JP2021127336A - Compound - Google Patents

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JP2021127336A
JP2021127336A JP2021016391A JP2021016391A JP2021127336A JP 2021127336 A JP2021127336 A JP 2021127336A JP 2021016391 A JP2021016391 A JP 2021016391A JP 2021016391 A JP2021016391 A JP 2021016391A JP 2021127336 A JP2021127336 A JP 2021127336A
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ring
group
compound
carbon atoms
formula
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Inventor
悠司 淺津
Yuji Asazu
悠司 淺津
由紀 西上
Yuki Nishigami
由紀 西上
信孝 国見
Nobutaka Kunimi
信孝 国見
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/06Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40Oxygen atoms
    • C07D211/44Oxygen atoms attached in position 4
    • C07D211/46Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
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    • C07C255/00Carboxylic acid nitriles
    • C07C255/45Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/46Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
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    • C07D203/08Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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    • C07D203/14Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom with carbocyclic rings directly attached to the ring nitrogen atom
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    • C07D207/34Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D211/08Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
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    • C07D211/06Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/26Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
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    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/06Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D295/12Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract

To provide a novel compound which has high absorption selectivity for the long-wavelength ultraviolet to near ultraviolet regions close to a wavelength of 400 nm, exhibits high weathering resistance, and has a merocyanine skeleton, wherein a layer formed from a composition containing the compound can provide a thin film layer which has excellent light absorption in the regions without causing bleeding of the compound even when the quantity of the compound added to the composition is increased.SOLUTION: Provided is a compound having a polymerizable group and a partial structure represented by formula (X) [In the formula (X), a ring W1 denotes a ring structure which has a double bond as a constituent element of the ring and is not aromatic, and the ring W1 may have a substituent group. R3 denotes a monovalent substituent group].SELECTED DRAWING: None

Description

本発明は、化合物に関する。 The present invention relates to compounds.

従来から、人体や樹脂材料を紫外線による劣化から守るため、様々な用途・製品で紫外線吸収剤が使用されている。紫外線吸収剤は、大別して無機系紫外線吸収剤と有機系吸収剤に分けられる。無機系紫外線吸収剤は耐候性や耐熱性等の耐久性が良好である反面、吸収波長の制御や有機材料との相溶性に劣る傾向にある。一方、有機系紫外線吸収剤は、無機系紫外線吸収剤よりも耐久性の点では劣るが、有機系紫外線吸収剤における分子の構造の自由度から、吸収波長や有機材料との相溶性等のコントロールが可能で、日焼け止めや塗料、光学材料や建材、自動車材等、幅広い分野で使用される。 Traditionally, UV absorbers have been used in various applications and products to protect the human body and resin materials from deterioration due to UV rays. Ultraviolet absorbers are roughly classified into inorganic ultraviolet absorbers and organic absorbers. Inorganic UV absorbers have good durability such as weather resistance and heat resistance, but tend to be inferior in controlling absorption wavelength and compatibility with organic materials. On the other hand, the organic UV absorber is inferior to the inorganic UV absorber in terms of durability, but the absorption wavelength and compatibility with the organic material are controlled from the degree of freedom of the molecular structure of the organic UV absorber. It is possible to use it in a wide range of fields such as sunscreens, paints, optical materials, building materials, and automobile materials.

代表的な有機系紫外線吸収剤としては、トリアゾール骨格、ベンゾフェノン骨格、トリアジン骨格を有する化合物が挙げられる。しかしながら、前記骨格を有する有機系紫外線吸収剤の多くが波長360nm以下に極大吸収(λmax)を示すため波長400nm付近(例えば、波長380nm〜400nm)の長波紫外線〜近紫外線領域を効率よく吸収できず、この領域の光を十分に吸収するためには使用量を非常に多くする必要があった。しかしながら、使用量を増やすと紫外線吸収剤を含む組成物から紫外線吸収剤が析出するという課題があった。 Typical organic UV absorbers include compounds having a triazole skeleton, a benzophenone skeleton, and a triazine skeleton. However, since most of the organic ultraviolet absorbers having the skeleton show maximum absorption (λmax) at a wavelength of 360 nm or less, they cannot efficiently absorb long-wave ultraviolet to near-ultraviolet regions having a wavelength of around 400 nm (for example, a wavelength of 380 nm to 400 nm). , It was necessary to use a very large amount in order to sufficiently absorb the light in this region. However, there is a problem that the ultraviolet absorber is precipitated from the composition containing the ultraviolet absorber when the amount used is increased.

波長400nm付近の光を効率よく吸収する化合物として、例えば、特許文献1には下記式で表されるようなメロシアニン骨格を有する化合物が提案されている。

Figure 2021127336
As a compound that efficiently absorbs light having a wavelength of around 400 nm, for example, Patent Document 1 proposes a compound having a merocyanine skeleton as represented by the following formula.
Figure 2021127336

特開2019−089997号公報Japanese Unexamined Patent Publication No. 2019-08997

しかしながら、メロシアニン骨格を有する化合物は耐久性(特に耐候性)が弱く、耐候性に対して厳しい要求がある用途には適用が困難であり、特許文献1に記載された化合物も耐候性は十分ではない場合があった。また、十分に波長400nm付近の光を吸収するために添加量を増やした場合、化合物が析出される可能性があった。 However, the compound having a merocyanine skeleton has weak durability (particularly weather resistance), and it is difficult to apply it to applications where there are strict requirements for weather resistance, and the compound described in Patent Document 1 also has sufficient weather resistance. Sometimes it wasn't. Further, when the addition amount was increased in order to sufficiently absorb the light having a wavelength of around 400 nm, there was a possibility that the compound was precipitated.

本発明は以下の発明を含む。
[1]重合性基と下記式(X)で表される部分構造とを有する化合物。

Figure 2021127336

[式(X)中、環Wは、環の構成要素として二重結合を有し、かつ芳香族性を有さない環構造を表し、環Wは置換基を有していてもよい。
は、1価の置換基を表す。]
[2]重合性基と式(X)で表される部分構造とを有する化合物が、式(I)で表される化合物〜式(IX)で表される化合物のいずれかである[1]に記載の化合物。
Figure 2021127336

Figure 2021127336

[式(I)〜式(IX)中、環W及びRは、前記と同じ意味を表す。
環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、それぞれ独立して、環の構成要素として少なくとも1つの二重結合を有する環構造を表す。環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、置換基を有していてもよい。
環W111は、構成要素として窒素原子を2つ有する複素環を表す。
環W112、環W113及び環W114は、それぞれ独立して、構成要素として窒素原子を1つ有する環を表す。
、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82、R92、R102及びR112は、それぞれ独立して、水素原子、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−NR12A−、−SO−、−CO−、−O−、−COO−、−OCO−、−CONR13A−、−NR14A−CO−、−S−、−SO−、−SO−、−CF−又は−CHF−に置換されていてもよい。
13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123は、それぞれ独立して、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−、−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
1A、R2A、R3A、R4A、R5A、R6A、R7A、R8A、R9A、R10A、R11A、R12A、R13A及びR14Aは、それぞれ独立して、水素原子又は炭素数1〜6のアルキル基を表す。
、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R25、R35、R75、R85及びR125は、それぞれ独立して、電子求引性基又は重合性基を含む基を表す。
及びRは互いに結合して環を形成してもよい。
41及びR42は互いに結合して環を形成してもよい。
51及びR52は互いに結合して環を形成してもよい。
61及びR62は互いに結合して環を形成してもよい。
91及びR92は互いに結合して環を形成してもよい。
101及びR102は互いに結合して環を形成してもよい。
111及びR112は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
12及びR13は互いに結合して環を形成してもよい。
42及びR43は互いに結合して環を形成してもよい。
52及びR53は互いに結合して環を形成してもよい。
62及びR63は互いに結合して環を形成してもよい。
72及びR73は互いに結合して環を形成してもよい。
82及びR83は互いに結合して環を形成してもよい。
92及びR93は互いに結合して環を形成してもよい。
102及びR103は互いに結合して環を形成してもよい。
112及びR113は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
14及びR15は互いに結合して環を形成してもよい。
24及びR25は互いに結合して環を形成してもよい。
34及びR35は互いに結合して環を形成してもよい。
74及びR85は互いに結合して環を形成してもよい。
84及びR85は互いに結合して環を形成してもよい。
124及びR125は互いに結合して環を形成してもよい。
及びRは、それぞれ独立して、2価の連結基を表す。
及びR126は、それぞれ独立して、単結合又は2価の連結基を表す。
及びR10は、それぞれ独立して、3価の連結基を表す。
11は、4価の連結基を表す。
ただし、式(I)においては、R、R、R及びRのうち少なくとも一つは重合性基を含む基を表す。
式(II)においては、R、R、R、R12、R13、R14及びR15のうち少なくとも一つは重合性基を含む基を表す。
式(III)のおいては、R、R、R23、R24及びR25のうち少なくとも一つは重合性基を含む基を表す。
式(IV)においては、R、R、R33、R34及びR35のうち少なくとも一つは重合性基を含む基を表す。
式(V)においては、R、R、R、R41、R42、R43及びR44のうち少なくとも一つは重合性基を含む基を表す。
式(VI)においては、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64のうち少なくとも一つは重合性基を含む基を表す。
式(VII)においては、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85のうち少なくとも一つは重合性基を含む基を表す。
式(VIII)においては、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114のうち少なくとも一つは重合性基を含む基を表す。
式(IX)においては、R、R、R、R123、R124及びR125のうち少なくとも一つは重合性基を含む基を表す。]
[3]R及びRからなる群から選ばれる少なくとも一方が、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基、フルオロアリール基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である[2]に記載の化合物。
[4]R及びRからなる群から選ばれる少なくとも一方が、ニトロ基、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である[2]又は[3]に記載の化合物。
[5]R及びRからなる群から選ばれる少なくとも一方が、シアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である[2]〜[4]のいずれかに記載の化合物。
[6]R及びRからなる群から選ばれる少なくとも一方が、シアノ基である[2]〜[5]のいずれかに記載の化合物。
[7]Rがシアノ基であり、
がシアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である[2]〜[6]のいずれかに記載の化合物。
[8]R及びRがともにシアノ基である[2]〜[7]のいずれかに記載の化合物。
[9]R及びRが、それぞれ独立して、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基である[2]〜[8]のいずれかに記載の化合物。
[10]R及びRが互いに連結して環を形成する[2]〜[8]のいずれかに記載の化合物。
[11]R及びRが互いに連結して形成する環が、脂肪族複素環である[10]に記載の化合物。
[12]R及びRからなる群から選ばれる少なくとも一方が、重合性基を含む基である[2]〜[9]のいずれかに記載の化合物。
[13]R及びRが互いに連結して環を形成し、かつ、R及びRが互いに連結した環が重合性基を有する[2]〜[8]のいずれかに記載の化合物。
[14]環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、芳香族性を有さない環である[2]〜[13]のいずれかに記載の化合物。
[15]環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、5〜7員環構造である[2]〜[14]のいずれかに記載の化合物。
[16]環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、6員環構造である[15]に記載の化合物。
[17]Rがニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基、フルオロアリール基、−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)である[1]〜[16]のいずれかに記載の化合物。
[18]Rがシアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)である[1]〜[17]のいずれかに記載の化合物。
[19]Rがシアノ基である[1]〜[18]のいずれかに記載の化合物。
[20]環Wが5〜7員環である[1]〜[19]のいずれかに記載の化合物。
[21]環Wが6員環である[20]に記載の化合物。
[22]極大吸収波長におけるグラム吸光係数εが50L/(g・cm)以上である[1]〜[21]のいずれかに記載の化合物。
[23]ε(λmax)/ε(λmax+30nm)≧5である[1]〜[22]のいずれかに記載の化合物。
[ε(λmax)は、重合性基と式(X)で表される部分構造とを有する化合物における極大吸収波長におけるグラム吸光係数を表す。
ε(λmax+30nm)は、重合性基と式(X)で表される部分構造とを有する化合物の(極大吸収波長+30nm)におけるグラム吸光係数を表す。
グラム吸光係数の単位は、L/(g・cm)である。]
[24][1]〜[23]のいずれかに記載の化合物を含む組成物。
[25]さらに開始剤を含む[24]に記載の組成物。
[26]前記開始剤がラジカル重合開始剤である[25]に記載の組成物。
[27]前記開始剤が光ラジカル重合開始剤である[26]に記載の組成物。
[28]さらにラジカル重合性成分を含む[24]〜[27]のいずれかに記載の組成物。
[29]前記ラジカル重合性成分が(メタ)アクリレート化合物である[28]に記載の組成物。
[30]前記ラジカル重合性成分が多官能(メタ)アクリレート化合物である[29]に記載の組成物。
[31]さらに、樹脂(A)を含む[24]〜[30]のいずれかに記載の組成物。
[32]前記樹脂(A)は、ガラス転移温度が40℃以下の樹脂である[31]に記載の組成物。
[33]前記ガラス転移温度が40℃以下の樹脂が、(メタ)アクリル系樹脂である[32]に記載の組成物。
[34]さらに、架橋剤(E)を含む[31]〜[33]のいずれかに記載の組成物。
[35]前記架橋剤(E)が、イソシアネート架橋剤である[34]に記載の組成物。
[36][24]〜[30]のいずれかに記載の組成物から形成されるハードコート層。
[37][31]〜[35]のいずれかに記載の組成物からなる粘着剤層。
[38][24]に記載の組成物から形成される成形物。
[39]式(X)で表される部分構造を有する樹脂。
Figure 2021127336

[式(X)中、環Wは、環の構成要素として二重結合を有し、かつ芳香族性を有さない環構造を表し、環Wは置換基を有していてもよい。
は、1価の置換基を表す。]
[40][39]に記載の樹脂を含む組成物。 The present invention includes the following inventions.
[1] A compound having a polymerizable group and a partial structure represented by the following formula (X).
Figure 2021127336

[In formula (X), ring W 1 represents a ring structure having a double bond as a component of the ring and having no aromaticity, and ring W 1 may have a substituent. ..
R 3 represents a monovalent substituent. ]
[2] The compound having a polymerizable group and a partial structure represented by the formula (X) is any one of the compound represented by the formula (I) to the compound represented by the formula (IX) [1]. The compound described in.
Figure 2021127336

Figure 2021127336

[In formulas (I) to (IX), rings W 1 and R 3 have the same meanings as described above.
Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. Independently, it represents a ring structure having at least one double bond as a component of the ring. Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 are replaced. It may have a group.
Ring W 111 represents a heterocycle having two nitrogen atoms as a component.
Ring W 112 , ring W 113, and ring W 114 each independently represent a ring having one nitrogen atom as a component.
R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 and R 112. Independently, hydrogen atom, heterocyclic group, halogen atom, nitro group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, Represents a group containing a polymerizable group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. -CH 2- and -CH = contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group are independently -NR 12A- , -SO 2- , -CO-, -O-,-, respectively. COO -, - OCO -, - CONR 13A -, - NR 14A -CO -, - S -, - SO -, - SO 2 -, - CF 2 - or may be substituted in -CHF-.
R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 are independently heterocyclic groups, halogen atoms and nitros, respectively. Group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, group containing polymerizable group, carbon number which may have substituent Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have 1 to 25 aliphatic hydrocarbon groups or substituents, and is contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group -CH. 2- and -CH = are independently -O-, -S-, -NR 1A- , -CO-, -CO-O-, -O-CO-, -O-CO-O-, respectively. -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A- CO-O-, -NR 6A- CO-NR 7A- , -CO-S-, -S-CO -S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O -CS-, -CS-O-, -NR 10A -CS-, -NR 11A-CS It may be substituted with -S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO 2-.
R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A and R 14A are independent hydrogen atoms, respectively. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.
R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 25 , R 35. , R 75 , R 85 and R 125 each independently represent a group containing an electron-attracting group or a polymerizable group.
R 1 and R 2 may be combined with each other to form a ring.
R 41 and R 42 may be combined with each other to form a ring.
R 51 and R 52 may be combined with each other to form a ring.
R 61 and R 62 may be combined with each other to form a ring.
R 91 and R 92 may be combined with each other to form a ring.
R 101 and R 102 may be combined with each other to form a ring.
R 111 and R 112 may be combined with each other to form a ring.
R 2 and R 3 may be combined with each other to form a ring.
R 12 and R 13 may be combined with each other to form a ring.
R 42 and R 43 may be combined with each other to form a ring.
R 52 and R 53 may be combined with each other to form a ring.
R 62 and R 63 may be combined with each other to form a ring.
R 72 and R 73 may be combined with each other to form a ring.
R 82 and R 83 may be combined with each other to form a ring.
R 92 and R 93 may be combined with each other to form a ring.
R 102 and R 103 may be combined with each other to form a ring.
R 112 and R 113 may be combined with each other to form a ring.
R 4 and R 5 may be combined with each other to form a ring.
R 14 and R 15 may be combined with each other to form a ring.
R 24 and R 25 may be combined with each other to form a ring.
R 34 and R 35 may be combined with each other to form a ring.
R 74 and R 85 may be combined with each other to form a ring.
R 84 and R 85 may be combined with each other to form a ring.
R 124 and R 125 may be combined with each other to form a ring.
R 6 and R 8 each independently represent a divalent linking group.
R 7 and R 126 each independently represent a single bond or a divalent linking group.
R 9 and R 10 each independently represent a trivalent linking group.
R 11 represents a tetravalent linking group.
However, in the formula (I), at least one of R 1 , R 2 , R 4 and R 5 represents a group containing a polymerizable group.
In formula (II), at least one of R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 represents a group containing a polymerizable group.
In formula (III), at least one of R 4 , R 5 , R 23 , R 24 and R 25 represents a group containing a polymerizable group.
In formula (IV), at least one of R 4 , R 5 , R 33 , R 34 and R 35 represents a group containing a polymerizable group.
In formula (V), at least one of R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 represents a group containing a polymerizable group.
In formula (VI), at least one of R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , R 54 , R 61 , R 62 , R 63 and R 64 contains a polymerizable group. Represents a group.
In formula (VII), at least one of R 2 , R 4 , R 5 , R 72 , R 73 , R 74 , R 75 , R 82 , R 83 , R 84 and R 85 contains a polymerizable group. Represents a group.
In formula (VIII), R 1 , R 2 , R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112 , R 113 and R. At least one of 114 represents a group containing a polymerizable group.
In formula (IX), at least one of R 2 , R 4 , R 5 , R 123 , R 124 and R 125 represents a group containing a polymerizable group. ]
[3] At least one selected from the group consisting of R 4 and R 5 is a nitro group, a cyano group, a halogen atom, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , fluoroalkyl group, fluoroaryl group. , -CO-O-R 222 or -SO 2- R 222 (R 222 may have a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, which may have a substituent, or a substituent. The compound according to [2], which represents an aromatic hydrocarbon group having 6 to 18 carbon atoms.
[4] At least one selected from the group consisting of R 4 and R 5 is a nitro group, a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO-O-R 222 or -SO 2 -R 222 (R 222 represents a hydrogen atom, an aromatic alkyl group or a substituent having 6 to 18 carbon atoms which may have a good 25 carbon atoms which may have a substituent carbide The compound according to [2] or [3], which represents a hydrogen group.
[5] At least one selected from the group consisting of R 4 and R 5 has a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 has a hydrogen atom and a substituent. It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 25 carbon atoms or a substituent may have a substituent (2) according to any one of [2] to [4]. Compound.
[6] The compound according to any one of [2] to [5], wherein at least one selected from the group consisting of R 4 and R 5 is a cyano group.
[7] R 4 is a cyano group and
R 5 has a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 has a hydrogen atom, an alkyl group or substituent having 1 to 25 carbon atoms which may have a substituent. The compound according to any one of [2] to [6], which represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be used.
[8] The compound according to any one of [2] to [7], wherein both R 4 and R 5 are cyano groups.
[9] The description in any one of [2] to [8], wherein R 1 and R 2 are aliphatic hydrocarbon groups having 1 to 25 carbon atoms which may independently have a substituent. Compound.
[10] The compound according to any one of [2] to [8], wherein R 1 and R 2 are linked to each other to form a ring.
[11] The compound according to [10], wherein the ring formed by connecting R 1 and R 2 to each other is an aliphatic heterocycle.
[12] The compound according to any one of [2] to [9], wherein at least one selected from the group consisting of R 1 and R 2 is a group containing a polymerizable group.
[13] R 1 and R 2 are linked together to form a ring, and A compound according to any one of the rings R 1 and R 2 are linked to each other has a polymerizable group [2] to [8] ..
[14] Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 However, each of the compounds according to any one of [2] to [13], which is a ring having no aromaticity independently.
[15] Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 However, each of the compounds according to any one of [2] to [14] having a 5- to 7-membered ring structure independently.
[16] Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 However, each of the compounds according to [15] has a 6-membered ring structure independently.
[17] R 3 is a nitro group, a cyano group, a halogen atom, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , fluoroalkyl group, fluoroaryl group, -CO-O-R 111A or -SO 2. -R 112A (R 111A and R 112A each independently represent an alkyl group having 1 to 24 carbon atoms which may have a halogen atom), which is one of [1] to [16]. The compound described.
[18] R 3 is a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO- OR 111A or -SO 2- R 112A (R 111A and R 112A are each. The compound according to any one of [1] to [17], which independently represents an alkyl group having 1 to 24 carbon atoms which may have a halogen atom.
[19] R 3 is a cyano group [1] A compound according to any one of - [18].
[20] The compound according to any one of [1] to [19], wherein ring W 1 is a 5 to 7-membered ring.
[21] The compound according to [20], wherein the ring W 1 is a 6-membered ring.
[22] The compound according to any one of [1] to [21], wherein the gram absorption coefficient ε at the maximum absorption wavelength is 50 L / (g · cm) or more.
[23] The compound according to any one of [1] to [22], wherein ε (λmax) / ε (λmax + 30 nm) ≧ 5.
[Ε (λmax) represents the gram absorption coefficient at the maximum absorption wavelength in a compound having a polymerizable group and a partial structure represented by the formula (X).
ε (λmax + 30 nm) represents the gram absorption coefficient at (maximum absorption wavelength + 30 nm) of a compound having a polymerizable group and a partial structure represented by the formula (X).
The unit of the gram extinction coefficient is L / (g · cm). ]
[24] A composition containing the compound according to any one of [1] to [23].
[25] The composition according to [24], which further comprises an initiator.
[26] The composition according to [25], wherein the initiator is a radical polymerization initiator.
[27] The composition according to [26], wherein the initiator is a photoradical polymerization initiator.
[28] The composition according to any one of [24] to [27], which further contains a radically polymerizable component.
[29] The composition according to [28], wherein the radically polymerizable component is a (meth) acrylate compound.
[30] The composition according to [29], wherein the radically polymerizable component is a polyfunctional (meth) acrylate compound.
[31] The composition according to any one of [24] to [30], which further comprises the resin (A).
[32] The composition according to [31], wherein the resin (A) is a resin having a glass transition temperature of 40 ° C. or lower.
[33] The composition according to [32], wherein the resin having a glass transition temperature of 40 ° C. or lower is a (meth) acrylic resin.
[34] The composition according to any one of [31] to [33], which further comprises a cross-linking agent (E).
[35] The composition according to [34], wherein the cross-linking agent (E) is an isocyanate cross-linking agent.
[36] A hard coat layer formed from the composition according to any one of [24] to [30].
[37] An adhesive layer comprising the composition according to any one of [31] to [35].
[38] A molded product formed from the composition according to [24].
[39] A resin having a partial structure represented by the formula (X).
Figure 2021127336

[In formula (X), ring W 1 represents a ring structure having a double bond as a component of the ring and having no aromaticity, and ring W 1 may have a substituent. ..
R 3 represents a monovalent substituent. ]
[40] A composition containing the resin according to [39].

