JPH0439367A - Near infrared photo-setting ink - Google Patents
Near infrared photo-setting inkInfo
- Publication number
- JPH0439367A JPH0439367A JP2146741A JP14674190A JPH0439367A JP H0439367 A JPH0439367 A JP H0439367A JP 2146741 A JP2146741 A JP 2146741A JP 14674190 A JP14674190 A JP 14674190A JP H0439367 A JPH0439367 A JP H0439367A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- printing
- near infrared
- infrared light
- infrared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 27
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000003505 polymerization initiator Substances 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 37
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000000123 paper Substances 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000003981 vehicle Substances 0.000 description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- -1 benzoin alkyl ethers Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000003854 Surface Print Methods 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- LEPMNRDLCZJGTG-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C LEPMNRDLCZJGTG-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- LULWTBQRAIOSQN-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCO.C(C(=C)C)(=O)OCO LULWTBQRAIOSQN-UHFFFAOYSA-N 0.000 description 1
- ZZXXBDPXXIDUBP-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical compound C(C=C)(=O)OCO.C(C=C)(=O)OCO ZZXXBDPXXIDUBP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（１）産業上の利用分野
本発明は、印刷インキに好適に使用し得る近赤外光硬化
型インキに関する。DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention relates to a near-infrared light-curable ink that can be suitably used as a printing ink.
（２）従来の技術
近年、印刷インキの無溶剤化による公害防止、急速硬化
による生産性の向上、あるいは、硬化皮膜の物性改良を
目的として紫外光硬化型インキの開発が盛んに進められ
ている（例えば、特開平１−２２９０８４、特開平１−
２７１４８９及び特開平２−２２３７０）。特開平２−
２２３７０明細書には、ポリ （メタ）アクリル酸エス
テルと紫外光重合開始剤を含むことを特徴とし、硬化速
度及び皮膜硬度の優れた紫外光硬化型インキについて開
示されている。(2) Conventional technology In recent years, the development of ultraviolet light-curable inks has been actively promoted with the aim of preventing pollution by making printing inks solvent-free, improving productivity by rapid curing, and improving the physical properties of cured films. (For example, JP-A-1-229084, JP-A-1-229084, JP-A-1-229084,
271489 and JP-A-2-22370). JP-A-2-
22370 discloses an ultraviolet light-curable ink that is characterized by containing a poly(meth)acrylic acid ester and an ultraviolet photopolymerization initiator, and has excellent curing speed and film hardness.
（３）発明が解決しようとする課題
紫外光硬化インキは、２００〜４００ｎ閣の紫外光を照
射することによってカチオン重合あるいはラジカル重合
によって重合性モノマーが急速硬化するものである。紫
外光硬化インキの基本的な組成は色材、光活性ビヒクル
、光重合開始剤及び助剤からなり、このうち色材につい
ては一般に使用される顔料、染料が用いられる。また、
活性ビヒクルの主体は実用的にはアクリル酸エステル及
びその誘導体であるモノマー、プレポリマーである。光
重合開始剤には、アセトフェノン誘導体、ベンゾイン誘
導体、及びベンゾフェノン誘導体と水素供与体であるア
ミン類による水素引き抜き型の開始剤あるいはベンゾイ
ンアルキルエーテルのような直接光分解型の開始剤か用
いられている。(3) Problems to be Solved by the Invention The ultraviolet light-curable ink is one in which a polymerizable monomer is rapidly cured by cationic polymerization or radical polymerization by irradiation with ultraviolet light of 200 to 400 nm. The basic composition of an ultraviolet light-curable ink consists of a coloring material, a photoactive vehicle, a photopolymerization initiator, and an auxiliary agent. Among these, commonly used pigments and dyes are used as the coloring material. Also,
Practically speaking, the main active vehicle is monomers and prepolymers that are acrylic esters and their derivatives. As photopolymerization initiators, acetophenone derivatives, benzoin derivatives, hydrogen abstraction type initiators using benzophenone derivatives and amines as hydrogen donors, or direct photodecomposition type initiators such as benzoin alkyl ethers are used. .
