JP2008138082A - Ink composition for scratch sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a scratch sheet enabling sufficient formation of a coating film even in active energy ray printing, having coagulation in the scratched off slag (waste) when it is scratched off, and being not deposited on the clothes and hands/legs. <P>SOLUTION: In the scratch sheet having confidential information data, a resin layer and a peelable hiding layer on a base material in this order, the resin layer and the peelable hiding layer are the active energy ray-curing type layer. Further, in the scratch sheet, a reactive urethane oligomer is contained in the peelable hiding layer as a binder. Further, in the scratch sheet, a glass transition point of a cured film of the reactive urethane oligomer used for the peelable hiding layer is -60 to 10°C. Further, in the scratch sheet, 5 to 30% of the reactive urethane oligomer used for the peelable hiding layer is contained in the ink composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a scratch sheet in which confidential information data such as lottery tickets and game cards are concealed by a peelable concealment layer. More specifically, the peelable concealment layer of the scratch sheet is scratched off (scratched) with a coin or the like. The present invention relates to a peelable concealing ink composition for scratch sheets that recognizes confidential information data.

  Conventionally, for example, in an instant lottery ticket or a game card, in order to conceal confidential information data such as “winning”, “out of” or a picture corresponding thereto, it has a concealing property and a scratch property. Scratch prints are known and used in various fields where a layer is concealed and a purchased customer uses a coin or the like to scratch off and visually recognizes confidential information data when used.

  As described above, a printed material with a scratch concealing layer, on which a confidential information data such as a pattern, characters, or numbers is printed on a substrate such as paper, and a resin such as a transparent peeling varnish covering the confidential information data A layer is formed, and a scratch concealment layer is applied on the resin layer.

  Customers who purchase this scratch print can scratch the scratch concealment layer with a coin or nail, etc., and visually confirm confidential information data such as “hits”, “peel”, etc. It is like that.

  As a method for realizing such a scratch card, a method is disclosed in which concealment information is formed by offset printing or letterpress printing, and a peelable concealment layer is formed by a screen printing method or a gravure printing method (for example, Patent Documents). 1).

  Further, the scratch concealment layer used for concealing confidential information is made of an aluminum for concealing and scratching an ink binder mainly composed of a rubber-based resin (for example, SBR) in order to retain a certain amount of stickiness. It is a thermosetting or solvent-type ink composition to which powder is added.

  Since the scratch concealment layer is a concealment function for confidential information data, it is completely opaque in silver or gray. (Note: There is no difference in density on the printed surface or white missing parts, and it is completely covered with printing ink. The ink is formed to have a thickness of about 4 to 10 μm, and as the ink, for example, 15 to 25 parts by weight of an aluminum powder, 15 to 25 parts by weight of a pigment including an extender pigment such as alumina powder, aggregability 15 to 25 parts by weight of a synthetic rubber resin such as SBR or NBR, and further 35 to 45 parts by weight of an aromatic hydrocarbon solvent such as toluene, xylene or methyl isobutyl ketone and 5 to 15 parts by weight of an auxiliary agent such as an antifoaming agent. For example, because of a scratch concealing layer having a thickness of about 4 to 10 μm and cohesiveness by screen printing using this ink. Even when printed on top of this, the defect that the scratches (scraps) scratched off by coins, nails or the like are aggregated and adhered to clothes or hands can be avoided (Patent Document 1).

  However, since aromatic hydrocarbon solvents such as toluene are used in the scratch ink that forms the scratch concealing layer, facilities and management systems that comply with the Fire Service Act and regulations are not required. There is provided a scratch concealment layer formed of a water-based emulsion ink mainly composed of a metal paste that can be in-lined and a polyurethane or acrylic synthetic resin (Patent Document 2).

  In addition, confidential information data and a transparent easy peeling layer to cover the confidential information data in a predetermined area on the substrate and a scratch concealing layer for concealing the confidential information data are applied thereon, and a white ink layer is applied thereon. When the scratch-off is performed by applying a transparent and cohesive scratch medium layer on the print layer on the white ink layer, a printed matter is provided in which scratch-off wrinkles (dust) do not adhere to clothes and limbs. There is a method (Patent Document 3).

When the scratch concealing layer is made of an active energy ray curable composition, the coating film is tough, so the flexibility of the coating film is poor, the cohesive failure is poor due to scratch-off (scratching off), and the scratch concealing layer is made into UV. What was not done was the actual situation.
Japanese Patent Laid-Open No. 04-220399 JP 2002-187388 A JP 2004-17561 A

  The object of the present invention is that the active energy ray curable film generally has a tough film, so that scratches that are scratched off when the film is scratched off adhere to clothes and limbs. An object of the present invention is to provide an ink composition for a scratch sheet that solves the above problem.

