JP2023161230A - Active energy ray curable ink composition and printed material - Google Patents
Active energy ray curable ink composition and printed material Download PDFInfo
- Publication number
- JP2023161230A JP2023161230A JP2022071460A JP2022071460A JP2023161230A JP 2023161230 A JP2023161230 A JP 2023161230A JP 2022071460 A JP2022071460 A JP 2022071460A JP 2022071460 A JP2022071460 A JP 2022071460A JP 2023161230 A JP2023161230 A JP 2023161230A
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- active energy
- energy ray
- compound
- curable ink
- 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
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- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- OOORLLSLMPBSPT-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,3-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC(C(=O)OCC=C)=C1 OOORLLSLMPBSPT-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 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 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000001592 prop-2-enyl (2E,4E)-hexa-2,4-dienoate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、活性エネルギー線硬化型インキ組成物および該活性エネルギー線硬化型インキ組成物を印刷してなる印刷物に関する。さらに詳しくは、セラミックスなどの難接着基材に対する密着性に優れ、且つ湿度によらず硬化性、耐溶剤性に優れる活性エネルギー線硬化型インキ組成物およびその印刷物に関する。 The present invention relates to an active energy ray-curable ink composition and printed matter printed with the active energy ray-curable ink composition. More specifically, the present invention relates to an active energy ray-curable ink composition that has excellent adhesion to difficult-to-adhere substrates such as ceramics, and has excellent curability and solvent resistance regardless of humidity, and printed matter thereof.
ガラスなどのセラミックス製品の被覆、すなわちコーティングや印刷などに用いるインキ組成物としては、基材であるセラミックスとの強固な密着性が要求されるため、専用の被覆用組成物が用いられている。セラミックス用インキなどの汎用のセラミックス被覆用組成物は、基材に印刷または被覆後に１５０℃～６００℃程度の高温で焼付け処理を行い、インキの模様や表示または被膜を基材に密着させている。しかしながら、この方法では、焼付け工程に多量のエネルギーを必要とすること、作業環境の点から生産効率が低いこと、乾燥炉の設置場所の確保や揮発成分の処理設備の設置にコストが掛かり高コスト化に繋がるなどの欠点を有する。また、ある種のセラミックス被覆用組成物は、ガラス成分の融着剤として鉛、カドミウム、クロム、マンガンなどの重金属が含まれていたり、溶剤などとして有機揮発性成分（ＶＯＣ）を必要としたりすることから、環境の観点からも望ましくない。 Ink compositions used for coating ceramic products such as glass, ie, coating, printing, etc., require strong adhesion to the ceramic base material, so special coating compositions are used. General-purpose ceramic coating compositions such as ceramic inks are printed or coated on the substrate and then baked at a high temperature of about 150°C to 600°C to make the ink pattern, display, or coating adhere to the substrate. . However, this method requires a large amount of energy for the baking process, has low production efficiency due to the work environment, and is expensive due to the costs involved in securing a place to install a drying oven and installing volatile component processing equipment. It has disadvantages such as leading to Additionally, some types of ceramic coating compositions contain heavy metals such as lead, cadmium, chromium, and manganese as fusing agents for glass components, and require organic volatile components (VOCs) as solvents. Therefore, it is undesirable from an environmental perspective.
一般に活性エネルギー線硬化型インキ組成物は、紫外線等の活性エネルギー線を照射することで短時間にて硬化するため、高温での焼付け工程を省くことが可能である。さらに、活性エネルギー線硬化型インキ組成物は、ＶＯＣやその他の非水系溶剤をほとんどまたは全く含ませることなく調製することが可能なため、環境面、作業効率面および設備投資面などの観点から望ましいものといえる。しかしながら、活性エネルギー線硬化型インキ組成物をセラミックス製品の被覆または装飾に適用した場合、焼付けを必要とするセラミックス被覆用組成物と同等または製品として許容可能な範囲内の密着性を得ることが困難であった。 In general, active energy ray-curable ink compositions can be cured in a short time by irradiation with active energy rays such as ultraviolet rays, so it is possible to omit a baking step at high temperatures. Furthermore, active energy ray-curable ink compositions can be prepared with little or no inclusion of VOCs or other non-aqueous solvents, which is desirable from the viewpoint of the environment, work efficiency, and capital investment. It can be said to be a thing. However, when an active energy ray-curable ink composition is applied to coat or decorate ceramic products, it is difficult to obtain adhesion that is equivalent to that of ceramic coating compositions that require baking or within an acceptable range for the product. Met.
セラミックス基材との密着性を改善する方法として、ビスフェノールＡエポキシ樹脂を主成分とする塗料に、有機官能性シラン、陽イオン光重合開始剤およびフッ素化表面活性剤を配合したＵＶ硬化型組成物が提案されている（特許文献１）。しかしながら、この組成物はＵＶ硬化速度が極端に遅いために、前処理として基材を加温したり、光照射後に加温し後硬化したりすることが必要であるなど、ＵＶ硬化で最大のメリットである被覆の高速化(特に、多色印刷機使用時)が困難であるなどの課題を有する。 As a method for improving adhesion to ceramic substrates, a UV-curable composition is prepared by blending an organofunctional silane, a cationic photopolymerization initiator, and a fluorinated surfactant into a paint whose main component is bisphenol A epoxy resin. has been proposed (Patent Document 1). However, because this composition has an extremely slow UV curing speed, it is necessary to heat the substrate as a pre-treatment and to heat and post-cure after irradiation with light. It has problems, such as the difficulty of speeding up coating (especially when using a multicolor printing machine), which is an advantage.
また特許文献２には、脂環式エポキシ基を有するアクリル樹脂と光カチオン重合開始剤とを必須成分とする光架橋組成物が開示されている。しかしながら、この組成物では、従来の光カチオン組成物より硬化性が高いものの、セラミックス基材との相互作用(密着力)が弱いために、耐湿性、耐煮沸性など、セラミックス製品が使用される環境において要求される特性に劣り、場合によっては基材から被膜が剥離するなどの課題を有する。 Further, Patent Document 2 discloses a photocrosslinking composition containing as essential components an acrylic resin having an alicyclic epoxy group and a photocationic polymerization initiator. However, although this composition has higher curability than conventional photocationic compositions, it has weak interaction (adhesion) with the ceramic substrate, so ceramic products are used, such as moisture resistance and boiling resistance. The properties required in the environment are poor, and in some cases there are problems such as the coating peeling off from the base material.
