JP7371554B2 - Bisoxime ester photopolymerization initiator, polymerizable composition, cured product and method for producing the same - Google Patents
Bisoxime ester photopolymerization initiator, polymerizable composition, cured product and method for producing the same Download PDFInfo
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- JP7371554B2 JP7371554B2 JP2020059397A JP2020059397A JP7371554B2 JP 7371554 B2 JP7371554 B2 JP 7371554B2 JP 2020059397 A JP2020059397 A JP 2020059397A JP 2020059397 A JP2020059397 A JP 2020059397A JP 7371554 B2 JP7371554 B2 JP 7371554B2
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- meth
- acrylate
- polymerizable composition
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- 239000000203 mixture Substances 0.000 title claims description 56
- 239000003999 initiator Substances 0.000 title claims description 35
- 150000002148 esters Chemical class 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000003505 polymerization initiator Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- -1 oxime ester Chemical class 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000012043 crude product Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000976 ink Substances 0.000 description 10
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- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
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- 239000003960 organic solvent Substances 0.000 description 8
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- 238000007639 printing Methods 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
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- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 7
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- 150000001266 acyl halides Chemical class 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
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- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 7
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- 238000005406 washing Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 230000008033 biological extinction Effects 0.000 description 5
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
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- 230000007935 neutral effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
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- 229940125904 compound 1 Drugs 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、ビスオキシムエステル系光重合開始剤、重合性組成物、ならびに硬化物およびその製造方法に関する。 The present invention relates to a bisoxime ester photopolymerization initiator, a polymerizable composition, a cured product, and a method for producing the same.
高分子等を合成するために、重合開始剤として、熱または光、酸化-還元によりラジカルを発生させるラジカル重合開始剤が広く用いられている。特に、光重合開始剤は、光等の活性エネルギー線を吸収することで、光重合開始剤の結合開裂や基質からの水素引き抜きによりラジカルを発生させることができ、ラジカル重合性化合物の重合開始剤として利用される。例えば、オキシムエステル系誘導体やα-ヒドロキシアセトフェノン誘導体、α-アミノアセトフェノン誘導体、アシルホスフィンオキサイド誘導体、ハロメチルトリアジン誘導体、ベンジルケタール誘導体、チオキサントン誘導体等が利用されている。 Radical polymerization initiators that generate radicals by heat, light, or oxidation-reduction are widely used as polymerization initiators to synthesize polymers and the like. In particular, photopolymerization initiators can generate radicals by bond cleavage and hydrogen abstraction from substrates by absorbing active energy rays such as light. used as. For example, oxime ester derivatives, α-hydroxyacetophenone derivatives, α-aminoacetophenone derivatives, acylphosphine oxide derivatives, halomethyltriazine derivatives, benzyl ketal derivatives, thioxanthone derivatives, etc. are used.
上記のような光重合開始剤とラジカル重合性化合物からなる光重合性組成物は、光照射により速やかに硬化するため、コーティング剤や塗料、印刷インキ、感光性印刷版、接着剤、各種フォトレジスト等の用途に適用されている。 Photopolymerizable compositions consisting of a photopolymerization initiator and a radically polymerizable compound as described above are rapidly cured by light irradiation, so they can be used as coating agents, paints, printing inks, photosensitive printing plates, adhesives, and various photoresists. It is applied for such purposes.
特許文献1~4には、オキシムエステル系誘導体が記載されており、これらのオキシムエステル誘導体は、高感度な光重合開始剤としてブラックレジストやカラーレジスト等に用いられることが知られている。 Patent Documents 1 to 4 describe oxime ester derivatives, and these oxime ester derivatives are known to be used as highly sensitive photopolymerization initiators in black resists, color resists, and the like.
近年、液晶ディスプレイパネルなどで高い色純度が求められており、カラーレジストの作製においては顔料の含有量が増加していることから、硬化性を保つために光重合開始剤の含有量が増加する傾向にある。しかしながら、特許文献1に記載の側鎖にシクロアルキル基を有する1官能オキシムエステル系光重合開始剤は、感度が不十分であり、硬化性を保つために開始剤を多く配合しなければならない。よって、光重合開始剤の含有量が増加することで硬化物の着色が強くなり、液晶ディスプレイパネルなどの色再現性に悪影響を及ぼす。 In recent years, high color purity has been required for liquid crystal display panels, etc., and the content of pigments has increased in the production of color resists, so the content of photopolymerization initiators has increased to maintain curability. There is a tendency. However, the monofunctional oxime ester photopolymerization initiator having a cycloalkyl group in the side chain described in Patent Document 1 has insufficient sensitivity, and a large amount of the initiator must be blended in order to maintain curability. Therefore, as the content of the photopolymerization initiator increases, the coloring of the cured product becomes stronger, which adversely affects the color reproducibility of liquid crystal display panels and the like.
また、高感度な光重合開始剤として、特許文献2~4に記載の1分子中にオキシムエステル基を2つ有するビスオキシムエステル系光重合開始剤が提案されている。しかしながら、特許文献2~4に記載の化合物は結晶性の高い構造をしていることから、溶剤に対する溶解性が低いため、十分な光重合開始剤量を配合できないという問題がある。 Further, as a highly sensitive photopolymerization initiator, bisoxime ester photopolymerization initiators having two oxime ester groups in one molecule have been proposed as described in Patent Documents 2 to 4. However, since the compounds described in Patent Documents 2 to 4 have highly crystalline structures, they have low solubility in solvents, so there is a problem that a sufficient amount of photopolymerization initiator cannot be blended.
本発明は、上記の実情に鑑みてなされたものであり、波長365nm等の光に対する感度が高く、かつ溶解性の高い光重合開始剤を提供することを目的とする。 The present invention was made in view of the above circumstances, and an object of the present invention is to provide a photopolymerization initiator that is highly sensitive to light having a wavelength of 365 nm, etc., and has high solubility.
すなわち、本発明は、一般式(I):
また、本発明は、前記ビスオキシムエステル系光重合開始剤とラジカル重合性化合物を含有する重合性組成物、ならびに該重合性組成物から形成される硬化物およびその製造方法に関する。 The present invention also relates to a polymerizable composition containing the bisoxime ester photopolymerization initiator and a radically polymerizable compound, a cured product formed from the polymerizable composition, and a method for producing the same.
本発明にかかるビスオキシムエステル系光重合開始剤における効果の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。但し、本発明は、この作用メカニズムに限定して解釈されるものではない。 Although the details of the mechanism of action of the bisoxime ester photopolymerization initiator according to the present invention are unclear, it is presumed as follows. However, the present invention is not limited to this mechanism of action.
本発明のビスオキシムエステル系光重合開始剤は、光源から放出される365nm等の光を効率よく吸収して効率よくラジカルを発生でき、かつ非対称構造であることから、溶解性に優れる。よって、当該ビスオキシムエステル系光重合開始剤とラジカル重合性化合物を含む重合性組成物は、光の照射により良好に硬化することができる。 The bisoxime ester photopolymerization initiator of the present invention can efficiently absorb light of 365 nm or the like emitted from a light source to efficiently generate radicals, and has an asymmetric structure, so it has excellent solubility. Therefore, the polymerizable composition containing the bisoxime ester photopolymerization initiator and the radically polymerizable compound can be well cured by light irradiation.
<ビスオキシムエステル系光重合開始剤>
本発明のビスオキシムエステル系光重合開始剤は、下記一般式(1)で表すことができる。
The bisoxime ester photopolymerization initiator of the present invention can be represented by the following general formula (1).
前記一般式(1)中、R1及びR2は、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基、イソオクチル基、2-エチルヘキシル基、1,3,3-トリメチルブチル基等のアルキル基が挙げられる。また、R1またはR2は、非対称構造を形成して溶解性を高める観点から、どちらか一方がメチル基であることが好ましい。また、R3は、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基、イソオクチル基、2-エチルヘキシル基、1,3,3-トリメチルブチル基等のアルキル基;メトキシ基、エトキシ基等のアルコキシ基が挙げられる。また、R3は、感度を高める観点から、メチル基であることが好ましい。 In the general formula (1), R 1 and R 2 are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group. , n-octyl group, isooctyl group, 2-ethylhexyl group, and 1,3,3-trimethylbutyl group. Furthermore, from the viewpoint of forming an asymmetric structure and increasing solubility, either one of R 1 or R 2 is preferably a methyl group. Further, R 3 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-octyl group, an isooctyl group, Examples include alkyl groups such as 2-ethylhexyl group and 1,3,3-trimethylbutyl group; and alkoxy groups such as methoxy group and ethoxy group. Further, R 3 is preferably a methyl group from the viewpoint of increasing sensitivity.
以下に本発明のビスオキシムエステル系光重合開始剤の具体例を以下に示すが、本発明はこれらに限定されるものではない。
<ビスオキシムエステル系光重合開始剤の製造方法>
前記ビスオキシムエステル系光重合開始剤の製造方法は、特に制限されず、例えば、a)ジフェニルチオエーテルを出発原料とし、該出発原料とR1基を有するアシルハライドを、塩化アルミニウム等の作用で、フリーデル-クラフツ反応させて、ケトオキシムエステル系光開始剤の中間体Iを合成する、中間体Iの合成工程と、b)引き続き、中間体IとR2基を有するアシルハライドを、塩化アルミニウム等の作用で、フリーデル-クラフツ反応させて、ケトオキシムエステル系光開始剤の中間体II合成する、中間体IIの合成工程と、c)引き続き、中間体IIと亜硝酸イソアミルを、塩化水素、ナトリウムアルコラート、カリウムアルコラート等の触媒存在下で、酸化反応させて、ヒドロキシルアミン化合物である中間体IIIを生成する、中間体IIIの合成工程と、d)中間体IIIと塩化アセチル又は無水物をエステル化させて、ビスオキシムエステル系光開始剤を合成する、ビスオキシムエステル系光開始剤の合成工程、を含む方法が挙げられる。
<Method for producing bisoxime ester photopolymerization initiator>
The method for producing the bisoxime ester photopolymerization initiator is not particularly limited, and for example, a) diphenylthioether is used as a starting material, and the starting material and an acyl halide having R 1 group are reacted with aluminum chloride or the like, a) a step of synthesizing intermediate I in which intermediate I of the ketoxime ester photoinitiator is synthesized by a Friedel-Crafts reaction; c) Subsequently, Intermediate II and isoamyl nitrite are reacted with Friedel-Crafts to synthesize Intermediate II of the ketoxime ester photoinitiator, and c) d) a synthesis step of intermediate III in which intermediate III, which is a hydroxylamine compound, is produced by oxidation reaction in the presence of a catalyst such as sodium alcoholate, potassium alcoholate, etc.; and d) intermediate III and acetyl chloride or anhydride. Examples include a method including a step of synthesizing a bisoxime ester photoinitiator by esterifying it to synthesize a bisoxime ester photoinitiator.
