JP2002249679A - Imprinting layer forming ink and sheet with imprinting layer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an imprinting layer forming ink which is excellent in a printing ink aptitude, can print a necessary position of a substrate having no imprintability without damaging an original property of the substrate and can arrange an imprinting layer to be able to imprint and stamp-imprint, and the formed imprinting layer is not peeled off by OCR thermal head, and the like, and has an improved smoothness to control and prevent abrasion of the thermal head. SOLUTION: The imprinting layer forming ink obtained by to compounding porous fine particles to a vehicle including a radiation curing component including a urethane acrylate as an essential component is used. An ultraviolet ray curing type or an electron beam curing type is preferable as the radiation curing component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an ink for forming a marking layer with improved smoothness and a marking layer formed with the ink and having improved smoothness which can be used for stamping and stamping. It is about a sheet.

[0002]

2. Description of the Related Art In Japanese society, "seal" is performed everywhere for confirmation. On the other hand, business forms such as confidential information sheets such as folding cards, superimposing cards, and information hiding sheets, as well as various organization sheets, printing paper, copy paper, and various labels, are becoming more sophisticated.
Art paper and coated paper used in process color printing,
Also, business forms with a protective layer consisting of a laminated film or a resin overcoat on thermal paper, etc. are increasingly used, improving water resistance, rub resistance, and solvent resistance Therefore, the protective layer plays an important role.

However, business forms having a protective layer, such as pamphlets, catalogs and documents subjected to process color printing using art paper or coated paper, and receipts using thermal paper, have no stamping or stamping suitability. For example, in order to obtain a thermal paper that requires a sealability, a thermal paper that does not have a protective layer that is originally required has been used. However, there is a problem in that the thermal paper without the protective layer develops a color when rubbed with a nail or develops a color when contacted with a solvent such as acetone. For this reason, overcoat printing of OP varnish or the like is also performed except for the seal section, but the effect is inferior to that of the conventional protective layer and is insufficient. In particular, in the case of thermal paper, the thermal head rubs the surface. Therefore, in order to prevent wear of the thermal head, smoothness of the surface is strongly required.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to solve the conventional problems and to provide a protective layer on art paper, coated paper, heat-sensitive paper, or the like, which has no conventional stamping or stamping properties. Business forms that have a protective layer made of laminated paper or resin overcoated on paper (films, sheets, etc.), art paper or coated paper used in process color printing, or thermal paper. It is possible to easily form a marking layer by offset printing or the like (partial printing or spot printing) at a required predetermined location such as without impairing the original characteristics (for example, water resistance, rub resistance, solvent resistance, etc.) Is possible), and it is possible to impart stamping and stamping properties,
An object of the present invention is to provide an ink capable of forming a marking layer with improved smoothness. A second object of the present invention is to provide a sheet having a marking layer with improved smoothness formed using an ink capable of forming a marking layer with improved smoothness.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have used a vehicle containing a radiation-curable component containing a specific component as an essential component. The present inventors have found that the problem can be solved by using an ink containing fine particles, and have completed the present invention.

That is, the ink for forming a marking layer having improved smoothness according to claim 1 of the present invention is characterized in that porous fine particles are blended with a vehicle containing a radiation curing component containing urethane acrylate as an essential component. It is a feature. The ink for forming a marking layer having improved smoothness of the present invention is excellent in printing ink suitability, and can be used for offset printing or the like to form a film on art paper, coated paper, or thermal paper used in process color printing. Easy printing with improved smoothness that can be stamped or stamped by performing partial printing or spot printing on required parts such as business forms that have a protective layer consisting of laminated or resin overcoated Can be provided. Since the stamping layer is provided at a necessary position on the protective layer of the conventional substrate, the original characteristics (water resistance, rub resistance, solvent resistance, etc.) of the substrate are not impaired. The formed marking layer is excellent in mechanical suitability, does not peel off with an OCR reader or a thermal head, and has excellent surface smoothness, and can suppress or prevent abrasion of the thermal head.

According to a second aspect of the present invention, there is provided an ink for forming a marking layer having improved smoothness, wherein the radiation-curable component is an ultraviolet-curable type.

According to a third aspect of the present invention, there is provided an ink for forming a marking layer having improved smoothness, wherein the radiation-curable component is an electron beam-curable type. .