また特許文献３には、末端および／または側鎖にカチオン重合性官能基を有するアクリル樹脂とカップリング剤と光カチオン重合開始剤とを必須成分とする光架橋組成物が開示されている。しかしながら、この組成物では十分な硬化性が得られない上に、高湿度環境下では更に硬化性が低下するなどの課題があった。 Further, Patent Document 3 discloses a photocrosslinking composition containing as essential components an acrylic resin having a cationically polymerizable functional group at the terminal and/or side chain, a coupling agent, and a photocationic polymerization initiator. However, this composition had problems such as not only insufficient curability being obtained, but also curability further decreasing in a high humidity environment.
本発明の課題は、活性エネルギー線硬化型インキ組成物および該活性エネルギー線硬化型インキ組成物を印刷してなる印刷物を提供することにある。さらに詳しくは、セラミックスなどの難接着基材に対する密着性に優れ、湿度によらず硬化性、耐溶剤性に優れる活性エネルギー線硬化型インキ組成物およびその印刷物を提供することにある。 An object of the present invention is to provide an active energy ray-curable ink composition and a printed matter printed with the active energy ray-curable ink composition. More specifically, the object of the present invention is to provide an active energy ray-curable ink composition that has excellent adhesion to difficult-to-adhere substrates such as ceramics, and has excellent curability and solvent resistance regardless of humidity, and its printed matter.
上記課題を解決するために鋭意研究した結果、顔料、樹脂、エポキシ化合物、オキセタン化合物、光カチオン重合開始剤を含有してなる活性エネルギー線硬化型インキにおいて、特定の樹脂を含有し、特定の比率・量でエポキシ化合物とオキセタン化合物とを併用した活性エネルギー線硬化型インキ組成物が、セラミックスなどの難接着基材に対する密着性に優れ、且つ、湿度によらず硬化性、耐溶剤性に優れることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, we have found that active energy ray-curable inks containing pigments, resins, epoxy compounds, oxetane compounds, and photocationic polymerization initiators contain specific resins and have a specific ratio.・An active energy ray-curable ink composition containing a combination of an epoxy compound and an oxetane compound in different amounts has excellent adhesion to difficult-to-adhere substrates such as ceramics, and has excellent curability and solvent resistance regardless of humidity. They discovered this and completed the present invention.
すなわち、本発明は、（Ａ）顔料、（Ｂ）アリル樹脂、（Ｃ）エポキシ化合物、（Ｄ）オキセタン化合物、（Ｅ）光カチオン重合開始剤を含有し、下記（１）～（３）を特徴とする活性エネルギー線硬化型インキ組成物に関する。
（１）インキ組成物全量中、（Ｂ）アリル樹脂を３～２５重量％含有する。
（２）インキ組成物全量中、（Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物の合計が３０～６５重量％である。
（３）（Ｃ）エポキシ化合物／（Ｄ）オキセタン化合物で表される重量比率が、１～５の範囲である。
That is, the present invention contains (A) a pigment, (B) an allyl resin, (C) an epoxy compound, (D) an oxetane compound, and (E) a photocationic polymerization initiator, and the following (1) to (3). The present invention relates to a characteristic active energy ray-curable ink composition.
(1) The ink composition contains 3 to 25% by weight of (B) allyl resin.
(2) The total amount of (C) the epoxy compound and (D) the oxetane compound is 30 to 65% by weight in the total amount of the ink composition.
(3) The weight ratio expressed by (C) epoxy compound/(D) oxetane compound is in the range of 1 to 5.
また、本発明は、（Ｆ）増感剤としてアントラセン化合物を含有していることを特徴とする上記の活性エネルギー線硬化型インキ組成物に関するものである。 The present invention also relates to the above-mentioned active energy ray-curable ink composition, which contains an anthracene compound as (F) a sensitizer.
さらに、本発明は、（Ｄ）オキセタン化合物が分子中にオキセタン環を２個含有する化合物であることを特徴とする上記の活性エネルギー線硬化型インキ組成物に関するものである。 Furthermore, the present invention relates to the above active energy ray-curable ink composition, wherein the oxetane compound (D) is a compound containing two oxetane rings in the molecule.
さらに、本発明は、上記の活性エネルギー線硬化型インキ組成物を、基材に印刷してなる印刷物に関するものである。 Furthermore, the present invention relates to a printed matter obtained by printing the above active energy ray-curable ink composition on a base material.
本発明により、セラミックスなどの難接着基材に対する密着性に優れ、湿度によらず硬化性、耐溶剤性に優れる活性エネルギー線硬化型インキ組成物およびそれを印刷してなる印刷物を提供することが可能になった。 ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide an active energy ray-curable ink composition that has excellent adhesion to difficult-to-adhere substrates such as ceramics, and has excellent curability and solvent resistance regardless of humidity, and printed matter printed with the same. It's now possible.
本発明の活性エネルギー線硬化型インキ組成物は、活性エネルギー線照射によってカチオン重合反応を起こして硬化するインキ組成物であり、（Ａ）顔料、（Ｂ）アリル樹脂、（Ｃ）エポキシ化合物、（Ｄ）オキセタン化合物、（Ｅ）光カチオン重合開始剤を含有することを特徴とする。 The active energy ray-curable ink composition of the present invention is an ink composition that is cured by causing a cationic polymerization reaction by irradiation with active energy rays, and includes (A) a pigment, (B) an allyl resin, (C) an epoxy compound, ( It is characterized by containing D) an oxetane compound and (E) a photocationic polymerization initiator.
以下、各成分について具体的に説明する。 Each component will be specifically explained below.
本発明の（Ａ）顔料としては、各種の着色顔料または体質顔料が使用可能であり、耐熱性、耐光性、耐レトルト処理性を有するものであることが好ましい。着色顔料としては無機顔料、有機顔料が挙げられる。無機顔料は、酸化チタン、カーボンブラック等、有機顔料は、フタロシアニン系顔料、アゾ系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料、キノフタロン系顔料等、体質顔料は、酸化ケイ素、炭酸カルシウム、硫酸カルシウム、硫酸バリウムなどの公知公用の各種顔料が使用可能であり、それらは併用されてもよい。 As the pigment (A) of the present invention, various coloring pigments or extender pigments can be used, and it is preferable that the pigment has heat resistance, light resistance, and retort processing resistance. Coloring pigments include inorganic pigments and organic pigments. Inorganic pigments include titanium oxide and carbon black, organic pigments include phthalocyanine pigments, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments, and extender pigments include silicon oxide, calcium carbonate, and sulfuric acid. Various publicly known pigments such as calcium and barium sulfate can be used, and they may be used in combination.
（Ａ）顔料の含有量は、種類や目的によって適宜調整されるが、インキ組成物中、３質量％以上６０質量％以下が好ましく、５質量％以上４５質量％以下がより好ましい。 The content of the pigment (A) is suitably adjusted depending on the type and purpose, but is preferably 3% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 45% by mass or less in the ink composition.