前記工程aでは、例えば、出発原料と、塩化アルミニウムと有機溶剤Aとを攪拌・混合し、温度を0℃まで冷却し、次いで、R1基を有するアシルハライドと有機溶液Aの混合溶液を滴下し、温度を0~10℃の範囲に調整して、0.5~2時間をかけて滴下した後、温度を0~30℃に保ち、引き続き1~3時間攪拌して、反応液を得る。得られた反応液に洗浄処理等を行って、白色の固体中間体Iが得られる。出発原料と塩化アルミニウムとのモル比(出発原料/塩化アルミニウム)は、通常、0.1~1.5程度であり、0.5~1.0程度であることが好ましい。また、出発原料とR1基を有するアシルハライドとのモル比(出発原料/R1基を有するアシルハライド)は、通常、0.1~1.5程度であり、0.5~1.0程度であることが好ましい。 In step a, for example, the starting materials, aluminum chloride, and organic solvent A are stirred and mixed, the temperature is cooled to 0° C., and then a mixed solution of an acyl halide having R 1 group and organic solution A is added dropwise. Then, adjust the temperature to a range of 0 to 10°C, add dropwise over 0.5 to 2 hours, maintain the temperature at 0 to 30°C, and continue stirring for 1 to 3 hours to obtain a reaction solution. . The obtained reaction solution is subjected to a washing treatment, etc., to obtain a white solid intermediate I. The molar ratio between the starting material and aluminum chloride (starting material/aluminum chloride) is usually about 0.1 to 1.5, preferably about 0.5 to 1.0. Further, the molar ratio between the starting material and the acyl halide having R 1 group (starting material/acyl halide having R 1 group) is usually about 0.1 to 1.5, and 0.5 to 1.0. It is preferable that the degree of
前記有機溶剤Aは、例えば、ジクロロエタン、ジクロロメタン、四塩化炭素等が挙げられる。 Examples of the organic solvent A include dichloroethane, dichloromethane, and carbon tetrachloride.
前記工程bでは、例えば、上記の中間体Iと、塩化アルミニウムと上記の有機溶剤Aとを攪拌・混合し、温度を0℃まで冷却し、次いで、R2基を有するアシルハライドと有機溶液Aの混合溶液を滴下し、温度を0~10℃の範囲に調整して、0.5~2時間をかけて滴下した後、温度を0~30℃に保ち、引き続き1~3時間攪拌して、反応液を得る。得られた反応液に洗浄処理等を行って、白色の固体中間体IIが得られる。中間体Iと塩化アルミニウムとのモル比(中間体I/塩化アルミニウム)は、通常、0.1~1.5程度であり、0.1~0.5程度であることが好ましい。また、中間体IとR2基を有するアシルハライドとのモル比(中間体I/R2基を有するアシルハライド)は、通常、0.1~1.5程度であり、0.5~1.0程度であることが好ましい。 In step b, for example, the intermediate I, aluminum chloride, and the organic solvent A are stirred and mixed, the temperature is cooled to 0° C., and then the acyl halide having R 2 groups and the organic solution A are mixed. The mixed solution was added dropwise, the temperature was adjusted to a range of 0 to 10°C, and the dropwise addition took 0.5 to 2 hours.The temperature was maintained at 0 to 30°C, and the mixture was continuously stirred for 1 to 3 hours. , obtain a reaction solution. The obtained reaction solution is subjected to washing treatment and the like to obtain a white solid intermediate II. The molar ratio between Intermediate I and aluminum chloride (Intermediate I/aluminum chloride) is usually about 0.1 to 1.5, preferably about 0.1 to 0.5. Further, the molar ratio between intermediate I and acyl halide having 2 R groups (intermediate I/acyl halide having 2 R groups) is usually about 0.1 to 1.5, and 0.5 to 1 It is preferable that it is about .0.
前記工程cでは、例えば、工程bで生成した中間体IIと、有機溶剤Bと亜硝酸イソアミルとの混合溶液中に、塩化水素等の触媒を加え、常温で攪拌しながら1~10時間反応して、反応液を得る。得られた反応液に洗浄処理等を行って、粘稠状液体の中間体IIIが得られる。中間体IIと亜硝酸イソアミルとのモル比(中間体II/亜硝酸イソアミル)は、通常、0.2~0.5程度であり、0.2~0.3程度であることが好ましい。 In step c, for example, a catalyst such as hydrogen chloride is added to a mixed solution of intermediate II produced in step b, organic solvent B, and isoamyl nitrite, and the mixture is reacted for 1 to 10 hours with stirring at room temperature. to obtain a reaction solution. The obtained reaction solution is subjected to washing treatment and the like to obtain intermediate III as a viscous liquid. The molar ratio of intermediate II and isoamyl nitrite (intermediate II/isoamyl nitrite) is usually about 0.2 to 0.5, preferably about 0.2 to 0.3.
前記有機溶剤Bとしては、例えば、ジクロロエタン、テトラヒドロフラン等が挙げられる。 Examples of the organic solvent B include dichloroethane and tetrahydrofuran.
前記工程dでは、例えば、工程bで生成した中間体IIIと、ピリジン等のアミン系触媒と上記の有機溶剤Bを攪拌・混合し、温度を0℃まで冷却し、次いで、塩化アセチル又は無水物と有機溶剤Bを含む溶液を滴下し始め、0.5~1.5時間をかけて滴下し、続いて1~4時間攪拌して、反応液を得る。得られた反応液に洗浄処理等を行って、ビスオキシムエステル系光開始剤が得られる。中間体IIIと塩化アセチル又は無水物とのモル比(中間体III/塩化アセチル又は無水物)は、通常、0.2~0.5程度であり、0.2~0.3程度であることが好ましい。 In step d, for example, intermediate III produced in step b, an amine catalyst such as pyridine, and the above organic solvent B are stirred and mixed, the temperature is cooled to 0° C., and then acetyl chloride or anhydride is mixed. A solution containing organic solvent B and organic solvent B is started to be added dropwise over a period of 0.5 to 1.5 hours, and then stirred for 1 to 4 hours to obtain a reaction solution. The obtained reaction solution is subjected to washing treatment and the like to obtain a bisoxime ester photoinitiator. The molar ratio of intermediate III and acetyl chloride or anhydride (intermediate III/acetyl chloride or anhydride) is usually about 0.2 to 0.5, and should be about 0.2 to 0.3. is preferred.
<重合性組成物>
本発明の重合性組成物は、前記ビスオキシムエステル系光重合開始剤を含む重合開始剤およびラジカル重合性化合物を含有する。さらに、重合性組成物は、アルカリ可溶性樹脂を含有することで現像性を付与することができる。また、重合性組成物は、その他の成分を適宜組み合わせて含有させることができる。
<Polymerizable composition>
The polymerizable composition of the present invention contains a polymerization initiator including the bisoxime ester photopolymerization initiator and a radically polymerizable compound. Furthermore, the polymerizable composition can impart developability by containing an alkali-soluble resin. Moreover, the polymerizable composition can contain other components in appropriate combination.
<重合開始剤>
本発明の重合開始剤は、前記ビスオキシムエステル系光重合開始剤を含有する。前記重合開始剤は、活性エネルギー線により分解し、発生したラジカルがラジカル重合性化合物の重合(硬化)を開始する働きを有する。前記ビスオキシムエステル系光重合開始剤は、単独で用いてもよく2種類以上を併用してもよい。
<Polymerization initiator>
The polymerization initiator of the present invention contains the bisoxime ester photopolymerization initiator. The polymerization initiator is decomposed by active energy rays, and the generated radicals have the function of initiating polymerization (curing) of a radically polymerizable compound. The bisoxime ester photopolymerization initiator may be used alone or in combination of two or more types.
また、前記重合開始剤は、前記ビスオキシムエステル系光重合開始剤以外の重合開始剤(以下、他の重合開始剤とも称す)を含有することができる。吸収帯の異なる2種類以上のビスオキシムエステル系光重合開始剤や他の重合開始剤を使用することで、例えば、高圧水銀ランプ等の複数の波長の光が放射されるランプに対し、重合性組成物の高感度化を図ることができる。また、重合性組成物に含まれるラジカル重合性化合物の重合性、重合性組成物に含まれる光を吸収や散乱する顔料等の種類、硬化物の膜厚等を考慮して、他の重合開始剤を用いることで、重合性組成物の表面硬化性や深部硬化性、透明性等を改良することができる。 Further, the polymerization initiator may contain a polymerization initiator other than the bisoxime ester photopolymerization initiator (hereinafter also referred to as other polymerization initiator). By using two or more types of bisoxime ester photopolymerization initiators or other polymerization initiators with different absorption bands, for example, it is possible to improve the polymerizability of lamps that emit light of multiple wavelengths, such as high-pressure mercury lamps. High sensitivity of the composition can be achieved. In addition, considering the polymerizability of the radically polymerizable compound contained in the polymerizable composition, the type of pigment that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, etc., other polymerization initiation methods are determined. By using the agent, the surface curability, deep curability, transparency, etc. of the polymerizable composition can be improved.
