JPH08892B2 - Ink having UV curing and oxidative polymerization functions, and printed matter using the same - Google Patents
Ink having UV curing and oxidative polymerization functions, and printed matter using the sameInfo
- Publication number
- JPH08892B2 JPH08892B2 JP63119317A JP11931788A JPH08892B2 JP H08892 B2 JPH08892 B2 JP H08892B2 JP 63119317 A JP63119317 A JP 63119317A JP 11931788 A JP11931788 A JP 11931788A JP H08892 B2 JPH08892 B2 JP H08892B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- oxidative polymerization
- ultraviolet
- oxidative
- film
- 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.)
- Expired - Lifetime
Links
- 238000006116 polymerization reaction Methods 0.000 title claims description 61
- 230000001590 oxidative effect Effects 0.000 title claims description 53
- 238000003848 UV Light-Curing Methods 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000049 pigment Substances 0.000 claims description 24
- 238000007639 printing Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 56
- 239000010408 film Substances 0.000 description 25
- 238000001035 drying Methods 0.000 description 21
- 238000001723 curing Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920000180 alkyd Polymers 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000000935 solvent evaporation Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 230000002411 adverse Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、凹版印刷、スクリーン印刷等の皮膜層が厚
めの各種印刷に用いることのできる、高速表面乾燥（セ
ット）性インキに関する。TECHNICAL FIELD The present invention relates to a high-speed surface-drying (setting) ink that can be used for various kinds of printing such as intaglio printing and screen printing with a thick film layer.
印刷速度の高速化に伴い、紫外線照射により短時間で
硬化、乾燥するインキが一般化されつつある。しかし、
インキの必須成分である顔料が分散されているインキの
場合、良好な光重合開始剤や増感剤を用いたとしても硬
化しうるインキ皮膜の厚さは約10μｍ程度が限界であ
る。これは顔料が分散されているインキ等では、紫外線
がインキ皮膜内部まで透過しないためである。したがっ
て、インキ皮膜厚さが最大でも４μｍ程度であるオフセ
ット印刷等では紫外線乾燥が普及しているが、インキ皮
膜厚さが10数μｍを越えるスクリーン印刷や数10μｍ以
上である凹版印刷等ではこれらの高速乾燥システムは利
用されていない。これらの問題を解決するべく、紫外線
硬化性組成物に特殊な顔料を分散させたり、特殊な重合
促進剤や増感剤を添加する多くの方法、例えば特公昭49
−47889号、同49−47899号、同52−32989号、特開昭48
−28037号、同48−47534号、同115128号等の方法が提案
されている。しかし、これらのいずれの方法も使用でき
る顔料に制約があったり、インキ適性が劣る等の欠点が
あり十分には成功していない。With the increase in printing speed, inks that are cured and dried in a short time by ultraviolet irradiation are becoming popular. But,
In the case of an ink in which a pigment, which is an essential component of the ink, is dispersed, the thickness of the ink film that can be cured even if a good photopolymerization initiator or sensitizer is used is limited to about 10 μm. This is because ultraviolet rays do not penetrate to the inside of the ink film in the ink in which the pigment is dispersed. Therefore, UV drying is widely used in offset printing, etc., where the ink film thickness is at most about 4 μm, but in case of screen printing where the ink film thickness exceeds 10 several μm or intaglio printing where the ink film thickness is several 10 μm or more, these No fast drying system is used. In order to solve these problems, many methods of dispersing a special pigment in the ultraviolet curable composition or adding a special polymerization accelerator or sensitizer, for example, Japanese Patent Publication No.
No. 47889, No. 49-47899, No. 52-32989, JP-A-48
Methods such as -28037, 48-47534, and 115128 have been proposed. However, none of these methods has been sufficiently successful because of limitations such as pigments that can be used and poor ink suitability.
一方、紫外線硬化性成分と酸化重合性成分を併用し、
顔料分散性の改善や基材（被印刷体）との密着、接着性
を向上させる方法も提案されている。例えば、高級脂肪
酸（酸化重合性成分）を分子内に含んだ光重合性物質を
合成することは、特開昭49−97788号、同51−16107号、
同50−95006号等数多く提案されており、又光重合物質
にアルキド樹脂（酸化重合成分）を混合するものは特開
昭54−25941号で提案されている。しかし、これらの提
案はいずれも、顔料分散性の改善や基材との密着、接着
性の向上のみを目的としているので、本発明のごとき、
紫外線照射により皮膜表層部を瞬時に硬化させ、印刷あ
るいは塗工直後の積み重ねや二次加工を可能にし、その
後皮膜内部は酸化重合により自然乾燥させることを第一
義的な目的とした方法とは異なる。On the other hand, using a UV curable component and an oxidatively polymerizable component together,
Methods for improving pigment dispersibility, adhering to a substrate (printing material), and improving adhesiveness have also been proposed. For example, synthesizing a photopolymerizable substance containing a higher fatty acid (oxidatively polymerizable component) in the molecule is disclosed in JP-A-49-97788 and 51-16107.
No. 50-95006 and many others have been proposed, and those in which an alkyd resin (oxidative polymerization component) is mixed with a photopolymerization substance have been proposed in JP-A-54-25941. However, since all of these proposals are intended only to improve the pigment dispersibility, the adhesion to the substrate, and the adhesiveness, as in the present invention,
The primary purpose of the method is to cure the surface layer of the film instantaneously by UV irradiation, enable stacking and secondary processing immediately after printing or coating, and then naturally dry the inside of the film by oxidative polymerization. different.
従来のインキの紫外線硬化（乾燥）では、印刷された
インキ等が高速に硬化、乾燥すること、及び硬化皮膜の
耐薬品性、耐摩擦性、堅牢性等の耐性が優れている等の
長所を有する半面、硬化しうるインキ膜厚が薄く、顔料
分散性、印刷適性、基材に対する密着、接着性等のイン
キ適性が劣る等の欠点があった。また、酸化重合乾燥で
はこれとは反対に、顔料分散性、印刷適性、基材に対す
る密着、接着性等のインキ、塗料適性が優れている反
面、乾燥速度が遅く、硬化皮膜の耐薬品性、耐摩擦性、
堅牢性等の耐性が劣る等の欠点がある。In conventional UV curing (drying) of ink, the printed ink cures and dries at high speed, and the cured film has excellent chemical resistance, abrasion resistance, and robustness. On the other hand, there are drawbacks such as a thin film of curable ink and poor ink suitability such as pigment dispersibility, printability, adhesion to a substrate, and adhesiveness. On the other hand, in oxidative polymerization drying, on the contrary, pigment dispersibility, printability, adhesion to a substrate, ink such as adhesiveness, excellent paint suitability, on the other hand, the drying speed is slow, the chemical resistance of the cured film, Abrasion resistance,
There are drawbacks such as poor durability such as robustness.
本発明は、これらの紫外線硬化（乾燥）及び酸化重合
乾燥両者の長所を生かし、そして互いの欠点を補い合う
ような紫外線硬化、酸化重合併用インキを得ることを目
的としている。即ち、紫外線照射による高速乾燥性を有
し、紫外線乾燥によって乾燥し得ない皮膜内部層の未硬
化部を酸化重合により硬化、乾燥させ、更に顔料分散
性、印刷適性、基材に対する密着、接着性等のインキ適
性及び硬化皮膜の耐薬品性、耐摩擦性、堅牢性等の耐性
が優れたインキを得ることを目的としている。An object of the present invention is to obtain an ink for combined UV-curing and oxidative-polymerization, which makes use of the advantages of both UV-curing (drying) and oxidative-polymerization drying, and which complements each other's drawbacks. That is, it has high-speed drying property by ultraviolet irradiation, and the uncured part of the inner layer of the film that cannot be dried by ultraviolet drying is cured and dried by oxidative polymerization, and further pigment dispersibility, printability, adhesion to substrate, adhesiveness It is intended to obtain an ink having excellent ink suitability and the like, and a cured film having excellent chemical resistance, abrasion resistance, and fastness.
上記目的を達成するために、本発明のインキにおいて
は、紫外線硬化性組成物と酸化重合性組成物の混合体を
用いることにより、紫外線硬化（乾燥）と酸化重合乾燥
を併用しうるようなインキにしたものである。即ち、こ
の紫外線硬化、酸化重合併用インキは、紫外線照射によ
り皮膜表層部を瞬時に硬化させ、印刷あるいは塗工直後
の積み重ねや二次加工を可能にし、その後皮膜内部は酸
化重合により自然乾燥しうること、並びに顔料分散性、
印刷適性、基材に対する密着、接着性等のインキ適性及
び硬化皮膜の耐薬品性、耐摩擦性、堅牢性等の耐性が優
れていることを特徴としている。普通、酸素は重合禁止
剤としてアクリレートのような紫外線硬化成分のゲル化
を防止するために用いられているが、本発明ではアルキ
ド樹脂等の酸化重合成分と酸素を組み合わせて重合開始
剤として用いている。In order to achieve the above object, in the ink of the present invention, by using a mixture of an ultraviolet curable composition and an oxidative polymerization composition, an ink that can be used in combination with ultraviolet curing (drying) and oxidative polymerization drying. It is the one. That is, this ultraviolet curing and oxidative polymerization combined use ink instantaneously cures the surface layer of the film by irradiation with ultraviolet light, and enables stacking and secondary processing immediately after printing or coating, and thereafter the inside of the film can be naturally dried by oxidative polymerization. And pigment dispersibility,
It is characterized by excellent printability, ink suitability such as adhesion to substrates, adhesiveness, etc., and resistance of the cured film such as chemical resistance, abrasion resistance and fastness. Normally, oxygen is used as a polymerization inhibitor to prevent gelation of UV-curable components such as acrylates, but in the present invention, it is used as a polymerization initiator by combining an oxidative polymerization component such as an alkyd resin with oxygen. There is.
上記紫外線硬化、酸化重合併用インキにおいて、紫外
線硬化性組成物としては光硬化性樹脂化合物と光重合開
始剤もしくは増感剤との混合物を、又酸化重合性組成物
としては酸化重合性物質と酸化重合触媒の混合物を用い
る。これらの成分、つまり光硬化性樹脂化合物、光重合
開始剤、増感剤、酸化重合性物質、酸化重合触媒には、
紫外線硬化（乾燥）及び酸化重合乾燥型インキに使用さ
れている一般に公知の諸材料が使用できる。例えば、光
硬化性樹脂化合物としては１から６官能の各種アクリレ
ート及びメタクリレートのモノマー、プレポリマーであ
り、光重合開始剤としては開裂型のベンゾイン、ベンゾ
インエーテル等、水素引抜き型のベンジル、ベンゾフェ
ノン等、イオン反応型のアリルジアゾニウム塩類等であ
り、増感剤としては第三アミン類等である。又、酸化重
合性物質としてはあまに油、大豆油等の乾性油もしくは
半乾性油又はアルキド樹脂ワニスのような乾性油変性樹
脂ワニス等であり、酸化重合触媒としてはコバルト、マ
ンガン、鉛、鉄等の金属化合物である硼酸コバルト、オ
クチル酸コバルト、ナフテン酸コバルト、一酸化鉛等で
ある。In the above UV curable and oxidative polymerization combined ink, the UV curable composition is a mixture of a photocurable resin compound and a photopolymerization initiator or a sensitizer, and the oxidative polymerizable composition is an oxidative polymerizable substance and an oxidant. A mixture of polymerization catalysts is used. These components, that is, the photocurable resin compound, the photopolymerization initiator, the sensitizer, the oxidative polymerizable substance, the oxidative polymerization catalyst,
Generally known materials used for ultraviolet curing (drying) and oxidative polymerization drying type inks can be used. For example, the photocurable resin compound is a monomer or prepolymer of various 1 to 6 functional acrylates and methacrylates, and the photopolymerization initiator is a cleavage type benzoin, benzoin ether, etc., a hydrogen abstraction type benzyl, benzophenone, etc. Ion-reactive allyldiazonium salts and the like, and sensitizers include tertiary amines and the like. The oxidatively polymerizable substance is a linseed oil, a drying oil such as soybean oil or a semi-drying oil, or a drying oil-modified resin varnish such as an alkyd resin varnish, and the oxidative polymerization catalyst is cobalt, manganese, lead, iron. And other metal compounds such as cobalt borate, cobalt octylate, cobalt naphthenate, and lead monoxide.
上記インキの貯蔵安定性や機上安定性を向上させるに
は、紫外線硬化性を損なわずに酸化的重合速度のみを制
御しうる重合禁止（抑制）剤を添加することが効果的で
ある。紫外線硬化性、即ち紫外線硬化成分の紫外線照射
による硬化性に悪影響を及ぼさずに、酸化重合速度のみ
を抑制できる重合禁止（抑制）剤としては、紫外線硬化
において一般的に使用され、公知の重合禁止（抑制）
剤、例えば、ｐ−メトキシフェノール、ヒドロキノン等
が使用できる。In order to improve the storage stability and the on-machine stability of the ink, it is effective to add a polymerization inhibitor (inhibitor) capable of controlling only the oxidative polymerization rate without impairing the ultraviolet curability. As a polymerization inhibitor (suppressor) that can suppress only the oxidative polymerization rate without adversely affecting the ultraviolet curability, that is, the curability of the ultraviolet curable component by the irradiation of ultraviolet rays, it is commonly used in ultraviolet curing, and known polymerization inhibitors (Suppression)
Agents such as p-methoxyphenol and hydroquinone can be used.
上記紫外線硬化、酸化重合併用インキに利用可能な顔
料は、光学的な透明性、隠蔽性、反射性、発光性等の顔
料諸特性には全く制限を受けないため、どのような種類
の顔料でも使用できる。The pigment that can be used in the above-mentioned UV-curable and oxidative polymerization combined ink is not limited at all in terms of various properties such as optical transparency, hiding property, reflectivity, and luminescent property. Can be used.
上記のように、紫外線硬化性組成物と酸化重合性組成
物の混合体に各種の顔料を分散させたインキを用いた凹
版印刷物、スクリーン印刷物は、紫外線照射により皮膜
表層部が瞬時に硬化乾燥する。このため、印刷後直ちに
印刷物を積み重ねても裏移りやブロッキングを起こすこ
とがなく、又二次加工も可能な状態になる。そして、積
み重ねられたり、二次加工された印刷、塗工物上の皮膜
内部の未硬化層は、酸化重合により自然乾燥していく。
この酸化重合では、酸化重合成分が酸化重合するととも
に、その過程で発生するラジカル等の活性種により紫外
線硬化成分であるアクリレート等の重合反応も誘発され
皮膜全体の硬化乾燥が完結して行く。As described above, the intaglio printed matter and the screen printed matter using the ink in which various pigments are dispersed in the mixture of the ultraviolet curable composition and the oxidatively polymerizable composition, the film surface layer portion is instantly cured and dried by the ultraviolet irradiation. . Therefore, even if the printed matter is piled up immediately after printing, no offset or blocking occurs, and the secondary processing becomes possible. Then, the uncured layer inside the coating on the printed or coated material which is stacked or processed secondarily is naturally dried by oxidative polymerization.
In this oxidative polymerization, the oxidatively polymerized component is oxidatively polymerized, and the active species such as radicals generated in the process also induce a polymerization reaction of acrylate or the like which is an ultraviolet ray curable component to complete the curing and drying of the entire film.
つまり、酸化重合成分自体が重合開始剤として作用
し、未反応の紫外線硬化性組成物が酸化的な重合を促進
することになる。また、そのためには、酸化重合成分は
限定される必要があり、半乾性油または乾性油変性アル
キド樹脂のような、常温で徐々にラジカルを生成する物
質でなくてはならない。That is, the oxidative polymerization component itself acts as a polymerization initiator, and the unreacted UV-curable composition promotes oxidative polymerization. For that purpose, the oxidative polymerization component needs to be limited and must be a substance that gradually generates radicals at room temperature, such as a semi-drying oil or a drying oil-modified alkyd resin.
この場合、酸化重合成分同士の酸化重合速度より紫外
線硬化成分の酸化的反応速度の方が速いことを確認して
おり、したがって樹脂成分中の紫外線硬化成分の割合を
高めることができる。そうすることによって、硬化皮膜
は、耐薬品性、耐摩擦性、堅牢性等の耐性が優れたもの
になる。また、基材と接触している皮膜内部層は紫外線
照射によっても瞬時に硬化しないため、基材とのなじみ
が良好になるとともに、硬化にともなう内部応力の緩和
が十分になり歪みが生じにくくなる等のことも、基材に
対する硬化皮膜の密着、接着性を向上させる要因の一つ
になっている。In this case, it has been confirmed that the oxidative reaction rate of the UV-curable component is faster than the oxidative polymerization rate of the oxidative-polymerizable components, and thus the proportion of the UV-curable component in the resin component can be increased. By doing so, the cured film has excellent resistance such as chemical resistance, abrasion resistance, and robustness. In addition, the inner layer of the coating that is in contact with the base material does not instantly cure even when irradiated with ultraviolet rays, so that it is well compatible with the base material, and the internal stress associated with the cure is sufficiently relaxed to prevent distortion. Such factors are also one of the factors that improve the adhesion and adhesiveness of the cured film to the substrate.
上記のように、酸化重合過程で生じるラジカル等の活
性種によっても共重合しうるので、紫外線硬化速度を遅
らせることなく、酸化重合速度を抑制させるための重合
禁止（抑制）剤を必要に応じて添加することが望まし
い。As described above, since it can be copolymerized by active species such as radicals generated in the oxidative polymerization process, a polymerization inhibitor (suppressor) for suppressing the oxidative polymerization rate can be added as necessary without delaying the ultraviolet curing rate. It is desirable to add.
なお、上記硬化原理より明らかではあるが、使用する
顔料には前述のように何等制限がなく、何れの顔料でも
利用可能である。Although it is clear from the above-mentioned curing principle, the pigment to be used is not limited as described above, and any pigment can be used.
表１、表２に示した配合例に基づき諸材料を配合し、
３本ロールミルを用いて通常の方法で練合して紫外線硬
化、酸化重合併用型凹版インキ及びスクリーンインキを
作製した。Based on the formulation examples shown in Tables 1 and 2, various materials were blended,
Kneading was carried out by a conventional method using a three-roll mill to prepare an ultraviolet curing, oxidation polymerization combined use type intaglio ink and screen ink.
紫外線硬化、酸化重合併用型凹版インキは、凹版印刷
機を用いて、通常の方法で連続印刷した。連続して印刷
される印刷物は印刷後直ちに紫外線照射装置内を搬送さ
せた後、排紙部にそのまま積み重ねた。このときの印刷
条件及び紫外線照射条件等は次の通りである。印刷用
紙：証券用紙、印刷版面深度:130μｍ、印刷速度:25m/m
in、紫外線照射搬送速度:25m/min、紫外線ランプ：空冷
式,120w/cm,メタルハライドランプ２灯、排紙積み重ね
枚数:5000枚。The UV-curable and oxidative polymerization combined type intaglio ink was continuously printed by an ordinary method using an intaglio printing machine. The printed matter to be continuously printed was conveyed in the ultraviolet irradiation device immediately after printing, and then stacked as it was on the paper discharge section. The printing conditions and ultraviolet irradiation conditions at this time are as follows. Printing paper: Securities paper, printing plate surface depth: 130 μm, printing speed: 25 m / m
in, UV irradiation transfer speed: 25m / min, UV lamp: air-cooled, 120w / cm, 2 metal halide lamps, number of discharged sheets stack: 5000 sheets.
紫外線硬化、酸化重合併用型スクリーンインキは、ス
クリーン印刷機を用いて、通常の方法で印刷した。印刷
物は、印刷後直ちに紫外線照射した後、速やかに90゜折
り曲げ加工を行った。このときの印刷条件及び紫外線照
射条件等は次の通りである。印刷用紙：特アート紙、ス
クリーン線数:133線、印刷速度:25m/min、紫外線照射搬
送速度:25m/min、紫外線ランプ：空冷式,120w/cm,メタ
ルハライドランプ２灯。The ultraviolet curing and oxidative polymerization combined type screen ink was printed by a usual method using a screen printing machine. Immediately after printing, the printed matter was irradiated with ultraviolet rays and then quickly bent by 90 °. The printing conditions and ultraviolet irradiation conditions at this time are as follows. Printing paper: Special art paper, Screen line number: 133 lines, Printing speed: 25m / min, UV irradiation transfer speed: 25m / min, UV lamp: Air-cooled, 120w / cm, 2 metal halide lamps.
上記印刷実施の結果は次の通りであった。 The results of the above printing were as follows.
紫外線硬化、酸化重合併用型凹版インキ及びスクリー
ンインキは、従来型の凹版インキ（酸化重合型）及びス
クリーンインキ（溶剤蒸発型）と同等の印刷適性を示し
た。The UV-curable and oxidative polymerization combined type intaglio ink and screen ink showed printability equivalent to that of the conventional intaglio ink (oxidation polymerization type) and screen ink (solvent evaporation type).
紫外線硬化、酸化重合併用型凹版インキの連続凹版印
刷において、排紙部での印刷物5000枚の積み重ねにおい
ても、裏移り及びブロッキングは皆無であり、又紫外線
硬化、酸化重合併用型スクリーンインキのスクリーン印
刷直後の90゜折り曲げ加工においても、硬化皮膜の亀
裂、割れ、剥離等を生じることなく何等問題はなかっ
た。In continuous intaglio printing of UV curable and oxidative polymerization type intaglio ink, there is no set-off and blocking even when 5,000 sheets of printed matter are piled up at the discharge section, and screen printing of UV curable and oxidative polymerization type screen ink Even in the 90 ° bending process immediately after that, there were no problems such as cracks, cracks, and peeling of the cured film.
紫外線硬化、酸化重合併用型凹版インキ及びスクリー
ンインキの印刷物の耐薬品性、耐摩擦性は従来型の凹版
インキ（酸化重合型）及びスクリーンインキ（溶剤蒸発
型）の印刷物に比べ極めて優れており、又基材との接着
性は従来型インキ（酸化重合型及び溶剤蒸発型）と同等
に優れていた。UV-curing, oxidation polymerization combined type intaglio ink and screen ink printed matter are extremely superior in chemical resistance and abrasion resistance compared to conventional intaglio ink (oxidation polymerization type) and screen ink (solvent evaporation type) printed matter. In addition, the adhesion to the substrate was as good as that of conventional inks (oxidation polymerization type and solvent evaporation type).
紫外線硬化、酸化重合併用型凹版インキ及びスクリー
ンインキの機上安定性は良好であった。The on-press stability of the UV-curable and oxidative polymerization combined type intaglio ink and screen ink was good.
紫外線硬化、酸化重合併用型凹版インキ及びスクリー
ンインキ作製時の練合性は、従来型の凹版インキ（酸化
重合型）及びスクリーンインキ（溶剤蒸発型）と同等で
あった。The kneading properties at the time of preparation of ultraviolet curing, oxidation polymerization combined type intaglio ink and screen ink were the same as those of conventional intaglio ink (oxidation polymerization type) and screen ink (solvent evaporation type).
本発明の紫外線硬化、酸化重合併用インキは、以上説
明したような機能を有するので、以下に記載されるよう
な効果を奏する。The ultraviolet curing and oxidative polymerization combined ink of the present invention has the functions as described above, and therefore exhibits the effects described below.
本発明の紫外線硬化、酸化重合併用インキは、紫外線
硬化性組成物と酸化重合性組成物を適量混合することに
より、両者の長所を生かし、そして互いの欠点を補い合
うように作用する。即ち、紫外線硬化性組成物と酸化重
合性組成物の混合体に各種の顔料を分散させたインキを
用いた凹版印刷物、スクリーン印刷物は、紫外線照射に
より皮膜表層部が瞬時に硬化乾燥するため、印刷あるい
は塗工後直ちに印刷物を積み重ねても裏移りやブロッキ
ングを防止でき、又二次加工も可能な状態になる。そし
て、積み重ねられたり、二次加工された印刷上の皮膜内
部の未硬化層は、酸化重合により自然乾燥するため、そ
の後の保管中に皮膜全体の硬化乾燥が完結する。更に、
インキの顔料分散性、印刷適性、基材に対する硬化皮膜
の密着、接着性等は、酸化重合性組成物と同等に優れ、
又硬化皮膜の耐薬品性、耐摩擦性、堅牢性等の耐性は紫
外線硬化性組成物と同等に優れる。The ultraviolet curable and oxidative polymerization combined ink of the present invention, by mixing an appropriate amount of the ultraviolet curable composition and the oxidative polymerization composition, exerts the advantages of both and acts to complement each other's defects. That is, an intaglio printed matter using an ink in which various pigments are dispersed in a mixture of an ultraviolet curable composition and an oxidatively polymerizable composition, a screen printed matter, the surface layer of the film is instantaneously cured and dried by irradiation with ultraviolet rays. Alternatively, even if printed materials are piled up immediately after coating, set-off and blocking can be prevented, and secondary processing becomes possible. Then, the uncured layer inside the film on the stacked or secondary processed print is naturally dried by oxidative polymerization, so that the curing and drying of the entire film is completed during the subsequent storage. Furthermore,
The pigment dispersibility of the ink, printability, adhesion of the cured film to the substrate, adhesion, etc. are as excellent as those of the oxidatively polymerizable composition,
Further, the resistance of the cured film such as chemical resistance, abrasion resistance and fastness is as excellent as that of the ultraviolet curable composition.
紫外線硬化、酸化重合併用インキに、必要に応じて重
合禁止（抑制）剤を添加することにより、紫外線硬化性
を損ねることなくインキ、塗料の機上安定性、保存安定
性を向上させることができる。By adding a polymerization inhibitor (inhibitor) to the UV curing and oxidative polymerization combined ink, if necessary, it is possible to improve the on-machine stability and storage stability of the ink and paint without impairing the UV curability. .
なお、紫外線硬化、酸化重合併用型インキに使用でき
る顔料には、何等制限がないため、どのような種類の顔
料でも利用できる。There is no limitation on the pigment that can be used in the ultraviolet curing and oxidative polymerization combined type ink, and thus any type of pigment can be used.
Claims (5)
させ、印刷直後の積み重ねや二次加工を可能にし、その
後皮膜内部は酸化重合により自然乾燥することを特徴と
する、紫外線硬化性組成物と酸化重合性組成物の混合体
に各種顔料を練合した紫外線硬化、酸化重合併用イン
キ。1. An ultraviolet-curable composition characterized in that the surface layer of a film is instantly cured by irradiation of ultraviolet rays to enable stacking and secondary processing immediately after printing, and then the inside of the film is naturally dried by oxidative polymerization. A UV-curable, oxidative polymerization combined ink in which various pigments are kneaded in a mixture of a pigment and an oxidatively polymerizable composition.
合物と光重合開始剤もしくは増感剤との混合物、酸化重
合性組成物として酸化重合性物質と酸化重合触媒の混合
物を用いた請求項１記載の紫外線硬化、酸化重合併用イ
ンキ。2. A mixture of a photocurable resin compound and a photopolymerization initiator or a sensitizer is used as the ultraviolet curable composition, and a mixture of an oxidative polymerizable substance and an oxidative polymerization catalyst is used as the oxidative polymerizable composition. The ultraviolet curing and oxidative polymerization combined use ink described in 1.
混合体に、酸化重合速度を制御するための重合禁止（抑
制）剤を添加した請求項１記載の紫外線硬化、酸化重合
併用インキ。3. The ultraviolet curing and oxidative polymerization combined ink according to claim 1, wherein a polymerization inhibitor (inhibitor) for controlling the oxidative polymerization rate is added to the mixture of the ultraviolet curable composition and the oxidatively polymerizable composition. .
混合体に使用する顔料は、光学的な透明性、隠蔽性、反
射性、発光性等の顔料諸特性には全く制限を受けないこ
とを特徴とする請求項１記載の紫外線硬化、酸化重合併
用インキ。4. The pigment used in the mixture of the UV-curable composition and the oxidatively polymerizable composition is completely limited in various pigment characteristics such as optical transparency, hiding property, reflectivity and luminescent property. The ultraviolet curing and oxidative polymerization combined ink according to claim 1, wherein the ink is absent.
させ、印刷直後の積み重ねや二次加工を可能にし、その
後皮膜内部は酸化重合により自然乾燥することを特徴と
する、紫外線硬化性組成物と酸化重合性組成物の混合体
に各種顔料を練合した紫外線硬化、酸化重合併用インキ
組成物を使用した印刷物。5. An ultraviolet-curable composition, characterized in that the surface layer of the film is instantly cured by irradiation of ultraviolet rays to enable stacking and secondary processing immediately after printing, and then the inside of the film is naturally dried by oxidative polymerization. A printed material using an ink composition for ultraviolet curing and oxidative polymerization, which is obtained by kneading various pigments into a mixture of a pigment and an oxidatively polymerizable composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63119317A JPH08892B2 (en) | 1988-05-18 | 1988-05-18 | Ink having UV curing and oxidative polymerization functions, and printed matter using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63119317A JPH08892B2 (en) | 1988-05-18 | 1988-05-18 | Ink having UV curing and oxidative polymerization functions, and printed matter using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01289876A JPH01289876A (en) | 1989-11-21 |
| JPH08892B2 true JPH08892B2 (en) | 1996-01-10 |
Family
ID=14758458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63119317A Expired - Lifetime JPH08892B2 (en) | 1988-05-18 | 1988-05-18 | Ink having UV curing and oxidative polymerization functions, and printed matter using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08892B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009227702A (en) * | 2008-03-19 | 2009-10-08 | National Printing Bureau | Intaglio printing ink composition and printed matter obtained using the same |
| US9376579B2 (en) | 2009-10-16 | 2016-06-28 | National Printing Bureau, Incorporated Administrative Agency | Intaglio printing ink |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000265102A (en) * | 1999-03-17 | 2000-09-26 | Printing Bureau Ministry Of Finance Japan | UV curable ink combined with oxidative polymerization for flexographic printing and its printed matter |
| JP4660716B2 (en) * | 2000-07-25 | 2011-03-30 | 独立行政法人 国立印刷局 | Resin composition for intaglio ink, ink composition using the same, and printed matter thereof |
| DE10106011A1 (en) | 2001-02-05 | 2002-08-08 | Koenig & Bauer Ag | Method and device for preventing lay-off, smearing and marking in face and reverse printing |
| JPWO2003066759A1 (en) * | 2002-02-06 | 2005-06-02 | 独立行政法人 国立印刷局 | Ink printing ink composition and use thereof |
| JP4840687B2 (en) * | 2005-11-28 | 2011-12-21 | 独立行政法人 国立印刷局 | Ink composition for intaglio printing and method for producing intaglio print |
| MX2010000814A (en) * | 2007-07-20 | 2010-03-01 | Sicpa Holding Sa | Intaglio printing inks. |
| JP7190957B2 (en) * | 2019-04-03 | 2022-12-16 | サカタインクス株式会社 | Active energy ray-curable flexographic printing ink composition |
-
1988
- 1988-05-18 JP JP63119317A patent/JPH08892B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009227702A (en) * | 2008-03-19 | 2009-10-08 | National Printing Bureau | Intaglio printing ink composition and printed matter obtained using the same |
| US9376579B2 (en) | 2009-10-16 | 2016-06-28 | National Printing Bureau, Incorporated Administrative Agency | Intaglio printing ink |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01289876A (en) | 1989-11-21 |
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