本発明の（Ｂ）アリル樹脂としては、重合成分として少なくとも１種のアリルモノマーを含む樹脂をいう。アリルモノマーとしては、ジアリルフタレート、シクロヘキサンジカルボン酸ジアリル、アリルグリシジルエーテル、トリメチロールプロパンジアリルエーテル、ペンタエリスリトールトリアリルエーテル、トリメリット酸トリアリル、ピロメリット酸テトラアリル、ソルビン酸アリル、マレイン酸ジアリル、フマル酸ジアリル、クエン酸ジアリル等が挙げられる。これらの中でも、ジアリルフタレート、シクロヘキサンジカルボン酸ジアリルが好ましい。また、２種以上のアリル樹脂を含んでいてもよい。 The allyl resin (B) of the present invention refers to a resin containing at least one allyl monomer as a polymerization component. Allyl monomers include diallyl phthalate, diallyl cyclohexanedicarboxylate, allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, triallyl trimellitate, tetraallyl pyromellitate, allyl sorbate, diallyl maleate, diallyl fumarate. , diallyl citrate, and the like. Among these, diallyl phthalate and diallyl cyclohexanedicarboxylate are preferred. Moreover, two or more types of allyl resins may be included.
また、アリル樹脂の重量平均分子量（Ｍｗ）は、５０００以上１０００００以下が好ましく、１５０００以上７００００以下がより好ましい。Ｍｗは、ポリスチレンを標準物質としてゲル浸透クロマトグラフィーにより測定した値を意味し、ＪＩＳ Ｋ ７２５２－１：２０１６に準拠した方法により測定する。 Moreover, the weight average molecular weight (Mw) of the allyl resin is preferably 5,000 or more and 100,000 or less, more preferably 15,000 or more and 70,000 or less. Mw means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method based on JIS K 7252-1:2016.
（Ｂ）アリル樹脂としては、市販品を使用してもよい。例えば、（株）大阪ソーダ製のダイソーダップＡ、ダイソーダップＫ、ダイソーイソダップ、ＲＡＤＰＡＲ ＡＤ－０３２などを使用できる。 (B) As the allyl resin, commercially available products may be used. For example, Daiso Dapp A, Daiso Dapp K, Daiso Isodap, RADPAR AD-032 manufactured by Osaka Soda Co., Ltd., etc. can be used.
さらに、上記インキ組成物全量中、（Ｂ）アリル樹脂は３～２５重量％（好ましくは５～２０重量％、より好ましくは８～１６重量％）含有する事が必要である。この範囲でアリル樹脂を含有しない場合には、アリル樹脂の有効性が充分に発揮されず、アリル樹脂がこの範囲より少ないと難接着基材への密着性が低下し、この範囲より多いと硬化性が低下する。 Furthermore, it is necessary to contain the allyl resin (B) in an amount of 3 to 25% by weight (preferably 5 to 20% by weight, more preferably 8 to 16% by weight) in the total amount of the ink composition. If the allyl resin is not contained within this range, the effectiveness of the allyl resin will not be fully demonstrated; if the allyl resin is less than this range, the adhesion to difficult-to-adhesive substrates will decrease, and if it is more than this range, it will harden. Sexuality decreases.
本発明の（Ｃ）エポキシ化合物としては、１分子中にエポキシ基を１個以上有するエポキシ化合物であり、エポキシ当量７０～５，０００、好ましくは８０～３，０００のものを好適に使用することができる。 The epoxy compound (C) of the present invention is an epoxy compound having one or more epoxy groups in one molecule, and has an epoxy equivalent of 70 to 5,000, preferably 80 to 3,000. I can do it.
この（Ｃ）エポキシ化合物のエポキシ基は、シクロヘキセンオキサイドまたはシクロペンテンオキサイド構造などを有する脂環式エポキシ基；グリシジル基などの脂肪族エポキシ基のいずれであってもよく、１分子中に両者のエポキシ基が混在していてもよい。本発明においては、硬化性の観点から脂環式エポキシ化合物が好ましい。 The epoxy group of this epoxy compound (C) may be either an alicyclic epoxy group having a cyclohexene oxide or cyclopentene oxide structure, or an aliphatic epoxy group such as a glycidyl group, and both epoxy groups may be present in one molecule. may be mixed. In the present invention, alicyclic epoxy compounds are preferred from the viewpoint of curability.
脂環式エポキシ基を含有する脂環式エポキシ化合物としては、たとえばジシクロペンタジエンジオキサイド、（３，４－エポキシシクロヘキシル）メチル－３，４－エポキシシクロヘキサンカルボキシレート、ビス（２，３－エポキシシクロペンチル）エーテル、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート、（３，４－エポキシ－６－メチルシクロヘキシル）メチル－３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アセタール、エチレングリコールのビス（３，４－エポキシシクロヘキシル）エーテル、エチレングリコールの３，４－エポキシシクロヘキサンカルボン酸ジエステルなどが挙げられる。 Examples of alicyclic epoxy compounds containing an alicyclic epoxy group include dicyclopentadiene dioxide, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate, and bis(2,3-epoxycyclohexyl). ) ether, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, (3,4-epoxy-6-methylcyclohexyl)methyl-3,4-epoxy -6-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) acetal, bis(3,4-epoxycyclohexyl) ether of ethylene glycol, 3,4-epoxycyclohexanecarboxylic acid diester of ethylene glycol, etc. .
脂肪族エポキシ基を含有する脂肪族エポキシ化合物としては、たとえばエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、ジグリセリンテトラグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、スピログリコールジグリシジルエーテル、２，６－ジグリシジルフェニルエーテル、ソルビトールポリグリシジルエーテル、トリグリシジルイソシアヌレート、ビスフェノールＡジグリシジルエーテル、ブタジエンジオキサイド、フタル酸ジグリシジルエステル、ビスフェノール型エポキシ樹脂、ε－カプロラクトン変性ビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などが挙げられる。 Examples of aliphatic epoxy compounds containing an aliphatic epoxy group include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, spiroglycol diglycidyl ether, 2,6-diglycidylphenyl ether, sorbitol Polyglycidyl ether, triglycidyl isocyanurate, bisphenol A diglycidyl ether, butadiene dioxide, phthalic acid diglycidyl ester, bisphenol type epoxy resin, ε-caprolactone modified bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin Examples include.