The ink for forming a marking layer having improved smoothness according to claim 4 of the present invention is the ink for forming a marking layer according to any one of claims 1 to 3, wherein 100 mass of a vehicle other than urethane acrylate is used. The composition is characterized in that urethane acrylate is blended in an amount of 0.5 to 20 parts by mass per part.

According to a fifth aspect of the present invention, there is provided an ink for forming a marking layer having improved smoothness, wherein the ink for forming a marking layer according to any one of the first to fourth aspects contains urethane acrylate as an essential component. 10 to 5 parts of porous fine particles are added to 100 parts by mass of the vehicle containing the radiation curing component.
It is characterized in that 0 parts by mass is blended.

[0011] The sheet having the marking layer according to claim 6 of the present invention is characterized in that at least one surface of the substrate has a predetermined portion on a predetermined portion.
And a stamping layer formed by using the ink for forming a stamping layer with improved smoothness according to any one of claims 5 to 9 and which can be stamped.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The ink for forming a marking layer of the present invention comprises:
It is essential to use a vehicle containing a radiation-curable component containing urethane acrylate as an essential component, and the vehicle is prepared by blending porous fine particles with the vehicle.

The radiation curing component used in the present invention is an ultraviolet ray,
The component is not particularly limited as long as it is a component that can be cured by radiation such as an electron beam, an X-ray, an i-ray, and a g-ray.

The energy of ultraviolet light used for ultraviolet curing (free radical polymerization, cationic polymerization) is 3 to 6 eV
It is necessary to add a photoinitiator or sensitizer to accelerate the photochemical reaction because it takes only a few seconds or more to complete the curing, whereas it is generally used for electron beam curing (free radical polymerization) Even if the energy of the electron beam is low, the energy of the electron beam is as large as about 150 to 300 KeV, the reaction initiation mechanism is slightly different, and the polymerization and crosslinking reactions are started simultaneously with the irradiation. Therefore, these initiators and sensitizers are added. There is no need to complete the cure in a fraction of a second or less. A mercury lamp used as an ultraviolet light source emits a certain amount of infrared light in addition to ultraviolet light, and thus generates heat during irradiation. In the case of the following electron beams, the influence of heat is hardly a problem. In the present invention, it is preferable to use one or both of them, depending on the purpose, by utilizing the above characteristics of the ultraviolet curing type and the electron beam curing type.

In the present invention, urethane acrylate is used as an essential component in order to improve the smoothness of the surface of the seal layer. Urethane acrylate is not particularly limited,
Commercially available ones can be used. Specifically, for example, a urethane acrylate having a polyoxyalkylene segment or a saturated polyester segment or both linked via a urethane bond and having an acryloyl group or a methacryloyl group at both terminals, a rosin-modified urethane acrylate, and the like can be given. . Specific examples of commercially available products include, for example, the following. Sartomer C-9500 (bifunctional, aliphatic), Sartomer C-9501 (trifunctional, aliphatic), Sartomer C-9502 (trifunctional, aliphatic), Sartomer C-9503 (bifunctional, aliphatic), Sartomer C -95
04 (bifunctional, aliphatic), Sartomer C-9505 (aliphatic), Viscort 812 (Osaka organic, Mn530
0), VISCOAT 813 (Osaka organic, Mn1200),
VISCOAT 823 (Osaka Organic, Mn1350), Aronix M-1100, Toa Gosei, Aronix M-1
200, Toa Gosei, NK ester U-108-A (Shin Nakamura, bifunctional), NK ester U-4HA (Shin Nakamura, 4
XP-4200B (Nihon Gosei, IPDI base), XP-7000B (Nihon Gosei, IPDI base), XP-2700B (Nihon Gosei, TDI base),
XP-3000B (Nihon Gosei, IPDI base), XP
-2000B (Nihon Gosei, TDI base), XP-10
(Nihon Gosei, polyether type), Ebercryl series (Daicel UCB), UAS-10 (Sanyo Kokusaku pulp), Art Resin UN-1100 (Negami Industry, polyester type), Art Resin UN-5200
(Negami Industry, polyester type), Art Resin UN-6
060 (Negami Industry, aromatic), Art Resin UN-90
00 (Negami Industry, Polyester type), Art Resin UN-1255 (Negami Industry, Polyester type), Art Resin UN-2500 (Negami Industry, Polyester type),
Art resin UN-1255TM (Negami Industry, polyester type, urethane methacrylate), art resin SH
-380G (Negami Industry, alicyclic, trifunctional, urethane methacrylate), Art Resin SH-500 (Negami Industry,
Aliphatic, bifunctional, urethane methacrylate), art resin SH-9832 (Negami Kogyo, alicyclic, bifunctional, urethane methacrylate), polyester type) and the like.

