JP2005082609A - Photopolymerizable ink composition and method for drying the same - Google Patents
Photopolymerizable ink composition and method for drying the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000001035 drying Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title description 8
- 239000004922 lacquer Substances 0.000 claims abstract description 57
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 6
- BBFSKMPJXRPZFK-UHFFFAOYSA-N [phenyl-(2,4,5-trimethylbenzoyl)phosphoryl]-(2,4,5-trimethylphenyl)methanone Chemical compound C1=C(C)C(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC(C)=C(C)C=C1C BBFSKMPJXRPZFK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 230000009974 thixotropic effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 41
- 210000003298 dental enamel Anatomy 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 5
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 5
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006872 enzymatic polymerization reaction Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000843 powder Substances 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
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- -1 2,4,5-trimethylbenzoyl Chemical group 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Abstract
Description
本願発明は、含漆印刷インクの印刷適正および乾燥性を改善した光重合性インキ組成物およびその乾燥方法に関する。 The present invention relates to a photopolymerizable ink composition with improved printing suitability and drying property of a lacquer-containing printing ink and a drying method thereof.
古代から現在に到るまで使用され続ける漆の特徴は、漆塗りによって得られる美の発現と、これを長期間保持する耐久性にある。しかし、漆液は高湿度環境（「ムロ」と呼ばれている。）におけるラッカーゼ酵素による酸化反応の第１段階で漆液の酵素重合を行い、次いで常温常湿空気中における酸素による側鎖の自動酸化の第２段階を経て硬化するため、完全乾燥するまで３０日以上の長時間を要する欠点があることから、漆の乾燥促進に関する多くの発明が開示されている。 The characteristic of lacquer that has been used from ancient times to the present is the expression of the beauty obtained by lacquering and the durability to retain it for a long time. However, the lacquer liquid undergoes enzymatic polymerization of the lacquer liquid in the first stage of the oxidation reaction by the laccase enzyme in a high-humidity environment (called “Muro”), and then the side chains of oxygen in air at room temperature and humidity. Since it is cured through the second stage of auto-oxidation, it has a drawback that it takes a long time of 30 days or more until it is completely dried. Therefore, many inventions relating to acceleration of drying of lacquer have been disclosed.
特許文献１では、生漆とラジカル重合系光重合性オリゴマーとを混合して混練しかつ脱水したものを塗布して、上記第１段階に要する時間を著しく短縮することで、速やかに第２段階に移行して硬化させる技術を開示している。特許文献２では、多価アルコールを混合した生漆を攪拌して、ウルシオールのオリゴマー成分が５０％以上となるまで酵素重合せしめた漆塗料であり、上記第２段階のみにより硬化させる技術を開示している。一方、光重合性インキ組成物は造膜機構と乾燥機構によって大別され、オイルベース、リキツドベース、ＵＶベース、２液反応型樹脂ベースなどがある。また光重合性インキ組成物及びエナメルの特性として、印刷時における見かけの粘度が低く、印刷後は適当な膜厚を保ち、垂れないという相反する性質が要求される。このため光重合性インキ組成物及びエナメルには、揺変剤を加えて二次結合による網目構造をつくる方法がとられ、印刷時には高せん断力によって低粘度化させ、印刷後に網目構造を復元して高粘度化させている。
しかしながら、特許文献１および２では、漆美を印刷インキとして利用する場合の技術については考慮していない。すなわち、漆美は透漆による木目塗装や漆黒、朱色、黄色、緑色などの彩色エナメル仕上げによって発現するが、印刷インキにおいては、印刷適正と乾燥性を考慮する必要がある。印刷適正については、印刷時における印刷インキの垂れを止め、膜厚を適正に調整する等の必要がある。乾燥性については、漆の彩色エナメルを含む印刷インキでは光透過性が悪く、従来技術の紫外線照射による光重合性プレポリマーの光重合のみでは、印刷部分を完全硬化させることが困難であった。
本願発明は、上述した課題を解決することを目的としたものであり、光重合性印刷インキに漆のオリゴマー成分を添加して印刷時に必要な揺変性を付与し、かつ、印刷部分を常温常湿環境下において短時間で乾燥および硬化させることを可能とした、新規な、光重合性インキ組成物およびその乾燥方法を提供するものである。
However, Patent Documents 1 and 2 do not consider the technique when using lacquer as printing ink. In other words, lacquer beauty is manifested by wood-grain coating with translucent lacquer and colored enamel finishes such as jet black, vermilion, yellow, and green. However, in printing inks, it is necessary to consider printing suitability and drying properties. As for printing appropriateness, it is necessary to stop printing ink dripping at the time of printing and to adjust the film thickness appropriately. Regarding dryness, printing ink containing lacquered colored enamel has poor light transmission, and it has been difficult to completely cure the printed portion only by photopolymerization of a photopolymerizable prepolymer by ultraviolet irradiation according to the prior art.