本発明における（Ｄ）オキセタン化合物としては、オキセタン環を分子中に少なくとも１個含有する化合物であり、たとえば下記の式（Ｄ４－１）～（Ｄ４－４）で示される化合物などを挙げることができる。
式（Ｄ４－１）：
式（Ｄ４－２）：
式（Ｄ４－３）：
を示す）
式（Ｄ４－４）：
Formula (D4-1):
Formula (D4-2):
Formula (D4-3):
Formula (D4-4):
前記式（Ｄ４－１）で表されるオキセタン化合物の代表例としては、３－エチル－３－メトキシメチルオキセタン、３－エチル－３－エトキシメチルオキセタン、３－エチル－３－ブトキシメチルオキセタン、３－エチル－３－ヘキシルオキシメチルオキセタン、３－メチル－３－ヒドロキシメチルオキセタン、３－エチル－３－ヒドロキシメチルオキセタン、３－エチル－３－アリルオキシメチルオキセタン、３－エチル－３－（２’－ヒドロキシエチル）オキシメチルオキセタン、３－エチル－３－（２’－ヒドロキシ－３’－フェノキシプロピル）オキシメチルオキセタン、３－エチル－３－（２’－ヒドロキシ－３’－ブトキシプロピル）オキシメチルオキセタン、３－エチル－３－［２’－（２”－エトキシエチル）オキシメチル］オキセタン、３－エチル－３－（２’－ブトキシエチル）オキシメチルオキセタン、３－エチル－３－ベンジルオキシメチルオキセタン、３－エチル－３－（４－ｔｅｒｔ－ブチルベンジルオキシメチル）オキセタンなどを挙げることができる。 Representative examples of the oxetane compound represented by the formula (D4-1) include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, 3-ethyl-3-butoxymethyloxetane, and 3-ethyl-3-methoxymethyloxetane. -Ethyl-3-hexyloxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-allyloxymethyloxetane, 3-ethyl-3-(2' -hydroxyethyl)oxymethyloxetane, 3-ethyl-3-(2'-hydroxy-3'-phenoxypropyl)oxymethyloxetane, 3-ethyl-3-(2'-hydroxy-3'-butoxypropyl)oxymethyl Oxetane, 3-ethyl-3-[2'-(2''-ethoxyethyl)oxymethyl]oxetane, 3-ethyl-3-(2'-butoxyethyl)oxymethyloxetane, 3-ethyl-3-benzyloxymethyl Examples include oxetane, 3-ethyl-3-(4-tert-butylbenzyloxymethyl)oxetane, and the like.
前記式（Ｄ４－２）で表されるオキセタン化合物の代表例としては、式（Ｄ４－２）において、両方のＲ3がいずれもメチルまたはエチルである化合物を挙げることができる。 A typical example of the oxetane compound represented by the formula (D4-2) is a compound in which both R 3 are methyl or ethyl in the formula (D4-2).
前記式（Ｄ４－３）で表されるオキセタン化合物の代表例としては、式（Ｄ４－３）において、両方のＲ3がいずれもエチルで、Ｒ5がメチレン、エチレン、プロピレン、ブチレン、シクロヘキシレン、フェニレン、キシリレン、ポリ（エチレンオキシ）、ポリ（プロピレンオキシ）である化合物などを挙げることができる。 Representative examples of the oxetane compound represented by the formula (D4-3) include, in the formula (D4-3), both R 3 are ethyl and R 5 is methylene, ethylene, propylene, butylene, cyclohexylene. , phenylene, xylylene, poly(ethyleneoxy), poly(propyleneoxy), and the like.
前記式（Ｄ４－４）で表されるオキセタン化合物の代表例としては、３－メチル－３－オキセタニルメチルアクリレート、３－メチル－３－オキセタニルメチルメタクリレート、３－エチル－３－オキセタニルメチルアクリレート、３－エチル－３－オキセタニルメチルメタクリレートなどを挙げることができる。 Representative examples of the oxetane compound represented by the formula (D4-4) include 3-methyl-3-oxetanylmethyl acrylate, 3-methyl-3-oxetanylmethyl methacrylate, 3-ethyl-3-oxetanylmethyl acrylate, -ethyl-3-oxetanylmethyl methacrylate and the like.
本発明における（Ｄ）オキセタン化合物としては、分子中にオキセタン環を２個含有する化合物、すなわち式（Ｄ－２）、式（Ｄ－３）で表される化合物であることが好ましい。 The oxetane compound (D) in the present invention is preferably a compound containing two oxetane rings in the molecule, that is, a compound represented by formula (D-2) or formula (D-3).
さらに、（Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物との併用割合は、（Ｃ）エポキシ化合物／（Ｄ）オキセタン化合物で表される重量比率において１～５であり、１．５～４．５が好ましい。この範囲外であると目的とする効果が得られず、５を上回ると硬化性が低下し、１を下回ると高湿度環境下での硬化性が低下する。 Furthermore, the combined ratio of (C) epoxy compound and (D) oxetane compound is 1 to 5 in the weight ratio expressed by (C) epoxy compound/(D) oxetane compound, and is 1.5 to 4.5. is preferred. If it is outside this range, the desired effect will not be obtained, if it exceeds 5, the curability will decrease, and if it is below 1, the curability in a high humidity environment will decrease.
また、インキ組成物全量中、（Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物の合計量は、３０～６５重量％含有する事が必要である。この範囲外であると目的とする効果が得られず、この範囲を下回ると硬化性が低下し、この範囲を超えると難接着基材への密着性が低下する。 Furthermore, the total amount of the (C) epoxy compound and (D) oxetane compound in the total amount of the ink composition must be 30 to 65% by weight. If it is outside this range, the desired effect will not be obtained, if it is below this range, the curability will decrease, and if it exceeds this range, the adhesiveness to difficult-to-bond substrates will decrease.
本発明における（Ｅ）光カチオン重合開始剤としては、活性エネルギー線照射によって酸を発生し、被覆用組成物中に含まれるカチオン重合性の成分のカチオン重合性官能基（たとえばエポキシ基やオキセタニル基など）に作用してカチオン重合を開始させる化合物である。（Ｅ）光カチオン重合開始剤は１種または２種以上を併用可能である。活性エネルギー線としては、紫外線、電子線、放射線（β線、γ線）などが例示できる。 The (E) photocationic polymerization initiator in the present invention is a cationically polymerizable functional group (e.g., epoxy group or oxetanyl group) of a cationically polymerizable component contained in the coating composition that generates an acid upon irradiation with active energy rays. etc.) to initiate cationic polymerization. (E) The photocationic polymerization initiator can be used alone or in combination of two or more. Examples of active energy rays include ultraviolet rays, electron beams, and radiation (β rays, γ rays).
（Ｅ）光カチオン重合開始剤としては、一般的には、スルホニウム塩、ヨードニウム塩、メタロセン化合物、ベンゾイントシレートなどが知られており、多くの化合物が市販されている。本発明では市販の光カチオン重合開始剤を使用することができる。 (E) As the photocationic polymerization initiator, sulfonium salts, iodonium salts, metallocene compounds, benzointosylate, etc. are generally known, and many of these compounds are commercially available. In the present invention, commercially available photocationic polymerization initiators can be used.