Although the amount of the urethane acrylate is not particularly limited, it is preferable to add 0.5 to 20 parts by mass of urethane acrylate to 100 parts by mass of a vehicle other than urethane acrylate, and more preferably 2 to 15 parts by mass. It is particularly preferable to add 3 to 8 parts by mass. If the amount is less than 0.5 part by mass, the smoothness may not be improved. On the other hand, if the amount exceeds 20 parts by mass, the ink viscosity may increase and the printability may deteriorate.

The radiation-curing component other than urethane acrylate used in the present invention can be arbitrarily selected from known photopolymerizable monomers and / or photopolymerizable oligomers. Such photopolymerizable monomers include, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof, for example, alkyl-, cycloalkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl- , Tetrahydrofurfuryl-, allyl-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate,
Alkylene glycol, polyoxyalkylene glycol mono- or diacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, such as acrylamide, methacrylamide or derivatives thereof, for example, mono-substituted with an alkyl group or a hydroxyalkyl group Or allyl compounds such as disubstituted acrylamide and methacrylamide, diacetone acrylamide and methacrylamide, N, N'-alkylenebisacrylamide and methacrylamide, and maleic compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate and triallyl isocyanurate. Acid, maleic anhydride, fumaric acid or its ester such as alkyl, halogenated alcohol Kill and mono- or dimaleate and fumarates alkoxyalkyl, other unsaturated compounds, such as styrene, vinyltoluene, divinylbenzene, N- vinylcarbazole, etc. N- vinylpyrrolidone is used.

In the case of an application in which curing shrinkage is a problem, for example, isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or Such as methacrylate, acrylate or methacrylate of diethylene glycol dicyclopentenyl monoether, acrylate or methacrylate of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether, such as dicyclopentenyl cinnamate, dicyclopentenoxy 3,9-bis (1,1) such as ethyl cinnamate, dicyclopentenoxyethyl monofumarate or difumarate.
-Bismethyl-2-oxyethyl) -spiro [5,5]
Undecane, 3,9-bis (1,1-bismethyl-2-
(Oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) Mono-, diacrylate or mono-, such as -2,4,8,10-tetraoxaspiro [5,5] undecane, dimethacrylate, or mono-, ethylene- or propylene oxide addition polymers of these spiroglycols; Diacrylate, or mono-, dimethacrylate, or methyl ether of the above-mentioned monoacrylate or methacrylate, 1-azabicyclo [2,2,2] -3-octenyl acrylate or methacrylate, bicyclo [2,2,1] -5 Dicyclopentane such as heptene-2,3-dicarboxyl monoallyl ester Enyl acrylate or methacrylate, it can be used a photopolymerizable monomer, such as dicyclopentadienyl oxyethyl acrylate or methacrylate, dihydrodicyclopentadienyl acrylate or methacrylate. These photopolymerizable monomers may be used alone or in combination of two or more.

Examples of the photopolymerizable oligomer include acrylates of epoxy resins, such as diglycidyl ether diacrylate of bisphenol A, reaction products of epoxy resins with acrylic acid and methyltetrahydrophthalic anhydride, and epoxy resins with 2-hydroxy Epoxy resin prepolymers such as reaction products with ethyl acrylate, reaction products of diglycidyl ether of epoxy resin with diallylamine, ring-opening copolymers of glycidyl diacrylate with phthalic anhydride, and methacrylic acid dimers Unsaturated polyester prepolymers such as esters of phenols and polyols, polyesters obtained from acrylic acid, phthalic anhydride and propylene oxide, and reaction products of polyethylene glycol, maleic anhydride and glycidyl methacrylate A reaction product of polyvinyl alcohol and N-methylolacrylamide, a polyvinyl alcohol-based prepolymer such as one obtained by esterifying polyvinyl alcohol with succinic anhydride and then adding glycidyl methacrylate, and pyromellitic dianhydride. A polyamide prepolymer such as a prepolymer obtained by reacting a diallyl ester product with p, p'-diaminodiphenyl, a reaction product of an ethylene-maleic anhydride copolymer with allylamine, methyl vinyl ether-maleic anhydride Examples thereof include a reaction product of an acid copolymer and 2-hydroxyethyl acrylate, and a polyacrylic acid or maleic acid copolymer prepolymer such as a product obtained by further reacting glycidyl methacrylate with the reaction product. These photopolymerizable oligomers suitably have a weight average molecular weight in the range of about 2,000 to 30,000.