本発明は、波長400nm付近の長波紫外〜近紫外線の領域に対する高い吸収選択性を有し、かつ耐候性の高い、メロシアニン骨格を有する新規化合物を提供する。さらに、本発明の化合物を含む組成物から形成された層は、組成物への添加量を増やした場合でも化合物がブリードすることなく、上記領域の光吸収性に優れた薄膜層を提供できる。 The present invention provides a novel compound having a merocyanine skeleton, which has high absorption selectivity in the region of long-wave ultraviolet to near-ultraviolet rays having a wavelength of around 400 nm and high weather resistance. Further, the layer formed from the composition containing the compound of the present invention can provide a thin film layer having excellent light absorption in the above region without bleeding of the compound even when the amount added to the composition is increased.

本発明の化合物は、重合性基と式(X)で表される部分構造とを有する化合物(以下、化合物(X)という場合がある。)である。

Figure 2021127336

[式(X)中、環Wは、環の構成要素として二重結合を有し、かつ芳香族性を有さない環構造を表す。環Wは、置換基を有していてもよい。
は、1価の置換基を表す。] The compound of the present invention is a compound having a polymerizable group and a partial structure represented by the formula (X) (hereinafter, may be referred to as compound (X)).
Figure 2021127336

[In formula (X), ring W 1 represents a ring structure having a double bond as a component of the ring and having no aromaticity. Ring W 1 may have a substituent.
R 3 represents a monovalent substituent. ]

化合物(X)が有する重合性基は、特に制限されない。例えば、エポキシ基、オキセタニル基、オキサゾリノ基、アジリジノ基、ビニルエーテル基等のカチオン重合性基;エチレン性不飽和基等のラジカル重合性基;アルコキシシリル基が挙げられる。化合物(X)が有する重合性基は、エチレン性不飽和基等のラジカル重合性基であることが好ましい。エチレン性不飽和基の具体例としては、ビニル基、α−メチルビニル基、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、アリル基、スチリル基、(メタ)アクリルアミド基等が挙げられる。なお本明細書において、(メタ)アクリロイル基とは、アクリロイル基又はメタアクリロイル基のいずれでもよいことを意味し、他に、(メタ)アクリレートなどというときの「(メタ)」も同様の趣旨である。 The polymerizable group of compound (X) is not particularly limited. For example, a cationically polymerizable group such as an epoxy group, an oxetanyl group, an oxazolino group, an aziridino group and a vinyl ether group; a radically polymerizable group such as an ethylenically unsaturated group; and an alkoxysilyl group can be mentioned. The polymerizable group of the compound (X) is preferably a radically polymerizable group such as an ethylenically unsaturated group. Specific examples of the ethylenically unsaturated group include a vinyl group, an α-methylvinyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, an allyl group, a styryl group, a (meth) acrylamide group and the like. In the present specification, the (meth) acryloyl group means that it may be either an acryloyl group or a meta-acryloyl group, and in addition, "(meta)" in the case of (meth) acrylate or the like has the same meaning. be.

環Wは、環の構成要素として二重結合を1つ以上有する環であり、かつ芳香族性を有さない環であれば特に限定されない。環Wは単環であってもよいし、縮合環であってもよい。
環Wは、環の構成要件としてヘテロ原子(例えば、酸素原子、硫黄原子、窒素原子等)を含む複素環であってもよいし、炭素原子と水素原子とからなる脂肪族炭化水素環であってもよい。
環Wは、環の構成要件として二重結合を1つ以上有するが、環Wに含まれる二重結合は、通常1〜4であり、1〜3であることが好ましく、1又は2であることがより好ましく、1つであることがさらに好ましい。
Ring W 1 is not particularly limited as long as it is a ring having one or more double bonds as a component of the ring and does not have aromaticity. Ring W 1 may be a monocyclic ring or a condensed ring.
Ring W 1 may be a hetero ring containing a hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a constituent requirement of the ring, or an aliphatic hydrocarbon ring composed of a carbon atom and a hydrogen atom. There may be.
Ring W 1 has one or more double bonds as a constituent requirement of the ring, but the double bonds contained in ring W 1 are usually 1 to 4, preferably 1 to 3, and 1 or 2. Is more preferable, and one is more preferable.

環Wは、通常、炭素数5〜18の環であり、5〜7員環構造であることが好ましく、6員環構造であることがより好ましい。
環Wは、単環であることが好ましい。
Ring W 1 is usually a ring having 5 to 18 carbon atoms, preferably having a 5 to 7-membered ring structure, and more preferably a 6-membered ring structure.
Ring W 1 is preferably a single ring.

環Wとしては、例えば、下記に記載の基が挙げられる。

Figure 2021127336
Examples of the ring W 1 include the groups described below.
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336

[式中、*1は窒素原子との結合手を表し、*2は炭素原子との結合手を表す。]
Figure 2021127336

[In the formula, * 1 represents a bond with a nitrogen atom, and * 2 represents a bond with a carbon atom. ]

環Wは、置換基を有していてもよい。前記置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子;メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基等の炭素数1〜12のアルキル基;フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、2−フルオロエチル基、2,2−ジフルオロエチル基、2,2,2−トリフルオロエチル基、1,1,2,2−テトラフルオロエチル基、1,1,2,2,2−ペンタフルオロエチル基等の炭素数1〜12のハロゲン化アルキル基;メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等の炭素数1〜12のアルコキシ基;メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキシルチオ基等の炭素数1〜12のアルキルチオ基;モノフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメトキシ基、2−フルオロエトキシ基、1,1,2,2,2−ペンタフルオロエトキシ基等の炭素数1〜12のフッ素化アルコキシ基;アミノ基、メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、メチルエチル等の炭素数1〜6のアルキル基で置換されていてもよいアミノ基;メチルカルボニルオキシ基、エチルカルボニル基オキシ基等の炭素数2〜12のアルキルカルボニルオキシ基;メチルスルホニル基、エチルスルホニル基等の炭素数1〜12のアルキルスルホニル基;フェニルスルホニル基等の炭素数6〜12のアリールスルホニル基;重合性基を含む基;シアノ基;ニトロ基;ヒドロキシ基;チオール基;カルボキシル基;−SF;−SF;−SOH等が挙げられる。 Ring W 1 may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and the like. Alkyl group having 1 to 12 carbon atoms; fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 , 2,2-Tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl group and other alkyl halide groups having 1 to 12 carbon atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyl An alkoxy group having 1 to 12 carbon atoms such as an oxy group and a hexyloxy group; an alkylthio group having 1 to 12 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group; Fluorinated alkoxy group having 1 to 12 carbon atoms such as difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 1,1,2,2,2-pentafluoroethoxy group; amino group, methylamino group, ethyl Amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms such as an amino group, a dimethylamino group, a diethylamino group and methyl ethyl; an amino group having 2 to 12 carbon atoms such as a methylcarbonyloxy group and an ethylcarbonyl group oxy group. Alkylcarbonyloxy group; alkylsulfonyl group having 1 to 12 carbon atoms such as methylsulfonyl group and ethylsulfonyl group; arylsulfonyl group having 6 to 12 carbon atoms such as phenylsulfonyl group; group containing polymerizable group; cyano group; nitro group; hydroxy group; a thiol group; carboxyl group; -SF 3; -SF 5; -SO 3 H and the like.

重合性基を含む基としては、末端に重合性基を有する基であれば特に限定されないが、具体的には、式(I−2)で表される基が挙げられる。

Figure 2021127336

[式(I−2)中、Xは、重合性基を表す。
333は、単結合、置換基を有していてもよい炭素数1〜12のアルカンジイル基又は置換基を有していてもよい炭素数6〜18の2価の芳香族基炭化水素基を表し、該アルカンジイル基又は2価の芳香族基炭化水素基に含まれる−CH−は、−O−、−CO−、−CS−又は−NR334−に置き換わっていてもよい。
334は、水素原子又は炭素数1〜6のアルキル基を表す。
*は結合手を表す。] The group containing a polymerizable group is not particularly limited as long as it is a group having a polymerizable group at the terminal, and specific examples thereof include a group represented by the formula (I-2).
Figure 2021127336

[In formula (I-2), X 2 represents a polymerizable group.
R 333 is a single bond, an alcandiyl group having 1 to 12 carbon atoms which may have a substituent, or a divalent aromatic group hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. the stands, -CH 2 contained in the alkanediyl group or a divalent aromatic hydrocarbon group of - is, -O -, - CO -, - CS- , or -NR 334 - may be replaced with.
R 334 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
* Represents a bond. ]

で表される重合性基としては、上記した重合性基と同じものが挙げられ、好ましくはラジカル重合性基であり、より好ましくは(メタ)アクリロイル基である。 Examples of the polymerizable group represented by X 2 include the same polymerizable groups as those described above, preferably a radically polymerizable group, and more preferably a (meth) acryloyl group.

333で表される炭素数1〜12のアルカンジイル基としては、メチレン基、エチレン基、プロパン−1,3−ジイル基、ブタン−1,4−ジイル基、ペンタン−1,5−ジイル基及びヘキサン−1,6−ジイル基、エタン−1,1−ジイル基、プロパン−1,2−ジイル基、ブタン−1,3−ジイル基、2−メチルプロパン−1,3−ジイル基、2−メチルプロパン−1,2−ジイル基、ペンタン−1,4−ジイル基及び2−メチルブタン−1,4−ジイル基等が挙げられる。
333で表される炭素数1〜12のアルカンジイル基は、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、ヒドロキシ基等を有していてもよい。
Examples of the alkanediyl group having 1 to 12 carbon atoms represented by R 333 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. And hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2 -Methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like can be mentioned.
The arcandyl group having 1 to 12 carbon atoms represented by R 333 may have a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxy group or the like.

333で表される炭素数6〜18の2価の芳香族基炭化水素基としては、フェニレン基、ナフチレン基、フェニレンメチレン基等が挙げられる。
333で表される炭素数6〜18の2価の芳香族炭化水素基は、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、ヒドロキシ基等を有していてもよい。
334で表される炭素数1〜6のアルキル基としては、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、tert−ブチル基、sec−ブチル基、n−ペンチル基、イソペンチル基、n−ヘキシル基、イソヘキシル基等が挙げられる。
Examples of the divalent aromatic group hydrocarbon group having 6 to 18 carbon atoms represented by R 333 include a phenylene group, a naphthylene group, and a phenylene methylene group.
The divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 333 may have a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxy group or the like.
The alkyl group having 1 to 6 carbon atoms represented by R 334 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group and an n-pentyl group. , Isopentyl group, n-hexyl group, isohexyl group and the like.

環Wが有していてもよい置換基としては、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基、炭素数1〜12のアルキルチオ基又は炭素数1〜6のアルキル基で置換されていてもよいアミノ基であることが好ましい。 The substituent that the ring W 1 may have includes an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It is preferably an amino group that may be substituted with.

で表される1価の置換基は水素原子以外であれば特に限定されない。例えば、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基等が挙げられる。
なお、前記脂肪族炭化水素基又は前記芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−、−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
1A、R2A、R3A、R4A、R5A、R6A、R7A、R8A、R9A、R10A及びR11Aは、それぞれ独立して、水素原子又は炭素数1〜6のアルキル基を表す。
The monovalent substituent represented by R 3 is not particularly limited as long as it is a hydrogen atom. For example, even if it has a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxy group, a thiol group, a carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, and a substituent. Examples thereof include an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
Incidentally, -CH 2 contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group - and -CH = are each independently, -O -, - S -, - NR 1A -, - CO-, -CO-O-, -O-CO-, -O-CO-O-, -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A -CO-O-, -NR 6A -CO-NR 7A- , -CO-S-, -S-CO-S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O-CS -, -CS-O-, -NR 10A -CS-, -NR 11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO It may be replaced with 2-.
R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A and R 11A are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms. Represents.

で表される複素環基としては、ピリジル基、ピロリジル基、テトラヒドロフルフリル基、テトラヒドロチオフェン基、ピロール基、フリル基、チオフェノ基、ピぺリジン基、テトラヒドロピラニル基、テトラヒドロチオピラニル基、チアピラニル基、イミダゾリノ基、ピラゾール基、オキサゾール基、チアゾリル基、ジオキサニル基、モルホリノ基、チアジニル基、トリアゾール基、テトラゾール基、ジオキソラニル基、ピリダジニル基、ピリミジニル基、ピラジニル基、インドリル基、イソインドリル基、ベンゾイミダゾリル基、プリニル基、ベンゾトリアゾリル基、キノリニル基、イソキノリニル基、キナゾリニル基、キノキサリニル基、シンノリニル基、プテリジニル基、ベンゾピラニル基、アントリル基、アクリジニル基、キサンテニル基、カルバゾリル基、テトラセニル基、ポルフィニル基、クロリニル基、コリニル基、アデニル基、グアニル基、シトシル基、チミニル基、ウラシル基、キノリル基、チオフェニル基、イミダゾリル基、オキサゾリル基、チアゾリル基等の炭素数3〜16の脂肪族複素環及び炭素数3〜16の芳香族複素環基が挙げられ、ピロリジル基、ピぺリジル基、テトラヒドロフルフリル基、テトラヒドロピラニル基、テトラヒドロチオフェノ基、テトラヒドロチオピラニル基、ピリジル基であることが好ましい。 The heterocyclic group represented by R 3 includes a pyridyl group, a pyrrolidyl group, a tetrahydrofurfuryl group, a tetrahydrothiophene group, a pyrrole group, a furyl group, a thiopheno group, a piperidine group, a tetrahydropyranyl group and a tetrahydrothiopyranyl group. Group, thiapyranyl group, imidazolino group, pyrazole group, oxazole group, thiazolyl group, dioxanyl group, morpholino group, thiazinyl group, triazole group, tetrazole group, dioxolanyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, indolyl group, isoindrill group, Benomidazolyl group, prynyl group, benzotriazolyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, quinoxalinyl group, cinnolinyl group, pteridinyl group, benzopyranyl group, anthryl group, acridinyl group, xanthenyl group, carbazolyl group, tetrasenyl group, porphinyl group , Chlorinyl group, corinyl group, adenyl group, guanyl group, cytosyl group, timinyl group, uracil group, quinolyl group, thiophenyl group, imidazolyl group, oxazolyl group, thiazolyl group and other aliphatic heterocycles and carbons having 3 to 16 carbon atoms. Examples of the aromatic heterocyclic group having the number 3 to 16 include a pyrrolidyl group, a piperidyl group, a tetrahydrofurfuryl group, a tetrahydropyranyl group, a tetrahydrothiopheno group, a tetrahydrothiopyranyl group and a pyridyl group. ..

で表される炭素数1〜25の脂肪族炭化水素基としては、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、tert−ブチル基、sec−ブチル基、n−ペンチル基、イソペンチル基、n−ヘキシル基、イソヘキシル基、n−オクチル基、イソオクチル基、n−ノニル基、イソノニル基、n−デシル基、イソデシル基、n−ドデシル基、イソドデシル基、ウンデシル基、ラウリル基、ミリスチル基、セチル基、ステアリル基等の炭素数1〜25の直鎖又は分岐鎖のアルキル基:シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数3〜25のシクロアルキル基;シクロヘキシルメチル基等の炭素数4〜25のシクロアルキルアルキル基等が挙げられる。
で表される炭素数1〜25の脂肪族炭化水素基は、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜12のアルキル基であることがより好ましい。
で表される脂肪族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基、−SOH等が挙げられる。
Examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group and n. -Pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecil group, n-dodecyl group, isododecyl group, undecyl group, Linear or branched alkyl groups having 1 to 25 carbon atoms such as lauryl group, myristyl group, cetyl group and stearyl group: cycloalkyl group having 3 to 25 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Group: A cycloalkylalkyl group having 4 to 25 carbon atoms such as a cyclohexylmethyl group can be mentioned.
Aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R 3 is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon group substituents which may be possessed by represented by R 3, halogen atom, hydroxy group, nitro group, cyano group, -SO 3 H and the like.

で表される炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−,−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が置換される場合、−O−、−S−、−CO−O−又は−SO−で置換されることが好ましい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−O−で置換される場合、−O−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)で表されるアルコキシ基であることが好ましい。また、ポリエチレンオキシ基やポリプロピレンオキシ基等のポリアルキレンオキシ基であってもよい。−O−R’で表されるアルコキシ基としては、例えば、メトキシ基、エトキシ基、−OCF基、ポリエチレンオキシ基、ポリプロピレンオキシ基等が挙げられる。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−S−で置換される場合、−S−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)で表されるアルキルチオ基であることが好ましい。また、ポリエチレンチオ基やポリプロピレンチオ基等のポリアルキレンチオ基であってもよい。−S−R’で表されるアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、−SCF基、ポリエチレンチオ基、ポリプロピレンチオ基等が挙げられる。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−COO−で置換される場合、−COO−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)で表される基であることが好ましい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−SO−で置換された場合、−SO−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)で表される基であることが好ましく、−SOCHF基、−SOCHF基等であってもよい。
-CH 2- and -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R 3 are independently -O-, -S-, -NR 1A-, and -CO, respectively. -, -CO-O-, -O-CO-, -O-CO-O-, -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A -CO-O -, -NR 6A- CO-NR 7A- , -CO-S-, -S-CO-S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O -CS-, -CS-O-, -NR 10A -CS-, -NR 11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO 2 - may be substituted with.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted, -O-, -S-, -CO-O- or -SO 2- It is preferable to be replaced.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted with -O-, -OR'(R'has a halogen atom. It is preferably an alkoxy group represented by (representing an alkyl group having 1 to 24 carbon atoms). Further, it may be a polyalkyleneoxy group such as a polyethyleneoxy group or a polypropyleneoxy group. Examples of the alkoxy group represented by −O—R ′ include a methoxy group, an ethoxy group, three −OCF groups, a polyethyleneoxy group, a polypropyleneoxy group and the like.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted with -S-, -SR'(R'has a halogen atom. It is preferably an alkylthio group represented by (representing an alkyl group having 1 to 24 carbon atoms). Further, it may be a polyalkylene thio group such as a polyethylene thio group or a polypropylene thio group. Examples of the alkylthio group represented by −S—R ′ include methylthio group, ethylthio group, −SCF 3 group, polyethylene thio group, polypropylene thio group and the like.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted with -COO-, -COO-R'(R'has a halogen atom. It is preferably a group represented by (representing an alkyl group having 1 to 24 carbon atoms).
-CH 2 contained in the aliphatic hydrocarbon group in the 1 to 25 carbon atoms - and / or -CH = is -SO 2 - when it is substituted with, -SO 2 -R '(R' is have a halogen atom It is preferably a group represented by (representing an alkyl group having 1 to 24 carbon atoms), and may be a -SO 2 CHF 2 group, a -SO 2 CH 2 F group, or the like.

1A、R2A、R3A 4A、R5A、R6A、R7A、R8A、R9A、R10A及びR11Aで表される炭素数1〜6のアルキル基としては、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、tert−ブチル基、sec−ブチル基、n−ペンチル基、n−ヘキシル基、1−メチルブチル基等の直鎖又は分岐鎖状の炭素数1〜6のアルキルが挙げられる。 The alkyl groups having 1 to 6 carbon atoms represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A and R 11A include methyl groups. Linear or branched carbon such as ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 1-methylbutyl group. Alkyl numbers 1 to 6 can be mentioned.

で表される炭素数6〜18の芳香族炭化水素基としては、フェニル基、ナフチル基、アントラセニル基、テトラセニル基、ペンタセニル基、フェナントリル基、クリセニル基、トリフェニレニル基、テトラフェニル基、ピレニル基、ペリレニル基、コロネニル基、ビフェニル基等の炭素数6〜18のアリール基;ベンジル基、フェニルエチル基、ナフチルメチル基等の炭素数7〜18のアラルキル基、フェノキシエチル基、フェノキシジエチレングリコール基、フェノキシポリアルキレングリコール基のアリールアルコキシ基等が挙げられ、炭素数6〜18のアリール基であることが好ましく、フェニル基又はベンジル基であることがより好ましい。 Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 3 include a phenyl group, a naphthyl group, an anthracenyl group, a tetrasenyl group, a pentasenyl group, a phenanthryl group, a chrysenyl group, a triphenylenyl group, a tetraphenyl group and a pyrenyl group. , Aryl groups having 6 to 18 carbon atoms such as peryleneyl group, coronenyl group and biphenyl group; aralkyl groups having 7 to 18 carbon atoms such as benzyl group, phenylethyl group and naphthylmethyl group, phenoxyethyl group, phenoxydiethylene glycol group and phenoxy. Examples thereof include an arylalkoxy group of a polyalkylene glycol group, preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a benzyl group.

で表される炭素数6〜18の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子;ヒドロキシ基;チオール基;アミノ基;ニトロ基;シアノ基;−SOH基等が挙げられる。 The substituent that the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 3 may have is a halogen atom; a hydroxy group; a thiol group; an amino group; a nitro group; a cyano group; -SO 3. Examples include H group.

で表される炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−、−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が置換される場合、−O−又は−SO−で置換されることが好ましい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が−O−で置換される場合、フェノキシ基等の炭素数6〜26のアリールオキシ基;フェノキシエチル基、フェノキシジエチレングリコール基、フェノキシポリアルキレングリコール基のアリールアルコキシ基等であることが好ましい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が−SO−で置換される場合、当該芳香族炭化水素基は、−SO−R”(R”は炭素数6〜17のアリール基又は炭素数7〜17のアラルキル基を表す。)で表される基であることが好ましい。
-CH 2- and -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 3 are independently -O-, -S-, -NR 1A-, and -CO, respectively. -, -CO-O-, -O-CO-, -O-CO-O-, -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A-CO-O -, -NR 6A- CO-NR 7A- , -CO-S-, -S-CO-S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O -CS-, -CS-O-, -NR 10A -CS-, -NR 11A -CS-S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO 2 - may be substituted with.
If and / or -CH = is replaced, -O- or -SO 2 - - -CH 2 contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably substituted with.
When -CH 2- and / or -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted with -O-, an aryloxy group having 6 to 26 carbon atoms such as a phenoxy group; phenoxy. It is preferably an ethyl group, a phenoxydiethylene glycol group, an arylalkoxy group of a phenoxypolyalkylene glycol group, or the like.
When -CH 2- and / or -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted with -SO 2- , the aromatic hydrocarbon group is "-SO 2- R". (R "represents an aryl group having 6 to 17 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.) It is preferable that the group is represented by.