市販品としては、たとえばイルガキュア２５０（ＢＡＳＦジャパン（株）製）、ＣＰＩ－１００Ｐ（サンアプロ（株）製）などを代表例として挙げることができる。 Representative examples of commercially available products include Irgacure 250 (manufactured by BASF Japan Co., Ltd.) and CPI-100P (manufactured by Sun-Apro Co., Ltd.).
（Ｅ）光カチオン重合開始剤の含有量は、インキ組成物全量中、０．１質量％以上、好ましくは５質量％以上、また２５質量％以下、好ましくは２０質量％以下が好適である。光カチオン重合開始剤が少なすぎると重合が開始されないか重合速度が遅くなる傾向にあり、また多すぎると組成物中から析出（分離）する傾向にある。 (E) The content of the photocationic polymerization initiator is suitably 0.1% by mass or more, preferably 5% by mass or more, and 25% by mass or less, preferably 20% by mass or less, based on the total amount of the ink composition. If the amount of the photocationic polymerization initiator is too small, polymerization will tend not to start or the polymerization rate will be slow, and if it is too large, it will tend to precipitate (separate) from the composition.
本発明における（Ｆ）増感剤は、アントラセン化合物が好ましく、９，１０－ビス－（２－エチルヘキシルオキシ）アントラセン、９，１０－ビス－（ｎ－ドデシルオキシ）アントラセン、２－エチル－９，１０－ジエトキシアントラセン、９，１０－ジエトキシアントラセン、９，１０－ジブトキシアントラセンなどを挙げることができる。 The sensitizer (F) in the present invention is preferably an anthracene compound, such as 9,10-bis-(2-ethylhexyloxy)anthracene, 9,10-bis-(n-dodecyloxy)anthracene, 2-ethyl-9, Examples include 10-diethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.
（Ｆ）増感剤の配合量は、インキ組成物全量中、１０質量％以下が好ましく、２質量％以下がより好ましい。 (F) The blending amount of the sensitizer is preferably 10% by mass or less, more preferably 2% by mass or less, based on the total amount of the ink composition.
本発明のインキ組成物は、上記成分のほか、インキ組成物に通常配合される添加剤が任意成分として配合されてもよい。任意成分としては、顔料分散剤、消泡剤、レベリング剤、光安定剤、酸化防止剤、重合禁止剤、滑剤、ワックスなどを配合してもよい。 In addition to the above-mentioned components, the ink composition of the present invention may optionally contain additives that are normally added to ink compositions. As optional components, a pigment dispersant, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, a lubricant, a wax, etc. may be blended.
本発明のインキ組成物には連鎖移動剤となりえる水酸基含有化合物を配合してもよい。水酸基含有化合物としては、メタノール、エタノール、ｎ－およびｉ－プロパノール、ｎ－、ｉ－、ｓｅｃおよびｔ－ブタノール、エチレングリコールモノメチルエーテル、エチレングリーコールモノエチルエーテル、プロピレングリコール モノメチルエーテルなどが挙げられる。 The ink composition of the present invention may contain a hydroxyl group-containing compound that can serve as a chain transfer agent. Examples of the hydroxyl group-containing compound include methanol, ethanol, n- and i-propanol, n-, i-, sec and t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and the like.
また、本発明のインキ組成物には基本的に溶剤は不要であるが、組成物の粘度調整や塗工性を向上させるために、場合によっては適量使用してもよい。 Although the ink composition of the present invention basically does not require a solvent, an appropriate amount may be used depending on the case in order to adjust the viscosity of the composition and improve the coating properties.
また、本発明のインキ組成物には上記記載の（Ｂ）アリル樹脂に加え、従来、用いられるインキ用樹脂が併用されてもよい。たとえば、アルキッド樹脂、オイルフリーポリエステル樹脂、石油樹脂、エポキシ樹脂、ケトン樹脂、ロジン変性フェノール樹脂等である。 Furthermore, in addition to the allyl resin (B) described above, conventionally used ink resins may be used in combination with the ink composition of the present invention. Examples include alkyd resins, oil-free polyester resins, petroleum resins, epoxy resins, ketone resins, and rosin-modified phenolic resins.
本発明のインキ組成物の調製方法は特に限定されない。一例を挙げると、インキ組成物は、３本ロールミル、ボールミル、ビーズミル等を用いる事によって調製され得る。 The method for preparing the ink composition of the present invention is not particularly limited. For example, the ink composition can be prepared using a three-roll mill, a ball mill, a bead mill, or the like.
本発明のインキ組成物が印刷される難接着基材としてはセラミックスや金属板、オレフィン系樹脂フィルムなどが挙げられるが、それらに限定されない。一例を挙げると、セラミックス基材としては、ガラス、陶器、磁器、セメントなどが挙げられ、形態としては特に限定されず、容器、装飾物、装飾用小立像、花瓶、窓、タイルなどが含まれる。また、金属基材としては、ブリキ板、アルミニウム板であり、これらの基材は、化成処理、メッキ処理、サイズ塗装やホワイトコーティング、シルバーコーティング等が施されてもよい。また、オレフィン系樹脂フィルムとしては、ポリエチレンフィルム、プリプロピレンフィルムなどが挙げられる。 Examples of difficult-to-adhesive substrates on which the ink composition of the present invention is printed include, but are not limited to, ceramics, metal plates, olefin resin films, and the like. For example, ceramic substrates include glass, pottery, porcelain, cement, etc., and are not particularly limited in form, and include containers, ornaments, decorative figurines, vases, windows, tiles, etc. . Further, the metal base material is a tin plate or an aluminum plate, and these base materials may be subjected to chemical conversion treatment, plating treatment, size painting, white coating, silver coating, etc. Further, examples of the olefin resin film include polyethylene film and polypropylene film.
本発明のインキ組成物の印刷方法については特に制限はなく、たとえばシルクスクリーン印刷、グラビア印刷、フレキソ印刷、凸版印刷、樹脂凸版を使用したドライオフセット印刷などの方法の中から適宜選択して用いることができる。 There are no particular limitations on the printing method for the ink composition of the present invention, and the method may be appropriately selected from silk screen printing, gravure printing, flexographic printing, letterpress printing, dry offset printing using resin letterpress, etc. I can do it.
印刷物の硬化は、印刷後、０～１００℃、たとえば室温において活性エネルギー線を照射すればよい。使用する活性エネルギー線としては特に限定されず、たとえば紫外線、電子線、放射線（β線、γ線）などを挙げることができる。また、活性エネルギー線のエネルギー源としても特に限定されず、たとえば低圧水銀灯、中圧水銀灯、高圧水銀灯、メタルハライドランプ、ガリウムランプ、無電極ランプ、キセノンランプ、エキシマランプ、ＬＥＤランプなどの紫外線ランプ、走査型、非走査型の電子線照射装置などが挙げられる。 After printing, the printed material may be cured by irradiating it with active energy rays at 0 to 100° C., for example, at room temperature. The active energy rays to be used are not particularly limited, and include, for example, ultraviolet rays, electron beams, radiation (β rays, γ rays), and the like. The energy source of active energy rays is not particularly limited, and examples include ultraviolet lamps such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, gallium lamps, electrodeless lamps, xenon lamps, excimer lamps, and LED lamps, scanning type, non-scanning type electron beam irradiation equipment, etc.