The ink for forming a marking layer of the present invention usually comprises
A photopolymerization initiator is added, and such a photopolymerization initiator includes a pyrolytic radical polymerization initiator such as a peroxide or an azo compound that decomposes by heat to generate a radical [for example, benzoyl peroxide, Azobisisobutyronitrile,
Redox catalysts that increase the rate of radical generation by adding cumene hydroperoxide, tertiary butyl hydroperoxide, persulfate (potassium salt, ammonium salt), and a reducing agent, etc.], as well as benzoin and benzoin, for example. Ethyl ether, benzoin-n
-Propyl ether, benzoin-isopropyl ether, benzoin alkyl ethers such as benzoin isobutyl-ether, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, benzyl, diacetyl, diphenylsulfide, eosine, thionin,
9,10-anthraquinone, 2-ethyl-9,10-anthraquinone and the like. These photopolymerization initiators may be used alone or in combination of two or more. The content is usually preferably selected in the range of 5 to 15 parts by mass per 100 parts by mass of the radiation-curable component.

The porous fine particles used in the present invention can be either inorganic porous fine particles, organic porous fine particles, or any organic fine particles as long as they can impart printing or stamping properties to the above-mentioned substrate. A mixture of both may be used and is not particularly limited. Among them, inorganic porous fine particles can be preferably used.

Specific examples of the inorganic porous fine particles include, for example, silica fine particles such as Mizukasil P-526 and P-526.
801, P-527, P-603, P832, P-7
3, P-78A, P-78F, P-87, P-705,
P-707, P-707D (manufactured by Mizusawa Chemical), Nips
il E200, E220, SS-10F, SS-15
F, SS-50 (manufactured by Nippon Silica Industry Co., Ltd.), SYLYSI
For fine particles of calcium carbonate such as A730, 310 (manufactured by Fuji Silysia Chemical Ltd.), Brilliant-15, B
illiant-S15, Unibur-70, P
Z, PX, Tunex E, Vigot-10, Vigo
to-15, Unifant-15FR, Brilli
ant-1500, Homocal D, Gerton 50 (manufactured by Shiraishi Industry Co., Ltd.), and the like.
(Made by Shiraishi Industries Co., Ltd.)
-41G, AL-41, AL-42, AL-43, AL
-44, AL-41E, AL-42E, AL-M41,
AL-M42, AL-M43, AL-M44, AL-S
43, AM-21, AM-22, AM-25, AM-2
7 (manufactured by Sumitomo Chemical Co., Ltd.), aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd.), and titanium dioxide fine particles include titanium dioxide T805 and P25 (manufactured by Nippon Aerosil Co., Ltd.). These may be used alone or 2
It may be used in combination of more than one kind.

The amount of the porous fine particles used in the present invention is not particularly limited, but preferably, 10 parts of the porous fine particles are added to 100 parts by mass of a vehicle containing a radiation curing component containing urethane acrylate as an essential component. ~ 5
It is desirable to add 0 parts by mass, more preferably 30 to 40 parts by mass. If the amount is less than 10 parts by mass, there is a possibility that the stamping and stamping properties cannot be improved. If the amount is more than 50 parts by mass, the viscosity is increased and the suitability for printing ink may be reduced.

The ink for forming a marking layer of the present invention may further contain, if desired, commonly used additives such as a reactive diluent, a tackifier, a viscosity modifier, an antioxidant, an ultraviolet absorber, A stabilizer, a colorant, a lubricant, a sensitizer, and the like can be contained.

The printing method of the ink is most preferably performed by using an offset printing machine. At least one surface of the base material is coated by a coating means such as a gravure coater, flexo coater, air knife coater or bar coater. To form a sheet having a marking layer.

The substrate used in the present invention may be a stamp or a stamp.
It is a substrate without sealability, for example, if there is no penetration,
Or use less art paper or coated paper and a protective layer
Glued paper (film, sheet, etc.), process color mark
Printed brochures, catalogs and documents, and protection
Business forms with layers
You. In addition, the amount of ink applied to the substrate surface is particularly limited.
No, for example, 0.5 to 30 g / m^Two , Preferably 3 to
20g / m^Two And more preferably 5 to 15 g / m. ^Two Toss
You.

