JP4569095B2 - Cationic polymerizable composition, active energy ray-curable inkjet ink, method for producing cationic polymerizable composition, and method for producing active energy ray-curable inkjet ink - Google Patents
Cationic polymerizable composition, active energy ray-curable inkjet ink, method for producing cationic polymerizable composition, and method for producing active energy ray-curable inkjet ink Download PDFInfo
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- JP4569095B2 JP4569095B2 JP2003380928A JP2003380928A JP4569095B2 JP 4569095 B2 JP4569095 B2 JP 4569095B2 JP 2003380928 A JP2003380928 A JP 2003380928A JP 2003380928 A JP2003380928 A JP 2003380928A JP 4569095 B2 JP4569095 B2 JP 4569095B2
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- polymerizable composition
- cationic
- cationically polymerizable
- compound
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- 125000002091 cationic group Chemical group 0.000 title claims description 76
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- 238000010538 cationic polymerization reaction Methods 0.000 claims description 31
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- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
Description
本発明は、保存安定性、硬化性に優れたカチオン重合性組成物、活性エネルギー線硬化型インクジェットインク、カチオン重合性組成物の製造方法及び活性エネルギー線硬化型インクジェットインクの製造方法に関するものである。 The present invention relates to a cationic polymerizable composition excellent in storage stability and curability, an active energy ray-curable inkjet ink , a method for producing a cationic polymerizable composition, and a method for producing an active energy ray-curable inkjet ink. .
速乾性の印刷用インクとして、従来、紫外線等の活性エネルギー線照射によってラジカル重合して硬化する活性エネルギー線硬化型インクジェット用インク組成物（以下、インク組成物ともいう）が知られている。このラジカル重合型のインク組成物は、酸素の存在下では、硬化阻害を受けるという問題を抱えていた。 2. Description of the Related Art An active energy ray-curable inkjet ink composition (hereinafter, also referred to as an ink composition) that is cured by radical polymerization by irradiation with active energy rays such as ultraviolet rays has been known as a quick-drying printing ink. This radical polymerization type ink composition has a problem of being inhibited from curing in the presence of oxygen.
近年、活性エネルギー線照射によってカチオン重合して硬化するインク組成物が提案されている。このカチオン重合型のインク組成物としては、オキセタン化合物と光カチオン重合開始剤と顔料とからなり、必要に応じてエポキシ化合物を添加したものが提案されている（例えば、特開平８−１４３８０６号公報）。カチオン重合反応は、紫外線等の照射によってカチオン重合開始剤から発生するカチオンの存在により開始されるので、酸素によって重合が阻害されることがなく、特に、不活性雰囲気下で実施しなければならないという制限はなく、空気中で速やかに、かつ完全な重合を行うことができるという利点を有する。 In recent years, ink compositions that are cured by cationic polymerization by irradiation with active energy rays have been proposed. As this cationic polymerization type ink composition, an ink composition comprising an oxetane compound, a photocationic polymerization initiator, and a pigment, to which an epoxy compound is added if necessary has been proposed (for example, JP-A-8-143806). ). The cationic polymerization reaction is initiated by the presence of cations generated from the cationic polymerization initiator by irradiation with ultraviolet rays or the like, so that the polymerization is not inhibited by oxygen, and it must be carried out particularly in an inert atmosphere. There is no limitation, and there is an advantage that complete polymerization can be carried out quickly and completely in air.
しかし、オキセタン化合物やエポキシ化合物などのカチオン重合性化合物に、カチオン重合開始剤を添加した状態で長期間にわたり保存すると、紫外線が遮断された状態でも、カチオン重合開始剤からカチオンが自然発生することがあり、この発生したカチオンにより、カチオン重合性化合物の重合が開始して増粘やゲル化が生ずるという問題点があった。 However, if the cationic polymerization initiator is added to a cationically polymerizable compound such as an oxetane compound or an epoxy compound and stored for a long period of time, a cation may be spontaneously generated from the cationic polymerization initiator even when ultraviolet rays are blocked. There is a problem in that the generated cations cause polymerization of the cationic polymerizable compound to cause thickening and gelation.
上述の様な課題を解決する方法の１つとして、カチオン重合触媒とカチオン重合性有機材料とを必須成分とする組成物に、グアニジン系化合物、チアゾール系化合物、ベンゾチアゾール系化合物、チアゾールカルボン酸系化合物、スルフェンアミド系化合物、チオウレア系化合物、イミダゾール系化合物、ベンズイミダゾール系化合物、アルキルフェニルスルフィド系化合物の１種または２種以上を添加することで、該組成物の室温安定性（ポットライフ）を改善する方法が提案されている（例えば、特許文献２参照。）。 As one of the methods for solving the above-mentioned problems, a guanidine-based compound, a thiazole-based compound, a benzothiazole-based compound, a thiazolecarboxylic acid-based composition is added to a composition containing a cationic polymerization catalyst and a cationic polymerizable organic material as essential components. Addition of one or more of compounds, sulfenamide compounds, thiourea compounds, imidazole compounds, benzimidazole compounds, alkylphenyl sulfide compounds, room temperature stability of the composition (pot life) Has been proposed (see, for example, Patent Document 2).
また、オキセタン化合物に、塩基性化合物、例えば、アルカリ金属及びアルカリ土類金属の水酸化物、炭酸塩、アルコラートなどの塩基性無機化合物や、アミンその他の含窒素塩基性化合物などの塩基性有機化合物や、水分を添加することにより、オキセタン化合物の開環重合性を損なうことなく貯蔵安定性を改良する方法が提案されている（例えば、特許文献３〜５参照。）。 In addition, oxetane compounds include basic compounds such as basic inorganic compounds such as alkali metal and alkaline earth metal hydroxides, carbonates, alcoholates, and other basic organic compounds such as amines and other nitrogen-containing basic compounds. In addition, there has been proposed a method for improving storage stability by adding water without impairing the ring-opening polymerizability of the oxetane compound (see, for example, Patent Documents 3 to 5).
しかしながら、カチオン重合性化合物にカチオン重合開始剤が添加されている場合、上記塩基性化合物を添加しても、その保存安定性は十分に改良されない。特に、カチオン重合性化合物がオキセタン化合物と脂環式エポキシ化合物との混合系である場合、オキセタン化合物の単独系よりもカチオン重合開始剤存在下における反応性が非常に高いため、ゲル化を生じ、十分な保存安定性の改良効果が得られないのが現状である。 However, when a cationic polymerization initiator is added to the cationic polymerizable compound, the storage stability is not sufficiently improved even if the basic compound is added. In particular, when the cationically polymerizable compound is a mixed system of an oxetane compound and an alicyclic epoxy compound, the reactivity in the presence of a cationic polymerization initiator is much higher than that of a single oxetane compound, resulting in gelation. At present, sufficient improvement in storage stability cannot be obtained.
また、上述のような問題を解決するため、上記グアニジン系化合物や上記塩基性化合物等の添加量を増加させると、カチオン重合性化合物のゲル化の問題は解決されるが、その反面、硬化性が低下するという新たな問題が発生し、保存安定性と硬化性との両者を同時に満足することは困難であった。また、上記グアニジン系化合物や上記塩基性化合物等の中には有害な物質もあり、このような有害な物質を組成物中に多量に含有させることは環境適性上好ましくない。
本発明は、上記課題に鑑みなされたものであり、その目的は、カチオン重合開始剤を含有するカチオン重合性化合物の硬化性を阻害せずに長期間の保存安定性を確保でき、インクとしての吐出安定性に優れ、かつ環境適性に優れたカチオン重合性組成物、活性エネルギー線硬化型インクジェットインク、カチオン重合性組成物の製造方法及び活性エネルギー線硬化型インクジェットインクの製造方法を提供することである。 The present invention has been made in view of the above problems, and its purpose is to ensure long-term storage stability without inhibiting the curability of a cationic polymerizable compound containing a cationic polymerization initiator, and as an ink By providing a cationically polymerizable composition, an active energy ray-curable inkjet ink excellent in ejection stability and environmental suitability, a method for producing a cationic polymerizable composition, and a method for producing an active energy ray-curable inkjet ink is there.