印刷物を硬化させるために必要な活性エネルギー線の照射量としては、紫外線の場合は下限１０ｍＪ／ｃｍ2、上限１００００ｍＪ／ｃｍ2が好ましい。 In the case of ultraviolet rays, the amount of active energy ray irradiation required to cure the printed matter is preferably 10 mJ/cm 2 as a lower limit and 10,000 mJ/cm 2 as an upper limit.
また、必要に応じて活性エネルギー線を照射する前に予備加熱を行ったり、活性エネルギー線を照射したのちに後追い加熱を行ったりしてもよい。 Further, if necessary, preliminary heating may be performed before irradiation with active energy rays, or follow-up heating may be performed after irradiation with active energy rays.
照射後に後追い加熱することによって硬化皮膜中の未反応物量の低減、および活性エネルギー線照射による塗膜の硬化によって生じた塗膜の歪みの緩和を行うことができる。そのほか、後追い加熱によって塗膜の硬度や密着性が向上する場合もある。後追い加熱は、通常、５０～２５０℃の雰囲気温度で１～３０分間行うことが好ましい。 By post-heating after irradiation, it is possible to reduce the amount of unreacted substances in the cured film and to alleviate the distortion of the coating film caused by the curing of the coating film by irradiation with active energy rays. In addition, post-heating may improve the hardness and adhesion of the coating film. The follow-up heating is usually preferably carried out at an ambient temperature of 50 to 250° C. for 1 to 30 minutes.
本発明のインキ組成物を用い硬化させて得られる硬化皮膜は、湿度によらず硬化性、耐溶剤性に優れており、しかもセラミックスなどの難接着基材との密着性が特に向上したものである。 The cured film obtained by curing the ink composition of the present invention has excellent curability and solvent resistance regardless of humidity, and has particularly improved adhesion to difficult-to-adhere substrates such as ceramics. be.
以下に実施例をあげて本発明を詳細に説明するが、本発明はこれらの実施例のみに限定されるものでない。以下、表中の数字は、質量％を示す。 EXAMPLES The present invention will be explained in detail with reference to Examples below, but the present invention is not limited to these Examples. Below, the numbers in the table indicate mass %.
以下に示す処方により活性エネルギー線硬化型インキ組成物を作製した。 An active energy ray-curable ink composition was prepared using the formulation shown below.
＜インキ用ワニスの作製＞
各種樹脂を含有したインキ組成物については、インキ組成物を作製するに先立ち、ワニスを作製した。ワニスは、各種樹脂とエポキシ化合物とを１００℃で混合し、樹脂比率を６０重量％比率で溶解させて作製した。尚、樹脂を含有し、且つエポキシ化合物を含有していない比較例７および１３に関しては、エポキシ化合物の代わりにオキセタン化合物で樹脂を溶解させてワニスを作製した。
<Preparation of varnish for ink>
For ink compositions containing various resins, varnishes were prepared prior to producing the ink compositions. The varnish was prepared by mixing various resins and epoxy compounds at 100° C. and dissolving the resin at a ratio of 60% by weight. In addition, regarding Comparative Examples 7 and 13, which contained a resin and did not contain an epoxy compound, varnishes were prepared by dissolving the resin with an oxetane compound instead of the epoxy compound.
＜インキ組成物の作成＞
表１、２に記載される配合にて、３本ロールミルを用いて最大粒径が７．５μｍ以下になるように分散して、実施例１～１５、比較例１～１４のインキ組成物を作製した。
表中の材料を下記に示す。
・有機顔料：フタロシアニン系顔料（トーヨーカラー（株）製「ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ－７３５１」）
・体質顔料：非晶質シリカ（日本アエロジル（株）製「ＡＥＲＯＳＩＬ Ｒ９７６Ｓ」）
・アリル樹脂：（（株）大阪ソーダ製「ダイソーダップＫ（ジアリルフタレート系樹脂）」、「ダイソーダップＡ（ジアリルフタレート系樹脂）」、「ＲＡＤＰＡＲ ＡＤ－０３２」）
・ポリエステル樹脂：（東洋紡（株）製「バイロンＧＫ－６８０」）
・石油樹脂：（東ソー（株）製「ペトロタック９０」、「ペトコール１３０」）
・アクリル樹脂：（根上工業（株）製「ハイパールＧＭ－３０１１」）
・エポキシ化合物：脂環式エポキシ化合物（Ｄａｌｉａｎ Ｔｒｉｃｏ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ製「ＣＥＲ４２２１」）、（３，４－エポキシシクロヘキシル）メチル－３，４－エポキシシクロヘキサンカルボキシレート
・オキセタン化合物：２官能オキセタン化合物（東亞合成（株）製「アロンオキセタンＯＸＴ－２２１」）、式（Ｄ４－２）においてＲ３がエチル基である化合物
・光カチオン重合開始剤：オニウム塩系開始剤（サンアプロ（株）製「ＣＰＩ－１００Ｐ」）
・増感剤：アントラセン系増感剤（川崎化成工業（株）製「アントラキュアーＵＶＳ－１１０１」）
<Creation of ink composition>
The ink compositions of Examples 1 to 15 and Comparative Examples 1 to 14 were prepared by dispersing the formulations shown in Tables 1 and 2 using a three-roll mill so that the maximum particle size was 7.5 μm or less. Created.
The materials in the table are shown below.
・Organic pigment: Phthalocyanine pigment (“LIONOL BLUE FG-7351” manufactured by Toyo Color Co., Ltd.)
・Extender pigment: Amorphous silica (“AEROSIL R976S” manufactured by Nippon Aerosil Co., Ltd.)
・Allyl resin: (“Daiso Dapp K (diallyl phthalate resin)”, “Daiso Dapp A (diallyl phthalate resin)”, “RADPAR AD-032” manufactured by Osaka Soda Co., Ltd.)
・Polyester resin: (“Byron GK-680” manufactured by Toyobo Co., Ltd.)
・Petroleum resin: (“Petrotac 90”, “Petcol 130” manufactured by Tosoh Corporation)
・Acrylic resin: (“Hypal GM-3011” manufactured by Negami Kogyo Co., Ltd.)