The present invention is intended to solve the above-described problems, and by adding a lacquer oligomer component to a photopolymerizable printing ink to impart thixotropy necessary for printing, The present invention provides a novel photopolymerizable ink composition that can be dried and cured in a short time in a wet environment, and a drying method thereof.
上記課題を解決するため、本願発明に係る光重合性インキ組成物およびその乾燥方法は以下のように構成している。すなわち、本願発明の第一構成では、光重合性プレポリマーに対して、揺変剤として機能する漆のオリゴマー成分（ダイマー以上の成分を言う、以下同じ。）を揺変剤として添加したことを特徴とする。例えば、漆のオリゴマー（ウルシオールオリゴマー等）成分の分子量範囲は６４０〜１３００である。本願発明では、油中水滴（エマルション）中のゴム質の膨潤により発現する漆のオリゴマー成分の物理的な揺変性を利用して揺変剤としたものである。光重合性プレポリマーに対しては、漆のオリゴマー成分を含むなやし漆液をそのまま添加しても良いし、なやし漆液から漆のオリゴマー成分のみを抽出して添加するようにしても良い。ＪＩＳ−Ｋ５９５０に規定する「なやし」工程では脱水をせずに混練するため、なやし漆液を揺変剤として機能させるには漆のオリゴマー成分を概ね４０％以上まで高めてから添加することが好ましい。漆のモノマー成分の含有量が多いと、揺変剤として機能しないことに加えて、漆のモノマーの酵素重合によるオリゴマー化を必要とするから迅速な乾燥および硬化をさせることができないからである。 In order to solve the above problems, the photopolymerizable ink composition and the drying method thereof according to the present invention are configured as follows. That is, in the first configuration of the present invention, a lacquer oligomer component functioning as a thixotropic agent (referred to as a dimer or higher component, hereinafter the same) is added as a thixotropic agent to the photopolymerizable prepolymer. Features. For example, the molecular weight range of a lacquer oligomer (such as urushiol oligomer) component is 640 to 1300. In the present invention, a thixotropic agent is used by utilizing physical thixotropy of the lacquer oligomer component that develops due to swelling of the rubber in the water-in-oil (emulsion). For the photopolymerizable prepolymer, the lacquered lacquer solution containing the lacquer oligomer component may be added as it is, or only the lacquer oligomer component is extracted from the lacquer lacquer solution and added. Also good. In the “Nayashi” process stipulated in JIS-K5950, kneading is carried out without dehydration. To make the lacquer lacquer solution function as a thixotropic agent, the lacquer oligomer component is increased to approximately 40% or more and then added. It is preferable to do. This is because when the content of the lacquer monomer component is large, in addition to not functioning as a thixotropic agent, oligomerization by enzymatic polymerization of the lacquer monomer is required, so that rapid drying and curing cannot be performed.