印刷分野では、これらのインキを１〜３ρの薄膜として
印刷し、紫外光により乾燥硬化を行なっている。これら
の紫外光硬化インキはその高速硬化性という特徴から、
化粧品、食品パッケージに使用されるポリスチレンート
などを印刷する枚葉平板印刷、アルミフォイル紙、ポリ
エステル、ミラーコート紙、アートコート紙などのラベ
ルシートを印刷するラベルシート印刷、スチロール、発
泡スチール、ポリスチレン、ポリプロピレンなどの容器
を印刷する曲面印刷、電子部品、電子機器装置のパネル
などを印刷する凸オフ印刷、時計の文字盤、電子部品な
どを印判するタンポ印刷、コンパクトディスク、プラス
チック容器やプリント配線などを印刷するスクリーン印
判などに利用されている。また、消エネルギー、インキ
塗膜強度などの特徴から、食缶、飲料缶などを印刷する
金属板印刷、教科書などの印刷に用いられるオフ輪印刷
、帳票などを印刷す不ビジネスフォーム印刷などにも使
用されている。しかし、これらに使用されている紫外光
硬化型インキは、光重合開始剤が２００〜４００ｎｓの
紫外光に感度をもち、紫外光は基本的に七ツマ−に対す
る透過性が小さいため、不透明な塗料、あるいは厚膜の
場合には紫外光硬化型インキは不適当であり、膜厚が厚
くなると表面のみ硬化するか、あるいは硬化時間が長く
なるという問題点をもっている。In the printing field, these inks are printed as a thin film of 1 to 3 ρ and dried and cured using ultraviolet light. These ultraviolet light-curable inks are characterized by rapid curing,
Sheet-fed lithographic printing to print polystyrene used in cosmetics and food packaging, label sheet printing to print label sheets such as aluminum foil paper, polyester, mirror coated paper, art coated paper, styrene, foamed steel, polystyrene , curved surface printing for printing containers such as polypropylene, convex off-printing for printing electronic parts and panels for electronic devices, pad printing for stamping clock faces, electronic parts, etc., compact discs, plastic containers and printed wiring, etc. It is used for things such as screen stamps for printing. In addition, due to its features such as energy consumption and ink film strength, it is also suitable for metal plate printing for printing food cans, beverage cans, etc., off-wheel printing used for printing textbooks, etc., and non-business form printing for printing forms etc. It is used. However, in the ultraviolet light-curable inks used in these products, the photopolymerization initiator is sensitive to ultraviolet light of 200 to 400 ns, and ultraviolet light has basically low permeability to 700 ns, making it difficult to paint with opaque paints. Alternatively, in the case of a thick film, ultraviolet light curing ink is inappropriate, and as the film thickness increases, only the surface is cured or the curing time becomes longer.
本発明は、透過性に優れた近赤外光を用い硬化速度が早
く、印刷皮膜硬度の優れた近赤外光硬化型インキを提供
することを目的とする。An object of the present invention is to provide a near-infrared light-curable ink that uses near-infrared light with excellent transparency, has a fast curing speed, and has an excellent printed film hardness.
（４）課題を解決するための手段
本発明では、この課題を解決するために鋭意検討した結
果、一般に活性ビヒクルとして用いられるエチレン性イ
＼飽和基を含有するモノマー及びプレポリマーに光重合
開始剤として一般式（１）で表される近赤外光重合開始
剤を使用することによって近赤外光で硬化し、硬化速度
が早く印刷皮膜の硬度の優れた近赤外光硬化型インキを
見いだし、本発明を完成するに至った。(4) Means for Solving the Problem In the present invention, as a result of intensive studies to solve this problem, we have added a photopolymerization initiator to the monomer and prepolymer containing an ethylenic saturated group, which is generally used as an active vehicle. By using a near-infrared photopolymerization initiator represented by the general formula (1), we have discovered a near-infrared photocurable ink that cures with near-infrared light, has a fast curing speed, and provides an excellent printed film hardness. , we have completed the present invention.