で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of the halogen atom represented by R 3 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

は、ニトロ基;シアノ基;ハロゲン原子;−OCF;−SCF;−SF;−SF;フルオロアルキル基(好ましくは、炭素数1〜25のフルオロアルキル基);フルオロアリール基(好ましくは、炭素数6〜18のフルオロアリール基);−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)であることが好ましく、シアノ基;フッ素原子;塩素原子;−OCF;−SCF;炭素数1〜12のフルオロアルキル基;−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)であることがより好ましく、シアノ基であることがさらに好ましい。 R 3 is a nitro group; a cyano group; a halogen atom; -OCF 3; -SCF 3; -SF 5; -SF 3; fluoroalkyl group (preferably, a fluoroalkyl group having 1 to 25 carbon atoms); fluoroaryl group (Preferably, a fluoroaryl group having 6 to 18 carbon atoms); -CO-O-R 111A or -SO 2- R 112A (R 111A and R 112A may each independently have a halogen atom. It represents a good alkyl group having 1 to 24 carbon atoms), preferably a cyano group; a fluorine atom; a chlorine atom; -OCF 3 ; -SCF 3 ; a fluoroalkyl group having 1 to 12 carbon atoms; -CO-O. More preferably, it is −R 111A or −SO 2- R 112A (R 111A and R 112A each independently represent an alkyl group having 1 to 24 carbon atoms which may have a halogen atom). , Cyan groups are more preferred.

化合物(X)の分子量は、好ましくは5000以下であり、より好ましくは3000以下であり、さらに好ましくは1000以下である。また、好ましくは100以上であり、より好ましくは200以上であり、さらに好ましくは300以上である。 The molecular weight of compound (X) is preferably 5000 or less, more preferably 3000 or less, and even more preferably 1000 or less. Further, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

化合物(X)は、波長370〜波長420nmに極大吸収を示すことが好ましい。化合物(X)の極大吸収波長(λmax)が波長370〜波長420nmであると、波長380〜波長400nmの紫外〜近紫外光を効率よく吸収することができる。化合物(X)のλmaxは好ましくは波長375〜波長415nmであり、より好ましくは波長375〜波長410nmであり、さらに好ましくは波長380〜波長400nmである。 Compound (X) preferably exhibits maximum absorption at a wavelength of 370 to 420 nm. When the maximum absorption wavelength (λmax) of the compound (X) is 370 to 420 nm, it is possible to efficiently absorb ultraviolet to near-ultraviolet light having a wavelength of 380 to 400 nm. The λmax of compound (X) preferably has a wavelength of 375 to 415 nm, more preferably a wavelength of 375 to 410 nm, and even more preferably a wavelength of 380 to 400 nm.

化合物(X)は、極大吸収波長(λmax)におけるグラム吸光係数εが50以上であることが好ましく、より好ましくは75以上、特に好ましくは100以上である。上限は特に制限されないが、一般的には100000以下である。
化合物(X)のλmaxにおけるグラム吸光係数εが50以上であると、少量の添加量であっても波長380nm〜400nmの紫外〜近紫外光を効率よく吸収することができる。
なお、グラム吸光係数の単位は、L/(g・cm)である。
化合物(X)は、ε(λmax)/ε(λmax+30nm)が5以上であることが好ましく、よく好ましくは10以上、特に好ましくは15以上である。上限は特に制限されないが、一般的には1000以下である。ε(λmax)は、化合物(X)の極大吸収波長におけるグラム吸光係数を表し、ε(λmax+30nm)は、化合物(X)の(極大吸収波長+30nm)におけるグラム吸光係数を表す。
ε(λmax)/ε(λmax+30nm)が5以上であると、波長420nm以上の副吸収を最小限にすることができるため、着色を生じにくい。
The compound (X) preferably has a gram absorption coefficient ε at the maximum absorption wavelength (λmax) of 50 or more, more preferably 75 or more, and particularly preferably 100 or more. The upper limit is not particularly limited, but is generally 100,000 or less.
When the gram extinction coefficient ε at λmax of compound (X) is 50 or more, ultraviolet to near-ultraviolet light having a wavelength of 380 nm to 400 nm can be efficiently absorbed even with a small amount of addition.
The unit of the gram extinction coefficient is L / (g · cm).
The compound (X) preferably has ε (λmax) / ε (λmax + 30 nm) of 5 or more, preferably 10 or more, and particularly preferably 15 or more. The upper limit is not particularly limited, but is generally 1000 or less. ε (λmax) represents the gram extinction coefficient of compound (X) at the maximum absorption wavelength, and ε (λmax + 30 nm) represents the gram extinction coefficient of compound (X) at the (maximum absorption wavelength + 30 nm).
When ε (λmax) / ε (λmax + 30 nm) is 5 or more, sub-absorption at a wavelength of 420 nm or more can be minimized, so that coloring is unlikely to occur.

化合物(X)は、重合性基を少なくとも1つ有していればよいが、1つ〜4つの重合性基を有することが好ましい。
化合物(X)は、式(X)で表される部分構造を少なくとも1つ有していればよいが、式(X)で表される部分構造を1〜4つ有していることが好ましい。
Compound (X) may have at least one polymerizable group, but preferably has 1 to 4 polymerizable groups.
Compound (X) may have at least one partial structure represented by the formula (X), but preferably has 1 to 4 partial structures represented by the formula (X). ..

化合物(X)は、さらに、電子求引性基を有することが好ましい。 Compound (X) preferably further has an electron-attracting group.

化合物(X)としては、式(I)で表される化合物〜式(IX)で表される化合物のいずれかであることが好ましく、式(I)で表される化合物であることがより好ましい。

Figure 2021127336

[式(I)〜式(IX)中、環W及びRは、上記と同じ意味を表す。
環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、それぞれ独立して、環の構成要素として少なくとも1つの二重結合を有する環構造を表す。環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、置換基を有していてもよい。
環W111は、構成要素として窒素原子を2つ有する複素環を表す。
環W112、環W113及び環W114は、それぞれ独立して、構成要素として窒素原子を1つ有する複素環を表す。
、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82、R92、R102及びR112は、それぞれ独立して、水素原子、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−NR12A−、−SO−、−CO−、−O−、−COO−、−OCO−、−CONR13A−、−NR14A−CO−、−S−、−SO−、−SO−、−CF−又は−CHF−に置換されていてもよい。
13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123は、それぞれ独立して、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−、−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
1A、R2A、R3A、R4A、R5A、R6A、R7A、R8A、R9A、R10A、R11A、R12A、R13A及びR14Aは、それぞれ独立して、水素原子又は炭素数1〜6のアルキル基を表す。
、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R25、R35、R75、R85及びR125は、それぞれ独立して、電子求引性基又は重合性基を含む基を表す。
及びRは互いに結合して環を形成してもよい。
41及びR42は互いに結合して環を形成してもよい。
51及びR52は互いに結合して環を形成してもよい。
61及びR62は互いに結合して環を形成してもよい。
91及びR92は互いに結合して環を形成してもよい。
101及びR102は互いに結合して環を形成してもよい。
111及びR112は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
12及びR13は互いに結合して環を形成してもよい。
42及びR43は互いに結合して環を形成してもよい。
52及びR53は互いに結合して環を形成してもよい。
62及びR63は互いに結合して環を形成してもよい。
72及びR73は互いに結合して環を形成してもよい。
82及びR83は互いに結合して環を形成してもよい。
92及びR93は互いに結合して環を形成してもよい。
102及びR103は互いに結合して環を形成してもよい。
112及びR113は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
14及びR15は互いに結合して環を形成してもよい。
24及びR25は互いに結合して環を形成してもよい。
34及びR35は互いに結合して環を形成してもよい。
74及びR85は互いに結合して環を形成してもよい。
84及びR85は互いに結合して環を形成してもよい。
124及びR125は互いに結合して環を形成してもよい。
及びRは、それぞれ独立して、2価の連結基を表す。
及びR126は、それぞれ独立して、単結合又は2価の連結基を表す。
及びR10は、それぞれ独立して、3価の連結基を表す。
11は、4価の連結基を表す。
ただし、式(I)においては、R、R、R及びRのうち少なくとも一つは重合性基を含む基を表す。
式(II)においては、R、R、R、R12、R13、R14及びR15のうち少なくとも一つは重合性基を含む基を表す。
式(III)のおいては、R、R、R23、R24及びR25のうち少なくとも一つは重合性基を含む基を表す。
式(IV)においては、R、R、R33、R34及びR35のうち少なくとも一つは重合性基を含む基を表す。
式(V)においては、R、R、R、R41、R42、R43及びR44のうち少なくとも一つは重合性基を含む基を表す。
式(VI)においては、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64のうち少なくとも一つは重合性基を含む基を表す。
式(VII)においては、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85のうち少なくとも一つは重合性基を含む基を表す。
式(VIII)においては、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114のうち少なくとも一つは重合性基を含む基を表す。
式(IX)においては、R、R、R、R123、R124及びR125のうち少なくとも一つは重合性基を含む基を表す。] The compound (X) is preferably any one of a compound represented by the formula (I) to a compound represented by the formula (IX), and more preferably a compound represented by the formula (I). ..
Figure 2021127336

[In formulas (I) to (IX), rings W 1 and R 3 have the same meanings as described above.
Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. Independently, it represents a ring structure having at least one double bond as a component of the ring. Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 are replaced. It may have a group.
Ring W 111 represents a heterocycle having two nitrogen atoms as a component.
Ring W 112 , ring W 113, and ring W 114 each independently represent a heterocycle having one nitrogen atom as a component.
R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 and R 112. Independently, hydrogen atom, heterocyclic group, halogen atom, nitro group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, Represents a group containing a polymerizable group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. -CH 2- and -CH = contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group are independently -NR 12A- , -SO 2- , -CO-, -O-,-, respectively. COO -, - OCO -, - CONR 13A -, - NR 14A -CO -, - S -, - SO -, - SO 2 -, - CF 2 - or may be substituted in -CHF-.
R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 are independently heterocyclic groups, halogen atoms and nitros, respectively. Group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, group containing polymerizable group, carbon number which may have substituent Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have 1 to 25 aliphatic hydrocarbon groups or substituents, and is contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group -CH. 2- and -CH = are independently -O-, -S-, -NR 1A- , -CO-, -CO-O-, -O-CO-, -O-CO-O-, respectively. -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A- CO-O-, -NR 6A- CO-NR 7A- , -CO-S-, -S-CO -S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O -CS-, -CS-O-, -NR 10A -CS-, -NR 11A-CS It may be substituted with -S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO 2-.
R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A and R 14A are independent hydrogen atoms, respectively. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.
R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 25 , R 35. , R 75 , R 85 and R 125 each independently represent a group containing an electron-attracting group or a polymerizable group.
R 1 and R 2 may be combined with each other to form a ring.
R 41 and R 42 may be combined with each other to form a ring.
R 51 and R 52 may be combined with each other to form a ring.
R 61 and R 62 may be combined with each other to form a ring.
R 91 and R 92 may be combined with each other to form a ring.
R 101 and R 102 may be combined with each other to form a ring.
R 111 and R 112 may be combined with each other to form a ring.
R 2 and R 3 may be combined with each other to form a ring.
R 12 and R 13 may be combined with each other to form a ring.
R 42 and R 43 may be combined with each other to form a ring.
R 52 and R 53 may be combined with each other to form a ring.
R 62 and R 63 may be combined with each other to form a ring.
R 72 and R 73 may be combined with each other to form a ring.
R 82 and R 83 may be combined with each other to form a ring.
R 92 and R 93 may be combined with each other to form a ring.
R 102 and R 103 may be combined with each other to form a ring.
R 112 and R 113 may be combined with each other to form a ring.
R 4 and R 5 may be combined with each other to form a ring.
R 14 and R 15 may be combined with each other to form a ring.
R 24 and R 25 may be combined with each other to form a ring.
R 34 and R 35 may be combined with each other to form a ring.
R 74 and R 85 may be combined with each other to form a ring.
R 84 and R 85 may be combined with each other to form a ring.
R 124 and R 125 may be combined with each other to form a ring.
R 6 and R 8 each independently represent a divalent linking group.
R 7 and R 126 each independently represent a single bond or a divalent linking group.
R 9 and R 10 each independently represent a trivalent linking group.
R 11 represents a tetravalent linking group.
However, in the formula (I), at least one of R 1 , R 2 , R 4 and R 5 represents a group containing a polymerizable group.
In formula (II), at least one of R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 represents a group containing a polymerizable group.
In formula (III), at least one of R 4 , R 5 , R 23 , R 24 and R 25 represents a group containing a polymerizable group.
In formula (IV), at least one of R 4 , R 5 , R 33 , R 34 and R 35 represents a group containing a polymerizable group.
In formula (V), at least one of R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 represents a group containing a polymerizable group.
In formula (VI), at least one of R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , R 54 , R 61 , R 62 , R 63 and R 64 contains a polymerizable group. Represents a group.
In formula (VII), at least one of R 2 , R 4 , R 5 , R 72 , R 73 , R 74 , R 75 , R 82 , R 83 , R 84 and R 85 contains a polymerizable group. Represents a group.
In formula (VIII), R 1 , R 2 , R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112 , R 113 and R. At least one of 114 represents a group containing a polymerizable group.
In formula (IX), at least one of R 2 , R 4 , R 5 , R 123 , R 124 and R 125 represents a group containing a polymerizable group. ]

環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、それぞれ独立して、環の構成要素として二重結合を1つ以上有する環であれば特に限定されない。環W〜環W13はそれぞれ単環であってもよいし、縮合環であってもよい。また、環W〜環W13は芳香族性を有さない環(脂肪族環)であってもよいし、芳香環であってもよい。
環W〜環W13は、環の構成要素としてヘテロ原子(例えば、酸素原子、硫黄原子、窒素原子等)を含む複素環であってもよい。
Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. The ring is not particularly limited as long as it independently has one or more double bonds as a component of the ring. Rings W 2 to W 13 may be monocyclic or fused rings, respectively. Further, the ring W 2 ~ ring W 13 may be the ring having no aromaticity (aliphatic ring) may be an aromatic ring.
Rings W 1 to W 13 may be heterocycles containing a hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a component of the ring.

環W〜環W13は、それぞれ独立して、環の構成要件として二重結合を1つ以上有するが、環Wに含まれる二重結合は、通常1〜4であり、1〜3であることが好ましく、1又は2であることがより好ましく、1つであることがさらに好ましい。 Rings W 2 to W 13 each independently have one or more double bonds as a constituent requirement of the ring, but the double bonds contained in ring W 1 are usually 1 to 4, and rings 1 to 3. Is preferable, 1 or 2 is more preferable, and 1 is more preferable.

環W〜環W13は、通常それぞれ独立して、炭素数5〜18の環であり、5〜7員環構造であることが好ましく、6員環構造であることがより好ましい。
環W〜環W13は、それぞれ独立して、単環であることが好ましい。また環W〜環W13はそれぞれ独立して芳香族性を有さない環であることが好ましい。
環W〜環W13は、それぞれ独立して、置換基を有していてもよい。前記置換基としては、環Wが有していてもよい置換基と同じものが挙げられる。
Rings W 2 to W 13 are usually independently rings having 5 to 18 carbon atoms, preferably having a 5- to 7-membered ring structure, and more preferably a 6-membered ring structure.
It is preferable that the rings W 2 to W 13 are independently and monocyclic. Further, it is preferable that the rings W 2 to W 13 are independent rings having no aromaticity.
Rings W 2 to W 13 may each independently have a substituent. Examples of the substituent group, ring W 1 is the same as the like as the substituent which may have.

環W〜環W13が有していてもよい置換基としては、それぞれ独立して、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基、炭素数1〜12のアルキルチオ基又は炭素数1〜6のアルキル基で置換されていてもよいアミノ基であることが好ましい。 The substituents that the rings W 2 to W 13 may have are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylthio group having 1 to 12 carbon atoms. Alternatively, it is preferably an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms.

環W〜環W13の具体例としては、環Wの具体例と同じものが挙げられる。 Specific examples of the rings W 2 to W 13 include the same as the specific examples of the ring W 1 .

環W111は、環の構成要素として窒素原子を2つ含む複素環である。環W111は、単環であってもよいし、縮合環であってもよいが、単環であることが好ましい。
環W111は、通常5〜10員環であり、5〜7員環であることが好ましく、5員環又は6員環であることがより好ましい。
環W111は、置換基を有していてもよい。環W111が有していてもよい置換基としては、ヒドロキシ基;チオール基;アルデヒド基;メチル基、エチル基等の炭素数1〜6のアルキル基;メトキシ基、エトキシ基等の炭素数1〜6のアルコキシ基;メチルチオ基、エチルチオ基等の炭素数1〜6のアルキルチオ基;アミノ基、メチルアミノ基、ジメチルアミノ基、メチルエチル等の炭素数1〜6のアルキル基で置換されていてもよいアミノ基;−CONR1f2f(R1f及びR2fはそれぞれ独立して水素原子又は炭素数1〜6のアルキルを表す。);−COSR3f(R3fは炭素数1〜6のアルキルを表す。);−CSSR4f(R4fは炭素数1〜6のアルキルを表す。);−CSOR5f(R5fは炭素数1〜6のアルキルを表す。);−SO6f(R6fは炭素数6〜12のアリール基又はフッ素原子を有していてもよい炭素数1〜6のアルキルを表す)等が挙げられる。
Ring W 111 is a heterocycle containing two nitrogen atoms as a component of the ring. The ring W 111 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
The ring W 111 is usually a 5- to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.
Ring W 111 may have a substituent. Examples of the substituent that the ring W 111 may have include a hydroxy group; a thiol group; an aldehyde group; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; and a carbon number 1 such as a methoxy group and an ethoxy group. Alkyl group of ~ 6; Alkylthio group having 1 to 6 carbon atoms such as methylthio group and ethylthio group; Alkyl group having 1 to 6 carbon atoms such as amino group, methylamino group, dimethylamino group and methylethyl are substituted. May amino group; -CONR 1f R 2f (R 1f and R 2f each independently represent a hydrogen atom or an alkyl having 1 to 6 carbon atoms); -COSR 3f (R 3f is an alkyl having 1 to 6 carbon atoms). the expressed); -. CSSR 4f (R 4f represents an alkyl of 1 to 6 carbon atoms); -. CSOR 5f (R 5f represents an alkyl of 1 to 6 carbon atoms); -. SO 2 R 6f (R 6f represents an alkyl having 1 to 6 carbon atoms which may have an aryl group having 6 to 12 carbon atoms or a fluorine atom) and the like.

環W111は、例えば下記に記載の環等が挙げられる。

Figure 2021127336
Examples of the ring W 111 include the rings described below.
Figure 2021127336

環W112、環W113及び環W114は、それぞれ独立して、環の構成要素として窒素原子を1つ含む複素環である。環W112、環W113及び環W114は、それぞれ独立して、単環であってもよいし、縮合環であってもよいが、単環であることが好ましい。
環W112、環W113及び環W114は、それぞれ独立して、通常5〜10員環であり、5〜7員環であることが好ましく、5員環又は6員環であることがより好ましい。
環W112、環W113及び環W114は、それぞれ独立して、置換基を有していてもよい。環W112、環W113及び環W114が有していてもよい置換基としては、環Wの置換基と同じものが挙げられる。
Ring W 112 , ring W 113, and ring W 114 are each independently a heterocycle containing one nitrogen atom as a component of the ring. The ring W 112 , the ring W 113, and the ring W 114 may be independently a single ring or a condensed ring, but are preferably a single ring.
The ring W 112 , the ring W 113, and the ring W 114 are independent, usually 5 to 10-membered rings, preferably 5 to 7-membered rings, and more preferably 5- or 6-membered rings. preferable.
Ring W 112 , ring W 113, and ring W 114 may each independently have a substituent. Ring W 112, As the ring W 113 and the substituent which may have ring W 114 is, include those similar to the substituents of the ring W 1.

環W112、環W113及び環W114は、例えば下記に記載の環等が挙げられる。

Figure 2021127336
Examples of the ring W 112 , the ring W 113, and the ring W 114 include the rings described below.
Figure 2021127336

、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R35、R75、R85及びR125で表される電子求引性基としては、それぞれ独立して、例えば、ハロゲン原子、ニトロ基、シアノ基、カルボキシ基、ハロゲン化アルキル基、ハロゲン化アリール基、−OCF、−SCF、−SF、−SF、−SOH、−SOH、−SOCF、−SOCHF、−SOCHF、式(X−1)で表される基が挙げられる。

Figure 2021127336

[式(X−1)中、R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。
は、−CO−、−COO−、−OCO−、−CS−、−CSS−、−COS−、−CSO−、−SO−、−NR223CO−又は−CONR224−を表す。
223及びR224は、それぞれ独立して、水素原子、炭素数1〜6のアルキル基又はフェニル基を表す。
*は結合手を表す。] R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 35 , R 75. , R 85 and R 125 are independent of each other, for example, halogen atom, nitro group, cyano group, carboxy group, alkyl halide group, aryl halide group, -OCF 3 Table with -SCF 3, -SF 5, -SF 3 , -SO 3 H, -SO 2 H, -SO 2 CF 3, -SO 2 CHF 2, -SO 2 CH 2 F, wherein (X-1) The groups to be used are mentioned.
Figure 2021127336

[In the formula (X-1), R222 is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or an aromatic having 6 to 18 carbon atoms which may have a substituent. Represents a group hydrocarbon group.
X 1 is, -CO -, - COO -, - OCO -, - CS -, - CSS -, - COS -, - CSO -, - SO 2 -, - NR 223 CO- or -CONR 224 - represents a.
R223 and R224 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
* Represents a bond. ]

ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
ハロゲン化アルキル基としては、例えば、トリフルオロメチル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロイソプロピル基、ペルフルオロブチル基、ペルフルオロsec−ブチル基、ペルフルオロtert−ブチル基、ペルフルオロペンチル基及びペルフルオロヘキシル基等のフルオロアルキル基等が挙げられ、ペルフルオロアルキル基であることが好ましい。ハロゲン化アルキル基の炭素数としては、通常1〜25であり、好ましくは炭素数1〜12である。ハロゲン化アルキル基は、直鎖であってもよいし、分岐鎖であってもよい。
ハロゲン化アリール基としては、フルオロフェニル基、クロロフェニル基、ブロモフェニル基等が挙げられフルオロアリール基であることが好ましく、ペルフルオロアリール基であることがより好ましい。ハロゲン化アリール基の炭素数としては、通常6〜18であり、好ましくは炭素数6〜12である。
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl halide group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluorohexyl group. Fluoroalkyl group and the like, and a perfluoroalkyl group is preferable. The alkyl halide group usually has 1 to 25 carbon atoms, preferably 1 to 12 carbon atoms. The alkyl halide group may be a straight chain or a branched chain.
Examples of the aryl halide group include a fluorophenyl group, a chlorophenyl group, a bromophenyl group and the like, and a fluoroaryl group is preferable, and a perfluoroaryl group is more preferable. The aryl halide group usually has 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

は、−COO−又は−SO−であることが好ましい。
222で表される炭素数1〜25のアルキル基としては、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、tert−ブチル基、sec−ブチル基、n−ペンチル基、n−ヘキシル基、1−メチルブチル基、3−メチルブチル基、n−オクチル基、n−デシル、2−へキシル−オクチル基等の直鎖又は分岐鎖状の炭素数1〜25のアルキル基が挙げられる。R222は、炭素数1〜12のアルキル基であることが好ましい。
222で表される炭素数1〜25のアルキル基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基等が挙げられる。
222で表される炭素数6〜18の芳香族炭化水素基としては、フェニル基、ナフチル基、アントラセニル基、ビフェニル基等の炭素数6〜18のアリール基;ベンジル基、フェニルエチル基、ナフチルメチル基等の炭素数7〜18のアラルキル基等が挙げられる。
222で表される炭素数6〜18の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基等が挙げられる。
223及びR224で表される炭素数1〜6のアルキル基としては、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、tert−ブチル基、sec−ブチル基、n−ペンチル基、n−ヘキシル基、1−メチルブチル基等の直鎖又は分岐鎖状の炭素数1〜6のアルキル基が挙げられる。
X 1 is, -COO- or -SO 2 - is preferably.
The alkyl group having 1 to 25 carbon atoms represented by R 222, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, tert- butyl group, sec- butyl group, n- pentyl group , N-Hexyl group, 1-methylbutyl group, 3-methylbutyl group, n-octyl group, n-decyl, 2-hexyl-octyl group and other linear or branched alkyl groups with 1 to 25 carbon atoms. Can be mentioned. R 222 is preferably an alkyl group having 1 to 12 carbon atoms.
Examples of the substituent that the alkyl group have 1 to 25 carbon atoms represented by R 222, halogen atom, hydroxy group, and the like.
The aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 222, a phenyl group, a naphthyl group, an anthracenyl group, an aryl group having 6 to 18 carbon atoms such as biphenyl group; a benzyl group, phenylethyl group, naphthyl Examples thereof include an aralkyl group having 7 to 18 carbon atoms such as a methyl group.
The aromatic hydrocarbon group substituents which may be possessed by 6 to 18 carbon atoms represented by R 222, halogen atom, hydroxy group, and the like.
The alkyl group having 1 to 6 carbon atoms represented by R 223 and R 224, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, tert- butyl group, sec- butyl radical, n Examples thereof include a linear or branched alkyl group having 1 to 6 carbon atoms such as a-pentyl group, an n-hexyl group and a 1-methylbutyl group.