前記他の重合開始剤としては、公知のものが使用でき、例えば、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-プロピオフェノン、4’-(2-ヒドロキシエトキシ)-2-ヒドロキシ-2-メチルプロピオフェノン、2-ヒロドキシ-1-(4-(4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル)フェニル)-2-メチルプロパン-1-オン等のα―ヒドロキシアセトフェノン誘導体;2-メチル-4’-メチルチオ-2-モルホリノプロピオフェノン、2-ベンジル-2-(N,N-ジメチルアミノ)-1-(4-モルホリノフェニル)ブタン-1-オン、2-(ジメチルアミノ)-2-(4-メチルベンジル)-1-(4-モルホリノフェニル)ブタン-1-オン等のα―アミノアセトフェノン誘導体;ジフェニル-2,4,6-トリメチルベンゾイルホスフィンオキシド、フェニルビス(2,4,6-トリメチルベンゾイル)ホスフィンオキシド、エチル(メシチルカルボニル)フェニルホスフィナート等のアシルホスフィンオキサイド誘導体;1-[4-(フェニルチオ)フェニル]オクタン-1,2-ジオン-2-(O-ベンゾイルオキシム)、1-[({1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]エチリデン}アミノ)オキシ]エタノン、等のオキシムエステル誘導体;2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(3,4-ジメトキシスチリル)-4,6-ビス(トリクロロメチル)1,3,5-トリアジン、2-(4-エトキシナフチル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン等のハロメチルトリアジン誘導体;2,2-ジメトキシ-2-フエニルアセトフエノン等のベンジルケタール誘導体;イソプロピルチオキサントン等のチオキサントン誘導体、4-(4-メチルフェニルチオ)ベンゾフェノン等のベンゾフェノン誘導体;3-ベンゾイルー7-ジエチルアミノクマリン、3,3‘-カルボニルビス(7-ジエチルアミノクマリン)等のクマリン誘導体;2-(2-クロロフェニル)-1-[2-(2-クロロフェニル)-4,5-ジフェニル-1,3-ジアゾール-2-イル]-4,5-ジフェニルイミダゾール等のイミダゾール誘導体;3,3‘、4,4’-テトラキス(tert-ブチルペルオキシカルボニル)ベンゾフェノン、ジベンゾイルペルオキシド等の有機過酸化物;アゾビスイソブチロニトリル等のアゾ化合物;カンファーキノン等が挙げられる。他の重合開始剤は、単独で用いてもよく2種類以上を併用してもよい。 As the other polymerization initiators, known ones can be used, such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy)-2-hydroxy -2-Methylpropiophenone, α-hydroxyacetophenone derivatives such as 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, etc. ;2-Methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethyl α-Aminoacetophenone derivatives such as amino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2 , 4,6-trimethylbenzoyl)phosphine oxide, ethyl (mesitylcarbonyl) phenylphosphinate and other acylphosphine oxide derivatives; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O 2- (4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)1,3,5 -Triazine, halomethyltriazine derivatives such as 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 2,2-dimethoxy-2-phenylacetophenone, etc. benzyl ketal derivatives; thioxanthone derivatives such as isopropylthioxanthone; benzophenone derivatives such as 4-(4-methylphenylthio)benzophenone; 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), etc. Coumarin derivatives; imidazole derivatives such as 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole; Organic peroxides such as 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; and camphorquinone. Other polymerization initiators may be used alone or in combination of two or more.
<ラジカル重合性化合物>
本発明のラジカル重合性化合物としては、エチレン性不飽和基を有する化合物を好ましく用いることができる。前記ラジカル重合性化合物としては、例えば、(メタ)アクリル酸エステル類、スチレン類、マレイン酸エステル類、フマル酸エステル類、イタコン酸エステル類、桂皮酸エステル類、クロトン酸エステル類、ビニルエーテル類、ビニルエステル類、ビニルケトン類、アリルエーテル類、アリルエステル類、N-置換マレイミド類、N-ビニル化合物類、不飽和ニトリル類、オレフィン類等が挙げられる。これらの中でも、反応性が高い(メタ)アクリル酸エステル類を含むことが好ましい。前記ラジカル重合性化合物は、単独で用いてもよく2種類以上を併用してもよい。
<Radical polymerizable compound>
As the radically polymerizable compound of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of the radically polymerizable compounds include (meth)acrylic esters, styrenes, maleic esters, fumaric esters, itaconic esters, cinnamic esters, crotonic esters, vinyl ethers, and vinyl esters. Examples include esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, and olefins. Among these, it is preferable to include highly reactive (meth)acrylic esters. The radically polymerizable compounds may be used alone or in combination of two or more.
前記(メタ)アクリル酸エステル類は、単官能化合物および多官能化合物を使用することができる。単官能化合物としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート等のアルキル(メタ)アクリレート;シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレ-ト、ジシクロペンテニル(メタ)アクリレ-ト、ジシクロペンテニルオキシエチル(メタ)アクリレ-ト、2―エチル-2-アダマンチル(メタ)アクリレート等の(メタ)アクリル酸と脂環族アルコールとのエステル化合物;フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート等のアリール(メタ)アクリレート;2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、3-ヒドロキシ-1-アダマンチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等のヒドロキシ基を有するモノマー;メトキシエチル(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、2-フェニルフェノキシエチル(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-メチル-2-エチル-1,3-ジオキソラン-4-イル)メチル(メタ)アクリレート、(3-エチルオキセタン-3-イル)メチル(メタ)アクリレート、環状トリメチロールプロパンホルマール(メタ)アクリレート等の鎖状または環状のエーテル結合を有するモノマー等;N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、N-(メタ)アクリロイルオキシエチルヘキサヒドロフタルイミド等の窒素原子を有するモノマー;2-(メタ)アクリロイルオキシエチルイソシアネート等のイソシアネート基を有するモノマー;グリシジル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル等のエポキシ基を有するモノマー;リン酸2-((メタ)アクリロイルオキシ)エチル等のリン原子を有するモノマー;3-(メタ)アクリロキシプロピルトリメトキシシラン等のケイ素原子を有するモノマー;2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3,3-ペンタフルオロプロピル(メタ)アクリレート、2-(パーフルオロヘキシル)エチル(メタ)アクリレート等のフッ素原子を有するモノマー;(メタ)アクリル酸、コハク酸モノ(2-(メタ)アクリロイルオキシエチル)、フタル酸モノ(2-(メタ)アクリロイルオキシエチル)、マレイン酸モノ(2-(メタ)アクリロイルオキシエチル)、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレート等のカルボキシル基を有するモノマー等が挙げられる。 As the (meth)acrylic esters, monofunctional compounds and polyfunctional compounds can be used. Monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Alkyl (meth)acrylates such as acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth)acrylic acid and alicyclic alcohol such as acrylate and 2-ethyl-2-adamantyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate ; 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, polyethylene glycol mono(meth)acrylate Monomers with hydroxy groups such as acrylate and polypropylene glycol mono(meth)acrylate; methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic Monomers having a chain or cyclic ether bond such as trimethylolpropane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylate Nitrogen atoms such as acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, N-(meth)acryloyloxyethylhexahydrophthalimide, etc. Monomers having isocyanate groups such as 2-(meth)acryloyloxyethyl isocyanate; Monomers having epoxy groups such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether; Phosphoric acid 2-(( Monomers having a phosphorus atom such as meth)acryloyloxy)ethyl; monomers having a silicon atom such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2 , 3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, and other fluorine atom-containing monomers; (meth)acrylic acid, succinic acid mono(2-(meth)acrylate) Contains carboxyl groups such as mono(acryloyloxyethyl) phthalate (2-(meth)acryloyloxyethyl), mono(2-(meth)acryloyloxyethyl) maleate, and ω-carboxy-polycaprolactone mono(meth)acrylate. Examples include monomers.
前記多官能化合物としては、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、グリセリントリ(メタ)アクリレート、グリセリンプロポキシトリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンエチレンオキシド変性トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレートモノステアレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、2,2-ビス(4-(メタ)アクリロキシエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロキシポリエトキシフェニル)プロパン、9,9-ビス(4-(2-(メタ)アクリロイルオキシエトキシ)フェニル)フルオレン、9,9-ビス(4-(2-(2-(メタ)アクリロイルオキシエトキシ)エトキシ)フェニル)フルオレン、等の多価アルコールと(メタ)アクリル酸とのエステル化合物;ビス(4-(メタ)アクリロキシフェニル)スルフィド、ビス(4-(メタ)アクリロイルチオフェニル)スルフィド、トリス(2-(メタ)アクリロイルオキシエチル)イソシアヌレート、エチレンビス(メタ)アクリルアミド、(メタ)アクリル酸亜鉛、(メタ)アクリル酸ジルコニウム、脂肪族ウレタンアクリレート、芳香族ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート等が挙げられる。 Examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,4 -Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin propoxytri (meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Pentaerythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate Acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9,9-bis(4-(2- (meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-(2-(meth)acryloyloxyethoxy)ethoxy)phenyl)fluorene, and (meth)acrylic acid. Ester compounds; bis(4-(meth)acryloxyphenyl) sulfide, bis(4-(meth)acryloylthiophenyl) sulfide, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene bis(meth)acrylamide , zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, polyester acrylate, and the like.
前記(メタ)アクリル酸エステル類は、重合性組成物の感度の向上、酸素による硬化阻害の低減や、硬化物の塗膜の機械的強度や硬度、耐熱性、耐久性、耐薬品性の向上の観点から、前記多価アルコールと(メタ)アクリル酸とのエステル化合物が好ましく、特に、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンエチレンオキシド変性トリ(メタ)アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートが好ましい。 The above (meth)acrylic esters improve the sensitivity of the polymerizable composition, reduce curing inhibition caused by oxygen, and improve the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the cured coating. From this point of view, ester compounds of the polyhydric alcohol and (meth)acrylic acid are preferred, particularly trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred.