An object of the present invention is to provide an ink composition having an active energy ray-curable scratch concealing layer excellent in cohesive failure, and a printed matter thereof.
That is, the present invention includes that the reactive urethane oligomer is contained in the binder in the ink used for the peelable hiding layer in the scratch sheet having the confidential information data, the resin layer, and the peel hiding layer in order on the substrate. The present invention relates to an active energy ray-curable ink composition for scratch sheets.

  In addition, the present invention relates to the above-described ink composition for a scratch sheet, wherein a glass transition point of a cured film of a reactive urethane oligomer used for a release masking layer is −60 ° C. to 10 ° C.

  Furthermore, the present invention relates to the above-mentioned ink composition for a scratch sheet, wherein the reactive urethane oligomer used for the release concealing layer is contained in an amount of 5 to 30% or more in the ink composition.

  The present invention also relates to a scratch sheet using the above-described scratch sheet ink.

  According to the present invention, a good paint film can be formed even in active energy ray printing, and scratches that are scratched off when scratched off are cohesive and do not adhere to clothes or limbs. It became possible to provide.

  The active energy rays used in the present invention are ultraviolet rays and electron beams, but are not necessarily limited thereto.

The composition of the active energy ray-curable resin layer used in the present invention is a monomer or oligomer having an ethylenically unsaturated double bond 60 to 90% by weight
Radical polymerizable initiator 5-15% by weight
1-10% by weight of other additives
Etc. are mentioned as preferred compositions.

The composition of the active energy ray-curable peelable hiding layer used in the present invention is 5 to 30% by weight of a reactive urethane oligomer.
Oligomer or non-reactive resin having an ethylenically unsaturated double bond excluding reactive oligomer 0 to 25% by weight
Monomer having ethylenically unsaturated double bond 15 to 65% by weight
Pigment, metal paste 1-10% by weight
Radical polymerizable initiator 5-15% by weight
1-10% by weight of other additives
Etc. are mentioned as preferred compositions.

  In the present invention, the monomer means monofunctional or polyfunctional (meth) acrylates, and the resin layer is used in the range of 15 to 65% by weight.

  Monofunctional monomers include alkyl (having 2 to 18 carbon atoms) (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl ( Examples thereof include benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate.

  Polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth) acrylate (commonly called manda), Hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, bisphenol A tetraethylene oxide Adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (meth) acrylate , Water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolprop N-tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethylolbutanetetra ( (Meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipen Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, can be used tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, a tripentaerythritol octa (meth) acrylate.

  Furthermore, there is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound as the acrylic monomer of the present invention. Examples of the alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound include mono- or poly (1-20) alkylene (C2 to C20) oxide adducts (alkylene oxide) of an aliphatic alcohol compound. Carbon number as a monofunctional monomer 2-20 alkylene oxide adduct (meth) acrylate, such as methanol mono- or poly (1-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) Examples include acrylate, ethanol mono or poly (1-20) alkylene (C2 to C20) oxide adducts, etc. Further, ethylene glycol mono or poly (1-20) alkylene (C2 to C) as a bifunctional monomer. 20) Oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, diethylene glycol mono- or poly (2-20) alkylene (C2 to C20) oxide adducts, etc. Glycerin poly (2-20) alkylene (C2 to C20) oxide adduct (trialkylene, for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) alkylene as trifunctional monomer Examples include (C2 to C20) oxide adducts, but are not limited thereto.

  The poly (2-20) used in the present invention has a polymerization degree of an alkylene (C2 to C20) oxide adduct.

  Examples of initiators used in the present invention include hydrogen abstraction type initiators such as benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4- Aryl ketone initiators such as benzoyl-4′-methyl-diphenyl sulfide, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, 2,4 dichlorothioxanthone, acetophenone, 4,4′-bis ( Dialkylaminoaryl ketone initiators such as diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone Thioxanthone, polycyclic carbonyl-based initiators such xanthone of and halogen-substituted system is illustrated. Further, as a photocleavable initiator, benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylobenzoin, benzyl, Irgacure 907 (2-methyl-2-morpholino (4-thiol produced by Ciba Specialty Chemicals) Methylphenyl) propan-1-one), Irgacure 369 (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone manufactured by Ciba Specialty Chemicals), Irgacure 651 (Benzylmethyl manufactured by Ciba Specialty Chemicals) Ketal), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone made by Ciba Specialty Chemicals), Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropane-1 made by Merck) ON), Darocur 1116 (Merck 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one), 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, ZLI3331 (4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone, diethoxyacetophenone, Esacure KIP100 (manufactured by Ramberty) manufactured by Ciba Specialty Chemicals, Lucyrin TPO (manufactured by BASF) BTTB (manufactured by NOF Corporation), CGI1700 (manufactured by Ciba Specialty Chemicals, etc.).