、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R35、R75、R85及びR125で表される電子求引性基としては、それぞれ独立して、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基(好ましくは、炭素数1〜25のフルオロアルキル基)、フルオロアリール基(好ましくは、炭素数6〜18のフルオロアリール基)、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることが好ましく、ニトロ基、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることがより好ましく、シアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、ハロゲン原子を有していてもよい炭素数1〜25のアルキル基又はハロゲン原子を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることがさらに好ましい。 R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 35 , R 75. , R 85 and R 125 are independent of the nitro group, cyano group, halogen atom, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , fluoroalkyl. Group (preferably a fluoroalkyl group having 1 to 25 carbon atoms), fluoroaryl group (preferably a fluoroaryl group having 6 to 18 carbon atoms), -CO-O-R 222 or -SO 2- R 222 (R). 222 represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. It is preferable that a nitro group, a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO-O-R 222 or -SO 2- R 222 (R 222 is a hydrogen atom, It represents an alkyl group having 1 to 25 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent), more preferably cyano. Group, -CO-O-R 222 or -SO 2- R 222 (R 222 may have a hydrogen atom, a halogen atom, or may have an alkyl group or a halogen atom having 1 to 25 carbon atoms. It represents a good aromatic hydrocarbon group having 6 to 18 carbon atoms).

、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R35、R75、R85及びR125で表される重合性基を含む基としては、上記式(I−2)で表される基等が挙げられる。 R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 35 , R 75. , Examples of the group containing a polymerizable group represented by R 85 and R 125 include a group represented by the above formula (I-2).

及びRは互いに結合して環を形成してもよい。R及びRが互いに結合して形成する環は、単環であってもよいし、縮合環であってもよいが、単環であることが好ましい。また、R及びRが互いに結合して形成する環は、環の構成要素としてヘテロ原子(窒素原子、酸素原子、硫黄原子)等を含んでいてもよい。
及びRが互いに結合して形成する環は、通常3〜10員環であり、5〜7員環であることが好ましく、5員環又は6員環であることがより好ましい。
及びRが互いに結合して形成する環としては、例えば、下記に記載の構造が挙げられる。

Figure 2021127336

[式中、*は、炭素原子との結合手を表す。R1E〜R16Eは水素原子又は置換基を表す。] R 4 and R 5 may be combined with each other to form a ring. The ring formed by bonding R 4 and R 5 to each other may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. Further, the ring formed by bonding R 4 and R 5 to each other may contain a hetero atom (nitrogen atom, oxygen atom, sulfur atom) or the like as a component of the ring.
The ring formed by connecting R 4 and R 5 to each other is usually a 3 to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.
Examples of the ring formed by connecting R 4 and R 5 to each other include the structures described below.
Figure 2021127336

[In the formula, * represents a bond with a carbon atom. R 1E to R 16E represent a hydrogen atom or a substituent. ]

及びRが互いに結合して形成する環は、置換基(上記式中のR1E〜R16E)を有していてもよい。前記置換基は、例えば、環Wが有していてもよい置換基と同じものが挙げられる。前記R1E〜R16Eは、それぞれ独立して、好ましくは炭素数1〜12のアルキル基であり、より好ましくは炭素数1〜6のアルキル基であり、さらに好ましくはメチル基である。 The ring formed by bonding R 4 and R 5 to each other may have a substituent (R 1E to R 16E in the above formula). The substituents are, for example, ring W 1 is the same as the like as the substituent which may have. Each of the R 1E to R 16E is independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

14及びR15が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
24及びR25が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
34及びR35が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
74及びR75が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
84及びR85が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
124及びR125が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
Examples of the ring formed by connecting R 14 and R 15 to each other include the same ring formed by connecting R 4 and R 5 to each other.
Examples of the ring formed by connecting R 24 and R 25 to each other include the same ring formed by connecting R 4 and R 5 to each other.
Examples of the ring formed by connecting R 34 and R 35 to each other include the same ring formed by connecting R 4 and R 5 to each other.
Examples of the ring formed by connecting R 74 and R 75 to each other include the same ring formed by connecting R 4 and R 5 to each other.
Examples of the ring formed by connecting R 84 and R 85 to each other include the same ring formed by connecting R 4 and R 5 to each other.
Examples of the ring formed by connecting R 124 and R 125 to each other include the same ring formed by connecting R 4 and R 5 to each other.

、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される複素環基としては、Rで表される複素環基と同じものが挙げられ、ピロリジル基、ピぺリジル基、テトラヒドロフルフリル基、テトラヒドロピラニル基、テトラヒドロチオフェノ基、テトラヒドロチオピラニル基、ピリジル基であることが好ましい。 R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , R 112. Table with R 13, R 23, R 33 , R 43, R 53, R 63, R 73, R 83, R 93, R 103, examples of the heterocyclic group represented by R 113 and R 123, R 3 The same as the heterocyclic group to be used is mentioned, and a pyrrolidill group, a piperidyl group, a tetrahydrofurfuryl group, a tetrahydropyranyl group, a tetrahydrothiopheno group, a tetrahydrothiopyranyl group and a pyridyl group are preferable.

、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される炭素数1〜25の脂肪族炭化水素基としては、Rで表される炭素数1〜25の脂肪族炭化水素基と同じものが挙げられる。
前記炭素数1〜25の脂肪族炭化水素基は、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜12のアルキル基であることがより好ましい。
R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , R 112. , R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 , aliphatic hydrocarbons having 1 to 25 carbon atoms. the groups include the same as the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R 3.
The aliphatic hydrocarbon group having 1 to 25 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される脂肪族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基、ニトロ基、シアノ基、−SOH等が挙げられる。 R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , R 112. , R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123. as also substituent, a halogen atom, hydroxy group, nitro group, cyano group, -SO 3 H and the like.

また、R、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−NR12A−、−SO−、−CO−、−O−、−COO−、−OCO−、−CONR13A−、−NR14A−CO−、−S−、−SO−、−SO−、−CF−又は−CHF−に置換されていてもよい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が置換される場合、−O−、−S−、−CO−O−又は−SO−で置換されることが好ましい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−O−で置換される場合、−O−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基)で表されるアルコキシ基であることが好ましい。また、ポリエチレンオキシ基やポリプロピレンオキシ基等のポリアルキレンオキシ基であってもよい。−O−R’で表されるアルコキシ基としては、例えば、メトキシ基、エトキシ基、−OCF基、ポリエチレンオキシ基、ポリプロピレンオキシ基等が挙げられる。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−S−で置換される場合、−S−R’(R’はハロゲン原子を有していてもよい炭素数1〜24のアルキル基)で表されるアルキルチオ基であることが好ましい。また、ポリエチレンチオ基やポリプロピレンチオ基等のポリアルキレンチオ基であってもよい。−S−R’で表されるアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、−SCF基、ポリエチレンチオ基、ポリプロピレンチオ基等が挙げられる。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−COO−で置換される場合、−COO−R’(Rはハロゲン原子を有していてもよい炭素数1〜24のアルキル基)で表される基であることが好ましい。
前記炭素数1〜25の脂肪族炭化水素基に含まれる−CH−及び/又は−CH=が−SO−で置換される場合、−SO−R’(Rはハロゲン原子を有していてもよい炭素数1〜24のアルキル基)で表される基であることが好ましく、−SOCHF基、−SOCHF基等であってもよい。
In addition, R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , Aliphatic compounds with 1 to 25 carbon atoms represented by R 112 , R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123. -CH 2- and -CH = contained in the hydrocarbon group are independently -NR 12A- , -SO 2- , -CO-, -O-, -COO-, -OCO-, -CONR 13A. -, - NR 14A -CO -, - S -, - SO -, - SO 2 -, - CF 2 - or may be substituted in -CHF-.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted, -O-, -S-, -CO-O- or -SO 2- It is preferable to be replaced.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted with -O-, -OR'(R'has a halogen atom. It is preferably an alkoxy group represented by an alkyl group having 1 to 24 carbon atoms. Further, it may be a polyalkyleneoxy group such as a polyethyleneoxy group or a polypropyleneoxy group. Examples of the alkoxy group represented by −O—R ′ include a methoxy group, an ethoxy group, three −OCF groups, a polyethyleneoxy group, a polypropyleneoxy group and the like.
When -CH 2- and / or -CH = contained in the aliphatic hydrocarbon group having 1 to 25 carbon atoms is substituted with -S-, -SR'(R'has a halogen atom. It is preferably an alkylthio group represented by an alkyl group having 1 to 24 carbon atoms. Further, it may be a polyalkylene thio group such as a polyethylene thio group or a polypropylene thio group. Examples of the alkylthio group represented by −S—R ′ include methylthio group, ethylthio group, −SCF 3 group, polyethylene thio group, polypropylene thio group and the like.
-CH 2 contained in the aliphatic hydrocarbon group in the 1 to 25 carbon atoms - if and / or -CH = is replaced by -COO-, -COO-R '(R ' is substituted by a halogen atom It is preferably a group represented by an alkyl group having 1 to 24 carbon atoms.
And / or -CH = is -SO 2 - - -CH 2 contained in the aliphatic hydrocarbon group in the 1 to 25 carbon atoms if substituted with, -SO 2 -R '(R' is have a halogen atom It is preferably a group represented by an alkyl group having 1 to 24 carbon atoms, which may be used, and may be -SO 2 CHF 2 groups, -SO 2 CH 2 F group, or the like.

12A、R13A及びR14Aで表される炭素数1〜6のアルキル基をとしては、R1Aで表される炭素数1〜6のアルキル基と同じものが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 12A , R 13A and R 14A include the same alkyl group having 1 to 6 carbon atoms represented by R 1A.

、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される炭素数6〜18の芳香族炭化水素基としては、Rで表される炭素数6〜18の芳香族炭化水素基と同じものが挙げられ、炭素数6〜18のアリール基であることが好ましく、フェニル基又はベンジル基であることがより好ましい。
前記炭素数6〜18の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子;ヒドロキシ基;チオール基;アミノ基;ニトロ基;シアノ基;−SOH基等が挙げられる。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−NR12A−、−SO−、−CO−、−O−、−COO−、−OCO−、−CONR13A−、−NR14A−CO−、−S−、−SO−、−SO−、−CF−又は−CHF−に置換されていてもよい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が置換される場合、−O−又は−SO−で置換されることが好ましい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が−O−で置換される場合、フェノキシ基等の炭素数6〜26のアリールオキシ基;フェノキシエチル基、フェノキシジエチレングリコール基、フェノキシポリアルキレングリコール基のアリールアルコキシ基等であることが好ましい。
前記炭素数6〜18の芳香族炭化水素基に含まれる−CH−及び/又は−CH=が−SO−で置換される場合、当該芳香族炭化水素基は、−SO−R”(R”は炭素数6〜17のアリール基又は炭素数7〜17のアラルキル基を表す。)で表される基であることが好ましい。
R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , R 112. , R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 , aromatic hydrocarbons with 6 to 18 carbon atoms. it the group, the same ones listed as the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R 3, is an aryl group having 6 to 18 carbon atoms is preferably a phenyl group or a benzyl group Is more preferable.
The aromatic hydrocarbon group substituents which may be possessed by the 6 to 18 carbon atoms, a halogen atom; include such -SO 3 H group; hydroxy group; a thiol group; an amino group; a nitro group; a cyano group Be done.
-CH 2- and -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms are independently -NR 12A- , -SO 2- , -CO-, -O-, and -COO, respectively. -, - OCO -, - CONR 13A -, - NR 14A -CO -, - S -, - SO -, - SO 2 -, - CF 2 - or may be substituted in -CHF-.
If and / or -CH = is replaced, -O- or -SO 2 - - -CH 2 contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably substituted with.
When -CH 2- and / or -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted with -O-, an aryloxy group having 6 to 26 carbon atoms such as a phenoxy group; phenoxy. It is preferably an ethyl group, a phenoxydiethylene glycol group, an arylalkoxy group of a phenoxypolyalkylene glycol group, or the like.
When -CH 2- and / or -CH = contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms is substituted with -SO 2- , the aromatic hydrocarbon group is "-SO 2- R". (R "represents an aryl group having 6 to 17 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.) It is preferable that the group is represented by.

、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82 92、R102、R112、R13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123で表される重合性基を含む基としては、上記式(I−2)で表される基等が挙げられる。 R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 , R 112. , R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123. Examples thereof include a group represented by the formula (I-2).

及びRは、互いに連結して環を形成してもよい。R及びRが連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R及びRが連結して形成される環と環Wとで縮合環を形成する。R及びRが連結して形成される環と環Wとが形成する縮合環としては、具体的には、以下に記載の環構造が挙げられる。

Figure 2021127336
R 2 and R 3 may be connected to each other to form a ring. As a component of the ring formed by connecting R 2 and R 3 , a double bond constituting the ring W 1 is included. That is, a fused ring is formed by the ring formed by connecting R 2 and R 3 and the ring W 1 . Specific examples of the fused ring formed by the ring formed by connecting R 2 and R 3 and the ring W 1 include the ring structure described below.
Figure 2021127336

12及びR13は互いに結合して形成する環は、R12及びR13が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R12及びR13が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
42及びR43は互いに結合して形成する環は、R42及びR43が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R42及びR43が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
52及びR53は互いに結合して形成する環は、R52及びR53が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R52及びR53が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
62及びR63は互いに結合して形成する環は、R62及びR63が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R62及びR63が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
72及びR73は互いに結合して形成する環は、R72及びR73が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R72及びR73が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
82及びR83は互いに結合して形成する環は、R82及びR83が連結して形成される環の構成要素として、環Wを構成する二重結合を含む。つまり、R82及びR83が互いに結合して形成する環と環Wとで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
92及びR93は互いに結合して形成する環は、R92及びR93が連結して形成される環の構成要素として、環W12を構成する二重結合を含む。つまり、R92及びR93が互いに結合して形成する環と環W12とで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
102及びR103は互いに結合して形成する環は、R102及びR103が連結して形成される環の構成要素として、環W10を構成する二重結合を含む。つまり、R102及びR103が互いに結合して形成する環と環W10とで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
112及びR113は互いに結合して形成する環は、R112及びR113が連結して形成される環の構成要素として、環W11を構成する二重結合を含む。つまり、R112及びR113が互いに結合して形成する環と環W11とで縮合環を形成する。具体的には、R及びRが連結して形成される環と環Wとが形成する縮合環と同じものが挙げられる。
The ring formed by connecting R 12 and R 13 to each other includes a double bond forming ring W 2 as a component of the ring formed by connecting R 12 and R 13. That is, a fused ring is formed by a ring formed by combining R 12 and R 13 with each other and a ring W 2. Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 42 and R 43 to each other includes a double bond forming ring W 5 as a component of the ring formed by connecting R 42 and R 43. That is, a fused ring is formed by the ring formed by combining R 42 and R 43 with each other and the ring W 5 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 52 and R 53 to each other includes a double bond forming ring W 6 as a component of the ring formed by connecting R 52 and R 53. That is, a fused ring is formed by the ring formed by combining R 52 and R 53 with each other and the ring W 6 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 62 and R 63 to each other includes a double bond forming ring W 7 as a component of the ring formed by connecting R 62 and R 63. That is, a fused ring is formed by the ring formed by combining R 62 and R 63 with each other and the ring W 7 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 72 and R 73 to each other includes a double bond forming ring W 8 as a component of the ring formed by connecting R 72 and R 73. That is, a fused ring is formed by the ring formed by combining R 72 and R 73 with each other and the ring W 8 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 82 and R 83 to each other includes a double bond forming ring W 9 as a component of the ring formed by connecting R 82 and R 83. That is, a fused ring is formed by the ring formed by combining R 82 and R 83 with each other and the ring W 9 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 92 and R 93 to each other includes a double bond forming ring W 12 as a component of the ring formed by connecting R 92 and R 93. That is, a fused ring is formed by the ring formed by combining R 92 and R 93 with each other and the ring W 12 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 102 and R 103 to each other includes a double bond forming ring W 10 as a component of the ring formed by connecting R 102 and R 103. That is, a fused ring is formed by the ring formed by combining R 102 and R 103 with each other and the ring W 10 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.
The ring formed by connecting R 112 and R 113 to each other includes a double bond forming ring W 11 as a component of the ring formed by connecting R 112 and R 113. That is, a fused ring is formed by the ring formed by combining R 112 and R 113 with each other and the ring W 11 . Specifically, the same ring as the fused ring formed by the ring W 1 formed by connecting R 2 and R 3 can be mentioned.

及びRは、互いに結合して環を形成してもよい。R及びRが互いに結合して形成する環は、環の構成要素として窒素原子を1つ含む複素環である。R及びRが互いに結合して形成する環は、単環であってもよいし、縮合環であってもよいが、単環であることが好ましい。R及びRが互いに結合して形成する環は、環の構成要素としてさらにヘテロ原子(酸素原子、硫黄原子、窒素原子等)を含んでいてもよい。R及びRが互いに結合して形成する環は、芳香族性を有さない複素環(脂肪族複素環)であることが好ましく、不飽和結合を有さない脂肪族複素環であることがより好ましい。
及びRが互いに結合して形成する環は、通常3〜10員環であり、5〜7員環であることが好ましく、5員環又は6員環であることがより好ましい。
及びRが互いに結合して形成する環は置換基を有していてもよく、例えば、環W〜環W12が有していてもよい置換基と同じものが挙げられる。
及びRが互いに結合して形成する環としては、例えば、下記に記載の環が挙げられる。

Figure 2021127336
R 1 and R 2 may be combined with each other to form a ring. The ring formed by bonding R 1 and R 2 to each other is a heterocycle containing one nitrogen atom as a component of the ring. The ring formed by bonding R 1 and R 2 to each other may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. The ring formed by bonding R 1 and R 2 to each other may further contain a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.) as a component of the ring. The ring formed by bonding R 1 and R 2 to each other is preferably a heterocycle having no aromaticity (aliphatic heterocycle), and is an aliphatic heterocycle having no unsaturated bond. Is more preferable.
The ring formed by bonding R 1 and R 2 to each other is usually a 3 to 10-membered ring, preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.
The ring formed by bonding R 1 and R 2 to each other may have a substituent, and examples thereof include the same substituents that the rings W 2 to W 12 may have.
Examples of the ring formed by combining R 1 and R 2 with each other include the rings described below.
Figure 2021127336

41及びR42が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
51及びR52が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
61及びR62が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
91及びR92が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
101及びR102が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
111及びR112が互いに結合して形成する環は、R及びRが互いに結合して形成する環と同じものが挙げられる。
Examples of the ring formed by connecting R 41 and R 42 to each other include the same ring formed by connecting R 1 and R 2 to each other.
Examples of the ring formed by connecting R 51 and R 52 to each other include the same ring formed by connecting R 1 and R 2 to each other.
Examples of the ring formed by connecting R 61 and R 62 to each other include the same ring formed by connecting R 1 and R 2 to each other.
Examples of the ring formed by connecting R 91 and R 92 to each other include the same ring formed by connecting R 1 and R 2 to each other.
Examples of the ring formed by connecting R 101 and R 102 to each other include the same ring formed by connecting R 1 and R 2 to each other.
Examples of the ring formed by connecting R 111 and R 112 to each other include the same ring formed by connecting R 1 and R 2 to each other.

、R、R及びR126で表される2価の連結基としては、置換基を有していてもよい炭素数1〜18の2価の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の2価の芳香族炭化水素基等が挙げられる。前記2価の脂肪族炭化水素基及び2価の芳香族炭化水素基に含まれる−CH−は、−O−、−S−、−NR1B−(R1Bは水素原子又は炭素数1〜6のアルキル基を表す。)、−CO−、−SO−、−SO−、−PO−で置換されていてもよい。
また、前記2価の脂肪族炭化水素基及び2価の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基、アミノ基等が挙げられる。
As the divalent linking group represented by R 6 , R 7 , R 8 and R 126 , a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituent which may have a substituent is used. Examples thereof include a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may be possessed. -CH 2- contained in the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group is -O-, -S-, -NR 1B- (R 1B is a hydrogen atom or 1 to 1 carbon atoms. Represents an alkyl group of 6), -CO-, -SO 2- , -SO-, -PO 3- may be substituted.
Examples of the substituent that the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may have include a halogen atom, a hydroxy group, a carboxy group, an amino group and the like.