本発明の上記目的は、以下の構成により達成される。
（請求項１）
カチオン重合性化合物、カチオン重合開始剤を含有するカチオン重合性組成物において、Ｂ、Ｆ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｓ、Ｃｌ、Ｋ、Ｃａ、Ｃｕ、Ｂｒ、Ａｇ、Ｓｎ、Ｓｂ、Ａｓ及びＷから選ばれる少なくとも１種の元素を有するカチオン型不純物、金属不純物及び強酸性物質の総含有量が、５００ｐｐｍ以下であることを特徴とするカチオン重合性組成物。
（請求項２）
前記カチオン型不純物、金属不純物及び強酸性物質の総含有量が、１００ｐｐｍ以下であることを特徴とする請求項１に記載のカチオン重合性組成物。
（請求項３）
前記カチオン重合性化合物が、脂環式エポキシ化合物またはオキセタン化合物であることを特徴とする請求項１または２に記載のカチオン重合性組成物。
（請求項４）
カチオン重合性組成物全質量に対して、１〜１０質量％の水を含有することを特徴とする請求項１〜３のいずれか１項に記載のカチオン重合性組成物。
（請求項５）
前記水の含有量が、４質量％以下であることを特徴とする請求項１〜４のいずれか１項に記載のカチオン重合性組成物。
（請求項６）
水蒸発防止剤を含有することを特徴とする請求項１〜５のいずれか１項に記載のカチオン重合性組成物。
（請求項７）
２３℃における粘度が、５〜５０ｍＰａ・ｓであることを特徴とする請求項１〜６のいずれか１項に記載のカチオン重合性組成物。
（請求項８）
活性エネルギー線の照射により硬化する活性エネルギー線硬化型インクジェットインクにおいて、請求項１〜７のいずれか１項に記載のカチオン重合性組成物を含有することを特徴とする活性エネルギー線硬化型インクジェットインク。
（請求項９）
カチオン重合性化合物、カチオン重合開始剤及びカチオン重合性組成物から選ばれる少なくとも１つに、塩基性吸着剤による吸着処理、カラムクロマトグラフィー処理、活性炭処理、晶析処理及び再結晶処理から選ばれる１つの処理を施す工程、及び該処理によって、該カチオン重合性組成物中に存在するＢ、Ｆ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｓ、Ｃｌ、Ｋ、Ｃａ、Ｃｕ、Ｂｒ、Ａｇ、Ｓｎ、Ｓｂ、Ａｓ及びＷから選ばれる少なくとも１種の元素を有するカチオン型不純物、金属不純物及び強酸性物質の総含有量を５００ｐｐｍ以下とする工程を有することを特徴とするカチオン重合性組成物の製造方法。
（請求項１０）
前記処理が、塩基性吸着剤による吸着処理またはカラムクロマトグラフィー処理であることを特徴とする請求項９に記載のカチオン重合性組成物の製造方法。
（請求項１１）
前記カチオン重合性化合物、前記カチオン重合開始剤または前記カチオン重合性組成物中に存在する不純物の含有量を測定する工程を更に有することを特徴とする請求項９に記載のカチオン重合性組成物の製造方法。
（請求項１２）
請求項９〜１１のいずれか１項に記載のカチオン重合性組成物の製造方法によって製造されたカチオン重合性組成物と、顔料または染料とを混合する工程を有することを特徴とする活性エネルギー線硬化型インクジェットインクの製造方法。
The above object of the present invention is achieved by the following configurations.
(Claim 1)
In a cationically polymerizable composition containing a cationically polymerizable compound and a cationic polymerization initiator, B, F, Na, Mg, Al, P, S, Cl, K, Ca, Cu, Br, Ag, Sn, Sb, As and cationic impurities with at least one element selected from W, the total content of metal impurities and strongly acidic substance, cationically polymerizable composition, wherein the at 500ppm or less.
(Claim 2)
2. The cationically polymerizable composition according to claim 1, wherein the total content of the cationic impurities, the metal impurities, and the strongly acidic substance is 100 ppm or less.
(Claim 3)
The cationically polymerizable composition according to claim 1 or 2, wherein the cationically polymerizable compound is an alicyclic epoxy compound or an oxetane compound .
(Claim 4)
With respect to the total mass cationically polymerizable composition, the cationically polymerizable composition according to any one of claims 1 to 3, characterized that you containing from 1 to 10% by weight of water.
(Claim 5)
The cationically polymerizable composition according to any one of claims 1 to 4, wherein the water content is 4% by mass or less .
(Claim 6)
The cationically polymerizable composition according to claim 1, further comprising a water evaporation inhibitor.
(Claim 7)
The cationic polymerizable composition according to any one of claims 1 to 6, wherein the viscosity at 23 ° C is 5 to 50 mPa · s.
(Claim 8)
An active energy ray-curable inkjet ink that cures upon irradiation with an active energy ray, comprising the cationic polymerizable composition according to any one of claims 1 to 7. .
(Claim 9)
1 selected from adsorption treatment with a basic adsorbent, column chromatography treatment, activated carbon treatment, crystallization treatment and recrystallization treatment to at least one selected from a cationic polymerizable compound, a cationic polymerization initiator and a cationic polymerizable composition Two treatments, and B, F, Na, Mg, Al, P, S, Cl, K, Ca, Cu, Br, Ag, Sn, Sb present in the cationic polymerizable composition by the treatment the method of the cationically polymerizable composition characterized by have at least cationic impurities having one element, the step of the total content of metal impurities and strong acid with 500ppm or less selected from as and W .
(Claim 10)
The method for producing a cationically polymerizable composition according to claim 9, wherein the treatment is an adsorption treatment with a basic adsorbent or a column chromatography treatment.
(Claim 11)
The cationic polymerizable composition according to claim 9, further comprising a step of measuring a content of impurities present in the cationic polymerizable compound, the cationic polymerization initiator, or the cationic polymerizable composition. Production method.
(Claim 12)
An active energy ray comprising a step of mixing a cationically polymerizable composition produced by the method for producing a cationically polymerizable composition according to any one of claims 9 to 11, and a pigment or a dye. A method for producing a curable inkjet ink.
本発明によれば、カチオン重合開始剤を含有するカチオン重合性化合物の硬化性を阻害せずに長期間の保存安定性を確保でき、インクとしての吐出安定性に優れ、かつ環境適性に優れたカチオン重合性組成物、活性エネルギー線硬化型インクジェットインク、カチオン重合性組成物の製造方法及び活性エネルギー線硬化型インクジェットインクの製造方法を提供することができる。 According to the present invention, long-term storage stability can be ensured without impairing the curability of the cationically polymerizable compound containing the cationic polymerization initiator, the discharge stability as an ink is excellent, and the environmental suitability is excellent. A cationically polymerizable composition, an active energy ray-curable inkjet ink , a method for producing a cationically polymerizable composition, and a method for producing an active energy ray-curable inkjet ink can be provided.
以下、本発明を実施するための最良の形態について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.
本発明者は、上記課題に鑑み鋭意検討を行った結果、カチオン重合性化合物、カチオン重合開始剤を含有するカチオン重合性組成物において、Ｂ、Ｆ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｓ、Ｃｌ、Ｋ、Ｃａ、Ｃｕ、Ｂｒ、Ａｇ、Ｓｎ、Ｓｂ、Ａｓ及びＷから選ばれる少なくとも１種の元素を有するカチオン型不純物、金属不純物及び強酸性物質の総含有量が、５００ｐｐｍ以下であることを特徴とするカチオン重合性組成物により、カチオン重合開始剤を含有するカチオン重合性化合物の硬化性を阻害せずに長期間の保存安定性を確保でき、かつ環境適性を有するカチオン重合性組成物を実現できることを見出し、本発明に至った次第である。 As a result of intensive studies in view of the above problems, the present inventor has found that in a cationic polymerizable composition containing a cationic polymerizable compound and a cationic polymerization initiator, B, F, Na, Mg, Al, P, S, Cl , K, Ca, Cu, Br , Ag, Sn, Sb, cationic type impurity with at least one element selected from as and W, the total content of metal impurities and strong acid is 500ppm or less A cationically polymerizable composition that can ensure long-term storage stability without impairing the curability of a cationically polymerizable compound containing a cationic polymerization initiator and has environmental suitability by the cationic polymerizable composition that is characterized It is as soon as it has been found and can be realized.