一般式（１）
（式中、Ｄ＋は近赤外領域に吸収をもつ陽イオン色素で
あり、Ｒ、Ｒ、Ｒ及びＲ４は各々独立にアルキル、アリ
ール、アルカリール、アリル、アラルキル、アルケニル
、アルキニル、脂環式及び飽相または不飽和複素環式基
を示し、Ｒ１，Ｒ２，Ｒ３及びＲ４の中の少なくとも１
個は炭素原子数１〜８個のアルキル基である。）すなわ
ち、本発明は一般式（１）で示される近赤外光重合開始
剤を一般に印刷インキの活性ビヒクルとして用いられる
エチレン性不飽和基を含有するモノマー及びプレポリマ
ーに含有させることによって７００ｎｍ以上の近赤外光
に感度をもっことを特徴とする近赤外光硬化型インキに
関する。General formula (1) (wherein, D+ is a cationic dye having absorption in the near-infrared region, and R, R, R and R4 are each independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl , represents an alicyclic and saturated or unsaturated heterocyclic group, and at least one of R1, R2, R3 and R4
is an alkyl group having 1 to 8 carbon atoms. ) That is, the present invention incorporates a near-infrared photopolymerization initiator represented by general formula (1) into monomers and prepolymers containing ethylenically unsaturated groups, which are generally used as active vehicles for printing inks, thereby achieving polymerization of 700 nm or more. The present invention relates to a near-infrared light-curable ink characterized by being sensitive to near-infrared light.
本発明において、一般に印刷インキの活性ビヒクルとし
て用いられるエチレン性不飽和基を含有するモノマー及
びプレポリマーとは、１以上のエチレン性不飽和基、例
えば、ビニル基または、アリル基を有するモノマーなら
びに末端もしくは側鎖にエチレン性不飽和基を有するプ
レポリマーの両者を含有するものである。具体例として
は、ビスフェノールＡ型、フェノールノボラック型等の
エポキシ樹脂、エポキシ化大豆油、エポキシ化ロジン、
エポキシ化ポリブタジェン等のエポキシ樹脂とアクリル
酸及びメタクリル酸との反応物であるエポキシアクリレ
ート類、エポキシメタクリレート類、前記エポキシアク
リレート類及びメタクリレート類のウレタン変性物、脂
肪酸変性アルキッド樹脂のアクリル酸エステル及びメタ
クリル酸エステル等のエチレン性不飽和基含有樹脂、あ
るいは、ウレタンアクリレート、ウレタンメタクリレー
ト、エボキンアクリレート、エポキンメタクリレート、
ビスフェノールＡテトラエチレングリコールジアクリレ
ート、ビスフェノールＡテトラエチレングリコールジメ
タクリレート、ビスフェノールＦポリエチレングリコー
ルジアクリレート、ビスフェノールＦポリエチレングリ
コールジメタクリレート、トリシクロデカンジメチロー
ルジアクリレート、トリシクロデカンジメチロールジメ
タクリレート、トリメチロールプロパントリプロポキシ
トリアクリレート、トリメチロールプロパントリプロポ
キシトリメタクリレート、ジトリメチロールプロパンテ
トラアクリレート、ジトリメチロールプロパンテトラメ
タクリレート、トリメチロールプロパンポリエトキシト
リアクリレート、トリメチロールプロパンポリエトキン
トリメタクリレート、ヒドロキンピバリン酸ネオペンチ
ルグリコールジアクリレート、ヒドロキシピバリン酸ネ
オペンチルグリコールジメタクリレート、ジペンタエリ
スリトールペンタ（またはヘキサ）アクリレートまたは
メタクリレート等、トリペンタエリスリトール、テトラ
ペンタエリスリトールのアクリル酸エステル及びメタク
リル酸エステル等のエチレン性不飽和モノマー類か挙げ
られる。In the present invention, monomers and prepolymers containing ethylenically unsaturated groups, which are generally used as active vehicles for printing inks, are monomers and prepolymers containing one or more ethylenically unsaturated groups, such as vinyl groups or allyl groups, and terminal Or a prepolymer having an ethylenically unsaturated group in the side chain. Specific examples include epoxy resins such as bisphenol A type and phenol novolak type, epoxidized soybean oil, epoxidized rosin,
Epoxy acrylates and epoxy methacrylates that are reaction products of epoxy resins such as epoxidized polybutadiene with acrylic acid and methacrylic acid, urethane-modified products of the above-mentioned epoxy acrylates and methacrylates, acrylic esters and methacrylic acid of fatty acid-modified alkyd resins Ethylenically unsaturated group-containing resins such as esters, urethane acrylate, urethane methacrylate, Evoquin acrylate, Epoquin methacrylate,
Bisphenol A tetraethylene glycol diacrylate, bisphenol A tetraethylene glycol dimethacrylate, bisphenol F polyethylene glycol diacrylate, bisphenol F polyethylene glycol dimethacrylate, tricyclodecane dimethylol diacrylate, tricyclodecane dimethylol dimethacrylate, trimethylolpropane triacrylate Propoxy triacrylate, trimethylolpropane tripropoxytrimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, trimethylolpropane polyethoxy triacrylate, trimethylolpropane polyethquine trimethacrylate, hydroquinpivalic acid neopentyl glycol diacrylate, Ethylenically unsaturated monomers such as hydroxypivalic acid neopentyl glycol dimethacrylate, dipentaerythritol penta (or hexa) acrylate or methacrylate, tripentaerythritol, tetrapentaerythritol acrylic ester and methacrylic ester can be mentioned.