FIG. 1 is an explanatory view illustrating an embodiment of the sheet of the present invention. In FIG. 1, the sheet 1 of the present invention
Has a marking layer 3 formed at a predetermined location on the upper surface of a base material 2 such as thermal paper having a protective layer on the upper surface using the marking layer forming ink of the present invention.

FIG. 2 is an explanatory view showing another embodiment of the sheet having the marking layer of the present invention. The marking layer 3 is formed at a predetermined position on the upper surface of the sheet 1 of the present invention. The left end has an adhesive layer 4 that can be re-attached / removed via an anti-soak layer 6.

FIG. 3 is a perspective view showing an application example of the sheet 1 shown in FIG.
Are formed, and a plurality of sheets 1 having characters 7 and entry columns 8 printed using printing ink on the upper surface are laminated.

FIG. 4 shows the message memo IV-IV shown in FIG.
It is sectional drawing of a line. A plurality of sheets 1 having a stamping layer 3 on the upper surface and an adhesive layer 4 which can be re-attached and re-peelable on the left end of the lower surface via an anti-soak layer 6 are sequentially laminated. It is integrated on the mount 9. The sheet 1 can be used for applications such as turning over and peeling off one sheet at a time, and attaching it to another adherend.

[0031]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples. (Example 1) Polyethylene glycol diacrylate <trade name: ARONIX M-260 (manufactured by Toa Gosei Chemical Co., Ltd.)> 92 parts by mass and a photopolymerization initiator <trade name: VISCU>
RE55 (manufactured by Akzo Nobel)> 8 parts by mass. The urethane acrylate <trade name: EB>
2002 (manufactured by Daicel UPC)> 3 parts by mass. In this solution, synthetic silica fine particles <trade name: Nip
25 parts by mass of sil E-200 (manufactured by Nippon Silica Industry Co., Ltd.). Furthermore, after adding 0.1 parts by mass of methylhydroquinone (stabilizer) as an additive, the mixture was kneaded using a three-roll mill to prepare a printing layer forming ink of the present invention with improved smoothness. Next, the obtained ink for forming a marking layer having improved smoothness according to the present invention is obtained by using a resin relief printing plate and having a thermal paper having an overcoat layer (thermal paper 130).
LAB-1 (manufactured by Ricoh Co., Ltd.)> Was subjected to dry offset printing (cured with a high-pressure mercury lamp) to 1.5 g / m ² to evaluate printability and to provide a book having a printing layer with improved smoothness. A sheet of the invention was made. With respect to the printing layer of the obtained sheet of the present invention, printing properties, machine suitability and smoothness were evaluated by the following evaluation methods. Table 1 shows the evaluation results.
Shown in

(Evaluation Method of Sealing Property) Sealing is performed on the printing part of the marking layer by using a seal (trade name: Shachihata X stamper). After leaving for 5 seconds after the seal, the surface of the seal is wiped off with Kimwipe Wiper S-200 (trade name, manufactured by Crecia). At this time, "◎"
A slightly flowing thing was evaluated as "O", an imprint flowing but readable was evaluated as "Δ", and an imprint flowing and completely unreadable was evaluated as "x".

(Evaluation method for mechanical aptitude) A cellophane tape is stuck to the printing portion of the marking layer, and is closely adhered with a 2 kg roller having a width of 50 mm. After leaving for 1 minute, slowly remove the cellophane tape. At this time, the seal layer printed portion was not peeled off by the cellophane tape at all, "○", slightly peeled off "△", almost peeled off "x",
Was evaluated.

(Smoothness Evaluation Method) The measurement was carried out according to a method according to the JIS Beck-type smoothness measurement method (JIS P8119-1976 “Smoothness test method for paper and paperboard using a Beck tester”).

Example 2 Example 1 was repeated except that the urethane acrylate used in Example 1 was changed to 1.5 parts by mass.
The sheet of the present invention was prepared in the same manner as described above, and the printability, mechanical suitability and smoothness of the print layer were evaluated. Table 1 shows the evaluation results.
Shown in

(Example 3) A sheet of the present invention was prepared in the same manner as in Example 1 except that the urethane acrylate used in Example 1 was changed to 6 parts by mass, and the printability, mechanical suitability and smoothness of the print layer were obtained. The degree was evaluated. Table 1 shows the evaluation results.