漆のオリゴマー成分により揺変性が向上した光重合性インキ組成物は、漆のオリゴマー成分が二次結合による網目構造を形成するため、印刷時における見かけの粘度が低くなると共に、印刷後には適当な膜厚を保ち、垂れないという相反する性質を有することになる。漆のオリゴマー成分を得るために使用する濾過生漆は日本産（主成分ウルシオール）、中国産（主成分ウルシオール）、ベトナム産（主成分ラッコール）、ミャンマー産（主成分チチオール）のいずれでも良い。なやし漆は、濾過生漆に多価アルコールのペンタエリトリトールを加え、若しくは加えることなくＪＩＳ−Ｋ５９５０による「なやし」工程を施し或いはニーデングミキサーで混練し、漆のオリゴマー成分を４０％以上として得ることが出来る。 The photopolymerizable ink composition improved in thixotropy by the lacquer oligomer component has a low apparent viscosity at the time of printing because the lacquer oligomer component forms a network structure by secondary bonds, and is suitable after printing. It will have the contradictory property of keeping the film thickness and not dripping. The filtered raw lacquer used to obtain the oligomer component of lacquer may be any of Japan (main component urushiol), China (main component urushiol), Vietnam (main component raccol), or Myanmar (main component thiol). . Nayashi Lacquer is made from filtered lacquer with or without adding polyhydric alcohol pentaerythritol, or the kneading process is performed according to JIS-K5950, or kneaded with a kneading mixer, and the oligomer component of lacquer is 40% or more. Can be obtained as
本願発明の第２構成では、光重合性インキ組成物の主剤である光重合性プレポリマーを光重合性アクリレートオリゴマーとそのモノマーとしたことを特徴とする。本願発明の光重合性インキ組成物の主剤として使用可能な光重合性プレポリマーとしては、揺変剤である漆のオリゴマー成分との絡み合いによる揺変性の制御性や、印刷仕上がりの表面光沢の観点から光重合性アクリレート系プレポリマーが特に好適であり、ポリエステルアクリレート、ウレタンアクリレート、エポキシアクリレート、アクリルアクリレート等を用いることができ、必要に応じてこれらのモノマーにより適宜の希釈を行うことができる。 The second constitution of the present invention is characterized in that a photopolymerizable prepolymer which is a main component of the photopolymerizable ink composition is used as a photopolymerizable acrylate oligomer and a monomer thereof. As a photopolymerizable prepolymer that can be used as the main component of the photopolymerizable ink composition of the present invention, the controllability of thixotropic properties due to entanglement with the oligomer component of lacquer as a thixotropic agent, and the surface gloss of the printed finish To photopolymerizable acrylate-based prepolymers are particularly suitable, and polyester acrylate, urethane acrylate, epoxy acrylate, acrylic acrylate, and the like can be used. If necessary, appropriate dilution can be performed with these monomers.
本願発明の第３構成では、フェニルビス（２，４，５−トリメチルベンゾイル）−ホスフィンオキシドを光重合開始剤の主成分とすることを特徴とする。
本願発明では、光重合プレポリマーに加えて揺変剤である漆のオリゴマー成分も光重合する。従って、漆のオリゴマー成分が光重合の活性母体となり自動酸化反応が進行すると共に、この活性母体が光重合開始剤であるフェニルビス（２，４，５−トリメチルベンゾイル）−ホスフィンオキシドに効果的に作用して活性ラジカルの発生が容易になり光重合プレポリマー硬化も進行する。特に、光重合性インキ組成物の着色等により、照射光のインキ組成物内部への透過性が悪い状態でも、光重合性インキ組成物中に漆のオリゴマー成分が存在し、かつ、適切な光重合開始剤を選択することにより、インキ組成物の内部硬化が著しく阻害されることがなくなるという顕著な効果がある。
なお、光重合性インキ組成物をエナメル化する場合はキナクリドン系等の顔料を適量加えて着色し、ロールミキシング等をして光重合性インキ組成物（光重合性エナメル組成物）を得ることができる。
The third configuration of the present invention is characterized in that phenylbis (2,4,5-trimethylbenzoyl) -phosphine oxide is a main component of the photopolymerization initiator.
In the present invention, in addition to the photopolymerization prepolymer, the oligomer component of lacquer as a thixotropic agent is also photopolymerized. Therefore, the lacquer oligomer component becomes an active matrix for photopolymerization and the auto-oxidation reaction proceeds, and this active matrix is effective for phenylbis (2,4,5-trimethylbenzoyl) -phosphine oxide, which is a photopolymerization initiator. By acting, the generation of active radicals is facilitated, and photopolymerization prepolymer curing also proceeds. In particular, the lacquer oligomer component is present in the photopolymerizable ink composition even in a state where the transmittance of the irradiated light into the ink composition is poor due to coloring of the photopolymerizable ink composition, etc. By selecting the polymerization initiator, there is a remarkable effect that the internal curing of the ink composition is not significantly inhibited.