前記重合開始剤の含有量は、前記ラジカル重合性化合物100質量部に対して、0.1から40質量部であることが好ましく、0.5から20質量部であることがより好ましく、1から15質量部であることがさらに好ましい。前記重合開始剤の含有量は、前記ラジカル重合性化合物100質量部に対して、0.1質量部未満では硬化反応が進行しないため好ましくない。また、前記重合開始剤の含有量は、前記ラジカル重合性化合物100質量部に対して、40質量部より多い場合、ラジカル重合性化合物への溶解度が飽和に達し、重合性組成物の成膜時に重合開始剤の結晶が析出し、皮膜表面の荒れが問題になる場合や、重合開始剤の分解残渣の増加により、硬化物の塗膜の強度が低下する場合があるため、好ましくない。 The content of the polymerization initiator is preferably from 0.1 to 40 parts by mass, more preferably from 0.5 to 20 parts by mass, and from 1 to 20 parts by mass, based on 100 parts by mass of the radically polymerizable compound. More preferably, the amount is 15 parts by mass. If the content of the polymerization initiator is less than 0.1 parts by mass based on 100 parts by mass of the radically polymerizable compound, the curing reaction will not proceed, which is not preferable. In addition, when the content of the polymerization initiator is more than 40 parts by mass with respect to 100 parts by mass of the radically polymerizable compound, the solubility in the radically polymerizable compound reaches saturation, and when forming a film of the polymerizable composition, This is not preferable because crystals of the polymerization initiator may precipitate, causing a problem of roughening of the film surface, or the strength of the cured product may decrease due to an increase in decomposed residues of the polymerization initiator.
なお、前記重合開始剤に、前記他の重合開始剤を含む場合、他の重合開始剤の割合は、重合開始剤中、50質量%以下であることが好ましく、30質量%以下であることがさらに好ましい。 In addition, when the other polymerization initiator is included in the polymerization initiator, the proportion of the other polymerization initiator is preferably 50% by mass or less, and preferably 30% by mass or less in the polymerization initiator. More preferred.
<アルカリ可溶性樹脂>
前記重合性組成物は、さらにアルカリ可溶性樹脂を配合することにより、ネガ型レジストとして好適に使用することができる。前記アルカリ可溶性樹脂としては、ネガ型レジストに一般的に使用されるものを用いることができ、アルカリ水溶液に可溶な樹脂であれば特に限定されないが、カルボキシル基を含む樹脂であることが好ましい。前記アルカリ可溶性樹脂は、単独で用いてもよく2種類以上を併用してもよい。
<Alkali-soluble resin>
The polymerizable composition can be suitably used as a negative resist by further blending an alkali-soluble resin. As the alkali-soluble resin, those commonly used for negative resists can be used, and there are no particular limitations as long as the resin is soluble in an aqueous alkaline solution, but a resin containing a carboxyl group is preferable. The alkali-soluble resins may be used alone or in combination of two or more.
前記アルカリ可溶性樹脂には、例えば、カルボキシル基含有(メタ)アクリル酸エステル共重合物、カルボキシル基含有エポキシアクリレート樹脂等が好ましく使用される。 As the alkali-soluble resin, for example, a carboxyl group-containing (meth)acrylic acid ester copolymer, a carboxyl group-containing epoxy acrylate resin, etc. are preferably used.
前記カルボキシル基含有(メタ)アクリル酸エステル共重合物は、前述の(メタ)アクリル酸エステル類の単官能化合物から選ばれる少なくとも1種(但し、前記カルボキシル基を有するモノマーを除く)と、(メタ)アクリル酸、(メタ)アクリル酸の二量体、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル安息香酸、桂皮酸、コハク酸モノ(2-(メタ)アクリロイルオキシエチル)、フタル酸モノ(2-(メタ)アクリロイルオキシエチル)、マレイン酸モノ(2-(メタ)アクリロイルオキシエチル)、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレート、およびそれらの酸無水物等のエチレン性不飽和基含有カルボン酸から選ばれる少なくとも1種を含む共重合物である。 The carboxyl group-containing (meth)acrylic acid ester copolymer includes at least one type selected from the monofunctional compounds of the (meth)acrylic acid esters described above (excluding the monomer having the carboxyl group), and (meth)acrylic acid ester copolymer. ) Acrylic acid, (meth)acrylic acid dimer, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylbenzoic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl) succinate, monophthalic acid Ethylenically unsaturated groups such as (2-(meth)acryloyloxyethyl), mono(2-(meth)acryloyloxyethyl) maleate, ω-carboxy-polycaprolactone mono(meth)acrylate, and their acid anhydrides. It is a copolymer containing at least one kind selected from the carboxylic acids contained therein.
前記カルボキシル基含有(メタ)アクリル酸エステル共重合物としては、例えば、メチルメタクリレートと、シクロヘキシルメタクリレートと、メタクリル酸の共重合物等が挙げられる。さらに、スチレン、α-メチルスチレン、N-ビニル-2-ピロリドン、N-メチルマレイミド、N-フェニルマレイミド、N-シクロヘキシルマレイミド、フマル酸ジエチル、イタコン酸ジエチル等が共重合されても良い。 Examples of the carboxyl group-containing (meth)acrylic acid ester copolymer include copolymers of methyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Furthermore, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diethyl fumarate, diethyl itaconate, and the like may be copolymerized.
また、前記カルボキシル基含有(メタ)アクリル酸エステル共重合物は、ネガ型レジストの現像性と耐熱性、硬度、耐薬品性等の被膜特性を両立させる観点から、エチレン性不飽和基等の反応性基が側鎖に導入されたカルボキシル基含有(メタ)アクリル酸エステル共重合物も好ましく使用される。上記の側鎖にエチレン性不飽和基を導入する方法として、例えば、カルボキシル基含有(メタ)アクリル酸エステル共重合物のカルボキシル基の一部に、グリシジル(メタ)アクリレート等の分子内にエポキシ基とエチレン性不飽和基を有する化合物を付加させる方法や、エポキシ基およびカルボキシル基含有(メタ)アクリル酸エステル共重合物に、メタクリル酸等のエチレン性不飽和基含有モノカルボン酸を付加させる方法や、水酸基およびカルボキシル基含有(メタ)アクリル酸エステル共重合物に、2-(メタ)アクリロイルオキシエチルイソシアネート等の分子内にイソシアネート基とエチレン性不飽和基を有する化合物を付加させる方法等が挙げられる。 In addition, the above-mentioned carboxyl group-containing (meth)acrylic acid ester copolymer is suitable for the reaction of ethylenically unsaturated groups, etc., from the viewpoint of achieving both the developability of a negative resist and film properties such as heat resistance, hardness, and chemical resistance. A carboxyl group-containing (meth)acrylic acid ester copolymer in which a functional group is introduced into the side chain is also preferably used. As a method for introducing an ethylenically unsaturated group into the side chain described above, for example, an epoxy group may be added to a part of the carboxyl group of a carboxyl group-containing (meth)acrylic acid ester copolymer, such as glycidyl (meth)acrylate, etc. and a method of adding a compound having an ethylenically unsaturated group, or a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to a (meth)acrylic acid ester copolymer containing an epoxy group and a carboxyl group. , a method of adding a compound having an isocyanate group and an ethylenically unsaturated group in the molecule, such as 2-(meth)acryloyloxyethyl isocyanate, to a (meth)acrylic acid ester copolymer containing a hydroxyl group and a carboxyl group. .
前記カルボキシル基含有エポキシアクリレート樹脂としては、エポキシ化合物と前記エチレン性不飽和基含有カルボン酸との反応物であるエポキシアクリレート樹脂に、更に酸無水物を反応させた化合物が好適である。 As the carboxyl group-containing epoxy acrylate resin, a compound obtained by further reacting an epoxy acrylate resin, which is a reaction product of an epoxy compound and the ethylenically unsaturated group-containing carboxylic acid, with an acid anhydride is suitable.
前記エポキシ樹脂としては、例えば、(o,m,p-)クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビスフェニルフルオレン型エポキシ樹脂等が挙げられる。エポキシ樹脂は、単独で用いてもよく2種類以上を併用してもよい。 Examples of the epoxy resin include (o, m, p-)cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, bisphenylfluorene. Examples include molded epoxy resins. Epoxy resins may be used alone or in combination of two or more.
前記酸無水物としては、例えば、無水マレイン酸、無水コハク酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、4-メチルヘキサヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、無水クロレインド酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸ニ無水物、ビフェニルテトラカルボン酸ニ無水物、無水イタコン酸等が挙げられる。 Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and chlorindic anhydride. , trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, itaconic anhydride, and the like.
さらに、カルボキシル基含有エポキシアクリレート樹脂の合成の際に、必要に応じて、無水トリメリット酸等のトリカルボン酸無水物を用いて、反応後に残った酸無水物基を加水分解することにより、カルボキシル基を増やすことができる。また、エチレン性不飽和基含有の無水マレイン酸を用いて、更にエチレン性二重結合を増やすこともできる。 Furthermore, when synthesizing a carboxyl group-containing epoxy acrylate resin, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride is used to hydrolyze the acid anhydride group remaining after the reaction, thereby adding carboxyl groups to the epoxy acrylate resin. can be increased. Furthermore, the number of ethylenic double bonds can be further increased by using maleic anhydride containing an ethylenically unsaturated group.
前記アルカリ可溶性樹脂の酸価は、20から300mgKOH/gであることが好ましく、40から180mg/KOHであることがさらに好ましい。酸価が20mgKOH/gよりも少ない場合、アルカリ水溶液への溶解性が乏しいため、未露光部の現像が困難となるため好ましくない。また、酸価が300mgKOH/gよりも多い場合、現像時に露光部も基材から脱離しやすい傾向にあるため、好ましくない。 The acid value of the alkali-soluble resin is preferably from 20 to 300 mgKOH/g, more preferably from 40 to 180 mg/KOH. If the acid value is less than 20 mgKOH/g, the solubility in an alkaline aqueous solution is poor, making it difficult to develop unexposed areas, which is not preferable. In addition, if the acid value is more than 300 mgKOH/g, the exposed areas also tend to detach from the base material during development, which is not preferable.
