented by the chemical formula (Formula 16).

[0049]

[Chemical 15]

(However, R ₅ represents an alkylene group)

[0051]

[Chemical 16]

The constituent unit containing the elemental fluorine preferably accounts for 20 mol% or more of the solvent-soluble fluororesin before crosslinking. This is because if the number of constituent units containing elemental fluorine is less than this, the resistance to the oily solvent becomes insufficient, and the printing ink film of another printed material stored adjacently and under pressure tends to be transferred.

The invention according to claim 3 is based on such a technical reason. That is, the invention according to claim 3 is based on the invention according to claim 2, wherein the solvent-soluble fluorine-based resin comprises a structural unit containing a fluorine element, a structural unit ensuring solvent solubility, and a cross-linking structure. It is composed of a copolymer of three kinds of constitutional units having a substituent capable of forming a chemical bond to the agent, and the constitutional unit containing the above-mentioned elemental fluorine is 20 mol% or more of the solvent-soluble fluorine-based resin. It is characterized by occupying.

According to the third aspect of the present invention, the solvent-soluble fluorine-based resin comprises a structural unit containing a fluorine element, a structural unit that ensures solvent solubility, and a chemical agent for the crosslinking agent. It is composed of a copolymer of three types of structural units having a substituent capable of forming a bond, and the structural unit containing the above-mentioned elemental fluorine occupies 20 mol% or more of the solvent-soluble fluorine-based resin, It is possible to form a continuous transparent coating layer having no gaps by being dissolved in the solvent, and this continuous transparent coating layer has sufficient oil-based solvent resistance to suppress the transfer of the printing ink film of other printed matter. Therefore, even when the printed matter is stored adjacent to the other printed matter and in a state of being pressed against each other for a long period of time, the printed surface of the both printed matter is prevented from being damaged and the printing quality is kept high. It becomes possible.

As the above-mentioned copolymerized fluororesin, a random copolymer in which the constituent units constituting the same are bonded to each other in an arbitrary order can be used, but preferably, a constituent containing a fluorine element is used. It is preferable to use an alternating copolymer in which units and other structural units are alternately bonded to each other.

Next, a polyfunctional isocyanate compound such as a diisocyanate compound or a triisocyanate compound can be preferably used as a cross-linking agent that bonds with a structural unit having a hydrophilic group which constitutes the above copolymerized fluororesin,
The respective isocyanate groups of these polyfunctional isocyanate compounds are bonded to the above-mentioned hydrophilic groups of the fluororesin to crosslink the fluororesins, thereby increasing the resistance to the oily solvent.

Examples of such polyfunctional isocyanate compounds include 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, trans vinylene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 2- Chloro-1,4-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 3,
3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-
Diphenyl diisocyanate, triphenylmethane triisocyanate, etc. can be used.

The polyfunctional isocyanate compound may be used by mixing in an equivalent ratio of 0.3 or more with respect to the hydrophilic group. It is preferably 0.5 or more.

It is also possible to mix and use the polyfunctional isocyanate compound in an equivalent ratio of 1.0 or more with respect to the hydrophilic group. In this case, the crosslinking agent becomes excessive, but when the base material sheet has a hydrophilic group, the hydrophilic group and the isocyanate group of the base material sheet chemically bond to improve the adhesion between the two. For example, the equivalent ratio to the hydrophilic group is 1.0 to 1.5.

Since the hydrophilic group and the isocyanate group react with each other at room temperature over time, it is desirable that the fluororesin and the crosslinking agent are mixed and then immediately applied on the printing ink film. For example, within 2 days. Then, after coating, by heating and drying to remove the solvent,
A crosslinking reaction occurs promptly with this heating.

Next, the coating film according to the present invention may contain only the above-mentioned fluororesin as a resin component, but other resin components may be mixed in addition to this fluororesin. . As such a resin component, for example, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, styrene-maleic acid copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, Examples thereof include epoxy resin, alkyd resin, polyurethane resin, nitrocellulose resin, ethyl cellulose resin, ethyl hydroxycellose resin, coumarone-indene resin, petroleum resin and the like.

Next, as a solvent that can be used for preparing the coating material for forming the transparent coating layer according to the present invention, for example, a ketone solvent, an ester solvent, an aromatic solvent, an alicyclic solvent, a petroleum solvent can be used. Examples thereof include solvents. For example, methyl ethyl ketone, methyl isobutyl ketone, toluene,
Examples include xylene, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, cyclohexanone (anone), methylcyclohexanone and the like. And these solvents are selected according to the coating method of the transparent coating layer.