以下、本発明の詳細について説明する。 Details of the present invention will be described below.
本発明のカチオン重合性組成物は、少なくともカチオン重合性化合物及びカチオン重合開始剤を含有する。 The cationically polymerizable composition of the present invention contains at least a cationically polymerizable compound and a cationic polymerization initiator.
本発明で用いることのできるカチオン重合性化合物としては、特に制限はなく、例えば、カチオン重合性ビニル化合物、ラクトン類、環状エーテル類などが挙げられる。カチオン重合性ビニル化合物としては、スチレン、ビニールエーテルなどが挙げられる。環状エーテル類としては、エポキシ化合物、オキセタン化合物のほか、スピロオルソエステル類、ビシクロオルソエステル類、環状カーボナート類などが挙げられる。 The cationically polymerizable compound that can be used in the present invention is not particularly limited, and examples thereof include cationically polymerizable vinyl compounds, lactones, and cyclic ethers. Examples of the cationically polymerizable vinyl compound include styrene and vinyl ether. Examples of the cyclic ethers include spiro orthoesters, bicycloorthoesters, and cyclic carbonates in addition to epoxy compounds and oxetane compounds.
本発明で用いることのできるエポキシ化合物は、下記一般式（１）で示される三員環であるオキシラン基を有する化合物を意味し、芳香族エポキシ化合物及び脂環式エポキシ化合物などが包含される。 The epoxy compound that can be used in the present invention means a compound having an oxirane group that is a three-membered ring represented by the following general formula (1), and includes an aromatic epoxy compound and an alicyclic epoxy compound.
本発明で用いることのできるオキセタン化合物は、下記一般式（２）で示される四員環エーテルであるオキセタン環を有する化合物を意味する。 The oxetane compound which can be used in the present invention means a compound having an oxetane ring which is a four-membered ether represented by the following general formula (2).
本発明のカチオン重合性組成物において、好ましいカチオン重合性化合物は、カチオンの作用により開環重合する環状エーテル類であり、さらに好ましくは、脂環式エポキシ化合物及びオキセタン化合物である。特には、硬化性に優れていることから、脂環式エポキシ化合物とオキセタン化合物とを混合して使用することが好ましい。この場合、脂環式エポキシ化合物とオキセタン化合物の混合比率（脂環式エポキシ化合物／オキセタン化合物）は、質量比で５／９５〜９５／５、好ましくは１０／９０〜７０／３０である。オキセタン化合物の量が少な過ぎると、硬化物の屈曲性低下、耐溶剤性低下の傾向を生じ、反面、オキセタン化合物の量が多過ぎると、高湿環境下での硬化不良を引き起こす。 In the cationically polymerizable composition of the present invention, preferable cationically polymerizable compounds are cyclic ethers that undergo ring-opening polymerization by the action of a cation, and more preferably alicyclic epoxy compounds and oxetane compounds. In particular, since the curability is excellent, it is preferable to use a mixture of an alicyclic epoxy compound and an oxetane compound. In this case, the mixing ratio of the alicyclic epoxy compound and the oxetane compound (alicyclic epoxy compound / oxetane compound) is 5/95 to 95/5, preferably 10/90 to 70/30 in mass ratio. If the amount of the oxetane compound is too small, the cured product tends to be lowered in flexibility and solvent resistance. On the other hand, if the amount of the oxetane compound is too large, curing failure in a high humidity environment is caused.
本発明のカチオン重合性組成物において、好ましいオキセタン化合物としては、例えば、３−エチル−３−ヒドロキシメチルオキセタン、１，４ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン、３−エチル−３−（フェノキシメチル）オキセタン、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタンおよびジ［１−エチル（３−オキセタニル）］メチルエーテルなどのオキセタン類が挙げられる。 In the cationically polymerizable composition of the present invention, preferred oxetane compounds include, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3 Oxetanes such as -ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and di [1-ethyl (3-oxetanyl)] methyl ether.
また、好ましい脂環式エポキシ化合物としては、例えば、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（例えば、商品名ＵＶＲ６１０５、ＵＶＲ６１１０およびＣＥＬＬＯＸＩＤＥ２０２１等の市販品）、ビス（３，４−エポキシシクロヘキシルメチル）アジペート（例えば、商品名ＵＶＲ６１２８の市販品）、ビニルシクロヘキセンモノエポキサイド（例えば、商品名ＣＥＬＯＸＩＤＥ２０００の市販品）、ε−カプロラクトン変性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（例えば、商品名ＣＥＬＯＸＩＤＥ２０８１の市販品）、１−メチル−４−（２−メチルオキシラニル）−７−オキサビシクロ［４，１，０］ヘプタン（例えば、商品名ＣＥＬＯＸＩＤＥ３０００の市販品）などの脂環式エポキシ樹脂が挙げられる。上記のＵＶＲ６１０５、ＵＶＲ６１１０及びＵＶＲ６１２８の商品名を有する市販品は、いずれもユニオンカーバイト社から入手できる。上記ＣＥＬＯＸＩＤＥ２０００、ＣＥＬＬＯＸＩＤＥ２０２１、ＣＥＬＯＸＩＤＥ２０８１およびＣＥＬＯＸＩＤＥ３０００の商品名を有する市販品は、いずれもダイセル化学株式会社から入手できる。なお、ＵＶＲ６１０５はＵＶＲ６１１０の低粘度品である。 Preferred examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (for example, commercially available products such as trade names UVR6105, UVR6110, and CELLOXIDE2021), bis (3 , 4-epoxycyclohexylmethyl) adipate (for example, commercial product under the trade name UVR6128), vinylcyclohexene monoepoxide (for example, commercial product under the trade name CELOXIDE 2000), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl 3 ′, 4 ′ -Epoxycyclohexanecarboxylate (for example, commercial product under the trade name CELOXIDE 2081), 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4,1,0] heptane (eg , Commercially available trade name CELOXIDE3000) include alicyclic epoxy resins such as. Commercial products having the above-mentioned UVR 6105, UVR 6110, and UVR 6128 are commercially available from Union Carbide. Commercial products having the trade names of CELOXIDE 2000, CELLOXIDE 2021, CELOXIDE 2081 and CELOXIDE 3000 are all available from Daicel Chemical Industries, Ltd. UVR 6105 is a low viscosity product of UVR 6110.
また、カチオン重合性化合物の他の具体例は、特開平８−１４３８０６号公報、特開平８−２８３３２０号公報、特開２０００−１８６０７９号公報、特開２０００−３２７６７２号公報などにさらに詳細に記載されており、そこに例示されている化合物から適宜選択して、用いることもできる。 Other specific examples of the cationic polymerizable compound are described in more detail in JP-A-8-143806, JP-A-8-283320, JP-A 2000-186079, JP-A 2000-327672, and the like. It can be used by appropriately selecting from the compounds exemplified therein.