  Moreover, a photoinitiator auxiliary agent can also be used in combination with a photoinitiator. As the photoinitiator aid, tertiary amines which are hydrogen donors are used. Specifically, aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Aromatic amines such as isoamyl acid can be mentioned, and triethanolamine, methyldiethanolamine, dibutylethanolamine, triisopropanolamine, and 4,4′-diethylaminobenzophenone are preferable.

  The photopolymerization initiator is contained in the composition in an amount of 0.1% to 30%, preferably 5 to 15%.

  The reactive urethane oligomer used in the present invention has an ethylenically unsaturated double bond.

  The reactive urethane oligomer used in the present invention preferably has a molecular weight Mw of 5000 or more.

  The glass transition point of the cured film of the reactive urethane oligomer is preferably −60 to 10 ° C., more preferably −40 to 0 ° C., and further preferably −30 to −5 ° C.

  The glass transition point is measured by raising the temperature of the test piece from room temperature at a rate of 10 ° C./min, measuring the amount of thermal expansion in the heat direction with a thermal analyzer, and tangent the curves before and after the glass transition point. Measurement is performed by the TMA method for obtaining Tg from the intersection of the tangent lines.

  The reactive urethane oligomer is preferably used at 5 to 30% in the ink composition, more preferably 10 to 20%. In the case of 5% or less, the effect on the cohesive force is not exhibited. On the other hand, if it exceeds 30%, the ink shape becomes difficult to remove, and the drying of the ink film becomes worse.

  Any oligomer or non-reactive resin having an ethylenically unsaturated double bond, excluding reactive urethane oligomers, can be used in the present invention.

  Examples of the oligomer other than the reactive urethane oligomer include alkyd acrylate and epoxy acrylate.

  Non-reactive resins include, for example, polyvinyl chloride, poly (meth) acrylic acid ester, epoxy resin, polyurethane resin, cellulose derivatives (for example, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer. And synthetic rubbers such as polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, and butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof. In either case, a resin that is soluble in a monomer having an ethylenically unsaturated double bond is used.

  The oligomer or non-reactive resin having an ethylenically unsaturated double bond is preferably used in the range of 0 to 25% by weight in the ink.

The metal paste may be bronze powder, which is an alloy of copper and zinc, as the metal of the metal paste. However, aluminum powder is generally used due to cost and the like. An aluminum paste having a surface treated with a high boiling point hydrocarbon solvent (mineral spirit or the like) is used.
This includes pigments for yellow, red, indigo, or black used for general inks, and extender pigments such as titanium white.

  The pigment and the metal paste are used in the range of 1 to 20% by weight during the composition.

  As additives, for example, plant wax such as carnauba and wax, animal wax such as whale wax and lanolin, mineral wax such as montan, paraffin, Petroleum wax such as microcrystalline (natural wax), synthetic hydrocarbon wax such as sazol and polyethylene, silicone additive such as silicone oil, hydrogenated wax such as hardened castor oil, amide wax such as fatty acid amide, etc. Ketones, amines, imides, ester compounds, and polytetrafluoroethylene (synthetic wax) can be used.

The active energy ray-curable release layer varnish used in the present invention is a monomer or oligomer having an ethylenically unsaturated double bond 60 to 90% by weight
Radical polymerizable initiator 5-15% by weight
1-10% by weight of other additives
Is an active energy ray-curable coating varnish containing.

  EXAMPLES The present invention will be specifically described as examples, but the present invention is not limited to the following examples. Hereinafter, the numbers in the table indicate% by weight.

  Active energy ray-curable concealing layers were prepared according to the following formulations (Table 1: Examples 1 to 5, Table 2: Comparative Examples 1 to 5).