前記アルカリ可溶性樹脂の重量平均分子量は、1,000から100,000であることが好ましく、1,500から30,000であることが好ましい。重量平均分子量が1,000よりも小さい場合、露光部の耐熱性や硬度等が乏しいため、好ましくない。重量平均分子量が100,000よりも大きい場合は、未露光部の現像が困難となる場合があるため、好ましくない。尚、前記重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)法によって測定することができる。一例として、GPC装置としてHLC-8220GPC(東ソー社製)、カラムとして3本のTSKgelHZM-M(東ソー社製)を使用して、展開溶媒としてテトラヒドロフラン、カラム温度40℃、流速0.3ミリリットル/分、RI検出器、試料注入濃度0.5質量%、注入量10マイクロリットルの条件下、クロマトグラフィーを行ない、ポリスチレン換算の重量平均分子量として求めることができる。 The weight average molecular weight of the alkali-soluble resin is preferably from 1,000 to 100,000, and preferably from 1,500 to 30,000. If the weight average molecular weight is less than 1,000, the heat resistance and hardness of the exposed portion will be poor, which is not preferable. If the weight average molecular weight is greater than 100,000, it may be difficult to develop unexposed areas, which is not preferable. The weight average molecular weight can be measured by gel permeation chromatography (GPC). As an example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as a GPC device, three TSKgelHZM-M (manufactured by Tosoh Corporation) are used as columns, tetrahydrofuran is used as a developing solvent, the column temperature is 40°C, and the flow rate is 0.3 ml/min. , an RI detector, a sample injection concentration of 0.5% by mass, and an injection volume of 10 microliters.The weight average molecular weight can be determined as a polystyrene equivalent.
また、前記アルカリ可溶性樹脂の割合は、重合性組成物の全固形分中、10から70質量%であることが好ましく、15から60質量%であることがより好ましい。前記割合が10質量%よりも少ない場合、現像性が乏しいため、好ましくない。前記割合が70質量%よりも多い場合、パターン形状の再現性や耐熱性が低下するため、好ましくない。 Further, the proportion of the alkali-soluble resin is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, based on the total solid content of the polymerizable composition. When the proportion is less than 10% by mass, developability is poor, which is not preferable. If the proportion is more than 70% by mass, it is not preferable because the reproducibility of pattern shape and heat resistance will deteriorate.
なお、前記アルカリ可溶性樹脂は、合成反応後に有効成分であるアルカリ可溶性樹脂を単離精製したものを用いることができる他、合成反応により得られた反応溶液、その乾燥物等をそのまま用いることもできる。 In addition, the alkali-soluble resin may be one obtained by isolating and purifying the alkali-soluble resin as an active ingredient after the synthesis reaction, or the reaction solution obtained by the synthesis reaction, its dried product, etc. can also be used as they are. .
前記その他の成分として、重合性組成物には、コーティング剤や塗料、印刷インキ、感光性印刷版、接着剤、カラーレジストやブラックレジスト等の各種フォトレジスト等の用途で一般的に使用されている添加剤を配合できる。添加剤としては、例えば、増感剤(4,4’-ビス(ジエチルアミノ)ベンゾフェノン等のベンゾフェノン誘導体;イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体;9,10-ジブトキシアントラセン等のアントラセン誘導体;クマリン、ケトクマリン等のクマリン誘導体;アクリジンオレンジ、9-フェニルアクリジン等のアクリジン誘導体;4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル、安息香酸(2-ジメチルアミノ)エチル等の安息香酸エステル誘導体;トリエタノールアミン、メチルジエタノールアミン等のアルキルアミン誘導体;カンファーキノン等)、重合禁止剤(p-メトキシフェノール、ヒドロキノン、2,6-ジ-t-ブチル-4-メチルフェノール、フェノチアジン等)、紫外線吸収剤、赤外線吸収剤、光安定剤、酸化防止剤、レベリング剤、表面調整剤、界面活性剤、増粘剤、消泡剤、接着促進剤、可塑剤、エポキシ化合物、チオール化合物、エチレン性不飽和結合を有する樹脂、飽和樹脂、着色染料、蛍光染料、顔料(有機顔料、無機顔料)、炭素系材料(炭素繊維、カーボンブラック、黒鉛、黒鉛化カーボンブラック、活性炭、カーボンナノチューブ、フラーレン、グラフェン、カーボンマイクロコイル、カーボンナノホーン、カーボンエアロゲル等)、金属酸化物(酸化チタン、酸化イリジウム、酸化亜鉛、アルミナ、シリカ等)、金属(銀、銅等)、無機化合物(ガラス粉末、層状粘度鉱物、マイカ、タルク、炭酸カルシウム等)、分散剤、難燃剤等が挙げられる。添加剤は、単独で用いてもよく2種類以上を併用してもよい。 As the other components, the polymerizable composition includes coating agents, paints, printing inks, photosensitive printing plates, adhesives, and those commonly used in various photoresists such as color resists and black resists. Additives can be added. Examples of additives include sensitizers (benzophenone derivatives such as 4,4'-bis(diethylamino)benzophenone; thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone; anthracene derivatives such as 9,10-dibutoxyanthracene; coumarin, Coumarin derivatives such as ketocoumarin; acridine derivatives such as acridine orange and 9-phenylacridine; benzoic acid ester derivatives such as ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and (2-dimethylamino)ethyl benzoate; Alkylamine derivatives such as triethanolamine and methyldiethanolamine; camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers , infrared absorbers, light stabilizers, antioxidants, leveling agents, surface conditioning agents, surfactants, thickeners, antifoaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, ethylenically unsaturated bonds resin, saturated resin, colored dye, fluorescent dye, pigment (organic pigment, inorganic pigment), carbon-based material (carbon fiber, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotube, fullerene, graphene, carbon micro coils, carbon nanohorns, carbon airgel, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, layered clay minerals, mica, talc) , calcium carbonate, etc.), dispersants, flame retardants, etc. The additives may be used alone or in combination of two or more.
前記添加剤の含有量は、使用目的に応じて適宜選択され、特に制限されるものではないが、通常、前記ラジカル重合性化合物100質量部に対して、500質量部以下であることが好ましく、100質量部以下であることより好ましい。 The content of the additive is appropriately selected depending on the purpose of use and is not particularly limited, but it is usually preferably 500 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound. It is more preferable that the amount is 100 parts by mass or less.
前記重合性組成物には、粘度や塗装性、硬化膜の平滑性の改良のため、更に溶媒を加えることもできる。溶媒は、前記重合開始剤、前記ラジカル重合性化合物、前記アルカリ可溶性樹脂、前記その他の成分を、溶解または分散することができるものであり、乾燥温度において揮発する溶媒であれば、特に制限されるものではない。 A solvent can also be added to the polymerizable composition in order to improve the viscosity, paintability, and smoothness of the cured film. The solvent is one that can dissolve or disperse the polymerization initiator, the radically polymerizable compound, the alkali-soluble resin, and the other components, and is particularly limited as long as it evaporates at the drying temperature. It's not a thing.
前記溶媒としては、例えば、水、アルコール系溶媒、カルビトール系溶媒、エステル系溶媒、ケトン系溶媒、エーテル系溶媒、ラクトン系溶媒、不飽和炭化水素系溶媒、セロソルブアセテート系溶媒、カルビトールアセテート系溶媒やプロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル等が挙げられる。溶媒は、単独で用いてもよく2種類以上を併用してもよい。 Examples of the solvent include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, and carbitol acetate solvents. Examples include solvents, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like. The solvent may be used alone or in combination of two or more.
前記溶媒の使用量は、重合性組成物の固形分100質量部に対して、10から1000質量部であることが好ましく、20から500質量部であることがより好ましい。 The amount of the solvent used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the solid content of the polymerizable composition.
<重合性組成物の調製方法>
前記重合性組成物を調製する場合には、収納容器内に前記重合開始剤、前記ラジカル重合性化合物、必要に応じて、前記アルカリ可溶性樹脂や前記その他の成分を投入し、ペイントシェーカー、ビーズミル、サンドグラインドミル、ボールミル、アトライターミル、2本ロールミル、3本ロールミル等を用いて、常法に従って溶解または分散させればよい。また、必要に応じて、メッシュまたはメンブレンフィルター等を通してもろ過してもよい。
<Method for preparing polymerizable composition>
When preparing the polymerizable composition, the polymerization initiator, the radically polymerizable compound, and if necessary, the alkali-soluble resin and other components are placed in a storage container, and the mixture is heated using a paint shaker, a bead mill, It may be dissolved or dispersed according to a conventional method using a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, or the like. Furthermore, if necessary, it may be filtered through a mesh or membrane filter.
なお、前記重合性組成物の調製において、前記重合開始剤は、重合性組成物に最初から添加しておいてもよいが、重合性組成物を比較的長時間保存する場合には、使用直前に重合開始剤を、ラジカル重合性を含む組成物中に溶解または分散させることが好ましい。 In the preparation of the polymerizable composition, the polymerization initiator may be added to the polymerizable composition from the beginning, but if the polymerizable composition is to be stored for a relatively long time, it may be added immediately before use. It is preferable to dissolve or disperse a polymerization initiator in a radically polymerizable composition.
<硬化物の製造方法>
本発明の硬化物は、前記重合性組成物から形成されるものである。硬化物の製造方法は、重合性組成物を基材に塗布後、当該重合性組成物を活性エネルギー線で照射する工程を含む製造方法である。
<Method for producing cured product>
The cured product of the present invention is formed from the polymerizable composition. The method for producing a cured product includes a step of applying the polymerizable composition to a base material and then irradiating the polymerizable composition with active energy rays.
前記塗布方法としては、例えば、スピンコート法、バーコート法、スプレーコート法、ディップコート法、フローコート法、スリットコート法、ドクターブレードコート法、グラビアコート法、スクリーン印刷法、オフセット印刷法、インクジェット印刷法、ディスペンサー印刷法等の種々の方法が挙げられる。また、前記基材の材質は、例えば、ガラス、シリコン、金属、プラスチック等が挙げられ、制限されることは無い。また、前記基材の形状は、例えば、フィルム、シート、および立体形状の成形品等が挙げられ、制限されることは無い。 Examples of the coating method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, and inkjet coating. Various methods such as a printing method and a dispenser printing method can be used. Furthermore, the material of the base material is not limited, and examples thereof include glass, silicon, metal, and plastic. Further, the shape of the base material is not limited, and includes, for example, a film, a sheet, and a three-dimensional molded product.