In addition, when enamelizing a photopolymerizable ink composition, an appropriate amount of a pigment such as a quinacridone-based pigment is added and colored, and roll mixing is performed to obtain a photopolymerizable ink composition (photopolymerizable enamel composition). it can.
本願発明の第４構成では、光重合性インキ組成物の主剤である光重合性プレポリマーの不揮発成分が９０％以上であることを特徴とする。本願発明の揺変剤として利用する漆のオリゴマー成分は、不揮発成分が高い光重合性インキ組成物と組み合わせることで、漆のオリゴマー成分と光重合性プレポリマーの二次結合による網目構造を形成するため、高い揺変性を付与することができる。これにより、ハイソリッドインキや無溶剤インキのような、不揮発成分が多く揮発性有機溶剤を含まない安全性の高い低公害インキとすることができる。 The fourth configuration of the present invention is characterized in that the non-volatile component of the photopolymerizable prepolymer which is the main component of the photopolymerizable ink composition is 90% or more. The lacquer oligomer component used as the thixotropic agent of the present invention is combined with a photopolymerizable ink composition having a high non-volatile component to form a network structure by secondary bonds between the lacquer oligomer component and the photopolymerizable prepolymer. Therefore, high thixotropy can be imparted. Thereby, it can be set as the highly safe low pollution ink which has many non-volatile components and does not contain a volatile organic solvent like high solid ink and solventless ink.
本願発明の第５構成では、漆のオリゴマー成分を添加した光重合性プレポリマーの平行板粘度計（スプレッドメーター）による傾斜勾配ｙ＝ｔａｎαｘ＋ｈのｙ値が０．４〜０．６であることを特徴としている。本願発明では、平行板粘度計（スプレッドメーター）の傾斜勾配法ｙ＝ｔａｎαｘ＋ｈ（永瀬喜助：塗装技術，Ｎｏ８，３８（１９６７））により揺変性を規定している。すなわち、光重合性インキ組成物に漆のオリゴマー成分を添加して平行板粘度計（スプレッドメーター）の傾斜勾配ｙ＝ｔａｎαｘ＋ｈのｙ値を０．４〜０．６に調整して緩やかな揺変性を付与し、粘性と流動性のバランスを改善することができるからである。 In the fifth configuration of the present invention, the y value of the slope gradient y = tan αx + h by a parallel plate viscometer (spread meter) of a photopolymerizable prepolymer added with a lacquer oligomer component is 0.4 to 0.6. It is a feature. In this invention, thixotropic property is prescribed | regulated by the inclination gradient method y = tan (alpha) x + h (Kisuke Nagase: Coating technique, No8,38 (1967)) of a parallel plate viscometer (spread meter). That is, by adding a lacquer oligomer component to the photopolymerizable ink composition and adjusting the y value of the gradient y = tan αx + h of the parallel plate viscometer (spread meter) to 0.4 to 0.6, gentle thixotropy This is because the balance between viscosity and fluidity can be improved.