、R、R及びR126で表される2価の連結基は、それぞれ独立して、置換基を有していてもよい炭素数1〜18の2価の脂肪族炭化水素基であることが好ましく、置換基を有していてもよい炭素数1〜12の2価の脂肪族炭化水素基であることがより好ましい。 The divalent linking groups represented by R 6 , R 7 , R 8 and R 126 are each independently divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. It is more preferable that it is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

、R、R及びR126で表される2価の連結基の具体例としては、以下に記載の連結基が挙げられる。式中、*は結合手を表す。

Figure 2021127336
Specific examples of the divalent linking groups represented by R 6 , R 7 , R 8 and R 126 include the linking groups described below. In the formula, * represents a bond.
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

、R及びR126は、それぞれ独立して、置換基を有していてもよい炭素数1〜18の2価の脂肪族炭化水素基又は下記式で表される連結基であることが好ましく、置換基を有していてもよい炭素数1〜12の2価の脂肪族炭化水素基又は下記式で表される連結基であることがより好ましい。

Figure 2021127336
R 6 , R 7 and R 126 are each independently a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or a linking group represented by the following formula. Is preferable, and a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or a linking group represented by the following formula is more preferable.
Figure 2021127336

は、置換基を有していてもよい炭素数1〜18の2価の脂肪族炭化水素基又は下記式で表される連結基であることが好ましい。

Figure 2021127336
R 8 is preferably a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or a linking group represented by the following formula.
Figure 2021127336

及びR10で表される3価の連結基としては、それぞれ独立して、置換基を有していてもよい炭素数1〜18の3価の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の3価の芳香族炭化水素基が挙げられる。前記3価の脂肪族炭化水素基に含まれる−CH−は、−O−、−S−、−CS−、−CO−、−SO−、−NR11B(R11Bは水素原子又は炭素数1〜6のアルキル基を表す。)−で置き換わっていてもよい。
前記3価の脂肪族炭化水素基及び前記3価の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基、アミノ基等が挙げられる。
及びR10で表される3価の連結基は、それぞれ独立して、置換基を有していてもよい炭素数1〜12の3価の脂肪族炭化水素基であることが好ましい。
及びR10で表される3価の連結基の具体例としては、以下に記載の連結基が挙げられる。

Figure 2021127336
As the trivalent linking group represented by R 9 and R 10 , each independently has a trivalent aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituent which may have a substituent. Examples thereof include trivalent aromatic hydrocarbon groups having 6 to 18 carbon atoms which may be used. -CH 2- contained in the trivalent aliphatic hydrocarbon group is -O-, -S-, -CS-, -CO-, -SO- , -NR 11B (R 11B is a hydrogen atom or the number of carbon atoms). Represents an alkyl group of 1-6.)-May be replaced by −.
Examples of the substituent that the trivalent aliphatic hydrocarbon group and the trivalent aromatic hydrocarbon group may have include a halogen atom, a hydroxy group, a carboxy group, an amino group and the like.
The trivalent linking group represented by R 9 and R 10 is preferably a trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, which may independently have a substituent.
Specific examples of the trivalent linking groups represented by R 9 and R 10 include the linking groups described below.
Figure 2021127336

11で表される4価の連結基としては、置換基を有していてもよい炭素数1〜18の4価の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の4価の芳香族炭化水素基が挙げられる。前記4価の脂肪族炭化水素基に含まれる−CH−は、−O−、−S−、−CS−、−CO−、−SO−、−NR11C−(R11Cは水素原子又は炭素数1〜6のアルキル基を表す。)で置き換わっていてもよい。
前記4価の脂肪族炭化水素基及び前記4価の芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基、アミノ基等が挙げられる。
R11で表される4価の連結基は、それぞれ独立して、置換基を有していてもよい炭素数1〜12の4価の脂肪族炭化水素基であることが好ましい。
11で表される4価の連結基の具体例としては、以下に記載の連結基が挙げられる。

Figure 2021127336
The tetravalent linking group represented by R 11, carbon atoms which may have a tetravalent aliphatic hydrocarbon group or a substituent having 1 to 18 carbon atoms which may have a substituent 6 Examples include ~ 18 tetravalent aromatic hydrocarbon groups. -CH 2- contained in the tetravalent aliphatic hydrocarbon group is -O-, -S-, -CS-, -CO-, -SO- , -NR 11C- (R 11C is a hydrogen atom or carbon. It may be replaced by (representing an alkyl group of numbers 1 to 6).
Examples of the substituent that the tetravalent aliphatic hydrocarbon group and the tetravalent aromatic hydrocarbon group may have include a halogen atom, a hydroxy group, a carboxy group, an amino group and the like.
The tetravalent linking group represented by R11 is preferably a tetravalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, which may independently have a substituent.
Specific examples of the tetravalent linking group represented by R 11 include the linking groups described below.
Figure 2021127336

式(I)で表される化合物において、R、R、R及びRのうち少なくとも一つは重合性基を含む基である。なお、R、R、R及びRから選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R及びRのうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (I), at least one of R 1 , R 2 , R 4 and R 5 is a group containing a polymerizable group. When two groups selected from R 1 , R 2 , R 4 and R 5 form a ring (for example, when R 1 and R 2 are bonded to each other to form a ring), the formed ring is formed. If has a polymerizable group, it is considered that at least one of R 1 , R 2 , R 4 and R 5 contains a polymerizable group.

式(II)で表される化合物においては、R、R、R、R12、R13、R14及びR15のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R12、R13、R14及びR15から選ばれる2つの基が環を形成した場合(例えば、R14及びR15が互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R、R12、R13、R14及びR15のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (II), at least one of R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 is a group containing a polymerizable group. When two groups selected from R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 form a ring (for example, R 14 and R 15 are bonded to each other to form a ring). If the formed ring has a polymerizable group, at least one of R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 contains a polymerizable group. Consider it as.

式(III)で表される化合物においては、R、R、R23、R24及びR25のうち少なくとも一つは重合性基を含む基である。なお、R、R、R23、R24及びR25から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R23、R24及びR25のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (III), at least one of R 4 , R 5 , R 23 , R 24 and R 25 is a group containing a polymerizable group. When two groups selected from R 4 , R 5 , R 23 , R 24 and R 25 form a ring (for example, when R 4 and R 5 combine with each other to form a ring), the ring is formed. If the resulting ring has a polymerizable group, then at least one of R 4 , R 5 , R 23 , R 24 and R 25 is considered to contain a polymerizable group.

式(IV)で表される化合物においては、R、R、R33、R34及びR35のうち少なくとも一つは重合性基を含む基である。なお、R、R、R33、R34及びR35から選ばれる2つの基が環を形成した場合(例えば、R34及びR35が互いに結合して環を形成する場合)は、形成された環が重合性基を有していればR、R、R33、R34及びR35のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (IV), at least one of R 4 , R 5 , R 33 , R 34 and R 35 is a group containing a polymerizable group. When two groups selected from R 4 , R 5 , R 33 , R 34 and R 35 form a ring (for example, when R 34 and R 35 combine with each other to form a ring), the ring is formed. If the resulting ring has a polymerizable group, it is considered that at least one of R 4 , R 5 , R 33 , R 34 and R 35 contains a polymerizable group.

式(V)で表される化合物においては、R、R、R、R41、R42、R43及びR44のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R41、R42、R43及びR44から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R、R41、R42、R43及びR44のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (V), at least one of R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 is a group containing a polymerizable group. When two groups selected from R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 form a ring (for example, R 1 and R 2 are bonded to each other to form a ring). If the formed ring has a polymerizable group, at least one of R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 contains a polymerizable group. Consider it as.

式(VI)で表される化合物においては、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (VI), at least one of R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , R 54 , R 61 , R 62 , R 63 and R 64 is used. It is a group containing a polymerizable group. When two groups selected from R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , R 54 , R 61 , R 62 , R 63 and R 64 form a ring (for example, R). (When 1 and R 2 are bonded to each other to form a ring), if the formed ring has a polymerizable group, R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , At least one of R 54 , R 61 , R 62 , R 63 and R 64 is considered to contain a polymerizable group.

式(VII)で表される化合物においては、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by formula (VII), at least one of R 2, R 4, R 5 , R 72, R 73, R 74, R 75, R 82, R 83, R 84 and R 85 is It is a group containing a polymerizable group. When two groups selected from R 2 , R 4 , R 5 , R 72 , R 73 , R 74 , R 75 , R 82 , R 83 , R 84 and R 85 form a ring (for example, R). (When 4 and R 5 are bonded to each other to form a ring), if the formed ring has a polymerizable group, R 2 , R 4 , R 5 , R 72 , R 73 , R 74 , At least one of R 75 , R 82 , R 83 , R 84 and R 85 is considered to contain a polymerizable group.

式(VIII)で表される化合物においては、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)は、形成された環が重合性基を有していれば、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114のうち少なくとも一つが重合性基を含むとみなす。 In the compound represented by the formula (VIII), R 1 , R 2 , R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112. , R 113 and R 114 are groups containing a polymerizable group. 2 selected from R 1 , R 2, R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112 , R 113 and R 114. When one group forms a ring (for example, when R 1 and R 2 are bonded to each other to form a ring), if the formed ring has a polymerizable group, R 1 , R 2 , At least one of R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112 , R 113 and R 114 is considered to contain a polymerizable group. ..

式(IX)で表される化合物においては、R、R、R、R124及びR125のうち少なくとも一つは重合性基を含む基である。なお、R、R、R、R124及びR125から選ばれる2つの基が環を形成した場合(例えば、R及びRが互いに結合して環を形成する場合)、形成された環が重合性基を有していれば、R、R、R、R124及びR125のうち少なくとも一つは重合性基を含むとみなす。 In the compound represented by the formula (IX), at least one of R 2 , R 4 , R 5 , R 124 and R 125 is a group containing a polymerizable group. When two groups selected from R 2 , R 4 , R 5 , R 124 and R 125 form a ring (for example, when R 4 and R 5 combine with each other to form a ring), they are formed. If the ring has a polymerizable group, at least one of R 2 , R 4 , R 5 , R 124 and R 125 is considered to contain a polymerizable group.

は、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜10のアルキル基であることがより好ましい。
は、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜10のアルキル基であることがより好ましい。
とRとは互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、ピロリジン環またはピペリジン環構造を有することが特に好ましい。
は、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基(好ましくは、炭素数1〜25のフルオロアルキル基)、フルオロアリール基(好ましくは、炭素数6〜18のフルオロアリール基)、−CO−O−R111A又は−SO−R112A(R111A及びR112Aはそれぞれ独立して炭素数1〜24のアルキル基を表す。)であることが好ましく、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)であることがより好ましく、シアノ基、フッ素原子であることがさらに好ましく、特に好ましくはシアノ基である。
及びRは、それぞれ独立して、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基、フルオロアリール基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることが好ましく、ニトロ基、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることがより好ましく、シアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることがさらに好ましく、シアノ基であることが特に好ましい。
及びRのうちの少なくとも一方がシアノ基であることが好ましい。
がシアノ基であり、かつ、Rがシアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)であることが好ましい。
R 1 is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
R 2 is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
R 1 and R 2 are preferably linked to each other to form a ring, more preferably an aliphatic heterocycle, further preferably an aliphatic heterocycle having no unsaturated bond, and pyrrolidine. It is particularly preferred to have a ring or piperidine ring structure.
R 3 is a nitro group, a cyano group, a halogen atom, -OCF 3, -SCF 3, -SF 5, -SF 3, a fluoroalkyl group (preferably, a fluoroalkyl group having 1 to 25 carbon atoms), fluoroaryl group (Preferably, a fluoroaryl group having 6 to 18 carbon atoms), -CO-OR 111A or -SO 2- R 112A (R 111A and R 112A each independently represent an alkyl group having 1 to 24 carbon atoms. ), Preferably, cyano group, fluorine atom, chlorine atom, -OCF 3 , -SCF 3 , fluoroalkyl group, -CO-O-R 111A or -SO 2- R 112A (R 111A and R 112A). , Each independently represents an alkyl group having 1 to 24 carbon atoms which may have a halogen atom.) It is more preferably a cyano group and a fluorine atom, and particularly preferably cyano. It is a group.
R 4 and R 5 are independently nitro group, cyano group, halogen atom, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , fluoroalkyl group, fluoroaryl group, -CO-O-, respectively. R 222 or -SO 2 -R 222 (R 222 represents a hydrogen atom, a good 25 carbon atoms which may have a substituent group or a substituent of the optionally also be C 6-18 has It represents an aromatic hydrocarbon group), preferably a nitro group, a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO-O-R 222 or -SO 2. -R 222 ( R222 is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. (Represented) is more preferable, and it is more preferably a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 may have a hydrogen atom and a substituent and has 1 to 25 carbon atoms. It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have an alkyl group or a substituent.), And a cyano group is particularly preferable.
It is preferable that at least one of R 4 and R 5 is a cyano group.
R 4 is a cyano group, and R 5 is a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 may have a hydrogen atom and a substituent and has 1 carbon number. It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have an alkyl group of ~ 25 or a substituent.).

及びRは、同じ構造を有することが好ましい。
及びRは、ともにシアノ基であることが好ましい。
R 4 and R 5 preferably have the same structure.
It is preferable that both R 4 and R 5 are cyano groups.

41、R51、R61、R91、R101及びR111は、それぞれ独立して、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜10のアルキル基であることがより好ましい。
12、R42、R52、R62、R72、R82、R92、R102及びR112は、それぞれ独立して、炭素数1〜15のアルキル基であることが好ましく、炭素数1〜10のアルキル基であることがより好ましい。
41とR42とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
51とR52とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
61とR62とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
91とR92とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
101とR102とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
111とR112とは、互いに連結して環を形成することが好ましく、脂肪族複素環を形成することがより好ましく、不飽和結合を有さない脂肪族複素環であることがさらに好ましく、特に好ましくはピロリジン環またはピペリジン環構造を有することが好ましい。
R 41 , R 51 , R 61 , R 91 , R 101 and R 111 are each independently preferably an alkyl group having 1 to 15 carbon atoms, and preferably an alkyl group having 1 to 10 carbon atoms. More preferred.
R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 and R 112 are each independently preferably an alkyl group having 1 to 15 carbon atoms, preferably having 1 carbon atom. More preferably, it is an alkyl group of 10 to 10.
It is preferable that R 41 and R 42 are connected to each other to form a ring, more preferably an aliphatic heterocycle is formed, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.
R 51 and R 52 are preferably linked to each other to form a ring, more preferably an aliphatic heterocycle, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.
It is preferable that R 61 and R 62 are connected to each other to form a ring, more preferably an aliphatic heterocycle is formed, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.
R 91 and R 92 are preferably linked to each other to form a ring, more preferably an aliphatic heterocycle, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.
It is preferable that R 101 and R 102 are connected to each other to form a ring, more preferably an aliphatic heterocycle, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.
It is preferable that R 111 and R 112 are connected to each other to form a ring, more preferably an aliphatic heterocycle, and further preferably an aliphatic heterocycle having no unsaturated bond. Particularly preferably, it has a pyrrolidine ring or a piperidine ring structure.

13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123は、それぞれ独立して、ニトロ基;シアノ基;ハロゲン原子;−OCF;−SCF;−SF;−SF;炭素数1〜25のフルオロアルキル基;炭素数6〜18のフルオロアリール基;−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)であることが好ましく、シアノ基;フッ素原子;塩素原子;−OCF;−SCF;炭素数1〜12のフルオロアルキル基;−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)であることがより好ましく、シアノ基であることが特に好ましい。 R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 are independently nitro groups; cyano groups; halogen atoms. ; -OCF 3; -SCF 3; -SF 5; -SF 3; fluoroaryl group having 6 to 18 carbon atoms; fluoroalkyl group having 1 to 25 carbon atoms -CO-O-R 111A or -SO 2 -R It is preferably 112A (R 111A and R 112A each independently represent an alkyl group having 1 to 24 carbon atoms which may have a halogen atom), preferably a cyano group; a fluorine atom; a chlorine atom; -OCF 3 ; -SCF 3 ; fluoroalkyl group having 1 to 12 carbon atoms; -CO-O-R 111A or -SO 2- R 112A (R 111A and R 112A each have a halogen atom independently. It represents an alkyl group having 1 to 24 carbon atoms which may be used), and a cyano group is particularly preferable.

14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R15、R35、R75、R85及びR125は、それぞれ独立して、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、−CO−O−R222、−SO−R222、フルオロアルキル基(好ましくは、炭素数1〜25のフルオロアルキル基)又はフルオロアリール基(好ましくは、炭素数6〜18のフルオロアリール基)であることが好ましく、ニトロ基、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R222又は−SO−R222(R222は、ハロゲン原子を有していてもよい炭素数1〜25のアルキル基を表す。)ことがより好ましく、シアノ基、−CO−O−R222又は−SO−R222(R222は、ハロゲン原子を有していてもよい炭素数1〜25のアルキル基を表す。)であることがさらに好ましく、シアノ基であることが特に好ましい。 R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 15 , R 35 , R 75 , R 85 and R 125. Are independently nitro groups, cyano groups, halogen atoms, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , -CO-O-R 222 , -SO 2- R 222 , fluoroalkyl groups. (Preferably a fluoroalkyl group having 1 to 25 carbon atoms) or a fluoroaryl group (preferably a fluoroaryl group having 6 to 18 carbon atoms), a nitro group, a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , fluoroalkyl group, -CO-O-R 222 or -SO 2- R 222 (R 222 represents an alkyl group having 1 to 25 carbon atoms which may have a halogen atom. ) Is more preferable, and a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 represents an alkyl group having 1 to 25 carbon atoms which may have a halogen atom). Is more preferable, and a cyano group is particularly preferable.

14とR15とは同じ構造であることが好ましい。
24とR25とは同じ構造であることが好ましい。
34とR35とは同じ構造であることが好ましい。
74とR75とは同じ構造であることが好ましい。
84とR85とは同じ構造であることが好ましい。
124とR125とは同じ構造であることが好ましい。
It is preferable that R 14 and R 15 have the same structure.
It is preferable that R 24 and R 25 have the same structure.
It is preferable that R 34 and R 35 have the same structure.
It is preferable that R 74 and R 75 have the same structure.
It is preferable that R 84 and R 85 have the same structure.
It is preferable that R 124 and R 125 have the same structure.

及びRからなる群から選ばれる少なくとも一方が、重合性基を含む基であることが好ましく、R及びRが互いに連結して環を形成し、かつ、R及びRが互いに連結した環が重合性基を有することがより好ましい。 At least one selected from the group consisting of R 1 and R 2 is preferably a group containing a polymerizable group, R 1 and R 2 are linked to each other to form a ring, and R 1 and R 2 are It is more preferable that the rings connected to each other have a polymerizable group.

化合物(I)は、式(I−1A)で表される化合物、式(I−2A)で表される化合物又は式(I−3A)で表される化合物の何れかであることがより好ましい。

Figure 2021127336

[式中、R、R、R、R、Rは上記と同じ意味を表す。
Rx、Rx、Rx、Rx、Rx、Rx、Rx及びRxは、それぞれ独立して、水素原子又は置換基を表す。
m1は0〜4の整数を表し、m2は0〜5の整数を表す。
式(I−1A)のうち、R、R、R、R、R、Rx及びRxのうち少なくとも1つは重合性基を含む基を表す。
式(I−2A)のうち、R、R、Rx、Rx及びRxのうち少なくとも1つは重合性基を含む基を表す。
式(I−3A)のうち、R、R、Rx、Rx及びRxのうち少なくとも1つは重合性基を含む基を表す。] The compound (I) is more preferably any of a compound represented by the formula (I-1A), a compound represented by the formula (I-2A), or a compound represented by the formula (I-3A). ..
Figure 2021127336

[In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 have the same meanings as above.
Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 and Rx 8 independently represent hydrogen atoms or substituents.
m1 represents an integer from 0 to 4, and m2 represents an integer from 0 to 5.
Of the formula (I-1A), at least one of R 1 , R 2 , R 3 , R 4 , R 5 , Rx 1 and Rx 2 represents a group containing a polymerizable group.
In formula (I-2A), at least one of R 4 , R 5 , Rx 3 , Rx 4 and Rx 5 represents a group containing a polymerizable group.
Of formula (I-3A), at least one of R 4 , R 5 , Rx 6 , Rx 7 and Rx 8 represents a group containing a polymerizable group. ]

Rx〜Rxで表される置換基としては、環Wが有していてもよい置換基と同じものが挙げられる。
Rx、Rx、Rx、Rx、Rx、Rxは、それぞれ独立して、水素原子又は炭素数1〜12のアルキル基であることが好ましい。
m1が2以上の整数を表す場合、複数のRx5は同一の基であってもよいし異なる基であってもよい。また、m2が2以上の整数を表す場合、複数のRx8は同一の基であってもよいし異なる基であってもよい。
Rx及びRxは、それぞれ独立して、重合性基を含む基であることが好ましい。
Examples of the substituent represented by Rx 1 to Rx 8 include the same substituents that the ring W 1 may have.
It is preferable that Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 6 , and Rx 7 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms.
When m1 represents an integer of 2 or more, the plurality of R x5s may be the same group or different groups. Further, when m2 represents an integer of 2 or more, the plurality of R x8s may be the same group or different groups.
It is preferable that Rx 5 and Rx 8 are independent groups containing a polymerizable group.

式(I)で表される化合物(以下、化合物(I)という場合がある。)としては、以下に記載の化合物が挙げられる。なお、下記式中、Meはメチル基を表し、Etはエチル基を表す。

Figure 2021127336
Examples of the compound represented by the formula (I) (hereinafter, may be referred to as compound (I)) include the compounds described below. In the following formula, Me represents a methyl group and Et represents an ethyl group.
Figure 2021127336

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式(II)で表される化合物(以下、化合物(II)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (II) (hereinafter, may be referred to as compound (II)) include the compounds described below.
Figure 2021127336

Figure 2021127336
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式(III)で表される化合物(以下、化合物(III)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (III) (hereinafter, may be referred to as compound (III)) include the compounds described below.
Figure 2021127336

式(IV)で表される化合物(以下、化合物(IV)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (IV) (hereinafter, may be referred to as compound (IV)) include the compounds described below.
Figure 2021127336

式(V)で表される化合物(以下、化合物(V)という場合がある。)としては、以下に記載の化合物が挙げられる。なお、Meはメチル基を表す。

Figure 2021127336
Examples of the compound represented by the formula (V) (hereinafter, may be referred to as compound (V)) include the compounds described below. Me represents a methyl group.
Figure 2021127336

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式(VI)で表される化合物(以下、化合物(VI)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (VI) (hereinafter, may be referred to as compound (VI)) include the compounds described below.
Figure 2021127336

Figure 2021127336
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式(VII)で表される化合物(以下、化合物(VII)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (VII) (hereinafter, may be referred to as compound (VII)) include the compounds described below.
Figure 2021127336

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式(VIII)で表される化合物(以下、化合物(VIII)という場合がある。)としては、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (VIII) (hereinafter, may be referred to as compound (VIII)) include the compounds described below.
Figure 2021127336

Figure 2021127336
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式(IX)で表される化合物(以下、化合物(IX)という場合がある。)としては、例えば、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound represented by the formula (IX) (hereinafter, may be referred to as compound (IX)) include the compounds described below.
Figure 2021127336

<化合物(I)の製造方法>
化合物(I)の製造方法について説明する。例えば、Rが(メタ)アクリロイルオキシ基を有する化合物(I)(以下、化合物(I−1B)という場合がある。))は、式(M−A)で表される化合物(以下、化合物(M−A)という場合がある。)と式(M−B)で表される化合物(以下、化合物(M−B)という場合がある。)とを反応させることにより得ることができる。

Figure 2021127336

[式中、環W及びRは上記と同じ意味を表す。
、R及びRは、重合性基を含む基を表す場合を除くこと以外は上記と同じ意味を表す。
E1は2価の連結基を表し、RE2は(メタ)アクリロイル基を表し、Xはハロゲン原子を表す。] <Method for producing compound (I)>
The method for producing the compound (I) will be described. For example, compound (I) in which R 1 has a (meth) acryloyloxy group (hereinafter, may be referred to as compound (I-1B))) is a compound represented by the formula (MA) (hereinafter, compound). It can be obtained by reacting (sometimes referred to as (MA)) with a compound represented by the formula (MB) (hereinafter, sometimes referred to as compound (MB)).
Figure 2021127336

[In the equation, rings W 1 and R 3 have the same meanings as above.
R 2, R 4 and R 5, except that except when representing a group containing a polymerizable group represent the same meaning as the above.
R E1 represents a divalent linking group, R E2 represents a (meth) acryloyl group, X represents a halogen atom. ]

また、RとRとが互いに連結して環を形成し、かつR及びRが互いに連結した環が(メタ)アクリロイルオキシ基を有する化合物(I)(以下、化合物(I−1C)という場合がある。)は、式(M−A1)で表される化合物(以下、化合物(M−A1)という場合がある)と化合物(M−B)とを反応させることにより得ることができる。

Figure 2021127336

[式中、環W及びRは上記と同じ意味を表す。
及びRは、重合性基を含む基を表す場合を除くこと以外は上記と同じ意味を表す。
E2は(メタ)アクリロイル基を表し、RE3は単結合又は2価の連結基を表し、Xはハロゲン原子を表す。
環Wは、環の構成要素として窒素原子を含む複素環を表す。) Further, R 1 and R 2 are bonded to each other to form a ring, and a compound having the ring to which R 1 and R 2 are linked to each other a (meth) acryloyloxy group (I) (hereinafter, Compound (I-1C ) Can be obtained by reacting a compound represented by the formula (MA1) (hereinafter, may be referred to as a compound (MA1)) with a compound (MB). can.
Figure 2021127336

[In the equation, rings W 1 and R 3 have the same meanings as above.
R 4 and R 5 have the same meanings as described above except that they represent a group containing a polymerizable group.
R E2 represents a (meth) acryloyl group, R E3 represents a single bond or a divalent linking group, X represents a halogen atom.
Ring W 1 represents a heterocycle containing a nitrogen atom as a component of the ring. )

化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応は、化合物(M−A)又は化合物(M−A1)と化合物(M−B)とを混合することにより実施される。化合物(M−A)又は化合物(M−A1)と化合物(M−B)との混合は、化合物(M−A)又は化合物(M−A1)に化合物(M−B)を添加することが好ましい。 The reaction between compound (MA) or compound (MA1) and compound (MB) is to mix compound (MA) or compound (MA1) and compound (MB). Is carried out by. Mixing of compound (MA) or compound (MA1) with compound (MB) can be done by adding compound (MB) to compound (MA) or compound (MA1). preferable.