上記の重合性組成物を活性エネルギー線で照射する工程は、電子線、紫外線、可視光線、放射線等の活性エネルギー線の照射により、前記重合開始剤を分解させて、前記ラジカル重合性化合物を重合させることで、硬化物を得ることができるものである。 The step of irradiating the polymerizable composition with active energy rays includes decomposing the polymerization initiator and polymerizing the radically polymerizable compound by irradiating the polymerizable composition with active energy rays such as electron beams, ultraviolet rays, visible light, and radiation. By doing so, a cured product can be obtained.
活性エネルギー線は、活性エネルギー線の波長が250から450nmの光であることが好ましく、硬化を迅速に行うことができる観点から、300から410nmの光であることがより好ましい。 The active energy ray preferably has a wavelength of 250 to 450 nm, and more preferably has a wavelength of 300 to 410 nm from the viewpoint of rapid curing.
前記光の照射の光源としては、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、紫外線無電極ランプ、発光ダイオード(LED)、キセノンアークランプ、カーボンアークランプ、太陽光、YAGレーザー等の固体レーザー、半導体レーザー、アルゴンレーザー等のガスレーザー等を使用することができる。なお、前記重合開始剤の吸収が少ない可視光から赤外光の光を用いる場合には、前記添加剤として、その光を吸収する増感剤を使用することにより硬化を行なうことができる。 Examples of the light source for the light irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a light emitting diode (LED), a xenon arc lamp, a carbon arc lamp, sunlight, a YAG laser, etc. Solid state lasers, semiconductor lasers, gas lasers such as argon lasers, etc. can be used. In addition, when using visible light to infrared light that is poorly absorbed by the polymerization initiator, curing can be carried out by using a sensitizer that absorbs the light as the additive.
前記活性エネルギー線の露光量は、活性エネルギー線の波長や強度、重合性組成物の組成に応じて適宜設定すべきである。一例として、UV-A領域での露光量は、10から5,000mJ/cm2であることが好ましく、30から1,000mJ/cm2であることがより好ましい。 The exposure amount of the active energy rays should be appropriately set depending on the wavelength and intensity of the active energy rays and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably from 10 to 5,000 mJ/cm 2 , more preferably from 30 to 1,000 mJ/cm 2 .
また、前記重合組成物に前記溶媒を含む場合、前記硬化物の製造方法は、乾燥工程を含むことができる。特に、重合性組成物を基板上に塗布後に、続いて、前記活性エネルギー線で照射する工程を適用する場合、当該活性エネルギー線で照射する工程の前に、乾燥工程を設けることが好ましい。 Moreover, when the polymer composition contains the solvent, the method for producing the cured product can include a drying step. In particular, when applying the step of irradiating with the active energy rays after coating the polymerizable composition on the substrate, it is preferable to provide a drying step before the step of irradiating with the active energy rays.
前記乾燥工程において、溶媒を乾燥させる手法は、例えば、加熱乾燥、通風加熱乾燥、減圧乾燥等が挙げられる。加熱乾燥の方式としては、特に制限されることはないが、例えば、オーブン、ホットプレート、赤外線照射、電磁波照射等が挙げられる。また、通風加熱乾燥の方式としては、例えば、送風式乾燥オーブン等が挙げられる。 In the drying step, methods for drying the solvent include, for example, heating drying, ventilation heating drying, reduced pressure drying, and the like. The heating drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like. Further, examples of the ventilation heating drying method include a ventilation drying oven.
前記重合性組成物の乾燥膜厚(硬化物の膜厚)は、用途に応じて適宜設定されるが、0.05から300μmであることが好ましく、0.1から100μmであることがより好ましい。 The dry film thickness (thickness of the cured product) of the polymerizable composition is appropriately set depending on the application, but is preferably from 0.05 to 300 μm, more preferably from 0.1 to 100 μm. .
<パターン形成方法>
前記重合性組成物が前記アルカリ可溶性樹脂を含む場合、フォトリソグラフィー法によりパターンを形成することができる。前述と同様にして重合性組成物を基材に塗布し、必要に応じて、乾燥して乾燥被膜を形成する。そして、乾燥被膜にマスクを介して活性エネルギー線を照射することにより、露光部では前記ラジカル重合性化合物が重合することで硬化膜となる。一方、レーザーを用いた直接描画により、マスクを介さずに高精度なパターン形状を作製することもできる。
<Pattern formation method>
When the polymerizable composition contains the alkali-soluble resin, a pattern can be formed by photolithography. The polymerizable composition is applied to the substrate in the same manner as described above, and if necessary, dried to form a dry film. Then, by irradiating the dried film with active energy rays through a mask, the radically polymerizable compound polymerizes in the exposed area, resulting in a cured film. On the other hand, a highly accurate pattern shape can also be created by direct writing using a laser without using a mask.
上記の露光後、未露光部は、例えば、0.3から3質量%の炭酸ナトリウム水溶液等のアルカリ現像液により現像除去され、パターン化した硬化膜が得られる。さらに、硬化膜と基材との密着性を高めること等を目的に、後乾燥として180から250℃、20から90分でのポストベークが行われる。このようにして、硬化膜に基づく所望のパターンが形成される。 After the above exposure, the unexposed areas are developed and removed using an alkaline developer such as a 0.3 to 3% by mass aqueous sodium carbonate solution to obtain a patterned cured film. Further, post-drying is performed by post-baking at 180 to 250° C. for 20 to 90 minutes in order to improve the adhesion between the cured film and the base material. In this way, a desired pattern based on the cured film is formed.
本発明の重合性組成物は、ハードコート剤、光ディスク用コート剤、光ファイバー用コート剤、モバイル端末用塗料、家電用塗料、化粧品容器用塗料、光学素子用内面反射防止塗料、高・低屈折率コート剤、遮熱コート剤、放熱コート剤、防曇剤等の塗料・コーティング剤;オフセット印刷インキ、グラビア印刷インキ、スクリーン印刷インキ、インクジェット印刷インキ、導電性インキ、絶縁性インキ、導光板用インキ等の印刷インキ;感光性印刷版;ナノインプリント材料;3Dプリンター用樹脂;ホログラフィー記録材料;歯科用材料;導波路用材料;レンズシート用ブラックストライプ;コンデンサ用グリーンシートおよび電極材料;FPD用接着剤、HDD用接着剤、光ピックアップ用接着剤、イメージセンサー用接着剤、有機EL用シール剤、タッチパネル用OCA、タッチパネル用OCR等の接着剤・シール剤;カラーレジスト、ブラックレジスト、カラーフィルター用保護膜、フォトスペーサー、ブラックカラムスペーサー、額縁レジスト、TFT配線用フォトレジスト、層間絶縁膜等のFPD用レジスト;液状ソルダーレジスト、ドライフィルムレジスト等のプリント基板用レジスト;半導体レジスト、バッファーコート膜等の半導体用材料等の各種用途に使用でき、その用途に特に制限は無い。 The polymerizable composition of the present invention is a hard coating agent, a coating agent for optical discs, a coating agent for optical fibers, a coating agent for mobile terminals, a coating for home appliances, a coating for cosmetic containers, an internal antireflection coating for optical elements, and a high/low refractive index coating. Paints and coating agents such as coating agents, thermal barrier coating agents, heat dissipation coating agents, antifogging agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, inks for light guide plates Printing inks such as; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; dental materials; materials for waveguides; black stripes for lens sheets; green sheets and electrode materials for capacitors; adhesives for FPD; Adhesives and sealants for HDDs, optical pickups, image sensors, organic EL sealants, OCA for touch panels, OCR for touch panels, etc. Color resists, black resists, protective films for color filters, FPD resists such as photo spacers, black column spacers, picture frame resists, photo resists for TFT wiring, and interlayer insulating films; resists for printed circuit boards such as liquid solder resists and dry film resists; semiconductor materials such as semiconductor resists and buffer coat films. It can be used for various purposes such as, and there are no particular restrictions on its uses.
以下に実施例を挙げて本発明をさらに詳細に説明する。 The present invention will be explained in more detail with reference to Examples below.
<(1)ビスオキシムエステル系光重合開始剤の合成>
[合成例1-a(中間体I(化合物1-a)の合成)]
[Synthesis Example 1-a (Synthesis of Intermediate I (Compound 1-a))]
[合成例1-b(中間体II(化合物1-b)の合成)]
[合成例1-c(中間体III(化合物1-c)の合成)]
[合成例1-d(化合物1の合成)]
[合成例10-b(中間体II(化合物10-b)の合成)]
100mLの四つ口フラスコ中に0.02molの化合物1-a、0.09molのAlCl3、10mLのジクロロエタンを投入して、攪拌し、氷バスで冷却して温度が0℃までに低下した時に、0.02molのn-オクタノイルクロライドと40mLジクロロエタンの混合溶液を、温度を0℃以下に調整しながら、約20分をかけて添加した。温度を0℃に保ち、引き続き2時間攪拌した。その後、0℃の10%塩酸水中に反応液を徐々に投入し、分液漏斗で下層を分液し、上層を50mLのジクロロエタンで抽出した後、抽出液と下層液とを合わせた。その後、5%炭酸水素ナトリウム水溶液で洗浄し、更にpHの値が中性を呈するまでに200mL水で3回洗浄し、3g無水硫酸マグネシウムで乾燥して水分を除去した後、回転蒸発によりジクロロエタンを蒸発させた。蒸発が終わった後、回転蒸発瓶中の粗製品を酢酸エチルとヘキサンで精製し、化合物10-b(収量:7.5g、LC純度:96.0%、収率:94.5%)を得た。
[Synthesis Example 10-b (Synthesis of Intermediate II (Compound 10-b))]
0.02 mol of compound 1-a, 0.09 mol of AlCl 3 and 10 mL of dichloroethane were put into a 100 mL four-necked flask, stirred, and cooled in an ice bath until the temperature dropped to 0°C. A mixed solution of 0.02 mol of n-octanoyl chloride and 40 mL of dichloroethane was added over about 20 minutes while adjusting the temperature to below 0°C. The temperature was maintained at 0° C. and stirring continued for 2 hours. Thereafter, the reaction solution was gradually poured into 10% hydrochloric acid solution at 0° C., the lower layer was separated using a separatory funnel, the upper layer was extracted with 50 mL of dichloroethane, and the extract and lower layer were combined. Thereafter, it was washed with a 5% aqueous sodium bicarbonate solution, and then washed three times with 200 mL of water until the pH value became neutral, and after drying with 3 g of anhydrous magnesium sulfate to remove water, dichloroethane was removed by rotary evaporation. Evaporated. After the evaporation was completed, the crude product in the rotary evaporator was purified with ethyl acetate and hexane to obtain compound 10-b (yield: 7.5 g, LC purity: 96.0%, yield: 94.5%). Obtained.