ここで反応性ウレタンオリゴマー１としては、紫光ＵＶ−３０００Ｂ（ガラス転移点−５２℃、分子量18000、日本合成化学工業製）、反応性ウレタンオリゴマー２としては、ＣＮ−９６５（ガラス転移点が−３７℃、分子量6000、サートマー社製）、反応性ウレタンオリゴマー３としては、紫光ＵＶ６１００Ｂ（ガラス転移点が０℃分子量6700、日本合成化学工業製）。ここで非反応性樹脂としてはエポキシ樹脂であり、エチレン性不飽和二重結合を有するモノマーとして トリメチロールプロパンテトラエチレンオキサイド付加トリアクリレート、アルミペーストとして旭化成製１３Ｈ、光開裂型開始剤として１−ヒドロキシシクロヘキシルフェニルケトンを使用する。

Here, as the reactive urethane oligomer 1, purple light UV-3000B (glass transition point -52 ° C., molecular weight 18000, manufactured by Nippon Synthetic Chemical Industry), and as the reactive urethane oligomer 2, CN-965 (glass transition point is −37). As a reactive urethane oligomer 3, purple light UV6100B (glass transition point is 0 ° C. molecular weight 6700, manufactured by Nippon Synthetic Chemical Industry). Here, the non-reactive resin is an epoxy resin, trimethylolpropane tetraethylene oxide-added triacrylate as a monomer having an ethylenically unsaturated double bond, Asahi Kasei 13H as an aluminum paste, and 1-hydroxy as a photocleavable initiator. Cyclohexyl phenyl ketone is used.

ここで、反応性ウレタンオリゴマー４としては、紫光ＵＶ−７０００Ｂ（ガラス転移点５２℃、分子量3500、日本合成化学工業製）、反応性ウレタンオリゴマー５としては紫光ＵＶ−３５１０ＴＬ（ガラス転移点３８℃、分子量21000、日本合成化学工業製 ）。非反応性樹脂としては、※１はエポキシ樹脂、※２はジアリルフタレート樹脂であり、エチレン性不飽和二重結合を有するモノマーとしてトリメチロールプロパンテトラエチレンオキサイド付加トリアクリレート、アルミペーストとして旭化成製１３Ｈ、光開裂型開始剤として１−ヒドロキシシクロヘキシルフェニルケトンを使用する。

Here, as the reactive urethane oligomer 4, purple light UV-7000B (glass transition point 52 ° C., molecular weight 3,500, manufactured by Nippon Synthetic Chemical Industry), and as the reactive urethane oligomer 5, purple light UV-3510TL (glass transition point 38 ° C., Molecular weight 21000, manufactured by Nippon Synthetic Chemical Industry). As the non-reactive resin, * 1 is an epoxy resin, * 2 is a diallyl phthalate resin, trimethylolpropanetetraethylene oxide-added triacrylate as a monomer having an ethylenically unsaturated double bond, 13H manufactured by Asahi Kasei as an aluminum paste, 1-Hydroxycyclohexyl phenyl ketone is used as a photocleavable initiator.

  As the peelable masking varnish, the oligomer is 10% urethane acrylate, the monomer is 75% trimethylolpropane tetraethylene oxide-added triacrylate, the initiator is 14% 1-hydroxycyclohexyl phenyl ketone, and the additive is silicone. Use 1% acrylate.

  Hokuetsu Maricoat (Hokuetsu Paper Co., Ltd.) is coated with a peelable concealing layer with a bar coater and cured. Further, the active energy ray curable type shown in Examples 1 to 5 and Comparative Examples 1 to 5 The concealing layer ink was applied by a bar coater, and was cured by being placed on a conveyor at 30 m / min for 10 cm under one metal halide lamp having an intensity of 160 W / cm.

  Each of the obtained printed materials was scraped with a coin, and the cohesive force of scratched scraps was observed.

[Evaluation]
5: There is cohesion.

                4: Although there is a cohesive force, some shavings adhere to the hand.

                3: Although there is a cohesive force, about half of the shavings adhere.

                2: A lot of shavings adhere and there are some cohesive forces.

                1: Most shavings and no cohesive force.

本発明の活性エネルギー線硬化型隠蔽荘層インキは、実施例のようにスクラッチ時の屑の凝集性に優れたスクラッチシートの提供が可能である。

The active energy ray-curable cover-up layer ink of the present invention can provide a scratch sheet that is excellent in scrap cohesion during scratching, as in the examples.

Claims (4)

  An active energy ray characterized by containing a reactive urethane oligomer in a binder in an ink used for a peelable hiding layer in a scratch sheet having a confidential information data, a resin layer, and a peeling hiding layer in order on a substrate. A curable ink composition for a scratch sheet.   The ink composition for a scratch sheet according to claim 1, wherein a glass transition point of a cured film of the reactive urethane oligomer used for the release masking layer is -60 ° C to 10 ° C.   The ink composition for a scratch sheet according to claim 1 or 2, wherein the reactive urethane oligomer used in the release concealing layer contains 5 to 30% or more of the ink composition. A scratch sheet using the scratch sheet ink according to claim 1.