It is also possible to mix other additives in the transparent coating layer. That is, for example, a matting agent that adjusts the gloss of the transparent coating layer. Since the light transmittance of the transparent coating layer may be lowered by mixing the matting agent, it is desirable to use fine powder having an average particle diameter of 0.5 μm or less in order to prevent the light transmittance from being lowered. . More preferably, the average particle size is 0.2 μm or less.

Examples of such matting agents include fine powders of silica, calcium carbonate, barium sulfate and the like.

It is also possible to mix a leveling agent as the above additive. A surfactant is preferably applied as such a leveling agent, and for example, a metal salt of naphthenic acid, a partial fatty acid ester of polyacrylic acid, an alkylamino fatty acid, an alkyldiamine, an alkyltriamine and the like can be used.

Further, a thickener can be mixed as the above additive. Examples of such a thickener include aluminum chelate, aluminum alcoholate, organic bentonite, polyethylene oxide, long-chain aminoamide, polycarboxylic acid alkylamine and the like.

Further, in order to improve the light resistance or weather resistance of the printing ink film coated with the transparent coating layer, an ultraviolet absorber may be mixed as the above additive.
And, by mixing this ultraviolet absorber, ultraviolet rays are blocked without substantially affecting the transparency in the visible region,
The chemical stability of the printing ink film can be improved, and the printing quality can be stabilized for a long period of time. Examples of such an ultraviolet absorber include 2- (5-methyl-2-
Hydroxyphenyl) benzotriazole, 2- [2-
Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
t-octylphenyl) benzotriazole and the like can be used.

As a coating method for forming the transparent coating layer, for example, a coating method such as roll coating or curtain flow coating can be used.
Various methods generally known as printing methods can be used. For example, a silk screen printing method, a gravure printing method, an offset printing method, a relief printing method, a gravure offset printing method, and the like.

Next, in the printed matter according to the present invention, a printing ink film of another printed matter may be arranged adjacent to the transparent coating layer and pressed against each other. It can be expected that a printing ink film of another printed matter is adhered to the opposite side of the surface provided with.

In preparation for such a case, in order to prevent both or a part of the printing ink film of the other printed matter from being transferred during storage for a long period of time to damage these both printed matters, A transparent coating layer can be provided on both sides.

The invention according to claim 4 has been made in preparation for such a case. That is, the invention according to claim 4 is based on the invention according to claims 1 to 3, and is characterized in that the transparent coating layer is provided on both front and back surfaces.

According to the invention of claim 4, for example, the ink is stored in a bookcase or the like, the printing ink film of another printed material is adjacent to both front and back surfaces thereof, and is pressed for one year or more. Even when stored for a long period of time as described above, the transfer of the printing ink film of the other printed matter to the transparent coating layer is suppressed, and any of these printed matter is not damaged, It is possible to maintain high print quality.

The transparent coating layer can be applied to both sides of the base sheet, not only when it has printing ink coatings on both sides but also when it has printing ink coatings on only one side. In this case, it is possible to prevent the base sheet from being damaged during long-term storage.

Next, as the substrate sheet according to the present invention,
Any sheet type can be used, but among them, paper containing pulp as a main component, plastic film containing a synthetic resin as a main component, or a synthetic resin as a main component to improve its printing ink acceptance Synthetic paper or the like can be preferably used.

As the paper containing pulp as a main component, for example, waste paper, medium-quality paper, high-quality paper, etc. can be used. When these papers are used, a part of them is applied when the transparent coating layer is applied. Infiltration or entanglement with the pulp in the paper, solidified in such an impregnated or entangled state, cross-linked, or because the cross-linking agent and pulp chemically bond to each other to form a cross-linked structure, this transparent release layer It is possible to stably protect the surface of the printing ink film for an extremely long period of time without peeling from the paper.

The invention according to claim 5 has been made under such circumstances. That is, the invention according to claim 5 is based on the invention according to claims 1 to 4, and is characterized in that a paper containing pulp as a main component is used as a base material sheet.

Next, the invention according to claim 6 limits the base material sheet to synthetic paper. That is, the invention according to claim 6 is based on the invention according to claims 1 to 4, and is characterized in that synthetic paper is used as a base sheet.