[合成例10-c(中間体III(化合物10-c)の合成)]
100mLのナスフラスコ中に0.008molの化合物10-b、テトラヒドロフラン12mL、濃塩酸0.6g、亜硝酸イソアミル0.020mоlを投入して、常温で5時間攪拌した後、反応液をビーカーに入れ、酢酸エチルと10%食塩水で3回洗浄し、分液漏斗にて分層した。その後、5g無水硫酸マグネシウムを加入して乾燥した後、吸引ろ過を行い、更に、ろ液を回転蒸発させた。蒸発が終わった後、回転蒸発瓶中の粗製品を酢酸エチルとヘキサンで精製し、化合物10-c(収量:1.8g、LC純度:90.0%、収率:48.0%)を得た。
[Synthesis Example 10-c (Synthesis of Intermediate III (Compound 10-c))]
0.008 mol of compound 10-b, 12 mL of tetrahydrofuran, 0.6 g of concentrated hydrochloric acid, and 0.020 mol of isoamyl nitrite were placed in a 100 mL eggplant flask, and after stirring at room temperature for 5 hours, the reaction solution was placed in a beaker. It was washed three times with ethyl acetate and 10% saline, and the layers were separated using a separatory funnel. Thereafter, 5 g of anhydrous magnesium sulfate was added and dried, followed by suction filtration, and the filtrate was rotary evaporated. After the evaporation was completed, the crude product in the rotary evaporator was purified with ethyl acetate and hexane to obtain compound 10-c (yield: 1.8 g, LC purity: 90.0%, yield: 48.0%). Obtained.
[合成例10-d(化合物10の合成)]
100mLのナスフラスコ中に0.003molの化合物10-c、テトラヒドロフラン5mL、ピリジン0.8gを投入して、攪拌し、アセチルクロリド0.010mоlを、約0.5時間をかけて滴下した。引き続いて2時間攪拌した後、冷水500mLを滴下し始め、分液漏斗で分層した。その5%塩酸水で一回洗い、3%炭酸水素ナトリウム水溶液10mLで一回洗い、続いて10%食塩水10mLで洗った後、1g無水硫酸マグネシウムで乾燥し、溶剤を回転蒸発させて、除去し、粗製品を得た。該粗製品に適量の酢酸エチルとヘキサンを加入し、ろ過、乾燥して、化合物10(収量:0.9g、LC純度:94.4%、収率:52.6%)を得た。1H-NMRによる分析結果を表1に示す。
[Synthesis Example 10-d (Synthesis of Compound 10)]
0.003 mol of Compound 10-c, 5 mL of tetrahydrofuran, and 0.8 g of pyridine were placed in a 100 mL eggplant flask, stirred, and 0.010 mol of acetyl chloride was added dropwise over about 0.5 hours. After continued stirring for 2 hours, 500 mL of cold water was added dropwise and the layers were separated using a separatory funnel. After washing once with 5% hydrochloric acid solution, once with 10 mL of 3% sodium bicarbonate aqueous solution, and then with 10 mL of 10% saline solution, drying with 1 g of anhydrous magnesium sulfate, and removing the solvent by rotary evaporation. A crude product was obtained. Appropriate amounts of ethyl acetate and hexane were added to the crude product, filtered and dried to obtain Compound 10 (yield: 0.9 g, LC purity: 94.4%, yield: 52.6%). The analysis results by 1 H-NMR are shown in Table 1.
[合成例15-b(中間体II(化合物15-b)の合成)]
100mLの四つ口フラスコ中に0.02molの化合物1-a、0.09molのAlCl3、45mLのジクロロエタンを投入して、攪拌し、氷バスで冷却して温度が0℃までに低下した時に、0.02molのイソノナン酸クロライドと20mLのジクロロエタン10mLの混合溶液を、温度を0℃以下に調整しながら、約20分をかけて添加した。温度を0℃に保ち、引き続き2時間攪拌した。その後、0℃の10%塩酸水中に反応液を徐々に投入し、分液漏斗で下層を分液し、上層を50mLのジクロロエタンで抽出した後、抽出液と下層液とを合わせた。その後、5%炭酸水素ナトリウム水溶液で洗浄し、更にpHの値が中性を呈するまでに200mL水で3回洗浄し、3g無水硫酸マグネシウムで乾燥して水分を除去した後、回転蒸発によりジクロロエタンを蒸発させた。蒸発が終わった後、回転蒸発瓶中の粗製品を酢酸エチルとヘキサンで精製し、化合物15-b(収量:2.6g、LC純度:95.6%、収率:44.1%)を得た。
[Synthesis Example 15-b (Synthesis of Intermediate II (Compound 15-b))]
0.02 mol of compound 1-a, 0.09 mol of AlCl 3 and 45 mL of dichloroethane were put into a 100 mL four-necked flask, stirred, and cooled in an ice bath until the temperature dropped to 0°C. A mixed solution of 10 mL of 0.02 mol of isononanoyl chloride and 20 mL of dichloroethane was added over about 20 minutes while adjusting the temperature to 0° C. or lower. The temperature was maintained at 0° C. and stirring continued for 2 hours. Thereafter, the reaction solution was gradually poured into 10% hydrochloric acid solution at 0° C., the lower layer was separated using a separatory funnel, the upper layer was extracted with 50 mL of dichloroethane, and the extract and lower layer were combined. Thereafter, it was washed with a 5% aqueous sodium bicarbonate solution, and then washed three times with 200 mL of water until the pH value became neutral, and after drying with 3 g of anhydrous magnesium sulfate to remove water, dichloroethane was removed by rotary evaporation. Evaporated. After the evaporation was completed, the crude product in the rotary evaporator bottle was purified with ethyl acetate and hexane to obtain compound 15-b (yield: 2.6 g, LC purity: 95.6%, yield: 44.1%). Obtained.
[合成例15-c(中間体III(化合物15-c)の合成)]
100mLのナスフラスコ中に0.01molの化合物15-b、テトラヒドロフラン5mL、濃塩酸0.3g、亜硝酸イソアミル0.004mоlを投入して、常温で5時間攪拌した後、反応液をビーカーに入れ、酢酸エチルと10%食塩水で3回洗浄し、分液漏斗にて分層した。その後、5g無水硫酸マグネシウムを加入して乾燥した後、吸引ろ過を行い、更に、ろ液を回転蒸発させた。蒸発が終わった後、回転蒸発瓶中の粗製品を酢酸エチルとヘキサンで精製し、化合物15-c(収量:0.6g、LC純度:94.9%、収率:31.6%)を得た。
[Synthesis Example 15-c (Synthesis of Intermediate III (Compound 15-c))]
0.01 mol of compound 15-b, 5 mL of tetrahydrofuran, 0.3 g of concentrated hydrochloric acid, and 0.004 mol of isoamyl nitrite were placed in a 100 mL eggplant flask, and after stirring at room temperature for 5 hours, the reaction solution was placed in a beaker. It was washed three times with ethyl acetate and 10% saline, and the layers were separated using a separatory funnel. Thereafter, 5 g of anhydrous magnesium sulfate was added and dried, followed by suction filtration, and the filtrate was rotary evaporated. After the evaporation was completed, the crude product in the rotary evaporator bottle was purified with ethyl acetate and hexane to obtain compound 15-c (yield: 0.6 g, LC purity: 94.9%, yield: 31.6%). Obtained.
[合成例15-d(化合物15の合成)]
100mLのナスフラスコ中に0.001mоlの化合物15-c、テトラヒドロフラン2mL、ピリジン0.3gを投入して、攪拌し、アセチルクロリド0.004mоlを、約0.5時間をかけて滴下した。引き続いて2時間攪拌した後、冷水500mLを滴下し始め、分液漏斗で分層した。その5%塩酸水で一回洗い、3%炭酸水素ナトリウム水溶液10mLで一回洗い、続いて10%食塩水10mLで洗った後、1g無水硫酸マグネシウムで乾燥し、溶剤を回転蒸発させて、除去し、粗製品を得た。該粗製品に適量の酢酸エチルとヘキサンを加入し、ろ過、乾燥して、化合物15(収量:0.6g、LC純度:96.9%、収率:86.8%)を得た。1H-NMRによる分析結果を表1に示す。
[Synthesis Example 15-d (Synthesis of Compound 15)]
0.001 mol of Compound 15-c, 2 mL of tetrahydrofuran, and 0.3 g of pyridine were placed in a 100 mL eggplant flask, stirred, and 0.004 mol of acetyl chloride was added dropwise over about 0.5 hours. After continued stirring for 2 hours, 500 mL of cold water was added dropwise and the layers were separated using a separatory funnel. After washing once with 5% hydrochloric acid solution, once with 10 mL of 3% sodium bicarbonate aqueous solution, and then with 10 mL of 10% saline solution, drying with 1 g of anhydrous magnesium sulfate, and removing the solvent by rotary evaporation. A crude product was obtained. Appropriate amounts of ethyl acetate and hexane were added to the crude product, filtered and dried to obtain Compound 15 (yield: 0.6 g, LC purity: 96.9%, yield: 86.8%). The analysis results by 1 H-NMR are shown in Table 1.