なかでも、好適な例としてはエポキシ化大豆浦、エポキ
シ化ロジン等のエポキシアクリレート類及びウレタン変
性物、脂肪酸変性アルキッド樹脂のアクリル酸エステル
１、ウレタンアクリレート、ウレタンメタクリレート、
エポキンアクリレート、エポキシメタクリレート、ビス
フェノールＡテトラエチレングリコールジアクリレート
、トリメチロールプロパントリプロポキシトリアクリレ
ート、トリペンタエリスリトール、テトラペンタエリス
リトールのアクリル酸エステル及びメタクリル酸エステ
ル等を挙げることができる。Among these, preferred examples include epoxy acrylates and urethane modified products such as epoxidized Soyaura and epoxidized rosin, acrylic acid esters of fatty acid-modified alkyd resins 1, urethane acrylates, urethane methacrylates,
Epoquin acrylate, epoxy methacrylate, bisphenol A tetraethylene glycol diacrylate, trimethylolpropane triproxy triacrylate, tripentaerythritol, acrylic esters and methacrylic esters of tetrapentaerythritol, and the like can be mentioned.
本発明に用いられる近赤外光重合開始剤とし。As a near-infrared photopolymerization initiator used in the present invention.
では、一般式（１）で表される陽イオン性染料−ボレー
ト錯体であり、これを構成する陽イオン染料の特定な種
類は近赤外領域に吸収をもつシアニン、トリアリールメ
タン、アミニウム、ジインモニウム系色素であり、ボレ
ート陰イオンのＲ１，、Ｒ２Ｒ３及びＲ４は各々独立に
アルキル、アリール、アルカリール、アリル、アラルキ
ル、アルケニル、アルキニル、脂環式及び飽和または不
飽和複素環式基を示し、Ｒ、Ｒ、Ｒ及びＲ４の中の少な
くとも１個は炭素原子数１〜８個のアルキル基である。This is a cationic dye-borate complex represented by the general formula (1), and the specific types of cationic dyes that make up this complex include cyanine, triarylmethane, aminium, and diimmonium, which have absorption in the near-infrared region. R1, R2R3 and R4 of the borate anions each independently represent alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic group, and R , R, R and R4 is an alkyl group having 1 to 8 carbon atoms.
本発明に特に有用な開始剤の例を第１表に示す。Examples of initiators particularly useful in this invention are shown in Table 1.
本発明の近赤外光硬化型インキは、前記のエチレン性不
飽和基を含有するモノマー及びプレポリマーに近赤外光
重合開始剤を好ましくは、０，０１〜１０重量％、特に
０．１〜５重量％の割合で混合して形成したものが好ま
しい。本発明の近赤外光硬化型インキには、さらに必要
によって固形の非反応性樹脂、例えば、ジアリルフタレ
ート樹脂、環状ケトン樹脂、天然樹脂変性フェノール樹
脂、アクリル樹脂等を加えて、硬化皮膜等を改良するこ
とができるが、その配合量は、本発明の近赤外光硬化型
インキに対して３０％以下が適当である。In the near-infrared photocurable ink of the present invention, a near-infrared photopolymerization initiator is preferably added to the ethylenically unsaturated group-containing monomer and prepolymer in an amount of 0.01 to 10% by weight, particularly 0.1% by weight. It is preferable to form a mixture in a proportion of up to 5% by weight. If necessary, a solid non-reactive resin such as diallyl phthalate resin, cyclic ketone resin, natural resin-modified phenol resin, acrylic resin, etc. may be added to the near-infrared light-curable ink of the present invention to form a cured film. Although it can be improved, the appropriate amount is 30% or less based on the near-infrared light-curable ink of the present invention.
本発明の近赤外光硬化型インキには、着色顔料の外、必
要に応じて重合禁止剤、可塑剤、充填剤、溶剤並びに酸
素除去剤及び連鎖移動剤等の助剤類を併用することがで
きる。In the near-infrared light-curable ink of the present invention, in addition to color pigments, auxiliary agents such as polymerization inhibitors, plasticizers, fillers, solvents, oxygen scavengers, and chain transfer agents may be used in combination as necessary. I can do it.
本発明の近赤外光硬化型インキは、紫外光硬化型インキ
が使用されている枚葉平板印刷、金属板印刷、オフ輪印
刷、ビジネスフォーム印刷、ラベルンート印刷、曲面印
刷、凸オフ印刷、タンポ印刷、スクリーン印刷などの印
刷インキとして有用であるが、その他に、紙のつや出し
コーティング剤、保護コーティング、ソルダーレジスト
等としても有用である。The near-infrared light-curable ink of the present invention is suitable for use in sheet-fed planography, metal plate printing, off-circle printing, business form printing, label root printing, curved surface printing, convex off-printing, and tampon printing in which ultraviolet light-curable ink is used. It is useful as a printing ink for printing, screen printing, etc., but is also useful as a gloss coating agent for paper, a protective coating, a solder resist, etc.
本発明の近赤外光硬化型インキは、紙、プラスチック及
び金属などに印刷された後、半導体レーザー、ハロゲン
ランプ及び発光ダイオードなどにより近赤外光を照射し
硬化させ、強度の優れた印刷皮膜を得ることができる。The near-infrared light-curing ink of the present invention is printed on paper, plastic, metal, etc., and then cured by irradiating near-infrared light with a semiconductor laser, halogen lamp, light emitting diode, etc., to form a printed film with excellent strength. can be obtained.
印刷インキへの適用の具体的な例としては、枚葉平板印
刷インキとして使用でき、化粧品、食品パッケージに用
いられるアルミフォイル紙に、この近赤外光硬化型イン
キにて５μｓの厚さで印刷し、近赤外光照射装置で照射
することによって、浸透乾燥性のないアルミフォイル紙
へ乾燥定着を行うことができる。A specific example of application to printing ink is that it can be used as a sheet-fed lithography ink, and is printed at a thickness of 5 μs with this near-infrared light-curable ink on aluminum foil paper used for cosmetics and food packaging. However, by irradiating it with a near-infrared light irradiation device, dry fixing can be performed on aluminum foil paper that does not have penetrating drying properties.
以下、実施例をあげて本発明をさらに説明する。The present invention will be further explained below with reference to Examples.
実施例 １
ペンタエリスリトールトリアクリレート４０重量部、ウ
レタンアクリレート（新中村化学社製。Example 1 40 parts by weight of pentaerythritol triacrylate, urethane acrylate (manufactured by Shin Nakamura Chemical Co., Ltd.).
Ｕ −１０８−Ａ） ３５重量部、ビスフェノールＡテ
トラエチレングリコールジトリアクリレート５重量部、
Ｒｕｂｊｎｅ ＧＬ −ＳＥ （日本佐薬社製）１９重
量部及び近赤外光重合開始剤（開始剤番号１）１重量部
を３本ロールで練肉して近赤外光硬化型インキＡを得た
。U-108-A) 35 parts by weight, 5 parts by weight of bisphenol A tetraethylene glycol ditriacrylate,
19 parts by weight of Rubjne GL-SE (manufactured by Nippon Sayaku Co., Ltd.) and 1 part by weight of a near-infrared photopolymerization initiator (initiator number 1) were kneaded with three rolls to obtain near-infrared photocurable ink A. Ta.
実施例 ２
ペンタエリスリトールテトラアクリレート４０重量部、
エポキシアクリレート（日本化薬社製、カラヤッドＲ−
１６７）３０重量部、トリメチロールプロパントリプロ
ポキシトリアクリレート１０重量部、Ｒｕｂｉｎｅ Ｇ
Ｌ −Ｓ Ｅ （日本佐薬社製） １９重量部及び近赤
外光重合開始剤（開始剤番号１）１重量部を３本ロール
で練肉して近赤外光硬化型インキＢを得た。Example 2 40 parts by weight of pentaerythritol tetraacrylate,
Epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., Karayad R-
167) 30 parts by weight, 10 parts by weight of trimethylolpropane tripropoxytriacrylate, Rubine G
19 parts by weight of L-SE (manufactured by Nippon Sayakusha) and 1 part by weight of a near-infrared photopolymerization initiator (initiator number 1) were kneaded with three rolls to obtain near-infrared photocurable ink B. Ta.
実施例 ３
ペンタエリスリトールトリアクリレート４０重量部、ウ
レタンアクリレート（新中村化学社製。Example 3 40 parts by weight of pentaerythritol triacrylate, urethane acrylate (manufactured by Shin Nakamura Chemical Co., Ltd.).
Ｕ −１０８−Ａ） ３５重量部、ビスフェノールＡテ
トラエチレングリコールジトリアクリレート５重量部、
Ｎａｖｙ Ｂｌｕｅ ２Ｇ −Ｓ Ｆ ２００ （日本
佐薬社製）１９重量部及び近赤外光重合開始剤（開始剤
番号４Ａ）２重量部を３本ロールで練肉して近赤外光硬
化型インキＣを得た。U-108-A) 35 parts by weight, 5 parts by weight of bisphenol A tetraethylene glycol ditriacrylate,
19 parts by weight of Navy Blue 2G-S F 200 (manufactured by Nippon Sayaku Co., Ltd.) and 2 parts by weight of a near-infrared photopolymerization initiator (initiator number 4A) were kneaded using three rolls to obtain a near-infrared photocurable ink. I got a C.
実施例 ４
ジペンタエリスリトールペンタアクリレート４０重量部
、エポキシアクリレート（日本佐薬社製。Example 4 40 parts by weight of dipentaerythritol pentaacrylate, epoxy acrylate (manufactured by Nihon Sayaku Co., Ltd.).
カラヤッドＲ−１６７）３０重量部、ビスフェノールＡ
テトラエチレングリコールジトリアクリレート１０重量
部、Ｎａｖｙ Ｂｌｕｅ ２Ｇ −Ｓ Ｆ ２００ （
日本佐薬社製）１９重量部及び近赤外光重合開始剤（開
始剤番号６Ａ）０．５重量部を３本ロールで練肉して近
赤外光硬化型インキＤを得た。Karayad R-167) 30 parts by weight, bisphenol A
10 parts by weight of tetraethylene glycol ditriacrylate, Navy Blue 2G-SF 200 (
Near-infrared light-curable ink D was obtained by kneading 19 parts by weight (manufactured by Nippon Sayaku Co., Ltd.) and 0.5 parts by weight of a near-infrared photopolymerization initiator (initiator number 6A) using three rolls.
比較例 １
実施例１で、近赤外光重合開始剤（開始剤番号１）を０
−ベンゾイル安息香酸メチル１０重量部に変える以外は
実施例１と同様にして近赤外光硬化型インキＥを得た。Comparative Example 1 In Example 1, the near-infrared photopolymerization initiator (initiator number 1) was
-Near-infrared light-curable ink E was obtained in the same manner as in Example 1 except that the amount was changed to 10 parts by weight of methyl benzoylbenzoate.
インキ性能評価方法
硬化時間：実施例１〜４及びインキ０．６ｇをＲ１テス
ターを用いてカルトン紙に展色し、たたちにアルミニウ
ムコート型ハロゲンランプ（２Ｗ ／ ｃｊ ）で照射
した後、Ｒ１テスターによりアート紙に圧着し、インキ
が付着しなくなるまで要した照射時間（秒）を硬化時間
とした。Ink performance evaluation method Curing time: Examples 1 to 4 and 0.6 g of ink were spread on carton paper using an R1 tester, and then irradiated with an aluminum coated halogen lamp (2W/cj), and then cured using an R1 tester. The curing time was defined as the irradiation time (seconds) required until the ink stopped adhering to art paper.
皮膜硬度：硬質塩ビ板にバーコーターにより膜厚１０ミ
クロンになるように塗布し、アルミニウムコート型ハロ
ゲンランプ（２Ｗ／ｃｄ）で１秒間照射し硬化させた。Film hardness: The film was coated on a hard PVC board using a bar coater to a film thickness of 10 microns, and cured by irradiating it for 1 second with an aluminum coated halogen lamp (2W/cd).
ついで、ＪＩＳ−Ｋ−５４００に基ずいて、鉛筆硬度を
Ｍｊ定した。Then, the pencil hardness was determined based on JIS-K-5400.
硬化時間及び鉛筆硬度のＭ］定結果を第２表に示す。The curing time and pencil hardness results are shown in Table 2.
（６）発明の効果
本発明により、近赤外光で硬化し、硬化速度が速くかつ
皮膜硬度か大きい近赤外光硬化型インキが提供される。(6) Effects of the Invention The present invention provides a near-infrared light-curable ink that cures with near-infrared light, has a fast curing speed, and has a high film hardness.
Claims (1)
を特徴とする近赤外光硬化型インキ 一般式（１） ▲数式、化学式、表等があります▼ （式中、Ｄ＋は近赤外領域に吸収をもつ陽イオン色素で
あり、Ｒ＿１、Ｒ＿２、Ｒ＿３及びＲ＿４は各々独立に
アルキル、アリール、アルカリール、アリル、アラルキ
ル、アルケニル、アルキニル、脂環式及び飽和または不
飽和複素環式基を示し、Ｒ＿１、Ｒ＿２、Ｒ＿３及びＲ
＿４の中の少なくとも１個は炭素原子数１〜８個のアル
キル基である。）[Claims] Near-infrared light curing ink characterized by containing a near-infrared photopolymerization initiator represented by general formula (1) General formula (1) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, D+ is a cationic dye having absorption in the near-infrared region, and R_1, R_2, R_3 and R_4 are each independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and a saturated or unsaturated heterocyclic group, R_1, R_2, R_3 and R
At least one of _4 is an alkyl group having 1 to 8 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14674190A JP2918629B2 (en) | 1990-06-04 | 1990-06-04 | Near-infrared light curable ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14674190A JP2918629B2 (en) | 1990-06-04 | 1990-06-04 | Near-infrared light curable ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0439367A true JPH0439367A (en) | 1992-02-10 |
| JP2918629B2 JP2918629B2 (en) | 1999-07-12 |
Family
ID=15414546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14674190A Expired - Lifetime JP2918629B2 (en) | 1990-06-04 | 1990-06-04 | Near-infrared light curable ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2918629B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303271B1 (en) * | 1996-06-12 | 2001-10-16 | Kodak Polychrome Graphics Llc | Lithographic plates |
| GB2396620A (en) * | 2002-11-22 | 2004-06-30 | Konica Minolta Holdings Inc | Actinic ray curable ink and printed matter utilizing the same |
| JP2008081688A (en) * | 2006-09-29 | 2008-04-10 | Kimoto & Co Ltd | Hard coat paint, hard coat film using the same, and molded article |
| JP2008214576A (en) * | 2007-03-07 | 2008-09-18 | Nalux Co Ltd | Near-infrared curable ink composition and printing method using the same |
| DE102013009135A1 (en) * | 2013-05-31 | 2014-12-04 | Heidelberger Druckmaschinen Ag | NIR-crosslinkable printing ink |
-
1990
- 1990-06-04 JP JP14674190A patent/JP2918629B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303271B1 (en) * | 1996-06-12 | 2001-10-16 | Kodak Polychrome Graphics Llc | Lithographic plates |
| GB2396620A (en) * | 2002-11-22 | 2004-06-30 | Konica Minolta Holdings Inc | Actinic ray curable ink and printed matter utilizing the same |
| GB2396620B (en) * | 2002-11-22 | 2006-11-15 | Konica Minolta Holdings Inc | Actinic ray curable ink and printed matter utilizing the same |
| JP2008081688A (en) * | 2006-09-29 | 2008-04-10 | Kimoto & Co Ltd | Hard coat paint, hard coat film using the same, and molded article |
| JP2008214576A (en) * | 2007-03-07 | 2008-09-18 | Nalux Co Ltd | Near-infrared curable ink composition and printing method using the same |
| DE102013009135A1 (en) * | 2013-05-31 | 2014-12-04 | Heidelberger Druckmaschinen Ag | NIR-crosslinkable printing ink |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2918629B2 (en) | 1999-07-12 |
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