本発明で用いることのできるカチオン重合開始剤としては、公知のスルホニウム塩、アンモニウム塩などの他、ジアリールヨードニウム塩、トリアリールスルホニウム塩などが挙げられ、例えば、特開平８−１４３８０６号公報、特開平８−２８３３２０号公報などに記載のものから適宜選択して使用することができる。また、カチオン重合開始剤は、市販品をそのまま使用することができ、市販品の代表例として、例えば、商品名ＣＩ−１３７０、ＣＩ−２０６４、ＣＩ−２３９７、ＣＩ−２６２４、ＣＩ−２６３９、ＣＩ−２７３４、ＣＩ−２７５８、ＣＩ−２８２３、ＣＩ−２８５５およびＣＩ−５１０２等の市販品（以上、日本曹達株式会社製）、商品名ＰＨＯＴＯＩＮＩＴＩＡＴＯＲ２０４７等の市販品（ローディア社製）、商品名ＵＶＩ−６９７４、ＵＶＩ−６９９０等の市販品（以上、ユニオンカーバイト社製）などを挙げることができる。 Examples of the cationic polymerization initiator that can be used in the present invention include diaryl iodonium salts and triaryl sulfonium salts in addition to known sulfonium salts and ammonium salts. For example, JP-A-8-143806, It can be appropriately selected from those described in JP-A-8-283320. As the cationic polymerization initiator, commercially available products can be used as they are, and typical examples of commercially available products include, for example, trade names CI-1370, CI-2064, CI-2397, CI-2624, CI-2623, CI. -2734, CI-2758, CI-2823, CI-2855 and CI-5102 and other commercial products (Nippon Soda Co., Ltd.), commercial products such as PHOTOINITIATOR 2047 (Rhodia), commercial name UVI-6974 , Commercially available products such as UVI-6990 (manufactured by Union Carbide).
本発明のカチオン重合性組成物において、カチオン重合開始剤の使用量は、その種類、使用されるカチオン重合性化合物の種類および使用比、使用条件などによって異なるが、実用上、カチオン重合性組成物中のカチオン重合性化合物１００質量部に対して、通常は、０．１〜２０質量部、好ましくは１〜１０質量部、更に好ましくは３〜５質量部とされる。カチオン重合開始剤が上記の範囲を超える場合には、速やかに重合は進行するが保存安定性が損なわれやすくなり、逆の上記の範囲未満である場合には、硬化性が低下する。 In the cationic polymerizable composition of the present invention, the amount of the cationic polymerization initiator used varies depending on the type, the type and usage ratio of the cationic polymerizable compound used, the usage conditions, and the like. The amount is usually 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound therein. When the cationic polymerization initiator exceeds the above range, the polymerization proceeds rapidly, but the storage stability tends to be impaired. When the cationic polymerization initiator is less than the above range, the curability decreases.
本発明において、カチオン重合性組成物中に含まれるＢ、Ｆ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｓ、Ｃｌ、Ｋ、Ｃａ、Ｃｕ、Ｂｒ、Ａｇ、Ｓｎ、Ｓｂ、Ａｓ及びＷから選ばれる少なくとも１種の元素を有するカチオン型不純物、金属不純物および強酸性物質の総量は、５００ｐｐｍ以下であることが特徴であるが、好ましくは０ｐｐｍを含む１００ｐｐｍ以下である。 In the present invention, at least selected from B, F, Na, Mg, Al, P, S, Cl, K, Ca, Cu, Br, Ag, Sn, Sb, As, and W contained in the cationic polymerizable composition cationic impurities having one element, the total amount of metal impurities and strong acid is a feature that is 500ppm, preferably less than or equal to 100ppm including 0 ppm.
これらの不純物は、カチオン重合性組成物を調製する際に、カチオン重合性化合物やカチオン重合開始剤、あるいはその他の添加剤等から持ち込まれる。これら不純物が５００ｐｐｍを越えると、保存安定性が損なわれる。 These impurities are brought in from the cationic polymerizable compound, the cationic polymerization initiator, or other additives when preparing the cationic polymerizable composition. When these impurities exceed 500 ppm, storage stability is impaired.
上記カチオン型不純物または金属不純物としては、Ｂ、Ｆ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｓ、Ｃｌ、Ｋ、Ｃａ、Ｃｕ、Ｂｒ、Ａｇ、Ｓｎ、Ｓｂ、Ａｓ、Ｗ等を挙げることができる。 Examples of the cation impurity or metal impurity include B, F, Na, Mg, Al, P, S, Cl, K, Ca, Cu, Br, Ag, Sn, Sb, As, and W.
また、強酸性物質としては、例えば、硫酸、塩酸、硝酸、リン酸、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、ナフタレンスルホン酸、メタンスルホン酸、エタンスルホン酸、トリフルオロメタンスルホン酸、ＡｌＣｌ3、ＡｌＢｒ3、ＦｅＣｌ3、ＢＣｌ3、ＢＢｒ3、ＢＦ3・ＯＥｔ2、ＢＦ3、ＳｂＦ5、ＰＦ5、ＺｎＣｌ2、ＴｉＣｌ4等が挙げられる。 Examples of strongly acidic substances include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, AlCl 3 , AlBr. 3 , FeCl 3 , BCl 3 , BBr 3 , BF 3 .OEt 2 , BF 3 , SbF 5 , PF 5 , ZnCl 2 , TiCl 4 and the like.
本発明においては、不純物としてのカチオン型不純物、金属不純物、強酸性物質は、カチオン重合性化合物、カチオン重合開始剤、カチオン重合性組成物のいずれか１つを、塩基性吸着剤による吸着処理、カラムクロマトグラフィー（シリカゲルカラムクロマトグラフィーなど）、活性炭処理、晶析や再結晶等の分離精製手段による処理を施すことにより、総含有量が５００ｐｐｍ以下である本発明のカチオン重合性組成物を得ることができる。 In the present invention, the cation-type impurity, the metal impurity, and the strongly acidic substance as impurities are any one of a cation polymerizable compound, a cation polymerization initiator, and a cation polymerizable composition, an adsorption treatment with a basic adsorbent, Obtaining the cationically polymerizable composition of the present invention having a total content of 500 ppm or less by subjecting it to separation / purification means such as column chromatography (silica gel column chromatography), activated carbon treatment, crystallization or recrystallization. Can do.
特に、強酸性物質については、上記精製手段の中でも、塩基性吸着剤による吸着処理及びカラムクロマトグラフィーによる分離処理を施すことが好ましい。塩基性吸着剤としては、例えば、商品名「キョーワード」等の塩基性無機吸着剤（例えば、ハイドロタルサイトなど）を使用できる。塩基性吸着剤の使用量は、強酸性物質の種類や含有量により適宜選択できるが、通常、処理に供する化合物１００質量部に対して、１〜２００質量部程度である。塩基性吸着剤による吸着処理は、処理に供する化合物を溶解可能な溶媒び溶解して行われる。処理温度は、例えば、１０〜１００℃程度である。処理は、バッチ式、連続式、流動床方式、充填塔方式等の慣用の方法により行うことができる。 Particularly for strongly acidic substances, it is preferable to perform an adsorption treatment with a basic adsorbent and a separation treatment with column chromatography among the above purification means. As the basic adsorbent, for example, a basic inorganic adsorbent (for example, hydrotalcite) such as a trade name “KYOWARD” can be used. Although the usage-amount of a basic adsorbent can be suitably selected with the kind and content of a strongly acidic substance, it is about 1-200 mass parts normally with respect to 100 mass parts of compounds used for a process. The adsorption treatment with the basic adsorbent is performed by dissolving a solvent capable of dissolving the compound to be treated. Processing temperature is about 10-100 degreeC, for example. The treatment can be performed by a conventional method such as a batch method, a continuous method, a fluidized bed method, or a packed tower method.
なお、これら不純物の含有量は、高速液体クロマトグラフィー、ガスクロマトグラフィー、元素分析、原子吸光分析、赤外線吸収スペクトル法、ＮＭＲスペクトル法、質量分析法、滴定分析等の公知の分析手段により求めることができる。 The content of these impurities can be determined by known analytical means such as high performance liquid chromatography, gas chromatography, elemental analysis, atomic absorption analysis, infrared absorption spectroscopy, NMR spectroscopy, mass spectrometry, and titration analysis. it can.