・Epoxy compound: Alicyclic epoxy compound (“CER4221” manufactured by Dalian Trico Chemical Co., Ltd.), (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate oxetane compound: Bifunctional oxetane compound ( "Aronoxetane OXT-221" manufactured by Toagosei Co., Ltd.), a compound in which R 3 is an ethyl group in formula (D4-2) ・Photocationic polymerization initiator: Onium salt-based initiator ("CPI" manufactured by San-Apro Co., Ltd.) -100P”)
・Sensitizer: Anthracene-based sensitizer (“Anthracure UVS-1101” manufactured by Kawasaki Chemical Industries, Ltd.)
実施例１～１５および比較例１～１４のインキ組成物について、以下の方法でテストパネルを作製し、そのテストパネルを用いて、密着性、硬化性、耐溶剤性を評価した。 Test panels were prepared for the ink compositions of Examples 1 to 15 and Comparative Examples 1 to 14 by the following method, and the test panels were used to evaluate adhesion, curability, and solvent resistance.
＜テストパネルの作製＞
実施例１～１５、および比較例１～１４のインキ組成物について、バーコーターにて膜厚１０μｍとなるように、 ガラス板（アセトンで洗浄した市販の硬質ガラス板）もしくはアルミ板に印刷した。次いで、集光型メタルハライドランプ（アイグラフィックス（株）製、１２０Ｗ/ｃｍ）照射装置を用いて、印刷物との距離１１ｃｍ、コンベア速度１０ｍ／分で紫外線を印刷物に照射して硬化させ、テストパネルを得た。
<Preparation of test panel>
The ink compositions of Examples 1 to 15 and Comparative Examples 1 to 14 were printed on glass plates (commercially available hard glass plates cleaned with acetone) or aluminum plates using a bar coater to a film thickness of 10 μm. Next, using a concentrating metal halide lamp (manufactured by Eye Graphics Co., Ltd., 120 W/cm) irradiation device, the printed matter was irradiated with ultraviolet rays at a distance of 11 cm from the printed matter and at a conveyor speed of 10 m/min to cure it, and the test panel was I got it.
＜密着性の評価＞
ガラス板もしくはアルミ板上に印刷したテストパネルについて、セロハンテープ剥離試験（碁盤目テープ法）にて以下基準で評価を実施した。試験は紫外線照射１時間後のテストパネルを使用して実施した。実用面から「△」以上が望まれる。
〇：全く剥離していない。
△：僅かに剥離している。（剥離面積が試験面積の１０％未満）
×：剥離している。（剥離面積が試験面積の１０％以上）
<Evaluation of adhesion>
Test panels printed on glass plates or aluminum plates were evaluated using a cellophane tape peeling test (checkerboard tape method) based on the following criteria. The test was conducted using a test panel 1 hour after UV irradiation. From a practical standpoint, a score of "△" or better is desired.
○: Not peeled off at all.
△: Slight peeling. (Peeling area is less than 10% of the test area)
×: Peeling off. (Peeling area is 10% or more of the test area)
＜硬化性＞
ガラス板上に印刷したテストパネルについて、紫外線照射直後から指で触ってタック（粘着性）を感じなくなるまでの時間（秒数）を測定した。尚、湿度４０％と８０％の２種の条件下で紫外線を照射した。実用面から「△」以上が望まれる。
〇 ：１秒未満。
〇△：１秒以上、５秒未満
△ ：５秒以上、１０秒未満
× ：１０秒以上
<Curability>
For a test panel printed on a glass plate, the time (number of seconds) from immediately after UV irradiation until it no longer felt tack (adhesiveness) when touched with a finger was measured. The ultraviolet rays were irradiated under two conditions: 40% humidity and 80% humidity. From a practical standpoint, a score of "△" or better is desired.
〇: Less than 1 second.
〇△: 1 second or more, less than 5 seconds △: 5 seconds or more, less than 10 seconds ×: 10 seconds or more
＜耐溶剤性＞
ガラス板上に印刷したテストパネルについて、表面をエタノールを含浸させた綿棒で軽く１００回こすり（１００往復させる）、皮膜表面の劣化及び綿棒への色移りについて以下基準で評価を実施した。試験は紫外線照射１時間後のテストパネルを使用して実施した。尚、湿度４０％と８０％の２種の条件下で紫外線を照射した。実用面から「△」以上が望まれる。
〇 ：皮膜表面の劣化なし、綿棒への色移りなし
〇△：皮膜表面の劣化なし、綿棒へ僅かに色移りあり
△ ：皮膜表面の劣化なし、綿棒へ色移りあり
× ：皮膜表面の劣化あり、綿棒へ色移りあり
<Solvent resistance>
For test panels printed on glass plates, the surface was lightly rubbed 100 times with a cotton swab impregnated with ethanol (100 reciprocations), and the deterioration of the film surface and color transfer to the cotton swab were evaluated using the following criteria. The test was conducted using a test panel 1 hour after UV irradiation. The ultraviolet rays were irradiated under two conditions: 40% humidity and 80% humidity. From a practical standpoint, a score of "△" or better is desired.
〇: No deterioration of the film surface, no color transfer to the cotton swab 〇△: No deterioration of the film surface, slight color transfer to the cotton swab △: No deterioration of the film surface, color transfer to the cotton swab ×: Deterioration of the film surface , color transfer to cotton swab
実施例、比較例の処方設計は下記の通りである。
（１）表１（実施例１～１５）
・（Ａ）顔料、（Ｂ）アリル樹脂、（Ｃ）エポキシ化合物、（Ｄ）オキセタン化合物、（Ｅ）光カチオン重合開始剤を含有している。
・インキ組成物全量中、（Ｂ）アリル樹脂を３～２５重量％含有している。
・インキ組成物全量中、（Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物の合計が３０～６５重量％である。
・（Ｃ）エポキシ化合物／（Ｄ）オキセタン化合物で表される重量比率が、１～５の範囲である。
（２）表２（比較例１～５）
・実施例の組成物との相違点として、（Ｂ）アリル樹脂を含有していない。（比較例１～４はその他の樹脂を含有している。）
（３）表２（比較例６）
・実施例の組成物との相違点として、（Ｂ）アリル樹脂、（Ｄ）オキセタン化合物を含有していない。
（４）表２（比較例７）
・実施例の組成物との相違点として、（Ｂ）アリル樹脂、（Ｃ）エポキシ化合物を含有していない。
（５）表２（比較例８）
・実施例の組成物との相違点として、（Ｂ）アリル樹脂の含有量が３～２５重量％の範囲を超えている。
（６）表２（比較例９）
・実施例の組成物との相違点として、（Ｄ）オキセタン化合物を含有していない。
（７）表２（比較例１０～１２）
・実施例の組成物との相違点として、（Ｃ）エポキシ化合物／（Ｄ）オキセタン化合物で表される重量比率が、１～５の範囲でない。
（８）表２（比較例１３）
・実施例の組成物との相違点として、（Ｃ）エポキシ化合物を含有していない。
（９）表２（比較例１４）
・実施例の組成物との相違点として、Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物の合計が３０重量％未満である。
The formulation designs for Examples and Comparative Examples are as follows.