As the synthetic paper according to claim 6, for example,
It is possible to use a non-porous plastic film having a printing ink receptivity improved by coating an ink receptive coating on one or both sides and forming a coating film. As such a plastic film, for example, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyester film, etc. can be exemplified, and as the above-mentioned paint, one containing a matting agent can be used.
As the matting agent, silica, calcium carbonate, barium sulfate or the like can be used.

In addition to the above, as the above-mentioned synthetic paper, a plastic film is foamed to provide a large number of fine holes, and the ink having improved printing ink receptivity by the fine holes is mixed with a solvent-soluble fine powder. The above-mentioned fine powder of the formed plastic film is dissolved and removed with a solvent, and the fine powder existing portion thus removed is made into fine pores, and the fine ink improves the ink acceptability of the printing ink, or a fine powder is mixed. The plastic film thus formed is stretched, and a fine crack is generated between the fine powder and the plastic by this stretching, and a printing ink receptivity improved by the fine crack can be applied.

When the base sheet according to the present invention is provided with a coating layer in which a clayey material is dispersed in a synthetic resin binder on the surface thereof, regardless of the main component of the base sheet, It can be preferably used.

The invention according to claim 7 is made on the basis of the reason as described above. That is, the invention according to claim 7 is based on the invention according to claims 1 to 6, and is used as a base sheet. It is characterized in that a coating layer in which a clay-like material is dispersed in a synthetic resin binder is provided on one side or both sides.

Further, according to the invention of claim 7, since the base material sheet has the coating layer in which the clay material is dispersed in the synthetic resin binder, the fluorine-based resin is applied to the clay coating layer. It becomes possible to form a strong and continuous film by spreading moderately and spreading uniformly over the entire surface.

Examples of such a clay-like material include talc, clay, kaolin, etc., and synthetic resin binders include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinyl acetate,
Various synthetic resins such as vinyl chloride-vinyl acetate copolymer can be used. When polyolefin is used as the synthetic resin binder, it is desirable that the polyolefin on the surface of the coating layer be subjected to an oxidation treatment to increase the adhesion to the transparent coating layer. As the oxidation treatment, corona discharge treatment, flame treatment, ozone treatment and the like can be used. And
A hydrophilic group is generated in the polyolefin on the coating layer surface by this oxidation treatment, and the hydrophilic group and the crosslinking agent are crosslinked, or
The base sheet and the transparent coating layer are firmly adhered to each other by being entangled with the fluororesin. The surface of the coating layer is preferably flat.

The coating layer need only be provided on the surface side on which the transparent coating layer is formed, and need not necessarily be provided on both surfaces of the base sheet.

Next, as a printing ink film according to the present invention, a printing ink film known in the art can be applied. For example,
Printing ink film by silk screen printing, printing ink film by offset printing, printing ink film by letterpress printing, printing ink film by gravure printing, printing ink film by gravure offset printing, etc., not limited to one color, multi-color printing ink It may be a printing ink film having a multi-layered structure which is overprinted with.

The printing ink film need not be provided on the entire surface of the base material sheet, and may be provided on a part of the printing ink film in a shape forming visible information that can be recognized as a concept-driven type. Here, the concept-driven perceptible visual information means that the above information is perceived based on the existing knowledge of a visual information observer, and the visual information that relies solely on stimulus-driven perception (for example, wood grain Unlike decorative patterns such as patterns, etc., the shape of the printing ink film has a meaning and can recognize this meaning, and mainly means letters and symbols (for example, telephone and mail). Symbols, symbols used in weather charts that mean clear or rainy weather, symbols indicating copyright or trademark rights, railway symbols and contour lines used in maps, photographs of celebrities such as entertainers, etc.), or buildings These are various symbols and lines used for floor plans, and usually embody the value of the printed matter.

When the printing ink film constituting the concept-driven type recognizable visible information is provided on a part of the base material sheet, the transparent coating layer is the same as the printing ink film. Contact the base sheet at a nonexistent site,
The pulp contained in the base sheet, the surface of the synthetic resin having a porous structure, or the coating layer is brought into contact with and firmly fixed to these. Further, at the site where the printing ink film is present, the printing ink film is brought into contact with and firmly fixed.

Next, the printed matter according to the present invention can be applied to a single-printed matter such as a single-printed map or poster, and can also be used as a cover of a book.

When applied to a poster or the like that is stuck outdoors and used, it is possible to reduce the damage to the printing surface caused by wind and rain and to protect it for a long period of time.