本発明において、カチオン重合性組成物中の水の含有量は、カチオン重合性化合物の種類および含有量比、カチオン重合開始剤の種類および含有量比、保存条件、硬化条件などによって異なるが、カチオン重合性組成物全質量に対して、１質量％以上であることが好ましくは、より好ましくは２質量％以上である。水の含有量が不足するとカチオン重合性化合物の保存安定性を十分に向上させることができない。 In the present invention, the water content in the cationic polymerizable composition varies depending on the type and content ratio of the cationic polymerizable compound, the type and content ratio of the cationic polymerization initiator, storage conditions, curing conditions, and the like. The content is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total mass of the polymerizable composition. If the water content is insufficient, the storage stability of the cationically polymerizable compound cannot be sufficiently improved.
また、本発明においては、カチオン重合性組成物中に水を過剰に添加することを妨げるものではないが、水はカチオン重合性化合物中に溶解していることが好ましい。従って、水の含有量の上限は、通常、カチオン重合性組成物に溶解する水の量により決定され、一概に特定することはできないが、カチオン重合性組成物全量に対して、実用上、通常は１０質量％以下、好ましくは６質量％以下、さらに好ましくは４質量％以下とされる。水の添加量は、保存及び硬化時などにおける蒸発などによる損耗量を考慮して決定されるが、水の含有量が過剰になるとカチオン重合性化合物の硬化に長時間を要することになり、また、低温環境下で水が析出することがある。 Moreover, in this invention, although it does not prevent adding water excessively in a cationically polymerizable composition, it is preferable that water is melt | dissolving in the cationically polymerizable compound. Therefore, the upper limit of the water content is usually determined by the amount of water dissolved in the cationic polymerizable composition and cannot be specified in general, but for the total amount of the cationic polymerizable composition, in practice, Is 10% by mass or less, preferably 6% by mass or less, and more preferably 4% by mass or less. The amount of water added is determined in consideration of the amount of wear due to evaporation during storage and curing, but if the water content is excessive, the cationic polymerizable compound will take a long time to cure, Water may precipitate in a low temperature environment.
更に、本発明においては、カチオン重合性組成物中に水蒸発防止剤を含有することが好ましい。カチオン重合性組成物中に含有された水は、保存中の蒸発により損耗し、時間の経過に伴ってカチオン重合性組成物の保存安定性が低下する傾向にある。しかし、水蒸発防止剤を併用することにより、水の蒸発が防止されるため、カチオン重合性組成物の保存安定性を長期にわたり持続させることができる。水蒸発防止剤の使用は、カチオン重合性組成物を密閉系で保存する場合のみならず、とりわけ、インク用ビヒクルなどのように開放系で保存される場合に好ましい。本発明で用いることのできる水蒸発防止剤として、例えば、エチレングリコール、トリエチレングリコール、ジプロピレングリコール、ブチレングリコール、ポリエチレングリコール（分子量２００〜６００）、グリセリン、ソルビトール、乳酸ナトリウム、２−ピロリドン−５−カルボン酸ナトリウム、ヒアルロン酸ナトリウム、およびその他のアルコール類、糖類、グリコールエーテル類などの保湿作用を有する物質を使用することができる。 Furthermore, in this invention, it is preferable to contain a water evaporation inhibitor in a cationically polymerizable composition. Water contained in the cationic polymerizable composition is worn away by evaporation during storage, and the storage stability of the cationic polymerizable composition tends to decrease with the passage of time. However, when the water evaporation inhibitor is used in combination, the evaporation of water is prevented, so that the storage stability of the cationic polymerizable composition can be maintained for a long time. The use of the water evaporation inhibitor is preferable not only when the cationic polymerizable composition is stored in a closed system, but particularly when it is stored in an open system such as an ink vehicle. Examples of the water evaporation inhibitor that can be used in the present invention include ethylene glycol, triethylene glycol, dipropylene glycol, butylene glycol, polyethylene glycol (molecular weight 200 to 600), glycerin, sorbitol, sodium lactate, and 2-pyrrolidone-5. -Substances having a moisturizing action such as sodium carboxylate, sodium hyaluronate, and other alcohols, sugars, glycol ethers can be used.
本発明に係る水蒸発防止剤の使用量は、カチオン重合性化合物の種類、水蒸発防止剤の種類、保存状態、所望の保存期間などによって適宜調節することができるが、カチオン重合性組成物中に含有された水に対して、通常は１０〜２００質量％、好ましくは５０〜１００質量％とされる。 The amount of the water evaporation inhibitor according to the present invention can be appropriately adjusted depending on the type of the cationically polymerizable compound, the type of the water evaporation inhibitor, the storage state, the desired storage period, etc., but in the cationically polymerizable composition The water content is usually 10 to 200% by mass, preferably 50 to 100% by mass.
本発明のカチオン重合性組成物の粘度は、カチオン重合性組成物の用途に応じて、カチオン重合性化合物の分子量や組み合わせを選択することにより適宜調節できる。とりわけ、本発明のカチオン重合性組成物を、業務用インクジェットプリンタの紫外線硬化型インク用のビヒクルとして用いる場合には、２３℃における粘度が５〜５０ｍＰａ・ｓ、好ましくは１０〜３０ｍＰａ・ｓとなるように調整される。 The viscosity of the cationically polymerizable composition of the present invention can be appropriately adjusted by selecting the molecular weight and combination of the cationically polymerizable compounds according to the use of the cationically polymerizable composition. In particular, when the cationically polymerizable composition of the present invention is used as a vehicle for ultraviolet curable ink of a commercial inkjet printer, the viscosity at 23 ° C. is 5 to 50 mPa · s, preferably 10 to 30 mPa · s. To be adjusted.
本発明のカチオン重合性組成物は、常法の如く紫外線、Ｘ線、電子線などの活性エネルギー線や加熱により重合反応を開始させて硬化させることができる。なお、本発明のカチオン重合性組成物には、所望により、顔料、染料、増感剤、難燃剤および静電防止剤などの各種添加剤を添加することができ、例えば、インク、ビヒクル、艶出しワニス、塗料、接着剤、プリプレグ、封止材料、積層板および成形材料などに好適に使用される。 The cationically polymerizable composition of the present invention can be cured by initiating a polymerization reaction by active energy rays such as ultraviolet rays, X-rays, and electron beams, or by heating as usual. Various additives such as pigments, dyes, sensitizers, flame retardants and antistatic agents can be added to the cationic polymerizable composition of the present invention as desired. For example, ink, vehicle, gloss It is suitably used for dispensing varnishes, paints, adhesives, prepregs, sealing materials, laminates and molding materials.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
《カチオン重合開始剤の合成》
〔例示化合物１−１の合成〕
５００ｍｌの三口フラスコに四塩化スズを２０ｍｌ添加し、攪拌しながらアニソールを４８．１ｇを添加した。この溶液を氷冷して１０〜１５℃の温度範囲を維持しながら、塩化チオニルの６．７５ｇを滴下した。この時、反応物は暗褐色となった。そのまま室温で４時間撹拌を続けた後、この反応液に水を７０ｍｌ添加した。次いで、オイル層を取り出し、ジエチルエーテルで３回洗浄した。これに、ＫＰＦ6の１８．４ｇを１００ｇの水に溶解して添加し、一昼夜放置した。オイル層を再び取り出し、ジエチルエーテルで洗浄した後、減圧乾燥して、例示化合物１−１であるトリス（４−メトキシフェニル）スルホニウムヘキサフロロフォスフェートを、３２．３ｇ（収率５９．６％）の白色粉末として得た。なお、この例示化合物１−１は、赤外吸収スペクトル、元素分析及びＮＭＲにより構造を同定した。
<< Synthesis of cationic polymerization initiator >>
[Synthesis of Exemplified Compound 1-1]
20 ml of tin tetrachloride was added to a 500 ml three-necked flask, and 48.1 g of anisole was added with stirring. This solution was ice-cooled and 6.75 g of thionyl chloride was added dropwise while maintaining a temperature range of 10 to 15 ° C. At this time, the reaction became dark brown. Stirring was continued for 4 hours at room temperature, and 70 ml of water was added to the reaction solution. The oil layer was then removed and washed 3 times with diethyl ether. To this, 18.4 g of KPF 6 was dissolved in 100 g of water and added, and left overnight. The oil layer was taken out again, washed with diethyl ether, and then dried under reduced pressure to obtain 32.3 g (yield 59.6%) of Tris (4-methoxyphenyl) sulfonium hexafluorophosphate as the exemplary compound 1-1. As a white powder. In addition, the structure of this exemplary compound 1-1 was identified by infrared absorption spectrum, elemental analysis, and NMR.