Example 4 The procedure of Example 1 was repeated, except that the urethane acrylate used in Example 1 was changed to rosin-modified urethane acrylate (trade name: Beam Set 102 (manufactured by Arakawa Chemical Industries, Ltd.)). The sheet of the invention was prepared, and the printability, mechanical suitability and smoothness of the print layer were evaluated. Table 1 shows the evaluation results.

Example 5 A sheet of the present invention was prepared in the same manner as in Example 1 except that the synthetic silica fine particles used in Example 1 were changed to alumina fine particles (trade name: aluminum oxide C, manufactured by Nippon Aerosil Co., Ltd.). To make the marking layer
Machine suitability and smoothness were evaluated. Table 1 shows the evaluation results.

Example 6 Polyethylene glycol diacrylate used in Example 1 was replaced with trimethylolpropane triacrylate (trade name: ARONIX M-309)
(Manufactured by Toa Gosei Chemical Co., Ltd.)> A sheet of the present invention was prepared in the same manner as in Example 1 except that the printing properties, mechanical suitability and smoothness of the printing layer were evaluated. Table 1 shows the evaluation results.

(Comparative Example 1) Thermal paper having an overcoat layer used in Example 1 <thermal paper 130LAB-
1 (manufactured by Ricoh Co., Ltd.)> Was used without providing a printing layer, and the printing performance, machine suitability, and smoothness were evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 2 A sheet for comparison was prepared in the same manner as in Example 1 except that urethane acrylate was not used, and the printability, mechanical suitability and smoothness of the print layer were evaluated. . Table 1 shows the evaluation results.

Comparative Example 3 76 parts by mass of a rosin-modified phenolic resin varnish and 14 parts by mass of linseed oil varnish were mixed.
7 parts by mass of wood wax (baltimic acid glyceride) and 3 parts by mass of a dryer were mixed. To the obtained varnish, 35 parts by mass of synthetic silica fine particles (trade name: Nipsil AZ-200 (manufactured by Nippon Silica Industry Co., Ltd.)) were added, and a three-roll mill was used to prepare an ink for forming a marking layer for comparison. .
The obtained ink was subjected to dry offset printing to ² g / m ² on a thermal paper <Thermal Paper 130LAB-1 (manufactured by Ricoh Company)> having an overcoat layer using a resin letterpress, and a sheet for comparison was used. made. The printability, mechanical suitability and smoothness of the print layer were evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

(Comparative Example 4) Rosin-modified maleic acid (trade name: Tespol 11) was added to 93 parts by mass of diethylene glycol.
52 (manufactured by Hitachi Chemical Co., Ltd.)> 7 parts by mass are dissolved. To 100 parts by mass of the obtained liquid, 40 parts by mass of synthetic silica fine particles (trade name: Nipsil SS-50 (manufactured by Nippon Silica Industry Co., Ltd.)) are kneaded. Further, 5 parts by mass of glycerin as a roll transferability improver was added to the kneaded product and kneaded using a three-roll mill to prepare a printing layer forming ink for comparison. Next, the obtained ink was applied to a thermal paper (thermal paper 130LAB-1 (manufactured by Ricoh)) having an overcoat layer at 3 g / m 2 using a resin relief printing plate.
By performing dry offset printing so as to obtain No. ² , a sheet having a marking layer was prepared. The printing layer of the obtained sheet was evaluated for printability, machine suitability and smoothness in the same manner as in Example 1. Table 1 shows the evaluation results.

[0044]

[Table 1]

The inks for forming a marking layer of Examples 1 to 6 have excellent printability and Table 1 shows that they have excellent printability, mechanical suitability and smoothness. On the other hand, in the case of Comparative Example 1 in which a thermal paper having an overcoat layer was used without providing a printing layer, the mechanical suitability and smoothness were good, but the printing performance was poor, and in the case of Comparative Example 2, the printing performance was poor. And good mechanical suitability but poor smoothness. In the case of Comparative Example 3,
It can be seen that the printability, mechanical suitability, and mechanical suitability were poor, and in the case of Comparative Example 4, the printability, mechanical suitability, and smoothness were all poor.