本願発明の第６構成では、光重合性インキ組成物の印刷部分に可視光域の光線を照射した後、紫外域の光線を照射することにより、迅速に光重合性インキ組成物の印刷部分の内部まで硬化させる乾燥方法を特徴としている。特に、漆の彩色エナメルを用いた場合のように、光重合性インキ組成物の内部への照射光の透過性が低下した状態における硬化方法として有効である。
第一工程として、可視光域の光線を照射すると、光重合性インキ組成物の印刷部分の表面および内部まで到達するから、漆のオリゴマー成分を光重合の活性母体として自動酸化反応を進行させる。同時にこの活性母体は光重合開始剤に作用して活性ラジカルを発生させるから光重合プレポリマーの硬化も開始させる。なお、第一工程では、赤外域の光線を照射することでより深部まで到達させることもできる。
第二工程として、紫外域の光線を照射することで、光重合開始剤は活性ラジカルを発生させて光重合性プレポリマーの硬化を進行させるが、光重合性インキ組成物の印刷部分の内部への照射光の透過性が低い場合でも、第一工程で光重合プレポリマーの硬化が行われているから、迅速に光重合性インキ組成物の印刷部分の内部まで硬化することとなる。
例えば、本願発明の光重合性インキ組成物を常法のスクリーン印刷機でガラス板に模様を描き、印刷部分に可視光ランプを１〜２分間照射して予備乾燥した後、紫外線ランプを約１０〜１５秒照射することにより、目的とする印刷硬化膜が得られる。さらに、印刷部分への紫外線照射直後は、光重合性インキ組成物中に含まれる漆のオリゴマー成分は未だ完全硬化していないため、模様部分に金・銀粉などの微粉末を蒔きつけやすく加飾が容易である。また、蒔きつけ後は漆の自動酸化反応を経て、微粉末が印刷部分の表面に完全に固着して均一な光沢が得られる。
In the sixth configuration of the present invention, after irradiating the visible portion of the photopolymerizable ink composition with a light ray in the visible light region, the irradiated portion of the photopolymerizable ink composition can be rapidly irradiated with an ultraviolet ray. It is characterized by a drying method that cures the interior. In particular, it is effective as a curing method in a state in which the transmittance of irradiation light into the photopolymerizable ink composition is lowered as in the case of using lacquered colored enamel.
As a first step, irradiation with a light beam in the visible light region reaches the surface and the inside of the printed portion of the photopolymerizable ink composition, so that the auto-oxidation reaction proceeds with the lacquer oligomer component as the active matrix for photopolymerization. At the same time, since this active matrix acts on the photopolymerization initiator to generate active radicals, curing of the photopolymerization prepolymer is also initiated. In the first step, it is possible to reach the deeper part by irradiating with infrared rays.
As a second step, the photopolymerization initiator generates active radicals by irradiating with ultraviolet rays, and proceeds to cure the photopolymerizable prepolymer, but into the printed portion of the photopolymerizable ink composition. Even when the transmittance of the irradiation light is low, since the photopolymerization prepolymer is cured in the first step, the inside of the printed portion of the photopolymerizable ink composition is quickly cured.
For example, the photopolymerizable ink composition of the present invention is patterned on a glass plate with a conventional screen printer, and the printed portion is irradiated with a visible light lamp for 1-2 minutes and preliminarily dried, and then an ultraviolet lamp is applied for about 10 minutes. By irradiating for ˜15 seconds, the intended print cured film is obtained. In addition, the lacquer oligomer component contained in the photopolymerizable ink composition is not yet completely cured immediately after UV irradiation on the printed part, so it can be easily decorated with fine powders such as gold and silver powder. Is easy. In addition, after glazing, the fine powder adheres completely to the surface of the printed part through an auto-oxidation reaction of lacquer, and a uniform gloss is obtained.
本願発明によれば、光重合性インキ組成物の印刷作業適正に必要な粘性と流動性のバランスを、漆のオリゴマー成分由来の揺変剤により調整することができる。また、低公害で環境対応型の超ハイソリッドのインキ組成物を提供することも可能となる。さらに、彩色漆の印刷において問題となる光重合性インキ組成物の遅乾性の改良により、印刷部分を常温常湿環境下において短時間で乾燥および硬化させることを可能とした。本願発明により、伝統工芸的漆蒔絵の作業効率を向上させ、漆の美的機能を活かした工業印刷への応用が可能となる等、その産業的効果は顕著である。 According to the present invention, the balance between viscosity and fluidity necessary for proper printing operation of the photopolymerizable ink composition can be adjusted by the thixotropic agent derived from the lacquer oligomer component. It is also possible to provide an environment-friendly ultra-high solid ink composition with low pollution. Furthermore, by improving the slow drying property of the photopolymerizable ink composition, which is a problem in the printing of colored lacquer, the printed part can be dried and cured in a short time under a normal temperature and humidity environment. According to the present invention, the industrial effect is remarkable, such as improving the working efficiency of traditional craft lacquer lacquer and enabling application to industrial printing utilizing the aesthetic function of lacquer.