〔例示化合物１−２の合成〕
上記例示化合物１−１を塩化メチレンに溶解し、アルミナカラムを通した後、炭酸ナトリウム水溶液と混合攪拌した。次いで、塩化メチレン層を取り出し、硫酸マグネシウムで脱水処理後、塩化メチレンを除去乾燥し、メタノールで再結晶を行い、例示化合物１−１に塩基処理を施した例示化合物１−２の白色粉末を得た。
[Synthesis of Exemplified Compound 1-2]
The above exemplary compound 1-1 was dissolved in methylene chloride, passed through an alumina column, and then mixed and stirred with an aqueous sodium carbonate solution. Next, the methylene chloride layer was taken out, dehydrated with magnesium sulfate, methylene chloride was removed and dried, recrystallized with methanol, and a white powder of Exemplified Compound 1-2 obtained by subjecting Exemplified Compound 1-1 to base treatment was obtained. It was.
〔例示化合物２−１の合成〕
１０００ｍｌの三口フラスコに硫酸３００ｇを添加し、攪拌しながら４，４′−ジフルオロジフェニルスルフィドの４７．７ｇを加えた。次いで、４，４′−ジフルオロジフェニルスルフィドが完全に溶解するのを確認した後、３−クロロ−４−フェニルチオ−ベンゾフェノンの６５．０ｇを５回に分けて分割添加した。この時、添加と同時に反応物は暗褐色となった。そのまま室温で２４時間撹拌を続けた後、３０００ｍｌのビーカーに氷５００ｇとメタノールの５００ｇを混合しておき、ここに上記調製した反応液を投入し、更にトルエンの３００ｇを添加した。この溶液の下層部を取り出し、４０％水酸化ナトリウム水溶液で中和した後、酢酸エチルの１５００ｇを添加し撹拌した。次いで、ＫＳｂＦ6の４４．２ｇを添加し、２時間撹拌した。酢酸エチル層を水１０００ｇで２回洗浄した後、減圧濃縮することによって、例示化合物２−１である４−（２−クロロ−４−ベンゾイルフェニルチオ）フェニルビス（４−フロロフェニル）スルホニウムヘキサフロロフォスフェートの白色粉末を、１３９ｇ（収率８９％）得た。なお、この例示化合物２−１は、赤外吸収スペクトル、元素分析及びＮＭＲにより構造を同定した。
[Synthesis of Exemplary Compound 2-1]
300 g of sulfuric acid was added to a 1000 ml three-necked flask, and 47.7 g of 4,4′-difluorodiphenyl sulfide was added with stirring. Subsequently, after confirming that 4,4'-difluorodiphenyl sulfide was completely dissolved, 65.0 g of 3-chloro-4-phenylthio-benzophenone was added in 5 portions. At this time, the reaction became dark brown upon addition. Stirring was continued for 24 hours at room temperature, and then 500 g of ice and 500 g of methanol were mixed in a 3000 ml beaker, and the prepared reaction solution was added thereto, and 300 g of toluene was further added. The lower layer part of this solution was taken out and neutralized with 40% aqueous sodium hydroxide solution, and 1500 g of ethyl acetate was added and stirred. Next, 44.2 g of KSbF 6 was added and stirred for 2 hours. The ethyl acetate layer was washed twice with 1000 g of water and then concentrated under reduced pressure to give 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoro, which is exemplary compound 2-1. 139 g (89% yield) of a white phosphate powder was obtained. In addition, the structure of this exemplary compound 2-1 was identified by infrared absorption spectrum, elemental analysis, and NMR.
〔例示化合物２−２の合成〕
上記調製した例示化合物２−１を、上記例示化合物１−２の合成と同様にして塩基処理を施して、例示化合物２−２の白色粉末を得た。
[Synthesis of Exemplary Compound 2-2]
The prepared exemplary compound 2-1 was subjected to base treatment in the same manner as in the synthesis of the exemplary compound 1-2 to obtain a white powder of exemplary compound 2-2.
〔例示化合物３−１の合成〕
５００ｍｌの三口フラスコに、メタンスルホン酸の３１．７１ｇ（０．３３モル）、五酸化リンの３．４１ｇ（０．０２４モル）を添加し、７０℃に加熱して３時間撹拌して得られた均一溶液を室温まで冷却した。この溶液中に、４，４′−ジフルオロジフェニルスルホキシドの７．８６ｇ（０．０３３モル）、ジフェニルスルフィドの３．０７ｇ（０．０１６５モル）を添加し、室温で５時間撹拌した。この反応混合物を、３％テトラフェニルボレート・ナトリウム水溶液３８０ｍｌ（０．０３３３モル）に撹拌しながら、少しずつ滴下し、室温で３時間撹拌した。析出した固体をろ別、乾燥し、次いでイソプロパノールに加熱（７０℃）溶解し、０℃まで冷却し、次いでろ別、乾燥後、例示化合物３−１である白色固体のビス［４−（４−フロロ）ジフェニルスルフォニオフェニル］スルファイド、ビス（ヘキサフロロフォスフェート）を１４．１８ｇ（０．０１１２モル）得た。なお、この例示化合物３−１は、赤外吸収スペクトル、元素分析及びＮＭＲにより構造を同定した。
[Synthesis of Exemplary Compound 3-1]
To a 500 ml three-necked flask, 31.71 g (0.33 mol) of methanesulfonic acid and 3.41 g (0.024 mol) of phosphorus pentoxide were added, heated to 70 ° C. and stirred for 3 hours. The homogeneous solution was cooled to room temperature. To this solution, 7.86 g (0.033 mol) of 4,4′-difluorodiphenyl sulfoxide and 3.07 g (0.0165 mol) of diphenyl sulfide were added and stirred at room temperature for 5 hours. The reaction mixture was added dropwise little by little to 380 ml (0.0333 mol) of a 3% aqueous solution of tetraphenylborate / sodium, and stirred at room temperature for 3 hours. The precipitated solid was filtered off and dried, then dissolved in isopropanol (70 ° C.) by heating, cooled to 0 ° C., then filtered off and dried, and then the white solid bis [4- (4 -Fluoro) diphenylsulfoniophenyl] sulfide, 14.18 g (0.0112 mol) of bis (hexafluorophosphate) was obtained. In addition, the structure of this exemplary compound 3-1 was identified by infrared absorption spectrum, elemental analysis, and NMR.
〔例示化合物３−２の合成〕
上記調製した例示化合物３−１を、上記例示化合物１−２の合成と同様にして塩基処理を施して、例示化合物３−２の白色固体を得た。
[Synthesis of Exemplary Compound 3-2]
The prepared exemplary compound 3-1 was subjected to base treatment in the same manner as in the synthesis of the exemplary compound 1-2 to obtain a white solid of exemplary compound 3-2.
《カチオン重合性組成物の調製》
〔カチオン重合性組成物１〜３の調製：本発明〕
表１に記載の様に、分散剤（Ｓ３２００）を２質量部と、脂環式エポキシ化合物、オキセタン化合物、カチオン重合開始剤（例示化合物１−２、２−２、３−２）をステンレスビーカーに入れ、６５℃のホットプレート上で加熱しながら１時間かけて撹拌、混合して溶解させた。次いで、この溶液に顔料（Ｐ１）を表１に記載の量添加し、直径１ｍｍのジルコニアビーズ２００ｇと共にポリ瓶に入れ密栓し、ペイントシェーカーにて２時間分散処理を行った。次いで、ジルコニアビーズを取り除き、残りの各種添加剤を加えた後、これを０．８μｍメンブランフィルターで濾過して、カチオン重合性組成物１〜３を調製した。
<< Preparation of cationically polymerizable composition >>
[Preparation of Cationic Polymerizable Compositions 1 to 3: Present Invention]
As shown in Table 1, 2 parts by mass of the dispersing agent (S3200), an alicyclic epoxy compound, an oxetane compound, and a cationic polymerization initiator (Exemplary Compounds 1-2, 2-2, 3-2) are stainless steel beakers. The mixture was stirred for 1 hour while being heated on a hot plate at 65 ° C., mixed and dissolved. Next, the pigment (P1) was added to this solution in the amount shown in Table 1, and 200 g of zirconia beads having a diameter of 1 mm were placed in a plastic bottle and sealed, followed by dispersion treatment for 2 hours in a paint shaker. Next, after removing the zirconia beads and adding the remaining various additives, this was filtered through a 0.8 μm membrane filter to prepare cationically polymerizable compositions 1 to 3.
〔カチオン重合性組成物４〜６の調製：比較例〕
上記カチオン重合性組成物１〜３の調製において、塩基処理を行ったカチオン重合開始剤である例示化合物１−２、２−２、３−２に代えて、未処理品である例示化合物１−１、２−１、３−１をそれぞれ用いた以外は同様にして、カチオン重合性組成物４〜６を調製した。
[Preparation of Cationic Polymerizable Compositions 4 to 6: Comparative Example]
In the preparation of the cationic polymerizable compositions 1 to 3, instead of Exemplified Compounds 1-2, 2-2 and 3-2 which are cationic polymerization initiators subjected to base treatment, Exemplified Compound 1- which is an untreated product Cationic polymerizable compositions 4 to 6 were prepared in the same manner except that 1, 2-1, and 3-1 were used.
〔カチオン重合性組成物７の調製：本発明〕
上記調製したカチオン重合性組成物４に炭酸ナトリウムの粉体を懸濁させ、１時間攪拌した後、フィルターを用いて炭酸ナトリウムをろ過除去して、精製処理を施したカチオン重合性組成物７を調製した。
[Preparation of Cationic Polymerizable Composition 7: Present Invention]
After suspending sodium carbonate powder in the cationic polymerizable composition 4 prepared above and stirring for 1 hour, the sodium carbonate was filtered off using a filter, and the purified cationic polymerizable composition 7 was subjected to purification treatment. Prepared.
なお、表１に略称で記載した各添加剤の詳細は、以下の通りである。 In addition, the detail of each additive described with the abbreviation in Table 1 is as follows.
ＵＶＲ６１０５：３，４−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（脂環式エポキシ化合物 ユニオンカーバイト株式会社製、商品名；ＵＶＲ６１０５）
ＯＸＴ２２１：ジ〔１−エチル（３−オキセタニル）〕メチルエーテル（オキセタン化合物 東亞合成株式会社製、商品名；ＯＸＴ２２１）
ＴＥＧ：トリエチレングリコール
顔料Ｐ１：粗製銅フタロシアニン（東洋インク製造社製 銅フタロシアニン）の２５０部、塩化ナトリウムの２５００部及びポリエチレングリコール（東京化成社製 ポリエチレングリコール３００）の１６０部を、スチレン製３．７９Ｌ（１ガロン）ニーダー（井上製作所社製）に仕込み、３時間混練した。次に、この混合物を２．５リットルの温水に投入し、約８０℃に加熱しながらハイスピードミキサーで約１時間攪拌してスラリー状とした後、濾過、水洗を５回繰り返して塩化ナトリウムおよび溶剤を除き、次いで、スプレードライをして乾燥して分散処理を施した顔料Ｐ１を得た。
UVR6105: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (alicyclic epoxy compound, product of Union Carbide Co., Ltd., trade name: UVR6105)
OXT221: Di [1-ethyl (3-oxetanyl)] methyl ether (Oxetane compound, manufactured by Toagosei Co., Ltd., trade name: OXT221)
2. TEG: Triethylene glycol Pigment P1: 250 parts of crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Manufacturing Co., Ltd.), 2500 parts of sodium chloride and 160 parts of polyethylene glycol (polyethylene glycol 300 manufactured by Tokyo Chemical Industry Co., Ltd.) It was charged into a 79 L (1 gallon) kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and filtration and washing were repeated 5 times to remove sodium chloride and After removing the solvent, the pigment P1 was then spray-dried and dried to give a dispersion treatment.
Ｓ３２０００：顔料分散剤（脂肪族変性系分散剤 ソルスパーズ３２０００ ゼネカ社製）
《カチオン重合性組成物の特性値の測定及び評価》
〔粘度の測定〕
上記調製した各カチオン重合性組成物の粘度を、レオメータＭＣＲ３００（Ｐｈｙｓｉｃａ製）を用い、温度２３℃、Ｓｈｅａｒ Ｒａｔｅ＝１０００（１／ｓ）の条件下で測定した。その結果、カチオン重合性組成物のいずれもが、粘度としては２５〜２７ｍＰａ・ｓの範囲であった。
S32000: Pigment dispersant (aliphatic modified dispersant Solspers 32000, manufactured by Zeneca)
<< Measurement and Evaluation of Characteristic Values of Cationic Polymerizable Composition >>
(Measurement of viscosity)
The viscosity of each cationic polymerizable composition prepared above was measured using a rheometer MCR300 (manufactured by Physica) under the conditions of a temperature of 23 ° C. and a Shear Rate = 1000 (1 / s). As a result, all of the cationic polymerizable compositions had a viscosity in the range of 25 to 27 mPa · s.
〔含水量の測定〕
上記の各カチオン重合性組成物組成物を調製した直後、含水量（組成物全量中の水分量（質量％））を、カールフィッシャー法（自動水分測定装置 ＡＱＶ−２０００、平沼産業）により測定した。その結果、いずれのカチオン重合性組成物も、含水率は３．５〜４．０質量％の範囲であった。
[Measurement of water content]
Immediately after preparing each cationic polymerizable composition composition, the water content (water content (mass%) in the total composition) was measured by the Karl Fischer method (automatic moisture measuring device AQV-2000, Hiranuma Sangyo). . As a result, all the cationic polymerizable compositions had a water content in the range of 3.5 to 4.0% by mass.
〔不純物総量の測定〕
上記調製した各カチオン重合性組成物について、原子吸光分析、質量分析及び滴定分析を用いて不純物総量（ｐｐｍ）の測定を行った。なお、各不純物としては、Ｓｎ、Ｃｌ、Ｓ、Ｋ、Ｐ、Ｍｇ、Ｐ、Ｂ、Ｎａ、Ｆ、ＨＣｌ、ＨＰＦ６、リン酸、メタンスルホン酸を検出した。
(Measurement of total amount of impurities)
About each prepared cation polymerizable composition, the impurity total amount (ppm) was measured using atomic absorption analysis, mass spectrometry, and titration analysis. As impurities, Sn, Cl, S, K, P, Mg, P, B, Na, F, HCl, HPF6, phosphoric acid, and methanesulfonic acid were detected.
〔保存安定性の評価〕
上記調製した各カチオン重合性組成物を、ガラス容器に収納した後、蓋をした状態（以下、密閉系という）と蓋をしない状態（以下、開放系という）とで、約７０℃の恒温環境下で１週間の促進処理を行った後、それぞれのカチオン重合性組成物の状態を目視観察し、下記の基準に従って保存安定性の評価を行った。
[Evaluation of storage stability]
Each cation polymerizable composition prepared above is housed in a glass container, and then is kept in a constant temperature environment of about 70 ° C. with a lid (hereinafter referred to as a closed system) and without a lid (hereinafter referred to as an open system). Under the following accelerated treatment for 1 week, the state of each cationic polymerizable composition was visually observed, and storage stability was evaluated according to the following criteria.