In addition, even when it is used indoors for a long period of time, or when it is used for a single-printing map or the like that is repeatedly stuck and used, the damage on the printing surface is reduced. It is possible to protect the print quality for a long period of time.

Further, even when it is used as the cover of a book or the like, it is possible to protect the print quality for a long period of time when carrying the book or the like.

When applied to any printed matter, these printed matters are adjacent to other printed matter, and
Even when they are stored for a long period of time while their printing surfaces are pressed against each other (for example, when they are stored in a bookcase etc.), the printing ink film of the other printed matter adjacent to each other does not transfer, Thus, it is possible to keep the printing surfaces of both printed matters beautifully and to keep the printing quality high.

[0093]

DETAILED DESCRIPTION OF THE INVENTION

[First Embodiment] As shown in the cross-sectional explanatory view of FIG. 1 and the plan explanatory view of FIG. 2, the printed material according to the first embodiment is a base sheet 1 having a coating layer 12, and A printing ink film 2 provided on one side and having a map for education as visible information, a transparent coating layer 3 provided by covering the printing ink film 2, and a surface provided with the printing ink film 2 The main part of the transparent coating layer 4 is provided on the surface opposite to the transparent coating layer 4.

Each of the transparent coating layers 3 and 4 is formed of a coating which is continuously provided without a gap, and the main component thereof is a crosslinked fluorine resin.

The printed matter was manufactured by the following method. That is, first, a substrate sheet 1 having a coating layer 12 formed by mixing clay with a polyethylene resin binder on one surface of a non-porous polyethylene film 11 was prepared.

Then, a part of the surface of the coating layer is subjected to offset printing by TSP super-light-resistant ink manufactured by Toyo Ink Mfg. Co., Ltd. The ink film is provided so as to overlap each other at a predetermined position) to form a printing ink film 2. In addition, this printing ink film 2
Has the shape of the map as visible information.

Next, as the fluorine-based resin, a resin represented by the following structural formula (Formula 17) was used, and this was dissolved in anone to prepare a fluorine-based resin solution. The concentration is 50% by weight.

[0098]

[Chemical 17]

Next, using this fluororesin solution, a coating solution having the following composition was prepared. (Coating liquid composition) 100 parts by weight of the above fluororesin solution Cross-linking agent (hexamethylene diisocyanate) 5 parts by weight Matting agent (silica powder having an average particle size of 0.1 to 0.5 μm) 6 parts by weight Leveling agent (nonionic interface) Activator) 1 part by weight Solvent (toluene) 30 parts by weight

Immediately after preparing this coating solution,
By the silk screen method, the printing ink film 2 surface was coated and applied on substantially the entire surface of the substrate sheet, and the solvent in the coating solution was removed by heating and cross-linked to form the transparent coating layer 3.

Following this, the above coating liquid is applied to substantially the entire surface opposite to the surface provided with the printing ink film,
The transparent coating layer 4 was formed by heating to remove the solvent and crosslinking.

The thus-produced printed matter had a matte surface and could be well adhered to a wall or the like indoors or outdoors to recognize the meaning of the printing ink film. Further, since it is matte, the map information can be clearly recognized from any position regardless of the position of the light source.

Next, on the transparent coating layer 3 of the printed matter, the printing ink surface of the other printed matter of the gravure printing was overlaid, a pressure of 500 g / cm ² P was applied, and 80% R.I. H. , 6
Both prints were peeled off after being stored for 72 hours under the condition of 0 ° C. When the printed surfaces of these two printed materials were observed with the naked eye, no damage could be found on the printed surfaces of both printed materials, and no slight stain was found.

Second Embodiment The printing ink film 2 was formed on the base material sheet 1 in the same manner as in the second embodiment. Next, the above-mentioned fluororesin solution was used to prepare a coating solution having the following composition.

[0105]   (Composition of coating liquid)   100 parts by weight of the above fluororesin solution   Crosslinking agent (hexamethylene diisocyanate) 5 parts by weight   Matting agent (silica powder having an average particle size of 0.1 to 0.5 μm) 20 parts by weight   Leveling agent (nonionic surfactant) 7 parts by weight   Solvent (toluene) 210 parts by weight

Immediately after preparing this coating solution,
By the gravure printing method, the surface of the printing ink film 2 was coated and applied to almost the entire surface of the substrate sheet, and the solvent in the coating liquid was removed by heating and cross-linked to form the transparent coating layer 3.