化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応は、塩基存在下で行うことが好ましい。
塩基としては、アンモニア、トリエチルアミン、ジイソプロピルエチルアミン、エタノールアミン、ピロリジン、ピペリジン、ジアザビシクロウンデセン、ジアザビシクロノネン、グアニジン、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、ピリジン、アニリン、ジメトキシアニリン、酢酸アンモニウム、β-アラニン等のアミン化合物(好ましくはトリエチルアミン、ジイソプロピルエチルアミン等の3級アミン)、水酸化カリウム、水酸化ナトリウム、水酸化リチウム、ナトリウムターシャリーブトキシド、カリウムターシャリーブトキシド、水素化ナトリウム、炭酸ナトリウム、炭酸カリウム等が挙げられる。
塩基の使用量としては、化合物(M−A)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
The reaction between the compound (MA) or the compound (MA1) and the compound (MB) is preferably carried out in the presence of a base.
Bases include ammonia, triethylamine, diisopropylethylamine, ethanolamine, pyrrolidine, piperidine, diazabicycloundecene, diazabicyclononen, guanidine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyridine, aniline, dimethoxyaniline, acetic acid. Amine compounds such as ammonium and β-alanine (preferably tertiary amines such as triethylamine and diisopropylethylamine), potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium tertiary butoxide, potassium tertiary butoxide, sodium hydride, carbonic acid. Examples include sodium and potassium carbonate.
The amount of the base used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol, with respect to 1 mol of the compound (MA).

化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応は、溶剤存在下で行われることが好ましい。前記溶媒としては、クロロホルム、アセトニトリル、ベンゼン、トルエン、アセトン、酢酸エチル、ジクロロメタンジクロロエタン、モノクロロベンゼン、メタノール、エタノール、イソプロパノール、tert−ブタノール、2-ブタノン、テトラヒドロフラン、ジエチルエーテル、ジメチルスルホキシド、N,N−ジメチルアセトアミド、N,N-ジメチルホルムアミド、ジブチルヒドロキシトルエン、水、n−ヘキサン、n−ヘプタン等が挙げられる。 The reaction of compound (MA) or compound (MA1) with compound (MB) is preferably carried out in the presence of a solvent. Examples of the solvent include chloroform, acetonitrile, benzene, toluene, acetone, ethyl acetate, dichloromethanedichloroethane, monochlorobenzene, methanol, ethanol, isopropanol, tert-butanol, 2-butanone, tetrahydrofuran, diethyl ether, dimethylsulfoxide, N, N-. Examples thereof include dimethylacetamide, N, N-dimethylformamide, dibutylhydroxytoluene, water, n-hexane, n-heptane and the like.

化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応時間は、通常0.1〜100時間であり、好ましくは1〜30時間である。
化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応温度は、通常−80〜+150℃であり、好ましくは−30〜130℃である。
化合物(M−B)の使用量は、化合物(M−A)又は化合物(M−A1)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
The reaction time of compound (MA) or compound (MA1) and compound (MB) is usually 0.1 to 100 hours, preferably 1 to 30 hours.
The reaction temperature of compound (MA) or compound (MA1) and compound (MB) is usually −80 to + 150 ° C., preferably -30 to 130 ° C.
The amount of compound (MB) used is usually 0.1 to 10 mol and 0.5 to 5 mol per 1 mol of compound (MA) or compound (MA1). preferable.

化合物(M−B)としては、アクリル酸クロリド等が挙げられ、市場から入手することができる。
化合物(M−A)としては、例えば、以下に記載の化合物等が挙げられる。

Figure 2021127336

化合物(M−A1)としては、例えば、以下に記載の化合物等が挙げられる。
Figure 2021127336
Examples of the compound (MB) include acrylic acid chloride and the like, which can be obtained from the market.
Examples of the compound (MA) include the compounds described below.
Figure 2021127336

Examples of the compound (MA1) include the compounds described below.
Figure 2021127336

化合物(M−A)は、式(M−C)で表される化合物(以下、化合物(M−C)という場合がある。)と式(M−D)で表される化合物(以下、化合物(M−D)という場合がある。)とを反応させることより得ることができる。
化合物(M−A1)は、化合物(M−C)と式(M−E)で表される化合物(以下、化合物(M−E)という場合がある。)とを反応させることにより得ることができる。

Figure 2021127336

[式中、RE1、RE3、R、及び環Wは、上記と同じ意味を表す。
、R及びRは、重合性基を含む基を表す場合を除くこと以外は上記と同じ意味を表す。
環W1Aは、環構造を表す。] The compound (MA) is a compound represented by the formula (MC) (hereinafter, may be referred to as a compound (MC)) and a compound represented by the formula (MD) (hereinafter, a compound). It may be obtained by reacting with (MD).
Compound (MA1) can be obtained by reacting compound (MC) with a compound represented by the formula (ME) (hereinafter, may be referred to as compound (ME)). can.
Figure 2021127336

[In the formula, R E1 , R E3 , R 3 and ring W 1 have the same meanings as described above.
R 2, R 4 and R 5, except that except when representing a group containing a polymerizable group represent the same meaning as the above.
Ring W 1A represents a ring structure. ]

化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応は、通常、化合物(M−C)と化合物(M−D)又は化合物(M−E)とを混合することにより実施され、化合物(M−C)に化合物(M−D)又は化合物(M−E)を加えることが好ましい。
また、化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応は、塩基及びメチル化剤の存在下で、化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応とを混合することにより実施されることが好ましい。化合物(M−C)と、化合物(M−D)又は化合物(M−E)、塩基及びメチル化剤を混合することがより好ましく、化合物(M−C)とメチル化剤と塩基との混合物に化合物(M−D)又は化合物(M−E)を混合することがさらに好ましい。
The reaction between compound (MC) and compound (MD) or compound (ME) is usually carried out by combining compound (MC) with compound (MD) or compound (ME). It is carried out by mixing, and it is preferable to add compound (MD) or compound (ME) to compound (MC).
Further, the reaction between the compound (MC) and the compound (MD) or the compound (ME) is carried out between the compound (MC) and the compound (MC) in the presence of a base and a methylating agent. It is preferably carried out by mixing D) or a reaction with compound (ME). It is more preferable to mix compound (MC) with compound (MD) or compound (ME), a base and a methylating agent, and a mixture of compound (MC), a methylating agent and a base. It is more preferable to mix the compound (MD) or the compound (ME) with the compound (MD).

塩基としては、化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応に用いられる塩基と同じものが挙げられる。
塩基の使用量としては、化合物(M−C)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
Examples of the base include the same bases used in the reaction between the compound (MA) or the compound (MA1) and the compound (MB).
The amount of the base used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol, with respect to 1 mol of the compound (MC).

メチル化剤としては、ヨードメタン、硫酸ジメチル、メタンスルホン酸メチル、フルオロスルホン酸メチル、パラトルエンスルホン酸メチル、トリフルオロメタンスルホン酸メチル、トリメチルオキソニウムテトラフルオロボレート等が挙げられる。
メチル化剤の使用量としては、化合物(M−C)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
化合物(M−D)又は化合物(M−E)の使用量は、化合物(M−C)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応は、溶媒の存在下で行ってもよい。溶媒としては、メタノール、エタノール、イソプロパノール、トルエン、アセトニトリル等が挙げられる。
Examples of the methylating agent include iodomethane, dimethyl sulfate, methyl methanesulfonate, methyl fluorosulfonate, methyl paratoluenesulfonate, methyl trifluoromethanesulfonate, trimethyloxonium tetrafluoroborate and the like.
The amount of the methylating agent used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol, with respect to 1 mol of compound (MC).
The amount of compound (MD) or compound (ME) to be used is usually 0.1 to 10 mol and 0.5 to 5 mol per 1 mol of compound (MC). preferable.
The reaction of compound (MC) with compound (MD) or compound (ME) may be carried out in the presence of a solvent. Examples of the solvent include methanol, ethanol, isopropanol, toluene, acetonitrile and the like.

化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応時間は、通常0.1〜100時間である。
化合物(M−C)と、化合物(M−D)又は化合物(M−E)との反応温度は、通常−80〜+150℃である。
The reaction time between compound (MC) and compound (MD) or compound (ME) is usually 0.1 to 100 hours.
The reaction temperature of compound (MC) and compound (MD) or compound (ME) is usually −80 to + 150 ° C.

化合物(M−D)としては、(2−ヒドロキシ)エチルメチルアミン、(4−ヒドロキシ)ブチルアミン、4−ヒドロキシブチルメチルアミン、4−ヒドロキシブチルブチルアミン等が挙げられる。
化合物(M−E)としては、3−ヒドロキシピロリジン、3−ヒドロキシメチルピロリジン、4−ヒドロキシピペリジン、3−ヒドロキシピペリジン、3−ヒドロキシメチルピペリジン、4−(ヒドロキシメチル)ピペリジン等が挙げられる。また、化合物(M−E)を使用する際には、化合物(M−E)に含まれるヒドロキシ基をシリル基等で保護してもよい。
Examples of the compound (MD) include (2-hydroxy) ethylmethylamine, (4-hydroxy) butylamine, 4-hydroxybutylmethylamine, 4-hydroxybutylbutylamine and the like.
Examples of the compound (ME) include 3-hydroxypyrrolidine, 3-hydroxymethylpyrrolidine, 4-hydroxypiperidine, 3-hydroxypiperidine, 3-hydroxymethylpiperidine, 4- (hydroxymethyl) piperidine and the like. When the compound (ME) is used, the hydroxy group contained in the compound (ME) may be protected by a silyl group or the like.

化合物(M−C)は、例えば、以下に記載の化合物が挙げられる。

Figure 2021127336
Examples of the compound (MC) include the compounds described below.
Figure 2021127336

化合物(M−C)は、式(M−F)で表される化合物(以下、化合物(M−F)という場合がある。)と式(M−G)で表される化合物(以下、化合物(M−G)という場合がある。)とを反応させることにより得ることができる。

Figure 2021127336

[式中、環W1A及びRは、上記と同じ意味を表す。
及びRは、重合性基を含む基を表す場合を除くこと以外は上記と同じ意味を表す。
は脱離基を表す。] The compound (MC) is a compound represented by the formula (MF) (hereinafter, may be referred to as a compound (MF)) and a compound represented by the formula (MG) (hereinafter, a compound). It may be obtained by reacting with (MG).
Figure 2021127336

[In the formula, rings W 1A and R 3 have the same meanings as described above.
R 4 and R 5 have the same meanings as described above except that they represent a group containing a polymerizable group.
E 1 represents a leaving group. ]

で表される脱離基としては、ハロゲン原子、p−トルエンスルホニル基、トリフルオロメチルスルホニル基等が挙げられる。 Examples of the leaving group represented by E 1 include a halogen atom, a p-toluenesulfonyl group, a trifluoromethylsulfonyl group and the like.

化合物(M−F)と化合物(M−G)との反応は、化合物(M−F)と化合物(M−G)とを混合することにより実施することができる。
化合物(M−F)と化合物(M−G)との反応は、塩基の存在下で行うことが好ましい。塩基としては、化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応に用いられる塩基と同じものが挙げられる。好ましくは、炭酸カリウム、水酸化カリウム、カリウムターシャリーブトキシド、ジイソプロピルエチルアミンである。
塩基の使用量は、化合物(M−F)1モルに対して、通常0.1〜10モルであり、0.5〜5モルであることが好ましい。
化合物(M−F)と化合物(M−G)との反応は溶媒の存在下で行ってもよい。溶媒としては、トルエン、アセトニトリル、メタノール、エタノール、イソプロパノール等が挙げられる。
化合物(M−F)と化合物(M−G)との反応時間は、通常0.1〜100時間である。
化合物(M−F)と化合物(M−G)との反応温度は、通常−80〜+150℃である。
The reaction between the compound (MF) and the compound (MG) can be carried out by mixing the compound (MF) and the compound (MG).
The reaction between the compound (MF) and the compound (MG) is preferably carried out in the presence of a base. Examples of the base include the same bases used in the reaction between the compound (MA) or the compound (MA1) and the compound (MB). Preferred are potassium carbonate, potassium hydroxide, potassium tertiary butoxide, diisopropylethylamine.
The amount of the base used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol, based on 1 mol of the compound (MF).
The reaction between the compound (MF) and the compound (MG) may be carried out in the presence of a solvent. Examples of the solvent include toluene, acetonitrile, methanol, ethanol, isopropanol and the like.
The reaction time of compound (MF) and compound (MG) is usually 0.1 to 100 hours.
The reaction temperature of the compound (MF) and the compound (MG) is usually −80 to + 150 ° C.

化合物(M−G)としては、市販品を用いてもよい。例えば、クロロシアン、ブロモシアン、パラトルエンスルホニルシアニド、トリフルオロメタンスルホニルシアニド、1−クロロメチル−4−フルオロ−1,4−ジアゾニアビシクロ[2.2.2]オクタン ビス(テトラフルオロボラート(セレクトフロアー(Air Products and Chemicalsの登録商標)ともいう)、ベンゾイル(フェニルヨードニオ)(トリフルオロメタンスルホニル)メタニド、2,8−ジフルオロ−5−(トリフルオロメチル)−5H−ジベンゾ[b,d]チオフェン−5−イウムトリフルオロメタンスルホナート、N−ブロモスクシンイミド、N−クロロスクシンイミド、N−ヨードスクシンイミド等が挙げられる。 As the compound (MG), a commercially available product may be used. For example, chlorocyan, bromocyan, paratoluenesulfonyl cyanide, trifluoromethanesulfonylocyanide, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octanebis (tetrafluoroborate (select floor)). (Also known as a registered trademark of Air Products and Chemicals), Benzoyl (phenyliodonio) (trifluoromethanesulfonyl) metanide, 2,8-difluoro-5- (trifluoromethyl) -5H-dibenzo [b, d] thiophene- Examples thereof include 5-ium trifluoromethanesulfonate, N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide and the like.

化合物(M−F)は、例えば、下記に記載の化合物等が挙げられる。

Figure 2021127336
Examples of the compound (MF) include the compounds described below.
Figure 2021127336

化合物(M−F)は、化合物(M−H)と化合物(M−I)とを反応させることにより得ることができる。化合物(M−H)と化合物(M−I)との反応は、化合物(M−H)と化合物(M−I)とを混合することにより実施することができる。

Figure 2021127336

[式中、環W1Aは、上記と同じ意味を表す。
及びRは、重合性基を含む基を表す場合を除くこと以外は上記と同じ意味を表す。] Compound (MF) can be obtained by reacting compound (MH) with compound (MI). The reaction between the compound (MH) and the compound (MI) can be carried out by mixing the compound (MH) and the compound (MI).
Figure 2021127336

[In the formula, ring W 1A has the same meaning as above.
R 4 and R 5 have the same meanings as described above except that they represent a group containing a polymerizable group. ]

化合物(M−H)と化合物(M−I)との反応は、塩基の存在下で行うことが好ましい。塩基としては、化合物(M−A)又は化合物(M−A1)と化合物(M−B)との反応に用いられる塩基と同じものが挙げられる。塩基の使用量は、化合物(M−H)1モルに対して通常0.1〜5モルであり、0.5〜2モルであることが好ましい。化合物(M−H)と化合物(M−I)との反応は、溶媒の存在下で行ってもよい。溶媒としては、メタノール、エタノール、イソプロパノール、トルエン、アセトニトリル等が挙げられる。
化合物(M−H)と化合物(M−I)との反応時間は、通常0.1〜10時間である。
化合物(M−H)と化合物(M−I)との反応温度は、通常−50〜150℃である。
化合物(M−I)の使用量は、化合物(M−H)1モルに対して通常0.1〜10モルであり、0.5〜2モルであることが好ましい。
The reaction between compound (MH) and compound (MI) is preferably carried out in the presence of a base. Examples of the base include the same bases used in the reaction between the compound (MA) or the compound (MA1) and the compound (MB). The amount of the base used is usually 0.1 to 5 mol, preferably 0.5 to 2 mol, per 1 mol of compound (MH). The reaction between compound (MH) and compound (MI) may be carried out in the presence of a solvent. Examples of the solvent include methanol, ethanol, isopropanol, toluene, acetonitrile and the like.
The reaction time of compound (MH) and compound (MI) is usually 0.1 to 10 hours.
The reaction temperature of compound (MH) and compound (MI) is usually −50 to 150 ° C.
The amount of compound (MI) used is usually 0.1 to 10 mol, preferably 0.5 to 2 mol, per 1 mol of compound (MH).

化合物(M−I)としては市販品を用いてもよく、例えば、マロノニトリル等が挙げられる。
化合物(M−H)は下記に記載の化合物等が挙げられ、市場から入手できる。

Figure 2021127336
As the compound (MI), a commercially available product may be used, and examples thereof include malononitrile.
Examples of the compound (MH) include the compounds described below, which are available on the market.
Figure 2021127336

<式(X)で表される部分構造を有する樹脂>
本発明は、式(X)で表される部分構造を有する樹脂(以下、樹脂(1)という場合がある。)を含む。樹脂(1)は、式(X)で表される部分構造を樹脂の主鎖に含んでいてもよいし、側鎖に含んでいてもよい。樹脂(1)は側鎖に式(X)で表される部分構造を有することが好ましい。樹脂(1)は、化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)のホモポリマーであってもよいし、コポリマーであってもよい。
樹脂(1)がコポリマーである場合、例えば、化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)と重合性モノマーとの共重合体等が挙げられる。前記重合性モノマーとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル等の(メタ)アクリル酸エステル;(メタ)アクリル酸1−ヒドロキシメチル、(メタ)アクリル酸1−ヒドロキシエチル等のヒドロキシ基を有する(メタ)アクリル酸エステル単量体;酢酸ビニル、ブタジエン等のビニル系単量体;スチレン、メチルスチレン、フルオロスチレン等のスチレン系単量体;(メタ)アクリル酸、カルボキシエチル(メタ)アクリレート、マレイン酸等のカルボキシル基を有する単量体;アミノエチル(メタ)アクリレート、N,N−ジメチルアミノエチル(メタ)アクリレート等の置換若しくは無置換アミノ基を有する単量体等が挙げられる。
樹脂(1)がコポリマーの場合、化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)に由来する構造単位が樹脂(A)に含まれる全構造単位100質量部に対して、0.01〜90質量部であることが好ましく、より好ましくは0.1〜75質量部であり、さらに好ましくは0.5〜60質量部であり、特に好ましくは1〜50質量部である。
樹脂(1)は、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法などの公知の方法によって製造することができる。
<Resin having a partial structure represented by the formula (X)>
The present invention includes a resin having a partial structure represented by the formula (X) (hereinafter, may be referred to as resin (1)). The resin (1) may contain a partial structure represented by the formula (X) in the main chain of the resin or in the side chain. The resin (1) preferably has a partial structure represented by the formula (X) in the side chain. The resin (1) may be a homopolymer of compound (X) (preferably any one of compounds (I) to (IX)) or a copolymer.
When the resin (1) is a copolymer, for example, a copolymer of compound (X) (preferably any one of compound (I) to compound (IX)) and a polymerizable monomer can be mentioned. Examples of the polymerizable monomer include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; 1- (meth) acrylic acid. (Meta) acrylic acid ester monomer having a hydroxy group such as hydroxymethyl, 1-hydroxyethyl (meth) acrylate; vinyl-based monomer such as vinyl acetate and butadiene; styrene such as styrene, methylstyrene and fluorostyrene Monomer; Monomer having a carboxyl group such as (meth) acrylic acid, carboxyethyl (meth) acrylate, maleic acid; Aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc. Examples thereof include monomers having a substituted or unsubstituted amino group.
When the resin (1) is a copolymer, the structural unit derived from the compound (X) (preferably any one of the compounds (I) to (IX)) is contained in the resin (A) with respect to 100 parts by mass of all the structural units. It is preferably 0.01 to 90 parts by mass, more preferably 0.1 to 75 parts by mass, further preferably 0.5 to 60 parts by mass, and particularly preferably 1 to 50 parts by mass. be.
The resin (1) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method.