(1) Table 1 (Examples 1 to 15)
Contains (A) pigment, (B) allyl resin, (C) epoxy compound, (D) oxetane compound, and (E) photocationic polymerization initiator.
- Contains (B) allyl resin in an amount of 3 to 25% by weight based on the total amount of the ink composition.
- The total amount of (C) the epoxy compound and (D) the oxetane compound is 30 to 65% by weight in the total amount of the ink composition.
- The weight ratio expressed by (C) epoxy compound/(D) oxetane compound is in the range of 1 to 5.
(2) Table 2 (Comparative Examples 1 to 5)
- The difference from the composition of the example is that (B) it does not contain allyl resin. (Comparative Examples 1 to 4 contain other resins.)
(3) Table 2 (Comparative Example 6)
- As a difference from the composition of the example, it does not contain (B) allyl resin and (D) oxetane compound.
(4) Table 2 (Comparative Example 7)
- The difference from the composition of the example is that it does not contain (B) allyl resin and (C) epoxy compound.
(5) Table 2 (Comparative Example 8)
- The difference from the compositions of Examples is that the content of (B) allyl resin exceeds the range of 3 to 25% by weight.
(6) Table 2 (Comparative Example 9)
- As a difference from the composition of the example, it does not contain (D) an oxetane compound.
(7) Table 2 (Comparative Examples 10 to 12)
- As a difference from the compositions of Examples, the weight ratio expressed by (C) epoxy compound/(D) oxetane compound is not in the range of 1 to 5.
(8) Table 2 (Comparative Example 13)
- As a difference from the composition of the example, it does not contain (C) an epoxy compound.
(9) Table 2 (Comparative Example 14)
- The difference from the compositions of Examples is that the total amount of C) epoxy compound and (D) oxetane compound is less than 30% by weight.
表１～２に示されるように、本発明の実施例に記載の印刷インキ組成物を用いた場合、比較例の印刷インキ組成物を用いた場合と比べて、セラミックス等の難接着基材に対する密着性に優れ、且つ、湿度によらず硬化性、耐溶剤性に優れる活性エネルギー線硬化型インキを得ることができることが分った。 As shown in Tables 1 and 2, when the printing ink compositions described in the examples of the present invention were used, compared to the case where the printing ink compositions of the comparative examples were used, It has been found that it is possible to obtain an active energy ray-curable ink that has excellent adhesion, curability regardless of humidity, and excellent solvent resistance.
Claims (4)
（Ｂ）アリル樹脂
（Ｃ）エポキシ化合物
（Ｄ）オキセタン化合物
（Ｅ）光カチオン重合開始剤
を含有し、下記（１）～（３）を特徴とする活性エネルギー線硬化型インキ組成物。
（１）インキ組成物全量中、（Ｂ）アリル樹脂を３～２５重量％含有する。
（２）インキ組成物全量中、（Ｃ）エポキシ化合物と（Ｄ）オキセタン化合物とを合計で３０～６５重量％含有する。
（３）（Ｃ）エポキシ化合物／（Ｄ）オキセタン化合物で表される重量比率が、１～５の範囲である。 (A) Pigment (B) Allyl resin
(C) Epoxy compound
(D) Oxetane compound
(E) An active energy ray-curable ink composition containing a photocationic polymerization initiator and characterized by the following (1) to (3).
(1) The ink composition contains 3 to 25% by weight of (B) allyl resin.
(2) The ink composition contains a total of 30 to 65% by weight of (C) an epoxy compound and (D) an oxetane compound.
(3) The weight ratio expressed by (C) epoxy compound/(D) oxetane compound is in the range of 1 to 5.
A printed matter obtained by printing the active energy ray-curable ink composition according to claim 1 or 2 on a substrate.
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| JP2022071460A JP7198403B1 (en) | 2022-04-25 | 2022-04-25 | Active energy ray-curable ink composition and printed matter |
| PCT/JP2023/014450 WO2023210311A1 (en) | 2022-04-25 | 2023-04-07 | Actinic ray curable ink composition and printed matter |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02289611A (en) * | 1989-02-09 | 1990-11-29 | Kansai Paint Co Ltd | Photo-setting resin composition |
| JP2000507281A (en) * | 1996-03-08 | 2000-06-13 | レヴロン コンシューマー プロダクツ コーポレイション | Glass decorating method using bisphenol A epoxy resin and related compositions and articles |
| JP2007051244A (en) * | 2005-08-19 | 2007-03-01 | Konica Minolta Medical & Graphic Inc | Active energy ray curing composition, ink composition for ink jet and method for forming image |
| WO2007049488A1 (en) * | 2005-10-24 | 2007-05-03 | Matsui Chemical Co., Ltd. | Composition for coating ceramics |
| JP2007211200A (en) * | 2006-02-13 | 2007-08-23 | Fuji Seal International Inc | Active energy ray-curable resin composition for plastic film coating and its use |
| JP2020019915A (en) * | 2018-08-03 | 2020-02-06 | Ｄｉｃグラフィックス株式会社 | Active energy ray-curable offset ink composition, offset printing ink using the same and printed matter |
-
2022
- 2022-04-25 JP JP2022071460A patent/JP7198403B1/en active Active
-
2023
- 2023-04-07 WO PCT/JP2023/014450 patent/WO2023210311A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02289611A (en) * | 1989-02-09 | 1990-11-29 | Kansai Paint Co Ltd | Photo-setting resin composition |
| JP2000507281A (en) * | 1996-03-08 | 2000-06-13 | レヴロン コンシューマー プロダクツ コーポレイション | Glass decorating method using bisphenol A epoxy resin and related compositions and articles |
| JP2007051244A (en) * | 2005-08-19 | 2007-03-01 | Konica Minolta Medical & Graphic Inc | Active energy ray curing composition, ink composition for ink jet and method for forming image |
| WO2007049488A1 (en) * | 2005-10-24 | 2007-05-03 | Matsui Chemical Co., Ltd. | Composition for coating ceramics |
| JP2007211200A (en) * | 2006-02-13 | 2007-08-23 | Fuji Seal International Inc | Active energy ray-curable resin composition for plastic film coating and its use |
| JP2020019915A (en) * | 2018-08-03 | 2020-02-06 | Ｄｉｃグラフィックス株式会社 | Active energy ray-curable offset ink composition, offset printing ink using the same and printed matter |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7198403B1 (en) | 2023-01-04 |
| WO2023210311A1 (en) | 2023-11-02 |
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