<(2)UV吸収特性の評価>
表1に記載される化合物のアセトニトリル溶液について、UV-VISスペクトル測定装置(1.0cm石英セル、島津製作所製、UV-2450)を用いて、波長200から600nmにおけるUV-VISスペクトルを測定した。その結果を表2に示す。
<(2) Evaluation of UV absorption characteristics>
For acetonitrile solutions of the compounds listed in Table 1, UV-VIS spectra at wavelengths from 200 to 600 nm were measured using a UV-VIS spectrum measuring device (1.0 cm quartz cell, manufactured by Shimadzu Corporation, UV-2450). The results are shown in Table 2.
また、比較参考例として、化合物R1、化合物R2、化合物R3、および化合物R4の結果を表2に示す。
表2において、λmaxは最大吸収波長(nm)、εmaxは最大吸収波長にけるモル吸光係数(L・mol-1・cm-1)、ε313は波長313nmにおけるモル吸光係数(L・mol-1・cm-1)、ε365は波長365nmにおけるモル吸光係数(L・mol-1・cm-1)を示す。 In Table 2, λ max is the maximum absorption wavelength (nm), ε max is the molar extinction coefficient at the maximum absorption wavelength (L・mol −1・cm −1 ), and ε313 is the molar extinction coefficient at the wavelength of 313 nm (L・mol − 1 ·cm −1 ), ε365 indicates the molar extinction coefficient (L·mol −1 ·cm −1 ) at a wavelength of 365 nm.
一般に、露光波長における光重合開始剤のモル吸光係数が大きいほど、光が吸収されやすく、ラジカルの発生が起こりやすい。すなわち、光重合開始剤の高感度化には、露光波長におけるモル吸光係数が大きい化合物が好適である。UV硬化に使用されるや超高圧水銀ランプや高圧水銀ランプは波長365nm(i線)を主波長とし、波長313nm(j線)等の光を効率よく放出する。表2の結果より、本発明のビスオキシムエステル系光重合開始剤は、高圧水銀ランプ等から放出される波長365nm及び波長313nmのモル吸光係数が大きいことが分かる。さらに、LEDからは波長365nm等の単一の光が放出されるが、化合物1、化合物10、および化合物15は、波長365nmのモル吸光係数が大きいことが分かる。 Generally, the larger the molar extinction coefficient of a photopolymerization initiator at the exposure wavelength, the more light is absorbed and the more likely radicals are generated. That is, for increasing the sensitivity of a photopolymerization initiator, a compound having a large molar absorption coefficient at the exposure wavelength is suitable. Ultra-high-pressure mercury lamps and high-pressure mercury lamps used for UV curing have a main wavelength of 365 nm (i-line) and efficiently emit light with a wavelength of 313 nm (j-line), etc. From the results in Table 2, it can be seen that the bisoxime ester photopolymerization initiator of the present invention has a large molar absorption coefficient at wavelengths of 365 nm and 313 nm emitted from a high-pressure mercury lamp or the like. Furthermore, although a single light having a wavelength of 365 nm or the like is emitted from the LED, it can be seen that Compound 1, Compound 10, and Compound 15 have large molar extinction coefficients at a wavelength of 365 nm.
<実施例1~3、比較例1~4>
<重合性組成物(A)の調製>
表3に示す量のラジカル重合性化合物、アルカリ可溶性樹脂、その他の成分を混合撹拌し、さらに、重合開始剤を添加してよく撹拌し、実施例1~3および比較例1~4の重合性組成物(A)を調製した。
<Examples 1 to 3, Comparative Examples 1 to 4>
<Preparation of polymerizable composition (A)>
The amounts of the radically polymerizable compound, alkali-soluble resin, and other components shown in Table 3 were mixed and stirred, and then a polymerization initiator was added and stirred thoroughly. Composition (A) was prepared.
上記の表3中、
DPHAは、ジペンタエリスリトールペンタアクリレートおよびジペンタエリスリトールヘキサアクリレートの混合物(商品名:アロニックスM-402、東亞合成社製);
RD200は、メタクリル酸メチル/メタクリル酸/シクロヘキシルマレイミド(質量%:61/14/25)共重合物、重量平均分子量:17,000、酸価:90(合成品);
F-477は、フッ素系レベリング剤(商品名:メガファックF-477、DIC社製);
PGMEAは、プロピレングリコールモノメチルエーテルアセテート(富士フイルム和光純薬試薬);を示す。
In Table 3 above,
DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
RD200 is a methyl methacrylate/methacrylic acid/cyclohexylmaleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid value: 90 (synthetic product);
F-477 is a fluorine-based leveling agent (trade name: Megafac F-477, manufactured by DIC Corporation);
PGMEA represents propylene glycol monomethyl ether acetate (Fujifilm Wako Pure Chemicals Reagent);
<(3)感度の評価>
上記で調製した重合性組成物(A)を、スピンコーターを用いて、アルミニウム基板上に塗布した。塗布後、アルミニウム基板を90℃のクリーンオーブン中で2.5分間乾燥処理により溶媒を乾燥させ、厚さ1.5μmの均一な塗布膜を作製した。次いで、超高圧水銀灯を光源とするプロキシミティー露光機を用い、マスクパターンを介して10mJ/cm2の範囲で、段階露光を行った。露光後のアルミニウム基板を1.0質量%の炭酸ナトリウム水溶液に23℃で60秒間浸漬して、現像による未露光部の除去を行った。続いて純水にて30秒間洗浄を行い、パターン形状を得た。各重合開始剤の評価結果を、表5に示す。
〇:溶解せずに残膜する。
×:溶解して膜が残らない。
<(3) Sensitivity evaluation>
The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After coating, the solvent was dried by drying the aluminum substrate in a clean oven at 90° C. for 2.5 minutes to produce a uniform coating film with a thickness of 1.5 μm. Next, stepwise exposure was performed in a range of 10 mJ/cm 2 through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The exposed aluminum substrate was immersed in a 1.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds, and the unexposed areas were removed by development. Subsequently, washing was performed for 30 seconds with pure water to obtain a pattern shape. Table 5 shows the evaluation results for each polymerization initiator.
○: A film remains without dissolving.
×: Dissolved and no film remained.
<重合性組成物(B)の調製>
表4に示す量のラジカル重合性化合物、アルカリ可溶性樹脂、その他の成分を混合撹拌し、さらに、重合開始剤を添加してよく撹拌し、実施例1~3および比較例1~4の重合性組成物(B)を調製した。
<Preparation of polymerizable composition (B)>
The amounts of the radically polymerizable compound, alkali-soluble resin, and other components shown in Table 4 were mixed and stirred, and then a polymerization initiator was added and stirred thoroughly. Composition (B) was prepared.
上記の表4中、
PE4Aは、ペンタエリスリトールテトラアクリレート(東京化成工業試薬);
BYK302は、シリコン系表面調整剤(ビックケミージャパン社製);
PGMEAは、プロピレングリコールモノメチルエーテルアセテート(富士フイルム和光純薬試薬);を示す。
In Table 4 above,
PE4A is pentaerythritol tetraacrylate (Tokyo Kasei Kogyo Reagent);
BYK302 is a silicone surface conditioner (manufactured by BYK Chemie Japan);
PGMEA represents propylene glycol monomethyl ether acetate (Fujifilm Wako Pure Chemicals Reagent);
<(4)色差(b*値)の評価>
上記で調製した重合性組成物(B)を、スピンコーターを用いて、ガラス基板上に塗布した。塗布後、ガラス基板を90℃のクリーンオーブン中で2.5分間乾燥処理により溶媒を乾燥させ、厚さ1.5μmの均一な塗布膜を作製した。そして、高圧水銀ランプが設置されたコンベア式UV照射装置を使用して300mJ/cm2の照射を行い、試験片を作製した。得られた試験片の硬化度を測定した結果、すべての試験片において硬化度は90%以上であった。得られた試験片について、分光測色計(CM-3500d、ミノルタカメラ製)を用いてL*,a*,b*表色系の値をJIS-Z-8722に従って、透過法にて測定した。b*の値を黄色度の指標として評価し、b*が小さいほど黄色度が低い。その結果を表5に示す。
〇:b*値が1%未満である。
△:b*値が1%以上~2%未満である。
×:b*値が2%以上である。
<(4) Evaluation of color difference (b * value)>
The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After coating, the glass substrate was dried in a clean oven at 90° C. for 2.5 minutes to dry the solvent, thereby producing a uniform coating film with a thickness of 1.5 μm. Then, using a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp, irradiation was performed at 300 mJ/cm 2 to prepare a test piece. As a result of measuring the degree of hardening of the obtained test pieces, the degree of hardening was 90% or more in all test pieces. Regarding the obtained test piece, the values of L * , a * , b * color system were measured by the transmission method according to JIS-Z-8722 using a spectrophotometer (CM-3500d, manufactured by Minolta Camera). . The value of b * is evaluated as an index of yellowness, and the smaller b * is, the lower the yellowness is. The results are shown in Table 5.
○: b * value is less than 1%.
△:b * value is 1% or more and less than 2%.
×:b * value is 2% or more.
<(5)溶解性の評価>
表2に示す各重合開始剤をPGMEAに混合し、25℃、ミックスローターで攪拌した際に溶解する最大濃度を測定した。各光重合開始剤の溶解性を表5に示す。
〇:PGMEAに溶解する最大濃度が20%以上である。
×:PGMEAに溶解する最大濃度が20%未満である。
<(5) Evaluation of solubility>
Each polymerization initiator shown in Table 2 was mixed with PGMEA, and the maximum concentration dissolved when stirring with a mix rotor at 25° C. was measured. Table 5 shows the solubility of each photoinitiator.
○: The maximum concentration dissolved in PGMEA is 20% or more.
×: The maximum concentration dissolved in PGMEA is less than 20%.
評価(3)~(5)の結果、表に示されるように、本発明のビスオキシムエステル系光重合開始剤は、感度が高く、高い溶解性を示し、硬化膜の着色を抑えることが明らかである。 As shown in the table, the results of evaluations (3) to (5) indicate that the bisoxime ester photopolymerization initiator of the present invention has high sensitivity and high solubility, and suppresses coloration of the cured film. It is.
Claims (7)
7. The method for producing a cured product according to claim 6, comprising the step of irradiating the polymerizable composition with active energy rays.
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