<化合物(X)を含む組成物>
本発明は、化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)を含有する組成物も含む。
本発明の化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)を含む組成物は、化合物(X)(好ましくは化合物(I)〜化合物(IX)のいずれか)と樹脂とを含む樹脂組成物であることが好ましい。
本発明の組成物はあらゆる用途に使用可能であるが、中でも日光又は紫外線を含む光に晒される可能性のある用途に特に好適に使用できる。具体例としては、例えばガラス代替品とその表面コーティング材;住居、施設、輸送機器等の窓ガラス、採光ガラス及び光源保護ガラス用のコーティング材;住居、施設、輸送機器等のウインドウフィルム;住居、施設、輸送機器等の内外装材及び内外装用塗料及び該塗料によって形成させる塗膜;アルキド樹脂ラッカー塗料及び該塗料によって形成される塗膜;アクリルラッカー塗料及び該塗料によって形成される塗膜;蛍光灯、水銀灯等の紫外線を発する光源用部材;精密機械、電子電気機器用部材、各種ディスプレイから発生する電磁波等の遮断用材;食品、化学品、薬品等の容器又は包装材;ボトル、ボックス、ブリスター、カップ、特殊包装用、コンパクトディスクコート、農工業用シート又はフィルム材;印刷物、染色物、染顔料等の退色防止剤;ポリマー支持体用(例えば、機械及び自動車部品のようなプラスチック製部品用)の保護膜;印刷物オーバーコート;インクジェット媒体被膜;積層艶消し;オプティカルライトフィルム;安全ガラス/フロントガラス中間層;エレクトロクロミック/フォトクロミック用途;オーバーラミネートフィルム;太陽熱制御膜;日焼け止めクリーム、シャンプー、リンス、整髪料等の化粧品;スポーツウェア、ストッキング、帽子等の衣料用繊維製品及び繊維;カーテン、絨毯、壁紙等の家庭用内装品;プラスチックレンズ、コンタクトレンズ、義眼等の医療用器具;光学フィルタ、バックライトディスプレーフィルム、プリズム、鏡、写真材料等の光学用品;金型膜、転写式ステッカー、落書き防止膜、テープ、インク等の文房具;標示板、標示器等とその表面コーティング材等を挙げることができる。
<Composition containing compound (X)>
The present invention also includes compositions containing compound (X) (preferably any of compound (I) to compound (IX)).
The composition containing the compound (X) of the present invention (preferably any one of the compounds (I) to (IX)) and the compound (X) (preferably any one of the compounds (I) to (IX)). A resin composition containing a resin is preferable.
The compositions of the present invention can be used for all purposes, but are particularly preferably used for applications that may be exposed to light including sunlight or ultraviolet rays. Specific examples include, for example, glass substitutes and their surface coating materials; window glass for dwellings, facilities, transportation equipment, etc., coating materials for light-collecting glass and light source protection glass; window films for dwellings, facilities, transportation equipment, etc .; dwellings, Interior / exterior materials and interior / exterior paints for facilities, transportation equipment, etc. and coatings formed by the coatings; alkyd resin lacquer coatings and coatings formed by the coatings; acrylic lacquer coatings and coatings formed by the coatings; fluorescence Materials for light sources that emit ultraviolet rays such as lamps and mercury lamps; Materials for precision machinery, electronic and electrical equipment, materials for blocking electromagnetic waves generated from various displays; Containers or packaging materials for foods, chemicals, chemicals, etc .; Bottles, boxes, blister , Cups, special packaging, compact disc coats, agricultural and industrial sheets or film materials; anti-fading agents for printed matter, dyes, dyes, etc .; for polymer supports (eg, for plastic parts such as machine and automotive parts) ) Protective film; Printed matter overcoat; Inkjet medium coating; Laminated matte; Optical light film; Safety glass / front glass intermediate layer; Electrochromic / Photochromic applications; Overlaminated film; Solar heat control film; Sunscreen cream, shampoo, rinse , Cosmetics such as hairdressers; Textile products and textiles for clothing such as sportswear, stockings and hats; Household interiors such as curtains, rugs and wallpaper; Medical instruments such as plastic lenses, contact lenses and artificial eyes; Optical filters, Optical supplies such as backlight display films, prisms, mirrors, photographic materials; stationery such as mold films, transfer stickers, anti-doodle films, tapes, inks; marking boards, marking devices, etc. and their surface coating materials, etc. Can be done.

本発明の組成物より形成した成形物は、高分子成型品であることが好ましい。成形物の形状としては、平膜状、粉状、球状粒子、破砕粒子、塊状連続体、繊維状、管状、中空糸状、粒状、板状、多孔質状などのいずれの形状であってもよい。 The molded product formed from the composition of the present invention is preferably a polymer molded product. The shape of the molded product may be any of flat film-like, powder-like, spherical particles, crushed particles, massive continuum, fibrous, tubular, hollow thread-like, granular, plate-like, and porous. ..

本発明の組成物が樹脂組成物である場合、樹脂組成物に用いられる樹脂としては、公知の各種成形体、シート、フィルム等の製造に従来から使用されている熱可塑性樹脂及び熱硬化性樹脂等が挙げられる。
熱可塑性樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリシクロオレフィン樹脂等のオレフィン系樹脂、ポリ(メタ)アクリル酸エステル系樹脂、ポリスチレン系樹脂、スチレン−アクリロニトリル系樹脂、アクリロニトリル−ブタジエン−スチレン系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリ酢酸ビニル系樹脂、ポリビニルブチラール系樹脂、エチレン−酢酸ビニル系共重合体、エチレン−ビニルアルコール系樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、液晶ポリエステル樹脂等のポリエステル系樹脂、ポリアセタール樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリウレタン樹脂及びポリフェニレンサルファイド樹脂等が挙げられる。これらの樹脂を一種又は二種以上のポリマーブレンドあるいはポリマーアロイとして使用してもよい。
When the composition of the present invention is a resin composition, the resin used in the resin composition includes a thermoplastic resin and a thermosetting resin conventionally used in the production of various known molded products, sheets, films and the like. And so on.
Examples of the thermoplastic resin include olefin resins such as polyethylene resins, polypropylene resins, and polycycloolefin resins, poly (meth) acrylic acid ester resins, polystyrene resins, styrene-acrylonitrile resins, and acrylonitrile-butadiene-styrene resins. Resin, polyvinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin, polybutylene terephthalate resin, Examples thereof include polyester resins such as liquid crystal polyester resins, polyacetal resins, polyamide resins, polycarbonate resins, polyurethane resins and polyphenylene sulfide resins. These resins may be used as one or more polymer blends or polymer alloys.

熱硬化性樹脂としては、例えば、エポキシ樹脂、メラミン樹脂、不飽和ポリエステル樹脂、フェノール樹脂、尿素樹脂、アルキド樹脂、熱硬化性ポリイミド樹脂等が挙げられる。 Examples of the thermosetting resin include epoxy resin, melamine resin, unsaturated polyester resin, phenol resin, urea resin, alkyd resin, thermosetting polyimide resin and the like.

樹脂組成物を紫外線吸収フィルタや紫外線吸収膜として用いる場合、樹脂は透明樹脂であることが好ましい。 When the resin composition is used as an ultraviolet absorbing filter or an ultraviolet absorbing film, the resin is preferably a transparent resin.

樹脂組成物は、化合物(X)と樹脂とを混合することにより得ることができる。化合物(X)は、所望の性能を付与するために必要な量を含有すればよく、例えば、樹脂100質量部に対して0.01〜20質量部等含有することができる。 The resin composition can be obtained by mixing the compound (X) and the resin. The compound (X) may be contained in an amount necessary for imparting desired performance, for example, 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin.

本発明の組成物を光学フィルタ等の光学用品に用いる場合、例えば、光学液晶表示装置に適用することができる。樹脂組成物を光学液晶表示装置に適用する場合、樹脂組成物から形成される層は、フィルム層、粘着剤層、ハードコート層等のいずれに適用してもよく、粘着剤層、ハードコート層であることが好ましい。 When the composition of the present invention is used for optical products such as an optical filter, it can be applied to, for example, an optical liquid crystal display device. When the resin composition is applied to an optical liquid crystal display device, the layer formed from the resin composition may be applied to any of a film layer, an adhesive layer, a hard coat layer and the like, and the adhesive layer and the hard coat layer may be applied. Is preferable.

<粘着剤組成物>
本発明の組成物から形成される層が粘着剤層である場合、樹脂(A)、化合物(X)及び開始剤(C)を含む粘着剤組成物(以下、粘着剤組成物(1)という場合がある。)から形成される。粘着剤組成物(1)は、さらに、ラジカル硬化性成分(D)、架橋剤(E)、シラン化合物(F)、化合物(X)以外の光吸収化合物(G)(以下、光選択吸収化合物(G)という場合がある。)、帯電防止剤等を含んでいてもよく、ラジカル硬化性成分(D)、架橋剤(E)、シラン化合物(F)及び光選択吸収化合物(G)からなる群から選ばれる少なくとも1つを含むことが好ましい。
<Adhesive composition>
When the layer formed from the composition of the present invention is a pressure-sensitive adhesive layer, it is referred to as a pressure-sensitive adhesive composition containing a resin (A), a compound (X) and an initiator (C) (hereinafter referred to as a pressure-sensitive adhesive composition (1)). It may be formed from). The pressure-sensitive adhesive composition (1) further comprises a light-absorbing compound (G) other than the radical-curable component (D), a cross-linking agent (E), a silane compound (F), and a compound (X) (hereinafter, a light-selective absorbing compound). It may contain (may be referred to as (G)), an antistatic agent, or the like, and is composed of a radical curable component (D), a cross-linking agent (E), a silane compound (F), and a light selective absorption compound (G). It preferably comprises at least one selected from the group.

樹脂(A)は、粘着剤組成物に使用される樹脂であれば特に限定されない。樹脂(A)は、波長300nm〜波長780nmの範囲において極大吸収を示さないことが好ましい。
樹脂(A)は、ガラス転移温度(Tg)が40℃以下である樹脂であることが好ましい。樹脂(A)のガラス転移温度(Tg)は、20℃以下であることがより好ましく、10℃以下であることがさらに好ましく、0℃以下であることが特に好ましい。また、樹脂(A)のガラス転移温度は通常−80℃以上であり、−70℃以上であることが好ましく、−60℃以上であることがより好ましく、−55℃以上であることがさらに好ましく、−50℃以上であることが特に好ましい。樹脂(A)のガラス転移温度が40℃以下であると、粘着剤組成物(1)から形成される粘着剤層の被着体に対する密着性の向上に有利である。また、樹脂(A)のガラス転移温度が−80℃以上であると、粘着剤組成物(1)から形成される粘着剤層の耐久性の向上に有利である。なお、ガラス転移温度は示差走査熱量計(DSC)により測定できる。
The resin (A) is not particularly limited as long as it is a resin used in the pressure-sensitive adhesive composition. The resin (A) preferably does not exhibit maximum absorption in the wavelength range of 300 nm to 780 nm.
The resin (A) is preferably a resin having a glass transition temperature (Tg) of 40 ° C. or lower. The glass transition temperature (Tg) of the resin (A) is more preferably 20 ° C. or lower, further preferably 10 ° C. or lower, and particularly preferably 0 ° C. or lower. The glass transition temperature of the resin (A) is usually −80 ° C. or higher, preferably −70 ° C. or higher, more preferably −60 ° C. or higher, and even more preferably −55 ° C. or higher. , -50 ° C or higher is particularly preferable. When the glass transition temperature of the resin (A) is 40 ° C. or lower, it is advantageous to improve the adhesion of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (1) to the adherend. Further, when the glass transition temperature of the resin (A) is −80 ° C. or higher, it is advantageous to improve the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (1). The glass transition temperature can be measured by a differential scanning calorimeter (DSC).

樹脂(A)としては、(メタ)アクリル系樹脂、シリコーン系樹脂、ゴム系樹脂、ウレタン系樹脂等が挙げられ、(メタ)アクリル系樹脂であることが好ましい。 Examples of the resin (A) include (meth) acrylic resin, silicone resin, rubber resin, urethane resin and the like, and (meth) acrylic resin is preferable.

(メタ)アクリル系樹脂としては、(メタ)アクリル酸エステル由来の構成単位を主成分(好ましくは50質量%以上含む)とする重合体であることが好ましい。(メタ)アクリル酸エステルに由来する構造単位は、一種以上の(メタ)アクリル酸エステル以外の単量体に由来する構造単位(例えば、ヒドロキシ基、カルボキシル基、アミノ基等の極性官能基を有する単量体に由来する構造単位)を含んでもよい。 The (meth) acrylic resin is preferably a polymer containing a constituent unit derived from the (meth) acrylic acid ester as a main component (preferably containing 50% by mass or more). The structural unit derived from the (meth) acrylic acid ester has one or more structural units derived from a monomer other than the (meth) acrylic acid ester (for example, a polar functional group such as a hydroxy group, a carboxyl group, or an amino group). A structural unit derived from a monomer) may be contained.

樹脂(A)の含有量は、粘着剤組成物(1)の固形分100質量%中、通常50質量%〜99.9質量%であり、好ましくは60質量%〜95質量%であり、より好ましくは70質量%〜90質量%である。
化合物(X)の含有量は、樹脂(A)100質量部に対して通常0.01〜50質量部であり、好ましくは0.1〜20質量部であり、より好ましくは0.2〜10質量部であり、特に好ましくは0.5〜5質量部である。
The content of the resin (A) is usually 50% by mass to 99.9% by mass, preferably 60% by mass to 95% by mass, based on 100% by mass of the solid content of the pressure-sensitive adhesive composition (1). It is preferably 70% by mass to 90% by mass.
The content of the compound (X) is usually 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin (A). It is by mass, particularly preferably 0.5 to 5 parts by mass.

開始剤(C)は熱のエネルギーを吸収することにより重合反応を引き起こす化合物(熱重合開始剤)、光のエネルギーを吸収することにより重合反応を引き起こす化合物(光重合開始剤)のいずれであってもよい。なお、ここで光とは、可視光線、紫外線、X線、又は電子線のような活性エネルギー線であることが好ましい。 The initiator (C) is either a compound that induces a polymerization reaction by absorbing heat energy (thermal polymerization initiator) or a compound that induces a polymerization reaction by absorbing light energy (photopolymerization initiator). May be good. Here, the light is preferably an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam.

熱重合開始剤としては、加熱等によりラジカルを発生する化合物(熱ラジカル発生剤)、加熱等により酸を発生する化合物(熱酸発生剤)、加熱等により塩基を発生する化合物(熱塩基発生剤)等が挙げられる。
光重合開始剤としては、光のエネルギーを吸収することによりラジカルを発生する化合物(光ラジカル発生剤)、光のエネルギーを吸収することにより酸を発生する化合物(光酸発生剤)、光のエネルギーを吸収することにより塩基を発生する化合物(光塩基発生剤)等が挙げられる。
Examples of the thermal polymerization initiator include compounds that generate radicals by heating (thermal radical generators), compounds that generate acids by heating (thermal acid generators), and compounds that generate bases by heating (thermal base generators). ) Etc. can be mentioned.
Photopolymerization initiators include compounds that generate radicals by absorbing light energy (photoradical generators), compounds that generate acids by absorbing light energy (photoacid generators), and light energy. Examples thereof include compounds that generate a base by absorbing the above (photobase generator).

開始剤(C)は、後述するラジカル硬化性成分(D)の重合反応に適したものを選択することが好ましく、ラジカル重合開始剤であることが好ましく、光ラジカル重合開始剤であることがより好ましい。
ラジカル重合開始剤は、例えば、アルキルフェノン化合物、ベンゾイン化合物、ベンゾフェノン化合物、オキシムエステル化合物、ホスフィン化合物等が挙げられる。ラジカル重合開始剤は、光ラジカル重合開始剤であることが好ましく、重合反応の反応性の観点からオキシムエステル系光ラジカル重合開始剤であることがより好ましい。オキシムエステル系光ラジカル重合開始剤を使用することで、照度又は光量の弱い硬化条件であってもラジカル硬化成分(D)の反応率を高めることができる。
As the initiator (C), it is preferable to select an initiator (C) suitable for the polymerization reaction of the radical curable component (D) described later, preferably a radical polymerization initiator, and more preferably a photoradical polymerization initiator. preferable.
Examples of the radical polymerization initiator include an alkylphenone compound, a benzoin compound, a benzophenone compound, an oxime ester compound, a phosphine compound and the like. The radical polymerization initiator is preferably a photoradical polymerization initiator, and more preferably an oxime ester-based photoradical polymerization initiator from the viewpoint of the reactivity of the polymerization reaction. By using the oxime ester-based photoradical polymerization initiator, the reaction rate of the radical curing component (D) can be increased even under curing conditions where the illuminance or the amount of light is weak.

開始剤(C)の含有量は、樹脂(A)100質量部に対して、通常0.01〜20質量部であり、0.3〜10質量部であることが好ましく、0.5〜5質量部であることがより好ましく、0.75〜4質量部であることがさらに好ましく、特に好ましくは1〜3質量部である。 The content of the initiator (C) is usually 0.01 to 20 parts by mass, preferably 0.3 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably parts by mass, more preferably 0.75 to 4 parts by mass, and particularly preferably 1 to 3 parts by mass.

ラジカル硬化性成分(D)としては、ラジカル重合反応により硬化する化合物又はオリゴマー等のラジカル硬化性成分が挙げられる。
ラジカル重合性成分(D)としては、(メタ)アクリレート系化合物、スチレン系化合物、ビニル系化合物等が挙げられる。
粘着剤組成物(1)はラジカル硬化性成分(D)を2種以上含んでいてもよい。
Examples of the radical curable component (D) include radical curable components such as compounds or oligomers that are cured by a radical polymerization reaction.
Examples of the radically polymerizable component (D) include (meth) acrylate-based compounds, styrene-based compounds, and vinyl-based compounds.
The pressure-sensitive adhesive composition (1) may contain two or more radical curable components (D).

(メタ)アクリレート系化合物としては、分子内に少なくとも1個の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートモノマー、(メタ)アクリルアミドモノマー、及び、分子内に少なくとも2個の(メタ)アクリロイルオキシ基を有する(メタ)アクリルオリゴマー等の(メタ)アクリロイルオキシ基含有化合物を挙げることができる。(メタ)アクリルオリゴマーは好ましくは、分子内に少なくとも2個の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートオリゴマーである。(メタ)アクリレート系化合物は、1種のみを単独で用いてもよいし2種以上を併用してもよい。 Examples of the (meth) acrylate-based compound include a (meth) acrylate monomer having at least one (meth) acryloyloxy group in the molecule, a (meth) acrylamide monomer, and at least two (meth) acryloyloxy in the molecule. Examples thereof include (meth) acryloyloxy group-containing compounds such as (meth) acrylic oligomers having a group. The (meth) acrylic oligomer is preferably a (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in the molecule. As the (meth) acrylate compound, only one kind may be used alone, or two or more kinds may be used in combination.

(メタ)アクリレートモノマーとしては、分子内に1個の(メタ)アクリロイルオキシ基を有する単官能(メタ)アクリレートモノマー、分子内に2個の(メタ)アクリロイルオキシ基を有する2官能(メタ)アクリレートモノマー、分子内に3個以上の(メタ)アクリロイルオキシ基を有する多官能(メタ)アクリレートモノマーが挙げられる。
(メタ)アクリレート化合物であることが好ましく、多官能(メタ)アクリレート化合物であることがより好ましい。多官能(メタ)アクリレート化合物は3官能以上であることが好ましい。
The (meth) acrylate monomer includes a monofunctional (meth) acrylate monomer having one (meth) acryloyloxy group in the molecule and a bifunctional (meth) acrylate having two (meth) acryloyloxy groups in the molecule. Examples include monomers and polyfunctional (meth) acrylate monomers having three or more (meth) acryloyloxy groups in the molecule.
It is preferably a (meth) acrylate compound, and more preferably a polyfunctional (meth) acrylate compound. The polyfunctional (meth) acrylate compound is preferably trifunctional or higher.

ラジカル硬化性成分(D)の含有量は、樹脂(A)100質量部に対して、通常0.5〜100質量部であり、1〜70質量部であることが好ましく、3〜50質量部であることがより好ましく、5〜30質量部であることがさらに好ましく、7.5〜25質量部であることが特に好ましい。 The content of the radical curable component (D) is usually 0.5 to 100 parts by mass, preferably 1 to 70 parts by mass, and 3 to 50 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably 5 to 30 parts by mass, and particularly preferably 7.5 to 25 parts by mass.

架橋剤(E)としては、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤等が挙げられ、特に粘着剤組成物のポットライフ及び粘着剤層の耐久性、架橋速度などの観点から、イソシアネート系架橋剤であることが好ましい。
架橋剤(E)の含有量は、樹脂(A)100質量部に対して、通常0.01〜25質量部であり、好ましくは0.1〜15質量部であり、より好ましくは0.15〜7質量部であり、さらに好ましくは0.2〜5質量部であり、特に好ましくは0.25〜2質量部である。
Examples of the cross-linking agent (E) include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, a metal chelate-based cross-linking agent, and the like. From the viewpoint of speed and the like, an isocyanate-based cross-linking agent is preferable.
The content of the cross-linking agent (E) is usually 0.01 to 25 parts by mass, preferably 0.1 to 15 parts by mass, and more preferably 0.15 parts by mass with respect to 100 parts by mass of the resin (A). It is ~ 7 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.25 to 2 parts by mass.

シラン化合物(F)としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2−メトキシエトキシ)シラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルエトキシジメチルシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−クロロプロピルメチルジメトキシシラン、3−クロロプロピルトリメトキシシラン、3−メタクリロイルオキシプロピルトリメトキシシラン、3−メルカプトプロピルトリメトキシシラン等が挙げられる。
シラン化合物(F)は、シリコーンオリゴマーであってもよい。
シラン化合物(F)の含有量は、樹脂(A)100質量部に対して、通常0.01〜20質量部であり、好ましくは0.1〜10質量部であり、より好ましくは0.15〜7質量部であり、さらに好ましくは0.2〜5質量部であり、特に好ましくは0.25〜2質量部である。
Examples of the silane compound (F) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3 -Glysidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, Examples thereof include 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The silane compound (F) may be a silicone oligomer.
The content of the silane compound (F) is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.15 with respect to 100 parts by mass of the resin (A). It is ~ 7 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.25 to 2 parts by mass.

光選択吸収化合物(G)は、化合物(X)以外の光吸収性化合物であり、例えば、波長250nm〜波長380nm(好ましくは波長250nm以上波長360nm未満)の光を吸収する化合物(紫外線吸収剤)である。
光選択吸収化合物(G)は、波長250nm〜波長380nmの光を吸収する化合物であれば、その構造は特に限定されないが、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、サリチル酸系化合物、シアノアクリレート系化合物、ベンゾオキサジン系化合物等の化合物等が好ましい。
光選択吸収化合物(G)の含有量は、樹脂(A)100質量部に対して、通常0.1〜50質量部であり、好ましくは0.2〜40質量部であり、より好ましくは0.5〜30質量部であり、さらに好ましくは1〜25質量部であり、特に好ましくは2〜20質量部である。
The light selective absorption compound (G) is a light-absorbing compound other than the compound (X), and is, for example, a compound (ultraviolet absorber) that absorbs light having a wavelength of 250 nm to 380 nm (preferably a wavelength of 250 nm or more and less than 360 nm). Is.
The structure of the light selective absorption compound (G) is not particularly limited as long as it is a compound that absorbs light having a wavelength of 250 nm to 380 nm, but a benzotriazole compound, a benzophenone compound, a triazine compound, a salicylic acid compound, and cyano are not particularly limited. Compounds such as acrylate-based compounds and benzoxazine-based compounds are preferable.
The content of the light selective absorption compound (G) is usually 0.1 to 50 parts by mass, preferably 0.2 to 40 parts by mass, and more preferably 0 with respect to 100 parts by mass of the resin (A). It is 5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and particularly preferably 2 to 20 parts by mass.

粘着剤組成物(1)は、さらに、溶剤、架橋触媒、タッキファイヤー、可塑剤、軟化剤、顔料、防錆剤、無機フィラー、光散乱性微粒子等の添加剤を1種又は2種以上含有することができる。 The pressure-sensitive adhesive composition (1) further contains one or more additives such as a solvent, a cross-linking catalyst, a tack fire, a plasticizer, a softener, a pigment, a rust preventive, an inorganic filler, and light-scattering fine particles. can do.