以下に本願発明の光重合性インキ組成物およびその乾燥方法について、具体的実施例により詳細に説明する。 Hereinafter, the photopolymerizable ink composition of the present invention and the drying method thereof will be described in detail with reference to specific examples.
ウルシオールオリゴマーが４０％になるまで「なやし」処理した中国産濾過生漆１５部に、無溶剤型多官能ウレタンアクリレートプレポリマーを７０部及びそのモノマー１５部を加えて均一になるまで攪拌した後、有効成分１００％のフェニルビス（２，４，５−トリメチルベンゾイル）−ホスフィンオキシドを２部加えて攪拌混合し、光重合性含漆ハイソリッドインキ組成物を得た。このインキ組成物の平行板粘度計による傾斜勾配は０．４６であり、粘性と流動性のバランスが優れていることが確認された。この組成物を使用し、印刷局式グラビア印刷試験機で合成紙に模様を刷り、主波長３６０ナノメーターの可視光ランプで２分間照射して予備乾燥を行った後、主波長４２０ナノメーターの紫外線照射装置で１０〜１５秒間処理した印刷部分は凸面膜となり完全硬化した。 70 parts of solvent-free polyfunctional urethane acrylate prepolymer and 15 parts of the monomer were added to 15 parts of Chinese filtered raw lacquer that had been treated with “Nayashi” until the urushiol oligomer was 40% and stirred until uniform. Thereafter, 2 parts of phenylbis (2,4,5-trimethylbenzoyl) -phosphine oxide containing 100% of the active ingredient was added and mixed by stirring to obtain a photopolymerizable lacquer-containing high solid ink composition. The gradient of the ink composition measured by a parallel plate viscometer was 0.46, and it was confirmed that the balance between viscosity and fluidity was excellent. Using this composition, a pattern was printed on a synthetic paper with a printing bureau type gravure printing tester, preliminarily dried by irradiation with a visible light lamp having a main wavelength of 360 nm, and then having a main wavelength of 420 nm. The printed part treated with an ultraviolet irradiation device for 10 to 15 seconds became a convex film and was completely cured.
不揮発成分９５％の多官能エポキシアクリレートプレポリマーを６５部及びそのモノマー１５部の混合物に「なやし」処理したベトナム産濾過生漆２０部を加え、ニーダーミキサーでラッコールオリゴマーが４５％になるまで混練した。これに多環式顔料キナクリドンレッド１０部を加えガムテレピン１０部で希釈した後、らいかい機や３本ロール等で混練し、有効成分１００％のフェニルビス（２，４，５−トリメチルベンゾイル）−ホスフィンオキシドを２．５部加えて光重合性含漆ハイソリッドエナメル組成物を得た。これをガラス板にシルクスクリーン印刷機で模様を刷り、実施例１と同様の光重合処理を行った直後に、蒔絵用金丸粉６号及び金・銀箔を蒔き付けたところ印刷部分のみに完全に固着し、美麗な金蒔絵模様を現出させることができた。
Add 20 parts of Vietnamese filtered fresh lacquer treated with “Nayashi” to a mixture of 65 parts of polyfunctional epoxy acrylate prepolymer with 95% non-volatile content and 15 parts of its monomers, until the Rakkol oligomer is 45% with a kneader mixer Kneaded. After adding 10 parts of the polycyclic pigment quinacridone red to this and diluting with 10 parts of gum turpentine, the mixture is kneaded with a rake machine or three rolls, etc. to obtain phenylbis (2,4,5-trimethylbenzoyl)-with 100% active ingredient. 2.5 parts of phosphine oxide was added to obtain a photopolymerizable lacquer-containing high solid enamel composition. Immediately after the pattern was printed on a glass plate with a silk screen printing machine and the same photopolymerization treatment as in Example 1 was performed, gold mulch No. 6 and gold / silver foil for lacquer painting were applied, and only on the printed part. It stuck and was able to reveal a beautiful gold lacquer pattern.
Claims (6)
6. A photopolymerization characterized in that a printed portion printed using the photopolymerizable ink composition according to claim 1 is cured by irradiating with ultraviolet rays after irradiating visible rays. For drying a water-based ink composition.
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