○：密閉系及び開放系のいずれにおいても、カチオン重合性組成物のゲル化が認められなかった
△：開放系においてはカチオン重合性組成物のゲル化がやや認められたが、密閉系においては、カチオン重合性組成物のゲル化が認められなかった
×：開放系及び密閉系のいずれにおいても、カチオン重合性組成物の明らかなゲル化が認められた
〔硬化性の評価〕
厚さ１００μｍのポリエチレンテレフタレートフィルムの一方の面に、各カチオン重合性組成物をワイヤーバーを用いて塗布し、厚さ１０μｍの薄膜を形成した。このフィルムを、２０ｍ／分のベルト搬送速度で８０ワットの高圧水銀ランプ光源下を通過させ、薄膜に紫外線を照射して硬化した。この時、高圧水銀ランプの紫外線照射エネルギー量を変化させて、照射直後の薄膜を指で触ってもタックがなくなる時の紫外線照射エネルギー量（ｍＪ／ｃｍ2）を求め、これを硬化性の尺度とした。なお、数値が小さいほど硬化性が良好であることを表す。
○: Gelation of the cationic polymerizable composition was not observed in both the closed system and the open system. Δ: Gelation of the cationic polymerizable composition was slightly observed in the open system. No gelation of the cationic polymerizable composition was observed. ×: Clear gelation of the cationic polymerizable composition was observed in both the open system and the closed system [Evaluation of Curability]
Each cationic polymerizable composition was applied to one surface of a polyethylene terephthalate film having a thickness of 100 μm using a wire bar to form a thin film having a thickness of 10 μm. This film was passed through an 80 watt high-pressure mercury lamp light source at a belt conveyance speed of 20 m / min, and cured by irradiating the thin film with ultraviolet rays. At this time, the amount of ultraviolet irradiation energy of the high-pressure mercury lamp was changed to obtain the amount of ultraviolet irradiation energy (mJ / cm 2 ) when tacking disappeared even if the thin film immediately after irradiation was touched with a finger. It was. In addition, it represents that sclerosis | hardenability is so favorable that a numerical value is small.
〔吐出安定性の評価〕
各カチオン重合性組成物を、ザール（Ｘａａｒ）社製インクジェットプリンタの記録ヘッドから３０分間連続して吐出させ、各記録ヘッドのノズルからの射出状態を目視観察し、下記の基準に従って吐出安定性の評価を行った。
[Evaluation of ejection stability]
Each cationic polymerizable composition was continuously ejected from the recording head of an ink jet printer manufactured by Xaar for 30 minutes, the state of ejection from the nozzle of each recording head was visually observed, and the ejection stability was observed according to the following criteria. Evaluation was performed.
○：３０分連続出射しても、ノズル欠が発生しない
△：３０分連続出射でノズル欠がはじないが、わずかにサテライトが発生する
×：３０分連続出射で、数カ所以上のノズルでノズル欠が発生する
以上により得られた粘度及び含水率を除く各測定結果及び評価結果について、表１に示す。
○: No nozzle missing even after 30 minutes of continuous emission △: No nozzle missing at 30 minutes of continuous emission, but slightly satellite generated ×: No nozzle missing at several nozzles with 30 minutes of continuous emission Table 1 shows each measurement result and evaluation result excluding the viscosity and water content obtained as described above.
表１の結果より明らかなように、カチオン型不純物、金属不純物及び強酸性物質の総含有量が５００ｐｐｍ以下である本発明のカチオン重合性組成物は、比較例に対し、保存安定性、硬化性及び吐出安定性に優れていることが分かる。 As is clear from the results of Table 1, the cationic polymerizable composition of the present invention having a total content of cationic impurities, metal impurities and strongly acidic substances of 500 ppm or less is more stable than the comparative examples in terms of storage stability and curability. It can also be seen that the discharge stability is excellent.
また、本発明のカチオン重合性組成物について、兎の皮膚を用いた皮膚刺激性のパッチテストを実施した結果、いずれのカチオン重合性組成物でもかぶれの発生がないことを確認することができた。 In addition, as a result of conducting a skin irritation patch test using wrinkle skin for the cationic polymerizable composition of the present invention, it was confirmed that there was no rash in any cationic polymerizable composition. .
Claims (12)
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| JP2003380928A JP4569095B2 (en) | 2003-11-11 | 2003-11-11 | Cationic polymerizable composition, active energy ray-curable inkjet ink, method for producing cationic polymerizable composition, and method for producing active energy ray-curable inkjet ink |
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| JP4631279B2 (en) * | 2004-01-16 | 2011-02-16 | コニカミノルタエムジー株式会社 | Inkjet ink |
| JP2006089722A (en) * | 2004-08-26 | 2006-04-06 | Konica Minolta Medical & Graphic Inc | Cationically polymerizable composition, active energy ray-curable type inkjet ink and method for producing cationically polymerizable composition |
| JP5446902B2 (en) * | 2009-03-05 | 2014-03-19 | Ｄｉｃ株式会社 | Cationic polymerizable adhesive and polarizing plate obtained using the same |
| JP2010235911A (en) | 2009-03-11 | 2010-10-21 | Konica Minolta Ij Technologies Inc | Active energy ray curable ink-jet ink, ink-jet recording method, and printed matter |
| JP5964007B2 (en) | 2009-04-02 | 2016-08-03 | コニカミノルタ株式会社 | Active energy ray-curable inkjet ink, inkjet recording method, and printed matter |
| JP6521742B2 (en) * | 2015-05-27 | 2019-05-29 | キヤノン株式会社 | Method for producing cationically polymerizable ultraviolet-curable liquid developer |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH036213A (en) * | 1989-06-01 | 1991-01-11 | Matsushita Electric Ind Co Ltd | Ultraviolet-curable resin |
| JPH05132505A (en) * | 1991-04-08 | 1993-05-28 | Ciba Geigy Ag | Thermosetting composition |
| JPH06184093A (en) * | 1992-07-21 | 1994-07-05 | Ciba Geigy Ag | Selected new sulfonium compound particularly suitable as heat-curing initiator for cationically polymerizable material |
| JPH11100378A (en) * | 1997-07-30 | 1999-04-13 | Dainippon Ink & Chem Inc | Epoxy compound and polymerizable composition containing the compound |
| JP2003171440A (en) * | 2001-12-06 | 2003-06-20 | Mitsubishi Chemicals Corp | Method for producing alicyclic epoxy compound |
| JP2003252979A (en) * | 2002-03-05 | 2003-09-10 | Riso Kagaku Corp | Cationically polymerizable composition |
| JP2003292606A (en) * | 2002-04-05 | 2003-10-15 | Riso Kagaku Corp | Cationic-polymerizable composition |
| WO2003087187A1 (en) * | 2002-04-15 | 2003-10-23 | Toagosei Co., Ltd. | Actinic radiation hardenable resin composition and hardening product thereof |
-
2003
- 2003-11-11 JP JP2003380928A patent/JP4569095B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH036213A (en) * | 1989-06-01 | 1991-01-11 | Matsushita Electric Ind Co Ltd | Ultraviolet-curable resin |
| JPH05132505A (en) * | 1991-04-08 | 1993-05-28 | Ciba Geigy Ag | Thermosetting composition |
| JPH06184093A (en) * | 1992-07-21 | 1994-07-05 | Ciba Geigy Ag | Selected new sulfonium compound particularly suitable as heat-curing initiator for cationically polymerizable material |
| JPH11100378A (en) * | 1997-07-30 | 1999-04-13 | Dainippon Ink & Chem Inc | Epoxy compound and polymerizable composition containing the compound |
| JP2003171440A (en) * | 2001-12-06 | 2003-06-20 | Mitsubishi Chemicals Corp | Method for producing alicyclic epoxy compound |
| JP2003252979A (en) * | 2002-03-05 | 2003-09-10 | Riso Kagaku Corp | Cationically polymerizable composition |
| JP2003292606A (en) * | 2002-04-05 | 2003-10-15 | Riso Kagaku Corp | Cationic-polymerizable composition |
| WO2003087187A1 (en) * | 2002-04-15 | 2003-10-23 | Toagosei Co., Ltd. | Actinic radiation hardenable resin composition and hardening product thereof |
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