Following this, the above coating solution is applied to substantially the entire surface opposite to the surface provided with the printing ink film,
The transparent coating layer 4 was formed by heating to remove the solvent and crosslinking.

The thus-produced printed matter had a matte surface, and was able to be well adhered to a wall or the like indoors or outdoors to recognize the meaning of the composition of the printing ink film. Further, since it is matte, the map information can be clearly recognized from any position regardless of the position of the light source.

Next, on the transparent coating layer 3 of the printed matter, the printing ink surface of another printed matter of the gravure printing was superposed, and a pressure of 500 g / cm ² P was applied to the transparent coating layer 3 to obtain 80% R.P. H. , 6
Both prints were peeled off after being stored for 72 hours under the condition of 0 ° C. When the printed surfaces of these two printed materials were observed with the naked eye, no damage could be found on the printed surfaces of both printed materials, and no slight stain was found.

[0110]

According to the inventions according to claims 1 to 7, the transparent coating layer formed by coating the printing surface including the printing ink film forming the visible information capable of concept-driven recognition is a fluorine-containing material. Since it is a coating film containing a system resin, it is difficult to be compatible with both an aqueous solvent and an oily solvent, and contamination by these solvents can be effectively reduced.

Further, since the above-mentioned fluororesin is hard to be compatible with organic low molecular weight substances such as plasticizers, the printed matter and other printed matter are adjacent to each other, and the surfaces are pressed against each other for one year or Even when stored for a longer period of time, it is possible to easily separate the two printed materials while maintaining a beautiful printed state without damaging the surface and visible information of both printed materials. Has the effect of becoming.

The transparent coating layer is obtained by applying a coating solution containing a solvent-soluble fluororesin and then crosslinking the fluororesin.

According to the inventions of claims 2 to 7,
Since the transparent coating layer is formed by applying a coating solution containing a solvent-soluble fluororesin, a transparent coating containing a fluororesin continuously on the printed surface including a printing ink film of a printed matter and without a gap. It can be coated with a layer, and even when it is stored for a long time in a state of being adjacent to other printed matter and under pressure, the printing ink film of the above-mentioned printing ink film in the gap portion which is worried when using the fine particle fluororesin is used. There is no risk of metastasis.

For this reason, both prints are placed adjacent to each other and pressed while maintaining high quality and high print quality of both prints and without damaging the visible information constituting the printing ink film. In this state, for example, in a bookcase or the like, there is an effect that it can be stored for a long period of time.

[Brief description of drawings]

FIG. 1 is an explanatory cross-sectional view of a printed material according to a first embodiment of the present invention.

FIG. 2 is an explanatory plan view of a printed matter according to the first embodiment of the present invention.

[Explanation of symbols]

1 Base sheet 11 Polyethylene film 12 Coated layer 2 Printing ink film 3 Transparent coating layer 4 Transparent coating layer

Claims (7)

(57) [Claims] 1. A base material sheet, a printing ink film which is provided on at least a part of the base material sheet, and which constitutes visible information that can be recognized as a concept-driven type, and a printing surface including the printing ink film. In a printed matter having a transparent coating layer provided as above, the transparent coating layer contains a fluorine element.
And other constituent units are alternately connected to each other
A printed material with a transparent coating layer, which is a coating film containing a fluorine-based resin using the above alternating copolymer . 2. The transparent coating layer is obtained by applying a coating solution containing a solvent-soluble fluororesin and then crosslinking the fluororesin. Printed matter with a transparent coating layer. 3. The solvent-soluble fluororesin comprises a structural unit containing elemental fluorine, a structural unit that ensures solvent solubility, and a structural unit having a substituent capable of forming a chemical bond with a crosslinking agent. 3. The transparent coating according to claim 2, which is composed of a copolymer of three types of constitutional units, wherein the constitutional unit containing the fluorine element occupies 20 mol% or more of the solvent-soluble fluororesin. Printed material with layers. 4. The printed material with a transparent coating layer according to claim 1, wherein the transparent coating layer is provided on both front and back surfaces. 5. The printed material with a transparent coating layer according to claim 1, wherein a paper containing pulp as a main component is used as the base sheet. 6. The printed material with a transparent coating layer according to claim 1, wherein synthetic paper is used as the base sheet. 7. The printed material with a transparent coating layer according to claim 1, wherein a clayey coating layer is provided on one or both sides of the substrate sheet.