[0046]

The ink for forming a marking layer according to the first aspect of the present invention has excellent suitability for printing inks, and can be used in places where a substrate having no conventional printing or stamping properties is required by dry offset printing or the like. It is possible to easily provide a stamping layer that can be stamped or stamped by performing partial printing or spot printing without impairing the original properties of the base material (water resistance, rub resistance, solvent resistance, etc.) The formed marking layer is
Excellent in stamping, stamping and machine suitability,
In addition to the effect of not being peeled off by an OCR reader or a thermal head, it has a remarkable effect of suppressing or preventing abrasion of the thermal head due to its excellent surface smoothness.

The ink for forming a marking layer having improved smoothness according to the second aspect of the present invention is easily irradiated with ultraviolet light because the radiation-curable component is an ultraviolet-curing type in the ink for forming a marking layer according to the first aspect. It has a remarkable effect that it can be hardened.

The ink for forming a marking layer having improved smoothness according to the third aspect of the present invention is the same as the ink for forming a marking layer according to the first aspect, since the radiation-curable component is an electron beam-curable type. There is no remarkable effect that no curing agent or sensitizer is required, and even if it is thick, it can be easily cured by electron beam irradiation.

The ink for forming a marking layer having improved smoothness according to claim 4 of the present invention is the same as the ink for forming a marking layer according to any one of claims 1 to 3, except that 100 parts by mass of a vehicle other than urethane acrylate. Since 0.5 to 20 parts by mass of urethane acrylate is blended with respect to the parts, a remarkable effect that the surface smoothness can be improved within a range that does not impair the suitability for printing ink is exerted.

According to a fifth aspect of the present invention, there is provided an ink for forming a marking layer having improved smoothness, wherein the ink for forming a marking layer according to any one of the first to fourth aspects contains urethane acrylate as an essential component. 10 to 5 parts of porous fine particles are added to 100 parts by mass of the vehicle containing the radiation curing component.
The addition of 0 parts by mass has a remarkable effect that the printability, stamp pressability and mechanical suitability can be improved within a range that does not impair the print ink suitability.

According to the sixth aspect of the present invention, there is provided a sheet having a marking layer according to any one of the first to fifth aspects of the present invention, on a predetermined portion of at least one surface of the substrate. Since it has a stamping layer that can be stamped and stamped using ink for stamping,
It is excellent in mechanical suitability and surface smoothness, does not peel off with an OCR reader or a thermal head, and has a remarkable effect of suppressing or preventing abrasion of the thermal head.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an embodiment of a sheet having a marking layer of the present invention.

FIG. 2 is an explanatory view illustrating one application example of the sheet having the marking layer of the present invention shown in FIG.

FIG. 3 is an explanatory view showing another application example of a sheet having a marking layer of the present invention.

FIG. 4 is an explanatory sectional view taken along line IV-IV of the sheet having the marking layer of the present invention in FIG. 3;

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 sheet having stamping layer of the present invention 2 substrate 3 stamping layer 4 adhesive layer 7 characters 8 entry field 9 mount

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AB24 AB37 AB72 AB73 BA01 CA01 CA07 DA04 4J038 FA281 HA216 HA286 HA446 KA03 KA08 PA17 PC10 4J039 AD03 AD06 AD09 AD10 AD12 AD13 AD23 AE04 BA21 BE27 EA06 EA08 GA07

Claims (6)

[Claims] 1. An ink for forming a marking layer, wherein porous fine particles are blended with a vehicle containing a radiation curing component containing urethane acrylate as an essential component. 2. The ink for forming a marking layer according to claim 1, wherein the radiation-curable component is an ultraviolet-curable type. 3. The ink for forming a marking layer according to claim 1, wherein the radiation-curable component is an electron beam-curable type. 4. Vehicle 1 other than urethane acrylate
0.5 to 2 parts by mass of urethane acrylate per 100 parts by mass
The ink for forming a marking layer according to any one of claims 1 to 3, wherein the ink is blended in an amount of 0 parts by mass. 5. The method according to claim 1, wherein 10 to 50 parts by mass of porous fine particles are blended with 100 parts by mass of a vehicle containing a radiation curing component containing urethane acrylate as an essential component. An ink for forming a marking layer as described in Crab. 6. A stamping layer formed by using the stamping layer forming ink according to any one of claims 1 to 5 and having a stamping layer which can be stamped on at least a predetermined portion of at least one surface of the substrate. A sheet comprising: