JP2019156893A - Cure-type composition, cure-type inkjet ink, cured product, receiving container, 2-dimension or 3-dimension image forming apparatus, and 2-dimension or 3-dimension image forming method - Google Patents
Cure-type composition, cure-type inkjet ink, cured product, receiving container, 2-dimension or 3-dimension image forming apparatus, and 2-dimension or 3-dimension image forming method Download PDFInfo
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- JP2019156893A JP2019156893A JP2018041501A JP2018041501A JP2019156893A JP 2019156893 A JP2019156893 A JP 2019156893A JP 2018041501 A JP2018041501 A JP 2018041501A JP 2018041501 A JP2018041501 A JP 2018041501A JP 2019156893 A JP2019156893 A JP 2019156893A
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- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 27
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- 229920001577 copolymer Polymers 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 4
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- 239000000049 pigment Substances 0.000 abstract description 35
- -1 phenoxyethyl Chemical group 0.000 abstract description 19
- 239000002270 dispersing agent Substances 0.000 abstract description 9
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 abstract description 5
- QSJFDOVQWZVUQG-XLPZGREQSA-N 3',5'-cyclic dTMP Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@@H]2COP(O)(=O)O[C@H]2C1 QSJFDOVQWZVUQG-XLPZGREQSA-N 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
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- 238000001816 cooling Methods 0.000 description 4
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
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- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- XNLBCXGRQWUJLU-UHFFFAOYSA-N naphthalene-2-carbonyl chloride Chemical compound C1=CC=CC2=CC(C(=O)Cl)=CC=C21 XNLBCXGRQWUJLU-UHFFFAOYSA-N 0.000 description 3
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
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- LTHCQJZAUWAZAM-UHFFFAOYSA-N 2-hydroxyethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCCO)=CC=C21 LTHCQJZAUWAZAM-UHFFFAOYSA-N 0.000 description 2
- HUCWLQGHBYAFOS-UHFFFAOYSA-N 2-methylsulfonyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOS(C)(=O)=O HUCWLQGHBYAFOS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 150000001451 organic peroxides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004080 punching Methods 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Ink Jet (AREA)
Abstract
Description
本発明は、硬化型組成物、硬化型インクジェットインク、硬化物、収容容器、２次元又は３次元の像形成装置、及び２次元又は３次元の像形成方法に関する。 The present invention relates to a curable composition, a curable inkjet ink, a cured product, a container, a two-dimensional or three-dimensional image forming apparatus, and a two-dimensional or three-dimensional image forming method.
従来より、光重合性インクジェットインクは、オフセット、シルクスクリーン、トップコート剤などに供給、使用されており、乾燥工程の簡略化によるコストダウンや、環境対応として溶剤の揮発量低減などのメリットから近年使用量が増加している。 Conventionally, photopolymerizable inkjet inks have been supplied and used for offsets, silk screens, topcoats, etc. In recent years due to benefits such as cost reduction by simplifying the drying process and reduction of solvent volatilization as an environmental response. Usage is increasing.
インクジェットインクとしては水系と溶剤系が多く使用されており各々の特徴に応じて用途が使い分けられているが、工業用としては受容基材（インクが塗布される部材）に制限があること、耐水性が比較的悪い点、インクの乾燥エネルギーが大きいこと、また、乾燥によるヘッドへのインク成分付着などの問題点を有し、比較的揮発性の低い光重合性インクジェットインクへの置き換えが期待されている。 A lot of water-based and solvent-based inks are used as ink-jet inks, and the usage is properly used according to the characteristics of each. However, for industrial use, the receiving substrate (member to which the ink is applied) is limited, It is expected to be replaced with a photopolymerizable inkjet ink having relatively low volatility, a problem that ink drying energy is large, and adhesion of ink components to the head due to drying. ing.
そのため、例えば、印刷物に対して加工性が要求されるような印刷のために、硬化性に優れ、得られる画像の耐ブロッキング性、及び伸長性に優れる重合性インクが提案されている（例えば、特許文献１参照）。
また、Ｎ−ビニルカプロラクタム、芳香環を有する単官能アクリレート、脂肪族炭化水素環を有する単官能アクリレート、（メタ）アクリレート基を有するポリエーテル変性シリコーン化合物、及びガラス転移温度（Ｔｇ）が２０℃〜１００℃であるアクリル樹脂を含有するインクジェットインク組成物が提案されている（例えば、特許文献２参照）。
Therefore, for example, a polymerizable ink that is excellent in curability and has excellent blocking resistance and extensibility of the obtained image has been proposed for printing that requires processability on the printed matter (for example, Patent Document 1).
Further, N-vinylcaprolactam, monofunctional acrylate having an aromatic ring, monofunctional acrylate having an aliphatic hydrocarbon ring, a polyether-modified silicone compound having a (meth) acrylate group, and a glass transition temperature (Tg) of 20 ° C. to 20 ° C. An ink-jet ink composition containing an acrylic resin at 100 ° C. has been proposed (see, for example, Patent Document 2).
また、下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を含む共重合体を含有するインクが提案されている（例えば、特許文献３参照）。
本発明は、延伸性と耐ブロッキング性を兼ね備え、延伸時の濃度ムラを抑制できる硬化型組成物を提供することを目的とする。 An object of the present invention is to provide a curable composition that has both stretchability and blocking resistance and can suppress concentration unevenness during stretching.
前記課題を解決するための手段としての本発明の硬化型組成物は、Ｎ−ビニルカプロラクタムと、前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーと、下記一般式（１）で表される構造単位及び下記一般式（２）で表される構造単位を有する共重合体と、を含有する。 The curable composition of the present invention as a means for solving the above problems includes N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, and a structure represented by the following general formula (1) A copolymer having a unit and a structural unit represented by the following general formula (2).
［一般式（１）］
［一般式（２）］
本発明によると、延伸性と耐ブロッキング性を兼ね備え、延伸時の濃度ムラを抑制できる硬化型組成物を提供することができる。 According to the present invention, it is possible to provide a curable composition that has both stretchability and blocking resistance and can suppress concentration unevenness during stretching.
（硬化型組成物）
本発明の硬化型組成物は、Ｎ−ビニルカプロラクタムと、前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーと、下記一般式（１）で表される構造単位及び下記一般式（２）で表される構造単位を有する共重合体と、を含有し、更に必要に応じてその他の成分を含有する。
(Curable composition)
The curable composition of the present invention is represented by N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, a structural unit represented by the following general formula (1), and the following general formula (2). A copolymer having a structural unit, and, if necessary, other components.
［一般式（１）］
［一般式（２）］
本発明の硬化型組成物は、特許文献１の従来技術では、作製したインク膜が延伸時に濃度ムラが生じてしまうという知見に基づくものである。
また、特許文献３には、上記一般式（１）及び上記一般式（２）で表される構造単位を含む共重合体が開示されているが、この特許文献３の共重合体を用いて特許文献２に記載のＮ−ビニルカプロラクタムの顔料偏在による濃度ムラという課題を解決することついては記載も示唆もされていない。
The curable composition of the present invention is based on the knowledge that, in the prior art of Patent Document 1, density unevenness occurs when the produced ink film is stretched.
Further, Patent Document 3 discloses a copolymer containing the structural units represented by General Formula (1) and General Formula (2), and the copolymer of Patent Document 3 is used. There is no description or suggestion of solving the problem of density unevenness due to the uneven distribution of N-vinylcaprolactam described in Patent Document 2.
＜Ｎ−ビニルカプロラクタム＞
Ｎ−ビニルカプロラクタムは、Ｎ−ビニル−ε−カプロラクタムとも呼ばれ、下記構造式で表される重合性単官能モノマーである。
N-vinylcaprolactam is also called N-vinyl-ε-caprolactam and is a polymerizable monofunctional monomer represented by the following structural formula.
Ｎ−ビニルカプロラクタムの含有量は、重合性単官能モノマー全量１００質量部に対して、２０質量部以上５０質量部以下が好ましく、２８質量部以上３５質量部以下がより好ましい。Ｎ−ビニルカプロラクタムの含有量が重合性単官能モノマー全量１００質量部に対して、２０質量部以上５０質量部以下であると、耐ブロッキング性が向上する。 The content of N-vinylcaprolactam is preferably 20 parts by mass or more and 50 parts by mass or less, and more preferably 28 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monofunctional monomer. When the content of N-vinylcaprolactam is 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monofunctional monomer, blocking resistance is improved.
Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、フェノキシエチル（メタ）アクリレート、環式ＴＭＰホルマル（メタ）アクリレート、イソボルニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−（２−エトキシエトキシ）エチル（メタ）アクリレート、オクタ／デシル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレートなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
これらの中でも、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレートが好ましい。
The polymerizable monofunctional monomer other than N-vinylcaprolactam is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenoxyethyl (meth) acrylate, cyclic TMP formal (meth) acrylate, isobornyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, octa / decyl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) An acrylate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate are preferable.
本発明において、Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーとして、上記単官能重合性モノマー以外の多官能重合性モノマーを用いると、延伸性が低下してしまうという問題がある。 In the present invention, when a polyfunctional polymerizable monomer other than the monofunctional polymerizable monomer is used as the polymerizable monofunctional monomer other than N-vinylcaprolactam, there is a problem that stretchability is lowered.
＜硬化手段＞
本発明の硬化型組成物を硬化させる手段としては、加熱硬化又は活性エネルギー線による硬化が挙げられ、これらの中でも、活性エネルギー線による硬化が好ましい。
本発明の硬化型組成物を硬化させるために用いる活性エネルギー線としては、紫外線の他、電子線、α線、β線、γ線、Ｘ線等の、組成物中の重合性成分の重合反応を進める上で必要なエネルギーを付与できるものであればよく、特に限定されない。特に高エネルギーな光源を使用する場合には、重合開始剤を使用しなくても重合反応を進めることができる。また、紫外線照射の場合、環境保護の観点から水銀フリー化が強く望まれており、ＧａＮ系半導体紫外発光デバイスへの置き換えは産業的、環境的にも非常に有用である。更に、紫外線発光ダイオード（ＵＶ−ＬＥＤ）及び紫外線レーザダイオード（ＵＶ−ＬＤ）は小型、高寿命、高効率、低コストであり、紫外線光源として好ましい。
<Curing means>
Examples of means for curing the curable composition of the present invention include heat curing and curing with active energy rays, and among these, curing with active energy rays is preferable.
The active energy ray used for curing the curable composition of the present invention includes a polymerization reaction of polymerizable components in the composition such as electron beam, α ray, β ray, γ ray, X ray in addition to ultraviolet rays. There is no particular limitation as long as it can provide the energy necessary for proceeding the process. In particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. In the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are preferable as an ultraviolet light source.
＜重合開始剤＞
本発明の硬化型組成物は、重合開始剤を含有していてもよい。重合開始剤としては、活性エネルギー線のエネルギーによって、ラジカルやカチオンなどの活性種を生成し、重合性化合物（モノマーやオリゴマー）の重合を開始させることが可能なものであればよい。このような重合開始剤としては、公知のラジカル重合開始剤やカチオン重合開始剤、塩基発生剤等を、１種単独もしくは２種以上を組み合わせて用いることができ、中でもラジカル重合開始剤を使用することが好ましい。また、重合開始剤は、十分な硬化速度を得るために、組成物の総質量（１００質量％）に対し、５質量％〜２０質量％含まれることが好ましい。
ラジカル重合開始剤としては、例えば、芳香族ケトン類、アシルフォスフィンオキサイド化合物、芳香族オニウム塩化合物、有機過酸化物、チオ化合物（チオキサントン化合物、チオフェニル基含有化合物など）、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、及びアルキルアミン化合物などが挙げられる。
また、上記重合開始剤に加え、重合促進剤（増感剤）を併用することもできる。重合促進剤としては、特に限定されないが、例えば、トリメチルアミン、メチルジメタノールアミン、トリエタノールアミン、ｐ−ジエチルアミノアセトフェノン、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸−２−エチルヘキシル、Ｎ，Ｎ−ジメチルベンジルアミン及び４，４’−ビス（ジエチルアミノ）ベンゾフェノンなどのアミン化合物が好ましく、その含有量は、使用する重合開始剤やその量に応じて適宜設定すればよい。
<Polymerization initiator>
The curable composition of the present invention may contain a polymerization initiator. Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays and initiate polymerization of a polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more, and among them, radical polymerization initiators are used. It is preferable. The polymerization initiator is preferably contained in an amount of 5% by mass to 20% by mass with respect to the total mass (100% by mass) of the composition in order to obtain a sufficient curing rate.
Examples of radical polymerization initiators include aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. The polymerization accelerator is not particularly limited. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, N, Amine compounds such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.
＜色材＞
本発明の硬化型組成物は、色材を含有する。色材としては、本発明における組成物の目的や要求特性に応じて、ブラック、ホワイト、マゼンタ、シアン、イエロー、グリーン、オレンジ、金や銀等の光沢色、などを付与する種々の顔料を用いることができる。色材の含有量は、所望の色濃度や組成物中における分散性等を考慮して適宜決定すればよく、特に限定されないが、組成物の総質量（１００質量％）に対して、０．１質量％〜２０質量％であることが好ましい。
顔料としては、無機顔料又は有機顔料を使用することができ、１種単独で用いてもよく、２種以上を併用してもよい。
無機顔料としては、例えば、ファーネスブラック、ランプブラック、アセチレンブラック、チャネルブラック等のカーボンブラック（Ｃ．Ｉ．ピグメントブラック７）類、酸化鉄、酸化チタンを使用することができる。
有機顔料としては、例えば、不溶性アゾ顔料、縮合アゾ顔料、アゾレーキ、キレートアゾ顔料等のアゾ顔料、フタロシアニン顔料、ペリレン及びペリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサン顔料、チオインジゴ顔料、イソインドリノン顔料、キノフタロン顔料等の多環式顔料、染料キレート（例えば、塩基性染料型キレート、酸性染料型キレート等）、染色レーキ（塩基性染料型レーキ、酸性染料型レーキ）、ニトロ顔料、ニトロソ顔料、アニリンブラック、昼光蛍光顔料が挙げられる。
<Color material>
The curable composition of the present invention contains a color material. As the coloring material, various pigments imparting black, white, magenta, cyan, yellow, green, orange, glossy color such as gold or silver, etc. are used according to the purpose and required characteristics of the composition in the present invention. be able to. The content of the color material may be appropriately determined in consideration of a desired color density, dispersibility in the composition, and the like, and is not particularly limited. It is preferable that it is 1 mass%-20 mass%.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.
As the inorganic pigment, for example, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned.
本発明の硬化型組成物は、顔料分散剤を含む。
顔料分散剤としては、下記一般式（１）及び下記一般式（２）で表される構造単位を有する共重合体が用いられる。
The curable composition of the present invention contains a pigment dispersant.
As the pigment dispersant, a copolymer having a structural unit represented by the following general formula (1) and the following general formula (2) is used.
［一般式（１）］
［一般式（２）］
前記共重合体に含まれる一般式（１）の構造単位は、下記一般式（３）又は一般式（４）で表される構造単位であることが好ましく、前記一般式（３）で表される構造単位であることがより好ましい。 The structural unit of the general formula (1) contained in the copolymer is preferably a structural unit represented by the following general formula (3) or general formula (4), and is represented by the general formula (3). More preferred is a structural unit.
［一般式（３）］
［一般式（４）］
上記一般式（１）及び上記一般式（２）で表される構造単位を有する共重合体の製造方法は、特に制限はなく、種々の重合方法、例えば、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の公知の重合法により、合成することができる。前記重合反応は回分式、半連続式、連続式等の公知の操作で行うことができる。これらの重合法に限定されないが、重合操作及び分子量の調整が容易なことから、以下に示すラジカル重合開始剤を用いるラジカル重合が好ましく、有機溶剤と水の混合溶媒中で重合させる溶液重合法が更に好ましい。 The method for producing the copolymer having the structural unit represented by the general formula (1) and the general formula (2) is not particularly limited, and various polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension method, and the like. It can be synthesized by a known polymerization method such as a turbid polymerization method or an emulsion polymerization method. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system. Although not limited to these polymerization methods, radical polymerization using the radical polymerization initiator shown below is preferable because the polymerization operation and the adjustment of molecular weight are easy, and a solution polymerization method in which polymerization is performed in a mixed solvent of an organic solvent and water is used. Further preferred.
分散剤としての共重合体の本発明の硬化型組成物における含有量は、顔料１００質量部に対して１０質量部以上１００質量部以下が好ましい。 The content of the copolymer as a dispersant in the curable composition of the present invention is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment.
前記共重合体の同定方法としては、例えば、１Ｈ−ＮＭＲスペクトル、ＩＲスペクトルなどを用いて同定することができる。
前記１Ｈ−ＮＭＲスペクトルとしては、１Ｈ−ＮＭＲ（３００ＭＨｚ）（ＪＥＯＬ社製）等を用いて測定することができる。
前記ＩＲスペクトルとしては、ＦＴ−ＩＲ ＳｐｅｃｔｒｕｍＧＸ（ＰＥＲＫＩＮ ＥＬＭＥＲ社製）等を用いて測定することができる。
The copolymer can be identified using, for example, a 1 H-NMR spectrum, an IR spectrum, or the like.
The 1 H-NMR spectrum can be measured using 1 H-NMR (300 MHz) (manufactured by JEOL) or the like.
The IR spectrum can be measured using FT-IR Spectrum GX (manufactured by PERKIN ELMER).
＜有機溶媒＞
本発明の硬化型組成物は、有機溶媒を含んでもよいが、可能であれば含まない方が好ましい。有機溶媒、特に揮発性の有機溶媒を含まない（ＶＯＣ（Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓ）フリー）組成物であれば、当該組成物を扱う場所の安全性がより高まり、環境汚染防止を図ることも可能となる。なお、「有機溶媒」とは、例えば、エーテル、ケトン、キシレン、酢酸エチル、シクロヘキサノン、トルエンなどの一般的な非反応性の有機溶媒を意味するものであり、反応性モノマーとは区別すべきものである。また、有機溶媒を「含まない」とは、実質的に含まないことを意味し、０．１質量％未満であることが好ましい。
<Organic solvent>
The curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. An organic solvent, particularly a volatile organic solvent-free (VOC (Volatile Organic Compounds) free) composition, can further increase the safety of the place where the composition is handled and can prevent environmental pollution. . The “organic solvent” means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from a reactive monomer. is there. Further, “not including” an organic solvent means that it does not substantially include, and is preferably less than 0.1% by mass.
＜その他の成分＞
本発明の硬化型組成物は、必要に応じてその他の公知の成分を含んでもよい。その他の成分としては、特に制限されないが、例えば、従来公知の、界面活性剤、重合禁止剤、レべリング剤、消泡剤、蛍光増白剤、浸透促進剤、湿潤剤（保湿剤）、定着剤、粘度安定化剤、防黴剤、防腐剤、酸化防止剤、紫外線吸収剤、キレート剤、ｐＨ調整剤、及び増粘剤などが挙げられる。
<Other ingredients>
The curable composition of the present invention may contain other known components as necessary. Other components are not particularly limited. For example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration enhancers, wetting agents (humectants), Fixing agents, viscosity stabilizers, antifungal agents, antiseptics, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, thickeners and the like can be mentioned.
＜硬化型組成物の調製＞
本発明の硬化型組成物は、上述した各種成分を用いて作製することができ、その調製手段や条件は特に限定されないが、例えば、重合性モノマー、顔料、分散剤等をボールミル、キティーミル、ディスクミル、ピンミル、ダイノーミルなどの分散機に投入し、分散させて顔料分散液を調製し、当該顔料分散液に更に重合性モノマー、開始剤、重合禁止剤、界面活性剤などを混合させることにより調製することができる。
<Preparation of curable composition>
The curable composition of the present invention can be prepared using the various components described above, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant, and the like can be used as a ball mill, a kitty mill, By putting into a dispersing machine such as a disk mill, pin mill, dyno mill and dispersing to prepare a pigment dispersion, and further mixing a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. into the pigment dispersion. Can be prepared.
＜粘度＞
本発明の硬化型組成物の粘度は、用途や適用手段に応じて適宜調整すればよく、特に限定されないが、例えば、当該組成物をノズルから吐出させるような吐出手段を適用する場合には、２０℃〜６５℃の範囲における粘度、望ましくは２５℃における粘度が３〜４０ｍＰａ・ｓが好ましく、５ｍＰａ・ｓ〜１５ｍＰａ・ｓがより好ましく、６ｍＰａ・ｓ〜１２ｍＰａ・ｓが特に好ましい。また当該粘度範囲を、上記有機溶媒を含まずに満たしていることが特に好ましい。なお、上記粘度は、東機産業株式会社製コーンプレート型回転粘度計ＶＩＳＣＯＭＥＴＥＲ ＴＶＥ−２２Ｌにより、コーンロータ（１°３４’×Ｒ２４）を使用し、回転数５０ｒｐｍ、恒温循環水の温度を２０℃〜６５℃の範囲で適宜設定して測定することができる。循環水の温度調整にはＶＩＳＣＯＭＡＴＥ ＶＭ−１５０ＩＩＩを用いることができる。
<Viscosity>
The viscosity of the curable composition of the present invention may be appropriately adjusted according to the application and application means, and is not particularly limited.For example, when applying a discharge means that discharges the composition from a nozzle, The viscosity in the range of 20 ° C. to 65 ° C., desirably the viscosity at 25 ° C. is preferably 3 to 40 mPa · s, more preferably 5 mPa · s to 15 mPa · s, and particularly preferably 6 mPa · s to 12 mPa · s. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. In addition, the said viscosity uses a cone rotor (1 degree 34'xR24) by Toki Sangyo Co., Ltd. cone plate type rotational viscometer VISCOMETER TVE-22L, rotation speed is 50 rpm, and the temperature of constant temperature circulating water is 20 degreeC. It can be measured by appropriately setting in the range of ~ 65 ° C. VISCOMATE VM-150III can be used for temperature adjustment of circulating water.
＜用途＞
本発明の硬化型組成物の用途は、一般に硬化型材料が用いられている分野であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、成形用樹脂、塗料、接着剤、絶縁材、離型剤、コーティング材、シーリング材、各種レジスト、各種光学材料などが挙げられる。
更に、本発明の硬化型組成物は、インクとして用いて２次元の文字や画像、各種基材への意匠塗膜を形成するだけでなく、３次元の立体像（立体造形物）を形成するための立体造形用材料としても用いることができる。この立体造形用材料は、例えば、粉体層の硬化と積層を繰り返して立体造形を行う粉体積層法において用いる粉体粒子同士のバインダーとして用いてもよく、また、図２や図３に示すような積層造形法（光造形法）において用いる立体構成材料（モデル材）や支持部材（サポート材）として用いてもよい。なお、図２は、本発明の硬化型組成物を所定領域に吐出し、活性エネルギー線を照射して硬化させたものを順次積層して立体造形を行う方法であり（詳細後述）、図３は、本発明の硬化型組成物５の貯留プール（収容部）１に活性エネルギー線４を照射して所定形状の硬化層６を可動ステージ３上に形成し、これを順次積層して立体造形を行う方法である。
<Application>
The application of the curable composition of the present invention is not particularly limited as long as it is a field where curable materials are generally used, and can be appropriately selected according to the purpose. For example, a molding resin, a paint, an adhesive Insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Further, the curable composition of the present invention is used as an ink to form not only two-dimensional characters and images, and design coatings on various substrates, but also three-dimensional images (three-dimensional objects). It can also be used as a material for three-dimensional modeling. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeatedly curing and laminating a powder layer, as shown in FIGS. 2 and 3. You may use as a three-dimensional constituent material (model material) and support member (support material) which are used in such a layered modeling method (optical modeling method). 2 is a method of performing three-dimensional modeling by sequentially laminating the cured composition of the present invention onto a predetermined region and irradiating and curing the active energy ray (details will be described later). Irradiates the storage pool (accommodating part) 1 of the curable composition 5 of the present invention with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3, and sequentially laminates the three-dimensional model. It is a method to do.
本発明の硬化型組成物を用いて立体造形物を造形するための立体造形装置としては、公知のものを使用することができ、特に限定されないが、例えば、該組成物の収容手段、供給手段、吐出手段や活性エネルギー線照射手段等を備えるものが挙げられる。
また、本発明は、硬化型組成物を硬化させて得られた硬化物や当該硬化物が基材上に形成された構造体を加工してなる成形加工品も含む。前記成形加工品は、例えば、シート状、フィルム状に形成された硬化物や構造体に対して、加熱延伸や打ち抜き加工等の成形加工を施したものであり、例えば、自動車、ＯＡ機器、電気・電子機器、カメラ等のメーターや操作部のパネルなど、表面を加飾後に成形することが必要な用途に好適に使用される。
上記基材としては、特に限定されず、目的に応じて適宜選択することができ、例えば、紙、糸、繊維、布帛、皮革、金属、プラスチック、ガラス、木材、セラミックス、又はこれらの複合材料などが挙げられ、加工性の観点からはプラスチック基材が好ましい。
As a three-dimensional modeling apparatus for modeling a three-dimensional molded article using the curable composition of the present invention, a known one can be used, and is not particularly limited. And those provided with discharge means, active energy ray irradiation means and the like.
The present invention also includes a molded product obtained by processing a cured product obtained by curing a curable composition and a structure in which the cured product is formed on a substrate. The molded product is obtained by subjecting a cured product or structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications that require the surface to be molded after decorating, such as meters for electronic devices and cameras, and panels for operation units.
The substrate is not particularly limited and can be appropriately selected depending on the purpose. For example, paper, yarn, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof. From the viewpoint of processability, a plastic substrate is preferable.
＜組成物収容容器＞
本発明の組成物収容容器は、硬化型組成物が収容された状態の容器を意味し、上記のような用途に供する際に好適である。例えば、本発明の硬化型組成物がインク用途である場合において、当該インクが収容された容器は、インクカートリッジやインクボトルとして使用することができ、これにより、インク搬送やインク交換等の作業において、インクに直接触れる必要がなくなり、手指や着衣の汚れを防ぐことができる。また、インクへのごみ等の異物の混入を防止することができる。また、容器それ自体の形状や大きさ、材質等は、用途や使い方に適したものとすればよく、特に限定されないが、その材質は光を透過しない遮光性材料であるか、又は容器が遮光性シート等で覆われていることが望ましい。
<Composition container>
The composition storage container of the present invention means a container in which a curable composition is stored, and is suitable for use in the above applications. For example, when the curable composition of the present invention is used for ink, the container in which the ink is stored can be used as an ink cartridge or an ink bottle, thereby enabling operations such as ink transportation and ink replacement. This eliminates the need for direct contact with the ink and prevents dirt on fingers and clothes. In addition, foreign matters such as dust can be prevented from entering the ink. Further, the shape, size, material, and the like of the container itself may be suitable for use and usage, and are not particularly limited, but the material is a light-shielding material that does not transmit light, or the container is shielded from light. It is desirable to be covered with an adhesive sheet.
本発明の像の形成方法は、活性エネルギー線を用いてもよいし、加温なども挙げられる。本発明の硬化型組成物を活性エネルギー線で硬化させるためには、活性エネルギー線を照射する照射工程を有し、本発明の像の形成装置は、活性エネルギー線を照射するための照射手段と、本発明の硬化型組成物を収容するための収容部と、を備え、該収容部には前記容器を収容してもよい。更に、硬化型組成物を吐出する吐出工程、吐出手段を有していてもよい。吐出させる方法は特に限定されないが、連続噴射型、オンデマンド型等が挙げられる。オンデマンド型としてはピエゾ方式、サーマル方式、静電方式等が挙げられる。 In the image forming method of the present invention, active energy rays may be used, and heating may be mentioned. In order to cure the curable composition of the present invention with active energy rays, it has an irradiation step of irradiating with active energy rays, and the image forming apparatus of the present invention comprises irradiation means for irradiating with active energy rays. A container for accommodating the curable composition of the present invention, and the container may be accommodated in the container. Furthermore, you may have the discharge process and discharge means which discharge a curable composition. A method for discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.
図１は、インクジェット吐出手段を備えた像形成装置の一例である。イエロー、マゼンタ、シアン、ブラックの各色硬化型インクのインクカートリッジと吐出ヘッドを備える各色印刷ユニット２３ａ、２３ｂ、２３ｃ、２３ｄにより、供給ロール２１から供給された被記録媒体２２にインクが吐出される。その後、インクを硬化させるための光源２４ａ、２４ｂ、２４ｃ、２４ｄから、活性エネルギー線を照射して硬化させ、カラー画像を形成する。その後、被記録媒体２２は、加工ユニット２５、印刷物巻取りロール２６へと搬送される。各印刷ユニット２３ａ、２３ｂ、２３ｃ、２３ｄには、インク吐出部でインクが液状化するように、加温機構を設けてもよい。また必要に応じて、接触又は非接触により記録媒体を室温程度まで冷却する機構を設けてもよい。また、インクジェット記録方式としては、吐出ヘッド幅に応じて間欠的に移動する記録媒体に対し、ヘッドを移動させて記録媒体上にインクを吐出するシリアル方式や、連続的に記録媒体を移動させ、一定の位置に保持されたヘッドから記録媒体上にインクを吐出するライン方式のいずれであっても適用することができる。
被記録媒体２２は、特に限定されないが、紙、フィルム、セラミックスやガラス、金属、これらの複合材料等が挙げられ、シート状であってもよい。また片面印刷のみを可能とする構成であっても、両面印刷も可能とする構成であってもよい。一般的な記録媒体として用いられるものに限られず、ダンボール、壁紙や床材等の建材、コンクリート、Ｔシャツなど衣料用等の布、テキスタイル、皮革等を適宜使用することができる。
更に、光源２４ａ、２４ｂ、２４ｃからの活性エネルギー線照射を微弱にするか又は省略し、複数色を印刷した後に、光源２４ｄから活性エネルギー線を照射してもよい。これにより、省エネ、低コスト化を図ることができる。
本発明のインクにより記録される記録物としては、通常の紙や樹脂フィルムなどの平滑面に印刷されたものだけでなく、凹凸を有する被印刷面に印刷されたものや、金属やセラミックなどの種々の材料からなる被印刷面に印刷されたものも含む。また、２次元の画像を積層することで、一部に立体感のある画像（２次元と３次元からなる像）や立体物を形成することもできる。
FIG. 1 is an example of an image forming apparatus provided with an ink jet ejection unit. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by each color printing unit 23 a, 23 b, 23 c, and 23 d including ink cartridges and discharge heads for each color curable ink of yellow, magenta, cyan, and black. Thereafter, the light is cured by irradiating active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink, thereby forming a color image. Thereafter, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied by the ink discharge unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, as an ink jet recording system, a serial system in which ink is ejected onto a recording medium by moving the head relative to a recording medium that moves intermittently according to the ejection head width, or the recording medium is moved continuously, Any of the line systems in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, and examples thereof include paper, film, ceramics, glass, metal, a composite material thereof, and the like, and may be a sheet shape. Moreover, even if it is the structure which enables only single-sided printing, the structure which also enables double-sided printing may be sufficient. The material is not limited to those used as general recording media, and corrugated cardboards, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate.
Further, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and the active energy ray may be irradiated from the light source 24d after printing a plurality of colors. Thereby, energy saving and cost reduction can be achieved.
The recorded matter recorded by the ink of the present invention is not only printed on a smooth surface such as ordinary paper or resin film, but also printed on a surface to be printed having irregularities, such as metal or ceramic. It includes those printed on a printing surface made of various materials. Further, by stacking two-dimensional images, it is possible to form an image having a stereoscopic effect (an image composed of two and three dimensions) or a three-dimensional object.
図２は、本発明に係る別の像形成装置（３次元立体像の形成装置）の一例を示す概略図である。図２の像形成装置３９は、インクジェットヘッドを配列したヘッドユニット（ＡＢ方向に可動）を用いて、造形物用吐出ヘッドユニット３０から第一の硬化型組成物を、支持体用吐出ヘッドユニット３１、３２から第一の硬化型組成物とは組成が異なる第二の硬化型組成物を吐出し、隣接した紫外線照射手段３３、３４でこれら各組成物を硬化しながら積層するものである。より具体的には、例えば、造形物支持基板３７上に、第二の硬化型組成物を支持体用吐出ヘッドユニット３１、３２から吐出し、活性エネルギー線を照射して固化させて溜部を有する第一の支持体層を形成した後、当該溜部に第一の硬化型組成物を造形物用吐出ヘッドユニット３０から吐出し、活性エネルギー線を照射して固化させて第一の造形物層を形成する工程を、積層回数に合わせて、上下方向に可動なステージ３８を下げながら複数回繰り返すことで、支持体層と造形物層を積層して立体造形物３５を製作する。その後、必要に応じて支持体積層部３６は除去される。なお、図２では、造形物用吐出ヘッドユニット３０は１つしか設けていないが、２つ以上設けることもできる。 FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer the first curable composition from the molded article ejection head unit 30 to the support ejection head unit 31. 32, a second curable composition having a composition different from that of the first curable composition is ejected, and these compositions are laminated while being cured by the adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, the second curable composition is discharged from the discharge head units 31 and 32 for the support on the model support substrate 37, and solidified by irradiation with active energy rays to form the reservoir. After the first support layer is formed, the first curable composition is discharged from the discharge head unit 30 for a molded article to the reservoir, and is solidified by irradiation with active energy rays. The step of forming a layer is repeated a plurality of times while lowering the stage 38 that is movable in the vertical direction in accordance with the number of times of stacking, thereby stacking the support layer and the modeled object layer to manufacture the three-dimensional modeled object 35. Thereafter, the support laminate 36 is removed as necessary. In FIG. 2, only one shaped article discharge head unit 30 is provided, but two or more shaped article discharge head units 30 may be provided.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（合成例１）
［モノマーＭ１の合成］
６２．０ｇ（５２５ｍｍｏｌ）の１，６−ヘキサンジオール（東京化成工業株式会社製）を７００ｍＬの塩化メチレンに溶解し、２０．７ｇ（２６２ｍｍｏｌ）のピリジンを加えた。この溶液に、５０．０ｇ（２６２ｍｍｏｌ）の２−ナフタレンカルボニルクロリド（東京化成工業株式会社製）を１００ｍＬの塩化メチレンに溶解した溶液を、２時間かけて撹拌しながら滴下した後、室温で６時間撹拌した。得られた反応溶液を水洗した後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液として塩化メチレン／メタノール（体積比９８／２）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、５２．５ｇの２−ナフトエ酸−２−ヒドロキシエチルエステルを得た。
次に、４２．１ｇ（１５５ｍｍｏｌ）の２−ナフトエ酸−２−ヒドロキシエチルエステルを８０ｍＬの乾燥メチルエチルケトンに溶解し、６０℃まで加熱した。この溶液に、２４．０ｇ（１５５ｍｍｏｌ）の２−メタクリロイルオキシエチルイソシアネート（昭和電工株式会社製、カレンズＭＯＩ）を２０ｍＬの乾燥メチルエチルケトンに溶解した溶液を、１時間かけて撹拌しながら滴下した後、７０℃で１２時間撹拌した。室温まで冷却した後、溶媒を留去した。残留物を、溶離液として塩化メチレン／メタノール（体積比９９／１）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、５７．０ｇの下記構造式（１）で表される構造を有するモノマーＭ−１を得た。
(Synthesis Example 1)
[Synthesis of Monomer M1]
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added. A solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 6 hours. Stir. After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of 2-naphthoic acid-2-hydroxyethyl ester.
Next, 42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyethyl ester was dissolved in 80 mL of dry methyl ethyl ketone and heated to 60 ° C. To this solution, a solution prepared by dissolving 24.0 g (155 mmol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI) in 20 mL of dry methyl ethyl ketone was added dropwise over 1 hour with stirring. Stir at 12 ° C. for 12 hours. After cooling to room temperature, the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 99/1) as an eluent, and 57.0 g of a monomer having a structure represented by the following structural formula (1) M-1 was obtained.
［構造式（１）］
（合成例２）
［モノマーＭ−２の合成］
合成例１において、１，６−ヘキサンジオールに代えて、１，１６−ヘキサデカンジオール（東京化成工業株式会社製）を用いた以外は、合成例１と同様にして、下記構造式（２）で表される構造を有するモノマーＭ−２を得た。
(Synthesis Example 2)
[Synthesis of Monomer M-2]
In Synthesis Example 1, instead of 1,6-hexanediol, 1,16-hexadecanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and in the same manner as Synthesis Example 1, the following structural formula (2) Monomer M-2 having the structure represented was obtained.
［構造式（２）］
（合成例３）
［モノマーＭ−３の合成］
合成例１において、２−メタクリロイルオキシエチルイソシアネートに代えて、２−アクリロイルオキシエチルイソシアネートを用いた以外は、合成例１と同様にして、下記構造式（３）で表される構造を有するモノマーＭ−３を得た。
(Synthesis Example 3)
[Synthesis of Monomer M-3]
Monomer M having a structure represented by the following structural formula (3) in the same manner as in Synthesis Example 1 except that 2-acryloyloxyethyl isocyanate was used instead of 2-methacryloyloxyethyl isocyanate in Synthesis Example 1. -3 was obtained.
［構造式（３）］
（合成例４）
［モノマーＭ−４の合成］
６２．０ｇ（５２５ｍｍｏｌ）の１，６−ヘキサンジオール（東京化成工業株式会社製）を７００ｍＬの塩化メチレンに溶解し、２０．７ｇ（２６２ｍｍｏｌ）のピリジンを加えた。
この溶液に、５０．０ｇ（２６２ｍｍｏｌ）の２−ナフタレンカルボニルクロリド（東京化成工業株式会社製）を１００ｍＬの塩化メチレンに溶解した溶液を、２時間かけて撹拌しながら滴下した後、室温で６時間撹拌した。得られた反応溶液を水洗した後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液として塩化メチレン／メタノール（体積比９８／２）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、５２．５ｇの下記構造式（４）で表される反応中間体を得た。
(Synthesis Example 4)
[Synthesis of Monomer M-4]
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added.
A solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 6 hours. Stir. After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent, and 52.5 g of a reaction intermediate represented by the following structural formula (4) was obtained. Obtained.
［構造式（４）］
次に、４１．０ｇ（１５１ｍｍｏｌ）の構造式（４）の反応中間体を２５０ｍＬの塩化メチレンに溶解させ、２０．０ｇ（１９８ｍｍｏｌ）のトリエチルアミン（東京化成工業株式会社製）を加えた。この溶液を氷浴下で冷却し、２０．０ｇ（１９１ｍｍｏｌ）のメタクリル酸クロリド（東京化成工業株式会社製）を、３０分間かけて滴下した後、氷浴下で１時間撹拌、室温で３時間撹拌した。沈殿物をろ別し、ろ液を水、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗った後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／酢酸エチル（体積比６／１）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、３９．４ｇの下記構造式（５）で表される構造を有するモノマーＭ−４を得た。 Next, 41.0 g (151 mmol) of the reaction intermediate of the structural formula (4) was dissolved in 250 mL of methylene chloride, and 20.0 g (198 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The solution was cooled in an ice bath, and 20.0 g (191 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in an ice bath for 1 hour and at room temperature for 3 hours. Stir. The precipitate was filtered off and the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 6/1) as an eluent to obtain 39.4 g of a structure represented by the following structural formula (5). Monomer M-4 was obtained.
［構造式（５）］
（合成例５）
［モノマーＭ−５の合成］
１５０．０ｇ（１．２６ｍｏｌ）の１，６−ヘキサンジオール、及び５０．０ｇ（０．２６８ｍｏｌ）の１−ナフタレン酢酸（東京化成工業株式会社製）を反応容器に入れ、撹拌しながら７０℃に加熱し、溶解させた。１．３０ｇの濃硫酸を加え、７０℃で２時間撹拌した。室温まで冷却した後、１．０６ｇの水酸化ナトリウムを６００ｍＬの水に溶解させた溶液を投入し、洗浄した。酢酸エチル５００ｍＬを投入し、有機相を抽出した後、更に水洗した。有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／酢酸エチル（体積比３／２）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、６１．５ｇの下記構造式（６）で表される反応中間体を得た。
(Synthesis Example 5)
[Synthesis of Monomer M-5]
150.0 g (1.26 mol) of 1,6-hexanediol and 50.0 g (0.268 mol) of 1-naphthalene acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a reaction vessel and stirred at 70 ° C. Heat and dissolve. 1.30 g of concentrated sulfuric acid was added and stirred at 70 ° C. for 2 hours. After cooling to room temperature, a solution prepared by dissolving 1.06 g of sodium hydroxide in 600 mL of water was added and washed. Ethyl acetate (500 mL) was added, and the organic phase was extracted and further washed with water. The organic phase was isolated and dried over magnesium sulfate and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 3/2) as an eluent, and 61.5 g of a reaction intermediate represented by the following structural formula (6) Got the body.
［構造式（６）］
次に、４３．０ｇ（１５０ｍｍｏｌ）の前記構造式（６）で表される反応中間体を２５０ｍＬの塩化メチレンに溶解させ、２０．０ｇ（１９８ｍｍｏｌ）のトリエチルアミン（東京化成工業株式会社製）を加えた。この溶液を氷浴下で冷却し、１７．４ｇ（１９２ｍｍｏｌ）のアクリル酸クロリド（東京化成工業株式会社製）を、３０分間かけて滴下した後、氷浴下で１時間撹拌、室温で３時間撹拌した。沈殿物をろ別し、ろ液を水、飽和炭酸水素ナトリウム水溶液、及び飽和食塩水で洗った後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／酢酸エチル（体積比７／１）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、３７．６ｇの下記構造式（７）で表される構造を有するモノマーＭ−５を得た。 Next, 43.0 g (150 mmol) of the reaction intermediate represented by the structural formula (6) was dissolved in 250 mL of methylene chloride, and 20.0 g (198 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. It was. The solution was cooled in an ice bath, and 17.4 g (192 mmol) of acrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in the ice bath for 1 hour and at room temperature for 3 hours. Stir. The precipitate was filtered off and the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 7/1) as an eluent, and 37.6 g of a structure represented by the following structural formula (7) was obtained. Monomer M-5 was obtained.
［構造式（７）］
（合成例６）
［モノマーＭ−６の合成］
６４．０ｇ（３６７ｍｍｏｌ）の１，１０−デカンジオール（関東化学株式会社製）を９００ｍＬの乾燥テトラヒドロフランに溶解し、１７．４ｇ（２２０ｍｍｏｌ）のピリジンを加えた。
この溶液に、３５．０ｇ（１８３ｍｍｏｌ）の２−ナフタレンカルボニルクロリド（東京化成工業株式会社製）を１００ｍＬの塩化メチレンに溶解した溶液を、２時間かけて撹拌しながら滴下した後、室温で１２時間撹拌した。酢酸エチル５００ｍＬを加え、水洗した後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／酢酸エチル（体積比４／１）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、４３．１ｇの下記構造式（８）で表される反応中間体を得た。
(Synthesis Example 6)
[Synthesis of Monomer M-6]
64.0 g (367 mmol) of 1,10-decanediol (manufactured by Kanto Chemical Co., Inc.) was dissolved in 900 mL of dry tetrahydrofuran, and 17.4 g (220 mmol) of pyridine was added.
A solution prepared by dissolving 35.0 g (183 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 12 hours. Stir. After adding 500 mL of ethyl acetate and washing with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 4/1) as an eluent, and 43.1 g of a reaction intermediate represented by the following structural formula (8) Got the body.
［構造式（８）］
次に、３２．８ｇ（１００ｍｍｏｌ）の前記構造式（８）の反応中間体を４００ｍＬの塩化メチレンに溶解させ、１７．２ｇ（１７０ｍｍｏｌ）のトリエチルアミン（東京化成工業株式会社製）を加えた。この溶液を氷浴下で冷却し、１５．０ｇ（１４４ｍｍｏｌ）のメタクリル酸クロリド（東京化成工業株式会社製）を、３０分間かけて滴下した後、氷浴下で１時間撹拌、室温で４時間撹拌した。反応液から溶媒を留去し、酢酸エチル３００ｍＬに溶解させた後、水洗した。有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／塩化メチレン（体積比３／２）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、３２．１ｇの下記構造式（９）で表される構造を有するモノマーＭ−６を得た。 Next, 32.8 g (100 mmol) of the reaction intermediate of the structural formula (8) was dissolved in 400 mL of methylene chloride, and 17.2 g (170 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The solution was cooled in an ice bath, and 15.0 g (144 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in an ice bath for 1 hour and at room temperature for 4 hours. Stir. The solvent was distilled off from the reaction solution, dissolved in 300 mL of ethyl acetate, and washed with water. The organic phase was isolated and dried over magnesium sulfate and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / methylene chloride (volume ratio 3/2) as an eluent, and 32.1 g of the structure represented by the following structural formula (9) was obtained. Monomer M-6 having was obtained.
［構造式（９）］
（合成例７）
［モノマーＭ―７の合成］
２−ナフトール１４４ｇ、エチレングリコールモノ−２−クロロエチルエーテル２５０ｇ、炭酸カリウム２０５ｇを１，０００ｍＬのＮ−メチルピロリドン（ＮＭＰ）に加え、室温で１時間撹拌した。更に、１１０℃で１０時間撹拌した。反応後、溶液が室温に戻るまで冷却し、得られた溶液に純水５，０００ｍＬを加え、室温で１時間撹拌した。析出した固体をろ取し、減圧条件で乾燥した。上記の反応で得られた固体１３９ｇ、及びトリエチルアミン１２５ｍＬを５００ｍＬのテトラヒドロフラン（ＴＨＦ）に加え、０℃で３０分間撹拌した。この溶液に、７５ｇのメタクリル酸クロリドをゆっくり滴下し、更に、０℃で撹拌を３時間継続した。反応後、得られた溶液に酢酸エチル５００ｍＬ、及び２００ｍＬの純水を加えて撹拌した。分液漏斗を用いて酢酸エチル層を分液し、飽和食塩水溶液で洗浄し、無水硫酸マグネシウムで乾燥した。硫酸マグネシウムを濾別し、溶液を濃縮し、これをシリカクロマトグラフィーにて精製することにより１７４ｇの下記構造式（１０）で表される構造を有するＭ−７を得た。
(Synthesis Example 7)
[Synthesis of Monomer M-7]
144 g of 2-naphthol, 250 g of ethylene glycol mono-2-chloroethyl ether and 205 g of potassium carbonate were added to 1,000 mL of N-methylpyrrolidone (NMP) and stirred at room temperature for 1 hour. Furthermore, it stirred at 110 degreeC for 10 hours. After the reaction, the solution was cooled until it returned to room temperature, and 5,000 mL of pure water was added to the resulting solution, followed by stirring at room temperature for 1 hour. The precipitated solid was collected by filtration and dried under reduced pressure conditions. 139 g of the solid obtained in the above reaction and 125 mL of triethylamine were added to 500 mL of tetrahydrofuran (THF), and the mixture was stirred at 0 ° C. for 30 minutes. To this solution, 75 g of methacrylic acid chloride was slowly added dropwise, and stirring was further continued at 0 ° C. for 3 hours. After the reaction, 500 mL of ethyl acetate and 200 mL of pure water were added to the resulting solution and stirred. The ethyl acetate layer was separated using a separatory funnel, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solution was concentrated, and purified by silica chromatography to obtain 174 g of M-7 having a structure represented by the following structural formula (10).
［構造式（１０）］
（合成例８）
［モノマーＭ―８の合成］
メタクリル酸２−ヒドロキシエチル１３０ｇ、及びトリエチルアミン１６７ｍＬを１０００ｍＬの酢酸エチルに加え、０℃で３０分間撹拌した。この溶液に、１２０ｇのメタンスルホニルクロリドをゆっくり滴下し、更に、０℃で撹拌を３時間継続した。反応後、得られた溶液に５００ｍＬの純水を加えて撹拌した。分液漏斗を用いて酢酸エチル層を分液し、飽和食塩水溶液で洗浄し、無水硫酸マグネシウムで乾燥した。硫酸マグネシウムを濾別し、溶液を濃縮することで、メタクリル酸２−メタンスルホニルオキシエチルを２０７ｇ得た。合成したメタクリル酸２−メタンスルホニルオキシエチル４８ｇ、２−ナフトール３０ｇ、及び炭酸カリウム４３ｇを２００ｍＬのＮ−メチルピロリドン（ＮＭＰ）に加え、室温で１時間撹拌した。更に、８０℃で１０時間撹拌した。反応後、析出した不溶物をろ過して除去した後、得られた溶液に酢酸エチル５００ｍＬ、及び純水２００ｍＬを加えて撹拌した。酢酸エチル層を分液し、飽和食塩水溶液で洗浄し、無水硫酸マグネシウムで乾燥した。硫酸マグネシウムを濾別し、溶液を濃縮し、これをシリカクロマトグラフィーにて精製することにより、４８ｇの下記構造式（１１）で表される構造を有するモノマーＭ−８を得た。
(Synthesis Example 8)
[Synthesis of Monomer M-8]
130 g of 2-hydroxyethyl methacrylate and 167 mL of triethylamine were added to 1000 mL of ethyl acetate and stirred at 0 ° C. for 30 minutes. To this solution, 120 g of methanesulfonyl chloride was slowly added dropwise, and stirring was further continued at 0 ° C. for 3 hours. After the reaction, 500 mL of pure water was added to the resulting solution and stirred. The ethyl acetate layer was separated using a separatory funnel, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off and the solution was concentrated to obtain 207 g of 2-methanesulfonyloxyethyl methacrylate. 48 g of synthesized 2-methanesulfonyloxyethyl methacrylate, 30 g of 2-naphthol, and 43 g of potassium carbonate were added to 200 mL of N-methylpyrrolidone (NMP) and stirred at room temperature for 1 hour. Furthermore, it stirred at 80 degreeC for 10 hours. After the reaction, the precipitated insoluble matter was removed by filtration, and then 500 mL of ethyl acetate and 200 mL of pure water were added to the resulting solution and stirred. The ethyl acetate layer was separated, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solution was concentrated, and purified by silica chromatography to obtain 48 g of a monomer M-8 having a structure represented by the following structural formula (11).
［構造式（１１）］
（調製例１）
［共重合体ＣＰ−１の合成］
５．３５ｇ（１８．８３ｍｍｏｌ）のポリエチレングリコールモノメタクリレート（ｎ≒４．５）（日油株式会社製）、及び２．６８ｇ（６．３ｍｍｏｌ）のモノマーＭ−１を４０ｍＬの乾燥メチルエチルケトンに溶解してモノマー溶液を調製した。
モノマー溶液の１０質量％をアルゴン気流下で７５℃まで加熱した後、残りのモノマー溶液に０．２０６ｇ（１．２６ｍｍｏｌ）の２，２’−アゾイソ（ブチロニトリル）（東京化成工業株式会社製）を溶解した溶液を１．５時間かけて滴下し、７５℃で６時間撹拌した。室温まで冷却し、得られた反応溶液をヘキサンに投下した。析出した共重合体を回収し、テトラヒドロフラン（ＴＨＦ）で溶解させ、ロータリーエバポレーターを用いて溶媒を除去し、減圧乾燥して、８．００ｇの共重合体ＣＰ−１を得た。
(Preparation Example 1)
[Synthesis of Copolymer CP-1]
Dissolve 5.35 g (18.83 mmol) of polyethylene glycol monomethacrylate (n≈4.5) (manufactured by NOF Corporation) and 2.68 g (6.3 mmol) of monomer M-1 in 40 mL of dry methyl ethyl ketone. A monomer solution was prepared.
After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 0.206 g (1.26 mmol) of 2,2′-azoiso (butyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the remaining monomer solution. The dissolved solution was added dropwise over 1.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was collected, dissolved in tetrahydrofuran (THF), the solvent was removed using a rotary evaporator, and dried under reduced pressure to obtain 8.00 g of copolymer CP-1.
（調製例２）
［共重合体ＣＰ−２の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−２に変えた以外は、調製例１と同様にして、共重合体ＣＰ−２を得た。
(Preparation Example 2)
[Synthesis of Copolymer CP-2]
In Preparation Example 1, the same procedure as in Preparation Example 1 except that polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈4.5) and monomer M-2. Thus, a copolymer CP-2 was obtained.
（調製例３）
［共重合体ＣＰ−３の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、メトキシポリエチレングリコールメタクリレート（ｎ≒２３）及びモノマーＭ−３に変えた以外は、調製例１と同様にして、共重合体ＣＰ−３を得た。
(Preparation Example 3)
[Synthesis of Copolymer CP-3]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to methoxypolyethylene glycol methacrylate (n≈23) and monomer M-3 in the same manner as Preparation Example 1. Copolymer CP-3 was obtained.
（調製例４）
［共重合体ＣＰ−４の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒２）及びモノマーＭ−４に変えた以外は、調製例１と同様にして、共重合体ＣＰ−４を得た。
(Preparation Example 4)
[Synthesis of Copolymer CP-4]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈2) and monomer M-4 in the same manner as Preparation Example 1. Copolymer CP-4 was obtained.
（調製例５）
［共重合体ＣＰ−５の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、メトキシポリエチレングリコールメタクリレート（ｎ≒９０）、及びモノマーＭ−５に変えた以外は、調製例１と同様にして、共重合体ＣＰ−５を得た。
(Preparation Example 5)
[Synthesis of Copolymer CP-5]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to methoxypolyethylene glycol methacrylate (n≈90) and monomer M-5 in the same manner as in Preparation Example 1. As a result, a copolymer CP-5 was obtained.
（調製例６）
［共重合体ＣＰ−６の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒８）及びモノマーＭ−６に変えた以外は、調製例１と同様にして、共重合体ＣＰ−６を得た。
(Preparation Example 6)
[Synthesis of Copolymer CP-6]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈8) and monomer M-6 in the same manner as Preparation Example 1. Copolymer CP-6 was obtained.
（調製例７）
［共重合体ＣＰ−７の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒８）及びモノマーＭ−７に変えた以外は、調製例１と同様にして、共重合体ＣＰ−７を得た。
(Preparation Example 7)
[Synthesis of Copolymer CP-7]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈8) and monomer M-7 in the same manner as Preparation Example 1. Copolymer CP-7 was obtained.
（調製例８）
［共重合体ＣＰ−８の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒２）及びモノマーＭ−８に変えた以外は、調製例１と同様にして、共重合体ＣＰ−８を得た。
(Preparation Example 8)
[Synthesis of Copolymer CP-8]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈2) and monomer M-8 in the same manner as Preparation Example 1. Copolymer CP-8 was obtained.
（調製例９）
［共重合体ＣＰ−９の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、モノマーＭ−１に変えた以外は、調製例１と同様にして、共重合体ＣＰ−９を得た。
(Preparation Example 9)
[Synthesis of Copolymer CP-9]
A copolymer CP-9 was obtained in the same manner as in Preparation Example 1 except that polyethylene glycol monomethacrylate (n≈4.5) and the monomer M-1 were changed to the monomer M-1 in Preparation Example 1. .
（調製例１０）
［共重合体ＣＰ−１０の合成］
調製例１において、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）及びモノマーＭ−１を、ポリエチレングリコールモノメタクリレート（ｎ≒４．５）に変えた以外は、調製例１と同様にして、共重合体ＣＰ−１０を得た。
(Preparation Example 10)
[Synthesis of Copolymer CP-10]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈4.5). Combined CP-10 was obtained.
（顔料分散体Ｄ−１の調製例）
ＳＰＥＣＩＡＬ ＢＬＡＣＫ ２５０（チバスペシャルティケミカルズ社製）３００質量部、共重合体ＣＰ−１を１００質量部、及びフェノキシエチルアクリレート（東京化成工業株式会社製）６００質量部を撹拌混合し、顔料ミルベースを得た。なお、顔料ミルベースの調製はウィリー・エ・バッコーフェン社製「Ｄｙｎｏ Ｍｉｌｌ ＲＬ」で、直径０．５ｍｍのジルコニアビーズを用いて、ビーズ体積８０％となるように分散容器内に仕込み、３０分間処理を行った。
株式会社堀場製作所製「ｎａｎｏ Ｐａｒｔｉｃａ ＳＺ−１００」により、累積９０％粒径（Ｄ９０）が３００ｎｍ未満であることを確認した。
(Preparation Example of Pigment Dispersion D-1)
300 parts by mass of SPECIAL BLACK 250 (manufactured by Ciba Specialty Chemicals), 100 parts by mass of copolymer CP-1 and 600 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred and mixed to obtain a pigment mill base. . The pigment mill base was prepared by “Dyno Mill RL” manufactured by Willy et Bacofen, and charged with a zirconia bead having a diameter of 0.5 mm into a dispersion container so that the bead volume would be 80%, followed by a treatment for 30 minutes. went.
It was confirmed that the cumulative 90% particle size (D90) was less than 300 nm by “nano Partica SZ-100” manufactured by HORIBA, Ltd.
（顔料分散体Ｄ−２〜Ｄ−１１の調製例）
顔料分散体Ｄ−１の調製例において、分散剤としての共重合体ＣＰ−１を表１に示した分散剤に変更した以外は、顔料分散体Ｄ−１の調製例と同様にして、顔料分散体Ｄ−２〜Ｄ−１１を調製した。
(Preparation examples of pigment dispersions D-2 to D-11)
The pigment dispersion D-1 was prepared in the same manner as in the pigment dispersion D-1, except that the copolymer CP-1 as a dispersant was changed to the dispersant shown in Table 1. Dispersions D-2 to D-11 were prepared.
（顔料分散体Ｄ−１２の調製例）
顔料分散体Ｄ−１の調製例において、フェノキシエチルアクリレートをイソボルニルアクリレートに変更した以外は、顔料分散体Ｄ−１の調製例と同様にして、顔料分散体Ｄ−１２を調製した。
(Preparation Example of Pigment Dispersion D-12)
A pigment dispersion D-12 was prepared in the same manner as in the preparation of pigment dispersion D-1, except that phenoxyethyl acrylate was changed to isobornyl acrylate in the preparation example of pigment dispersion D-1.
（実施例１〜１３及び比較例１〜５）
−インクの作製−
表２〜表６に示すインク処方に基づき、常法により、混合して、実施例１〜１３及び比較例１〜５のインクを作製した。
次に、得られた各インクについて、以下のようにして、諸特性を評価した。結果を表２〜表６に示した。
(Examples 1-13 and Comparative Examples 1-5)
-Preparation of ink-
Based on the ink formulations shown in Tables 2 to 6, the inks of Examples 1 to 13 and Comparative Examples 1 to 5 were prepared by mixing in a conventional manner.
Next, various characteristics of each ink obtained were evaluated as follows. The results are shown in Tables 2-6.
＜延伸性＞
ＧＥＮ４ヘッド（リコープリンティングシステムズ社製）を搭載した吐出試験機を用いて、Ｆａｓｓｏｎ ＰＥ（膜厚１００μｍ、Ｆａｓｓｏｎ社製）上に、平均膜厚が２０μｍのベタ画像の描画を行った。
１８０℃破断伸び（引張り試験）について、引張り試験機（オートグラフ ＡＧＳ−５ｋＮＸ、株式会社島津製作所製）を用い、引張り速度：２０ｍｍ／ｍｉｎ、温度１８０℃、サンプル：ＪＩＳ Ｋ６２５１ ダンベル状（６号）の条件で測定し、比（引張り試験後の長さ）／（引張り試験前の長さ）を求めた。なお、比（引張り試験後の長さ）／（引張り試験前の長さ）が大きいほど延伸性に優れており、比（引張り試験後の長さ）／（引張り試験前の長さ）は２．０以上であることが実使用可能なレベルである。
<Extensible>
Using a discharge tester equipped with a GEN4 head (manufactured by Ricoh Printing Systems), a solid image having an average film thickness of 20 μm was drawn on Fasson PE (film thickness: 100 μm, manufactured by Fasson).
About 180 degreeC elongation at break (tensile test), using a tensile tester (Autograph AGS-5kNX, manufactured by Shimadzu Corporation), pulling speed: 20 mm / min, temperature 180 ° C., sample: JIS K6251 dumbbell shape (No. 6) The ratio (length after the tensile test) / (length before the tensile test) was determined. The larger the ratio (length after the tensile test) / (length before the tensile test), the better the stretchability. The ratio (length after the tensile test) / (length before the tensile test) is 2. It is a practically usable level to be 0.0 or more.
＜耐ブロッキング性＞
ＧＥＮ４ヘッド（リコープリンティングシステムズ株式会社製）を搭載した吐出試験機を用いて、エステルフィルムＥ５０００（東洋紡株式会社製）上に平均膜厚が２０μｍのベタ画像の描画を行った後、印刷物の硬化膜全体が覆われるように、未印刷のエステルフィルムＥ５０００を硬化膜上部に重ねた。更に、上部から０．２００ｇ／ｃｍ２の加重を加え、３０℃雰囲気下で１日間放置し、下記の基準により、耐ブロッキング性を評価した。
［評価基準］
４：上部フィルムへの転写、張り付きなし
３：上部フィルムへの転写が全フィルム面積の１％未満である
２：上部フィルムへの転写が全フィルム面積の１％以上５％未満である
１：上部フィルムへの転写が全フィルム面積の５％以上である。
<Blocking resistance>
Using a discharge tester equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.), a solid image having an average film thickness of 20 μm was drawn on an ester film E5000 (manufactured by Toyobo Co., Ltd.), and then a cured film of the printed material An unprinted ester film E5000 was overlaid on the cured film so as to be entirely covered. Further, a load of 0.200 g / cm 2 was applied from the top, and the mixture was left in an atmosphere at 30 ° C. for 1 day, and blocking resistance was evaluated according to the following criteria.
[Evaluation criteria]
4: Transfer to upper film, no sticking 3: Transfer to upper film is less than 1% of the total film area 2: Transfer to upper film is not less than 1% and less than 5% of the total film area 1: Top Transfer to film is 5% or more of the total film area.
＜延伸時の濃度ムラ＞
延伸性の評価と同様の条件で印刷物を、（引張り試験後の長さ）／（引張り試験前の長さ）が２．０となるまで延伸し、目視により延伸時の濃度ムラを以下の基準で評価した
Ａ：濃度ムラが見られない
Ｂ：濃度ムラがやや見られる
Ｃ：濃度ムラが顕著に見られる
<Concentration unevenness during stretching>
The printed material is stretched under the same conditions as the evaluation of stretchability until (length after tensile test) / (length before tensile test) reaches 2.0, and the density unevenness during stretching is visually checked as follows. A: Density unevenness is not seen B: Density unevenness is slightly seen C: Density unevenness is noticeable
表２〜表６中における成分の詳細については、以下のとおりである。
−重合性モノマー−
・Ｎ−ビニルカプロラクタム（東京化成工業株式会社製）
・フェノキシエチルアクリレート（東京化成工業株式会社製）
・ヘキサンジオールメタクリレート（東京化成工業株式会社製）
・イソボルニルアクリレート（東京化成工業株式会社製）
−重合開始剤−
・イルガキュア１８４（チバスペシャルティケミカルズ社製）
・イルガキュア８１９（チバスペシャルティケミカルズ社製）
−その他の成分−
・ヒドロキノンモノメチルエーテル（東京化成工業株式会社製）
・ベンゾフェノン（東京化成工業株式会社製）
Details of the components in Tables 2 to 6 are as follows.
-Polymerizable monomer-
・ N-Vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Hexanediol methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Polymerization initiator-
・ Irgacure 184 (Ciba Specialty Chemicals)
・ Irgacure 819 (Ciba Specialty Chemicals)
-Other ingredients-
・ Hydroquinone monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
・ Benzophenone (Tokyo Chemical Industry Co., Ltd.)
本発明の態様としては、例えば、以下のとおりである。
＜１＞ Ｎ−ビニルカプロラクタムと、前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーと、下記一般式（１）で表される構造単位及び下記一般式（２）で表される構造単位を有する共重合体と、を含有することを特徴とする硬化型組成物である。
［一般式（１）］
［一般式（２）］
＜２＞ 前記共重合体に含まれる前記一般式（１）で表される構造単位が、下記一般式（３）又は下記一般式（４）で表される構造単位である前記＜１＞に記載の硬化型組成物である。
［一般式（３）］
［一般式（４）］
＜３＞ 前記共重合体に含まれる前記一般式（１）で表される構造単位が、前記一般式（３）で表される構造単位である前記＜２＞に記載の硬化型組成物である。
＜４＞ 前記Ｎ−ビニルカプロラクタムの含有量が、重合性単官能モノマーの合計量１００質量部に対して、２０質量部以上５０質量部以下である前記＜１＞から＜３＞のいずれかに記載の硬化型組成物である。
＜５＞ 前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーの少なくとも１つ以上が、アクリレート又はメタクリレートである前記＜１＞から＜４＞のいずれかに記載の硬化型組成物である。
＜６＞ 前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーが、フェノキシエチル（メタ）アクリレート、環式ＴＭＰホルマル（メタ）アクリレート、イソボルニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−（２−エトキシエトキシ）エチル（メタ）アクリレート、オクタ／デシル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソデシル（メタ）アクリレート、及びラウリル（メタ）アクリレートから選択される少なくとも１種である前記＜１＞から＜５＞のいずれかに記載の硬化型組成物である。
＜７＞ 前記Ｎ−ビニルカプロラクタム以外の重合性単官能モノマーが、フェノキシエチル（メタ）アクリレート又はイソボルニル（メタ）アクリレートである前記＜１＞から＜６＞のいずれかに記載の硬化型組成物である。
＜８＞ 前記＜１＞から＜７＞のいずれかに記載の硬化型組成物からなることを特徴とする硬化型インクジェットインクである。
＜９＞ 前記＜１＞から＜７＞のいずれかに記載の硬化型組成物を含むことを特徴とする硬化物である。
＜１０＞ 前記＜１＞から＜７＞のいずれかに記載の硬化型組成物を容器中に収容してなることを特徴とする収容容器である。
＜１１＞ 前記＜１＞から＜７＞のいずれかに記載の硬化型組成物を収容する収容部と、活性エネルギー線を照射するための照射手段と、を有することを特徴とする２次元又は３次元の像形成装置である。
＜１２＞ 前記＜１＞から＜７＞のいずれかに記載の硬化型組成物に活性エネルギー線を照射して２次元又は３次元の像を形成することを特徴とする２次元又は３次元の像形成方法である。
As an aspect of this invention, it is as follows, for example.
<1> N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2) A curable composition comprising a copolymer.
[General formula (1)]
[General formula (2)]
<2> In the above <1>, the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the following general formula (3) or the following general formula (4). It is a curable composition of description.
[General formula (3)]
[General formula (4)]
<3> The curable composition according to <2>, wherein the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the general formula (3). is there.
<4> The content of the N-vinylcaprolactam is 20 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the total amount of the polymerizable monofunctional monomer. It is a curable composition of description.
<5> The curable composition according to any one of <1> to <4>, wherein at least one of the polymerizable monofunctional monomers other than the N-vinylcaprolactam is an acrylate or a methacrylate.
<6> Polymerizable monofunctional monomers other than the N-vinylcaprolactam are phenoxyethyl (meth) acrylate, cyclic TMP formal (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- ( <1>, which is at least one selected from 2-ethoxyethoxy) ethyl (meth) acrylate, octa / decyl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate To <5>.
<7> The curable composition according to any one of <1> to <6>, wherein the polymerizable monofunctional monomer other than the N-vinylcaprolactam is phenoxyethyl (meth) acrylate or isobornyl (meth) acrylate. is there.
<8> A curable inkjet ink comprising the curable composition according to any one of <1> to <7>.
<9> A cured product comprising the curable composition according to any one of <1> to <7>.
<10> A storage container comprising the curable composition according to any one of <1> to <7> in a container.
<11> Two-dimensional or characterized by comprising: a housing part that houses the curable composition according to any one of <1> to <7>, and an irradiation unit for irradiating active energy rays. A three-dimensional image forming apparatus.
<12> A two-dimensional or three-dimensional image, wherein the curable composition according to any one of <1> to <7> is irradiated with active energy rays to form a two-dimensional or three-dimensional image. An image forming method.
前記＜１＞から＜７＞のいずれかに記載の硬化型組成物、前記＜８＞に記載の硬化型インクジェット、前記＜９＞に記載の硬化物、前記＜１０＞に記載の収容容器、前記＜１１＞に記載の２次元又は３次元の像形成装置、及び前記＜１２＞に記載の２次元又は３次元の像形成方法によると、従来における諸問題を解決し、本発明の目的を達成することができる。 The curable composition according to any one of <1> to <7>, the curable ink jet according to <8>, the cured product according to <9>, the container according to <10>, According to the two-dimensional or three-dimensional image forming apparatus described in <11> and the two-dimensional or three-dimensional image forming method described in <12>, the conventional problems are solved, and the object of the present invention is achieved. Can be achieved.
Claims (10)
［一般式（１）］
［一般式（２）］
[General formula (1)]
[General formula (2)]
［一般式（３）］
［一般式（４）］
[General formula (3)]
[General formula (4)]
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