<ハードコート層>
本発明の組成物から形成される層がハードコート層である場合、化合物(X)、光硬化成分及び開始剤を含む活性エネルギー線硬化型組成物(以下、活性エネルギー線硬化型組成物(2)という場合がある)から形成されることが好ましい。ハードコート層とは、例えば、光学用品の最表面に積層される層であり、耐擦傷性の機能を有する層である。
活性エネルギー線硬化性組成物とは、活性エネルギー線の照射を受けて硬化する組成物を表す。活性エネルギー線としては、紫外線、電子線、X線、可視光等が挙げられ、好ましくは紫外線である。紫外線光源としては、波長400nm以下に発光分布を有する光源が好ましく、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ等を挙げることができる。
<Hard coat layer>
When the layer formed from the composition of the present invention is a hard coat layer, an active energy ray-curable composition containing the compound (X), a photocuring component and an initiator (hereinafter, active energy ray-curable composition (2). ) May be formed from). The hard coat layer is, for example, a layer laminated on the outermost surface of an optical product and has a scratch resistant function.
The active energy ray-curable composition represents a composition that is cured by being irradiated with active energy rays. Examples of the active energy ray include ultraviolet rays, electron beams, X-rays, visible light and the like, and ultraviolet rays are preferable. As the ultraviolet light source, a light source having an emission distribution having a wavelength of 400 nm or less is preferable, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp. be able to.

光硬化性成分としては、活性エネルギー線の照射によりラジカル重合反応により硬化する化合物又はオリゴマー(ラジカル重合性化合物)、活性エネルギー線の照射によりカチオン重合反応により硬化する化合物(カチオン重合性化合物)、及び、アニオン重合反応により硬化する化合物等が挙げられる。光硬化性成分は、ラジカル重合性化合物と、カチオン重合性化合物又はアニオン重合性化合物とを併用してもよい。
活性エネルギー線硬化型組成物(2)は、ラジカル重合性成分を含むことが好ましい。
The photocurable components include compounds or oligomers (radical polymerizable compounds) that are cured by a radical polymerization reaction when irradiated with active energy rays, compounds that are cured by a cationic polymerization reaction when irradiated with active energy rays (cationically polymerizable compounds), and , Compounds that are cured by anionic polymerization reaction and the like. As the photocurable component, a radical polymerizable compound and a cationically polymerizable compound or an anionic polymerizable compound may be used in combination.
The active energy ray-curable composition (2) preferably contains a radically polymerizable component.

ラジカル重合性化合物としては、上述したラジカル硬化性成分(D)と同じものが挙げられ、(メタ)アクリレート化合物であることが好ましく、多官能(メタ)アクリレート化合物であることがより好ましい。
光硬化性成分の含有量は、活性エネルギー線硬化性組成物(2)の固形分100質量%に対して、通常50〜99.5質量%であり、好ましくは70〜97質量%である。
化合物(X)の含有量は、光硬化性成分100質量部に対して、通常0.01〜50質量部であり、好ましくは0.1〜20質量部であり、より好ましくは0.5〜10質量部であり、さらに好ましくは0.5〜5質量部である。
Examples of the radically polymerizable compound include the same radically curable component (D) as described above, and a (meth) acrylate compound is preferable, and a polyfunctional (meth) acrylate compound is more preferable.
The content of the photocurable component is usually 50 to 99.5% by mass, preferably 70 to 97% by mass, based on 100% by mass of the solid content of the active energy ray-curable composition (2).
The content of compound (X) is usually 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the photocurable component. It is 10 parts by mass, more preferably 0.5 to 5 parts by mass.

活性エネルギー線硬化型組成物(2)が含んでもよい開始剤としては、上述した開始剤(C)と同じものが挙げられる。開始剤は、ラジカル重合開始剤であることが好ましく、光ラジカル重合開始剤であることがより好ましく、オキシムエステル系重合開始剤であることがさらに好ましい。
開始剤の含有量は、光硬化性成分100質量部に対して、通常、0.01〜20質量部であり、好ましくは0.1〜10質量部であり、さらに好ましくは0.5〜5重量部である。開始剤を0.5質量部以上配合することにより、活性エネルギー線硬化型組成物(2)を十分に硬化させることができる。
Examples of the initiator that the active energy ray-curable composition (2) may contain include the same initiators (C) as described above. The initiator is preferably a radical polymerization initiator, more preferably a photoradical polymerization initiator, and even more preferably an oxime ester-based polymerization initiator.
The content of the initiator is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the photocurable component. It is a part by weight. By blending 0.5 parts by mass or more of the initiator, the active energy ray-curable composition (2) can be sufficiently cured.

以下、実施例及び比較例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。例中、含有量ないし使用量を表す%及び部は、特に断りのない限り質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.

(実施例1)式(UVA−1)で表される化合物の合成

Figure 2021127336

窒素雰囲気下で、4−ヒドロキシピペリジン5部、ジクロロメタン40部、ターシャリーブチルジフェニルクロロシラン13.6部、イミダゾール6.7部を混合し、温度20〜30℃で3時間撹拌した、得られた混合物から溶媒を留去し、精製して、式(M−1)で表される化合物11.8部を得た。 (Example 1) Synthesis of compound represented by formula (UVA-1)
Figure 2021127336

Under a nitrogen atmosphere, 5 parts of 4-hydroxypiperidine, 40 parts of dichloromethane, 13.6 parts of tertiary butyldiphenylchlorosilane, and 6.7 parts of imidazole were mixed and stirred at a temperature of 20 to 30 ° C. for 3 hours. The solvent was distilled off from the mixture and purified to obtain 11.8 parts of the compound represented by the formula (M-1).

Figure 2021127336

窒素雰囲気下で、ジメドン50部、マロノニトリル47部、ジイソプロピルエチルアミン115部、エタノール150部を混合し、温度80℃で3時間撹拌した。得られた混合物から溶媒を留去し、精製して、式(M−2)で表される化合物40部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 50 parts of dimedone, 47 parts of malononitrile, 115 parts of diisopropylethylamine, and 150 parts of ethanol were mixed and stirred at a temperature of 80 ° C. for 3 hours. The solvent was distilled off from the obtained mixture and purified to obtain 40 parts of the compound represented by the formula (M-2).

Figure 2021127336

窒素雰囲気下で、式(M−2)で表される化合物2部、水酸化カリウム0.6部、パラトルエンスルホニルシアニド2.3部、イソプロパノール10部を混合し、温度20〜30℃で3時間撹拌した。得られた混合物から溶媒を留去し、精製して、式(M−3)で表される化合物1.5部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 2 parts of the compound represented by the formula (M-2), 0.6 part of potassium hydroxide, 2.3 parts of paratoluenesulfonyl cyanide and 10 parts of isopropanol were mixed and heated at a temperature of 20 to 30 ° C. The mixture was stirred for 3 hours. The solvent was distilled off from the obtained mixture and purified to obtain 1.5 parts of the compound represented by the formula (M-3).

Figure 2021127336

窒素雰囲気下で、式(M−3)で表される化合物4部、ジイソプロピルエチルアミン3.2部、メチルトリフラート4部、脱水アセトニトリル80部を混合し、温度20〜30℃で3時間撹拌した。混合物に式(M−1)で表される化合物8.3部を加えてさらに1時間撹拌し、得られた混合物から溶媒を留去し、精製して、式(M−4)で表される化合物7部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 4 parts of the compound represented by the formula (M-3), 3.2 parts of diisopropylethylamine, 4 parts of methyl triflate and 80 parts of dehydrated acetonitrile were mixed and stirred at a temperature of 20 to 30 ° C. for 3 hours. 8.3 parts of the compound represented by the formula (M-1) was added to the mixture, and the mixture was further stirred for 1 hour. The solvent was distilled off from the obtained mixture, and the mixture was purified and represented by the formula (M-4). 7 parts of the compound were obtained.

Figure 2021127336

窒素雰囲気下で、式(M−4)で表される化合物4.2部、テトラブチルアンモニウムフルオリド/テトラヒドロフラン1M溶液60部を混合し、温度20〜30℃で30時間撹拌した。得られた混合物から溶媒を留去し、精製して、式(M−5)で表される化合物1.6部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 4.2 parts of the compound represented by the formula (M-4) and 60 parts of a tetrabutylammonium fluoride / tetrahydrofuran 1M solution were mixed and stirred at a temperature of 20 to 30 ° C. for 30 hours. The solvent was distilled off from the obtained mixture and the mixture was purified to obtain 1.6 parts of the compound represented by the formula (M-5).

Figure 2021127336

窒素雰囲気下で、式(M−5)で表される化合物1.2部、ジイソプロピルエチルアミン0.7部、クロロホルム(トリクロロメタン)24部、ジブチルヒドロキシトルエン0.04部を混合し、氷浴下撹拌しながら、30分かけてアクリル酸クロリド0.8部を滴下した。そのまま氷浴下で3時間撹拌し、混合物から溶媒を留去し、精製して、式(UVA−1)で表される化合物0.5部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 1.2 parts of the compound represented by the formula (M-5), 0.7 parts of diisopropylethylamine, 24 parts of chloroform (trichloromethane), and 0.04 part of dibutylhydroxytoluene are mixed and placed in an ice bath. While stirring, 0.8 part of chloroform acid chloride was added dropwise over 30 minutes. The mixture was stirred as it was in an ice bath for 3 hours, the solvent was distilled off from the mixture, and the mixture was purified to obtain 0.5 part of the compound represented by the formula (UVA-1).

LC−MS測定及びH−NMR解析を行い、式(UVA−1)で表される化合物が生成したことを確認した。
H−NMR(重ジメチルスルホキシド(重DMSO))δ:1.00(s、6H)、1.38〜2.10(m、4H)、2.54(m、2H)、2.69(m、2H)、3.83〜3.96(m、4H)、5.12〜5.14(m、1H)、5.99〜6.41(m、3H)
LC−MS;[M+H]=351.5
LC-MS measurement and 1 H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (UVA-1) was produced.
1 1 H-NMR (heavy dimethyl sulfoxide (heavy DMSO)) δ: 1.00 (s, 6H), 1.38 to 2.10 (m, 4H), 2.54 (m, 2H), 2.69 ( m, 2H), 3.83 to 3.96 (m, 4H), 5.12 to 5.14 (m, 1H), 5.99 to 6.41 (m, 3H)
LC-MS; [M + H] + = 351.5

<極大吸収波長及びグラム吸光係数ε測定>
得られた式(UVA−1)で表される化合物の2−ブタノン溶液(0.006g/L)を1cmの石英セルに入れ、この石英セルを分光光度計UV−2450(株式会社島津製作所製)にセットし、ダブルビーム法により1nmステップ300〜800nmの波長範囲で吸光度を測定した。得られた吸光度の値、溶液中の式(UVA−1)で表される化合物の濃度、及び石英セルの光路長から、波長ごとのグラム吸光係数を算出した。
ε(λ)=A(λ)/CL
〔式中、ε(λ)は波長λnmにおける式(UVA−1)で表される化合物のグラム吸光係数[L/(g・cm)]を表し、A(λ)は波長λnmにおける吸光度を表し、Cは濃度(g/L)を表し、Lは石英セルの光路長[m]を表す。〕
得られた式(UVA−1)で表される化合物の極大吸収波長は385nmであった。得られた式(UVA−1)で表される化合物のε(λmax)は130.4L/(g・cm)、ε(λmax+30nm)は7L/(g・cm)、ε(λmax)/ε(λmax+30nm)は18.6であった。
<Maximum absorption wavelength and gram absorption coefficient ε measurement>
A 2-butanone solution (0.006 g / L) of the compound represented by the obtained formula (UVA-1) was placed in a 1 cm quartz cell, and the quartz cell was placed in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation). ), And the absorbance was measured in the wavelength range of 1 nm step 300 to 800 nm by the double beam method. The gram extinction coefficient for each wavelength was calculated from the obtained absorbance value, the concentration of the compound represented by the formula (UVA-1) in the solution, and the optical path length of the quartz cell.
ε (λ) = A (λ) / CL
[In the formula, ε (λ) represents the gram extinction coefficient [L / (g · cm)] of the compound represented by the formula (UVA-1) at the wavelength λ nm, and A (λ) represents the absorbance at the wavelength λ nm. , C represents the concentration (g / L), and L represents the optical path length [m] of the quartz cell. ]
The maximum absorption wavelength of the obtained compound represented by the formula (UVA-1) was 385 nm. The obtained compound represented by the formula (UVA-1) has ε (λmax) of 130.4 L / (g · cm), ε (λmax + 30 nm) of 7 L / (g · cm), and ε (λmax) / ε ( λmax + 30 nm) was 18.6.

(実施例2)式(UVA−2)で表される化合物の合成

Figure 2021127336

窒素雰囲気下で、式(M−3)で表される化合物1.1部、ジイソプロピルエチルアミン0.7部、メチルトリフラート0.9部、脱水アセトニトリル11部を混合し、温度20〜30℃で3時間撹拌した。混合物に(2−ヒドロキシ)エチルメチルアミン1.4部を加えてさらに1時間撹拌し、得られた混合物から溶媒を留去し、精製して、式(M−6)で表される化合物0.5部を得た。 (Example 2) Synthesis of compound represented by formula (UVA-2)
Figure 2021127336

Under a nitrogen atmosphere, 1.1 parts of the compound represented by the formula (M-3), 0.7 parts of diisopropylethylamine, 0.9 parts of methyl triflate, and 11 parts of dehydrated acetonitrile were mixed and 3 at a temperature of 20 to 30 ° C. Stirred for hours. 1.4 parts of (2-hydroxy) ethylmethylamine was added to the mixture, and the mixture was further stirred for 1 hour. The solvent was distilled off from the obtained mixture, and the mixture was purified to obtain compound 0 represented by the formula (M-6). .5 copies were obtained.

Figure 2021127336

窒素雰囲気下で、式(M−6)で表される化合物0.7部、ジイソプロピルエチルアミン0.7部、クロロホルム11部、ジブチルヒドロキシトルエン0.03部を混合し、氷浴下撹拌しながら、30分かけてアクリル酸クロリド0.5部を滴下した。そのまま氷浴下で3時間撹拌した。得られた混合物から溶媒を留去し、精製して、式(UVA−2)で表される化合物0.3部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 0.7 part of the compound represented by the formula (M-6), 0.7 part of diisopropylethylamine, 11 parts of chloroform, and 0.03 part of dibutylhydroxytoluene were mixed and stirred under an ice bath. 0.5 part of acrylic acid chloride was added dropwise over 30 minutes. The mixture was stirred as it was in an ice bath for 3 hours. The solvent was distilled off from the obtained mixture and the mixture was purified to obtain 0.3 part of the compound represented by the formula (UVA-2).

LC−MS測定及びH−NMR解析を行い、式(UVA−2)で表される化合物が生成したことを確認した。
H−NMR(重DMSO)δ:1.07(s、6H)、2.44(s、2H)、2.56(s、2H)、3.47(s、3H)、3.96(s、2H)、4.46〜4.48(m、2H)、5.94〜6.50(m、3H)
LC−MS;[M+H]=325.5
LC-MS measurement and 1 H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (UVA-2) was produced.
1 1 H-NMR (heavy DMSO) δ: 1.07 (s, 6H), 2.44 (s, 2H), 2.56 (s, 2H), 3.47 (s, 3H), 3.96 ( s, 2H) 4.46-4.48 (m, 2H) 5.94-6.50 (m, 3H)
LC-MS; [M + H] + = 325.5

また、上記と同様にして、極大吸収波長及びグラム吸光係数を測定した。得られた式(UVA−2)で表される化合物の極大吸収波長は380nmであった。得られた式(UVA−2)で表される化合物のε(λmax)は127.4L/(g・cm)、ε(λmax+30nm)は6.4L/(g・cm)、ε(λmax)/ε(λmax+30nm)は19.9であった。 Further, in the same manner as above, the maximum absorption wavelength and the gram absorption coefficient were measured. The maximum absorption wavelength of the compound represented by the obtained formula (UVA-2) was 380 nm. The obtained compound represented by the formula (UVA-2) has ε (λmax) of 127.4 L / (g · cm), ε (λmax + 30 nm) of 6.4 L / (g · cm), and ε (λmax) /. ε (λmax + 30 nm) was 19.9.

(実施例3)式(UVA−3)で表される化合物の合成

Figure 2021127336

窒素雰囲気下で、式(M−3)で表される化合物4部、ジイソプロピルエチルアミン2.8部、メチルトリフラート3.6部、アセトニトリル40部を混合し、温度20〜30℃で3時間撹拌した。混合物に3−ヒドロキシピロリジン4部を加えてさらに1時間撹拌し、得られた混合物から溶媒を留去し、精製して、式(M−7)で表される化合物2.6部を得た。 (Example 3) Synthesis of compound represented by formula (UVA-3)
Figure 2021127336

Under a nitrogen atmosphere, 4 parts of the compound represented by the formula (M-3), 2.8 parts of diisopropylethylamine, 3.6 parts of methyl triflate and 40 parts of acetonitrile were mixed and stirred at a temperature of 20 to 30 ° C. for 3 hours. .. 4 parts of 3-hydroxypyrrolidine was added to the mixture, and the mixture was further stirred for 1 hour. The solvent was distilled off from the obtained mixture and the mixture was purified to obtain 2.6 parts of the compound represented by the formula (M-7). ..

Figure 2021127336

窒素雰囲気下で、式(M−7)で表される化合物3.4部、ジイソプロピルエチルアミン3.9部、クロロホルム51部、ジブチルヒドロキシトルエン0.13部を混合し、氷浴下撹拌しながら、30分かけてアクリル酸クロリド2.7部を滴下した。そのまま氷浴下で3時間撹拌し、混合物から溶媒を留去し、精製して、式(UVA−3)で表される化合物1.6部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 3.4 parts of the compound represented by the formula (M-7), 3.9 parts of diisopropylethylamine, 51 parts of chloroform, and 0.13 parts of dibutylhydroxytoluene are mixed, and the mixture is stirred under an ice bath. 2.7 parts of chloroformic acid chloride was added dropwise over 30 minutes. The mixture was stirred as it was in an ice bath for 3 hours, the solvent was distilled off from the mixture, and the mixture was purified to obtain 1.6 parts of the compound represented by the formula (UVA-3).

LC−MS測定及びH−NMR解析を行い、式(UVA−3)で表される化合物が生成したことを確認した。
H−NMR(重DMSO)δ:0.94〜1.03(m、6H)、1.16〜1.19(m、2H)、1.99(s、2H)、2.66〜2.77(m、2H)、3.89〜4.06(m、4H)、5.42〜5.45(m、1H)、5.97〜6.41(m、3H)
LC−MS;[M+H]=337.5
LC-MS measurement and 1 H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (UVA-3) was produced.
1 1 H-NMR (heavy DMSO) δ: 0.94 to 1.03 (m, 6H), 1.16 to 1.19 (m, 2H), 1.99 (s, 2H), 2.66 to 2. .77 (m, 2H), 3.89-4.06 (m, 4H), 5.42-5.45 (m, 1H), 5.97-6.41 (m, 3H)
LC-MS; [M + H] + = 337.5

また、上記と同様にして、極大吸収波長及びグラム吸光係数を測定した。得られた式(UVA−3)で表される化合物の極大吸収波長は380nmであった。得られた式(UVA−3)で表される化合物のε(λmax)は109.5L/(g・cm)、ε(λmax+30nm)は2.1L/(g・cm)、ε(λmax)/ε(λmax+30nm)は52.1であった。 Further, in the same manner as above, the maximum absorption wavelength and the gram absorption coefficient were measured. The maximum absorption wavelength of the obtained compound represented by the formula (UVA-3) was 380 nm. The obtained compound represented by the formula (UVA-3) has ε (λmax) of 109.5 L / (g · cm), ε (λmax + 30 nm) of 2.1 L / (g · cm), and ε (λmax) /. ε (λmax + 30 nm) was 52.1.

(実施例4)式(UVA−4)で表される化合物の合成

Figure 2021127336

窒素雰囲気下で、式(M−3)で表される化合物4部、ジイソプロピルエチルアミン2.8部、メチルトリフラート3.6部、アセトニトリル40部を混合し、温度20〜30℃で3時間撹拌した。混合物に4−(ヒドロキシメチル)ピペリジン4部を加えてさらに1時間撹拌し、得られた混合物から溶媒を留去し、精製して、式(M−8)で表される化合物2部を得た。 (Example 4) Synthesis of compound represented by formula (UVA-4)
Figure 2021127336

Under a nitrogen atmosphere, 4 parts of the compound represented by the formula (M-3), 2.8 parts of diisopropylethylamine, 3.6 parts of methyl triflate and 40 parts of acetonitrile were mixed and stirred at a temperature of 20 to 30 ° C. for 3 hours. .. 4 parts of 4- (hydroxymethyl) piperidine was added to the mixture, and the mixture was further stirred for 1 hour. The solvent was distilled off from the obtained mixture and purified to obtain 2 parts of the compound represented by the formula (M-8). rice field.

Figure 2021127336

窒素雰囲気下で、式(M−8)で表される化合物0.9部、ジイソプロピルエチルアミン0.4部、クロロホルム4.7部、ジブチルヒドロキシトルエン0.07部を混合し、氷浴下撹拌しながら、30分かけてアクリル酸クロリド0.3部を滴下した。そのまま氷浴下で3時間撹拌し、混合物から溶媒を留去し、精製して、式(UVA−4)で表される化合物0.7部を得た。
Figure 2021127336

Under a nitrogen atmosphere, 0.9 part of the compound represented by the formula (M-8), 0.4 part of diisopropylethylamine, 4.7 parts of chloroform, and 0.07 part of dibutylhydroxytoluene are mixed and stirred under an ice bath. However, 0.3 part of acrylic acid chloride was added dropwise over 30 minutes. The mixture was stirred as it was in an ice bath for 3 hours, the solvent was distilled off from the mixture, and the mixture was purified to obtain 0.7 part of the compound represented by the formula (UVA-4).

LC−MS測定及びH−NMR解析を行い、式(UVA−4)で表される化合物が生成したことを確認した。
H−NMR(重DMSO)δ:0.95(s、6H)、1.36〜1.91(m、4H)、2.50(m、2H)、2.75(m、2H)、3.29〜3.33(m、3H)、4.03〜4.32(m、4H)、5.95〜6.37(m、3H)
LC−MS;[M+H]=365.5
LC-MS measurement and 1 H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (UVA-4) was produced.
1 1 H-NMR (heavy DMSO) δ: 0.95 (s, 6H), 1.36 to 1.91 (m, 4H), 2.50 (m, 2H), 2.75 (m, 2H), 3.29 to 3.33 (m, 3H), 4.03 to 4.32 (m, 4H), 5.95 to 6.37 (m, 3H)
LC-MS; [M + H] + = 365.5

また、上記と同様にして、極大吸収波長及びグラム吸光係数を測定した。得られた式(UVA−4)で表される化合物の極大吸収波長は385nmであった。得られた式(UVA−4)で表される化合物のε(λmax)は120.7L/(g・cm)、ε(λmax+30nm)は7.2L/(g・cm)、ε(λmax)/ε(λmax+30nm)は16.8であった。 Further, in the same manner as above, the maximum absorption wavelength and the gram absorption coefficient were measured. The maximum absorption wavelength of the obtained compound represented by the formula (UVA-4) was 385 nm. The obtained compound represented by the formula (UVA-4) has ε (λmax) of 120.7 L / (g · cm), ε (λmax + 30 nm) of 7.2 L / (g · cm), and ε (λmax) /. ε (λmax + 30 nm) was 16.8.

(実施例5)粘着剤組成物(1)の調製
<アクリル樹脂の調製>
[重合例1]:アクリル樹脂(A)の調製
冷却管、窒素導入管、温度計および撹拌機を備えた反応容器に、溶媒としての酢酸エチル81.8部、アクリル酸ブチル96部、アクリル酸2−ヒドロキシエチルメチル3部、およびアクリル酸1部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら内温を55℃に上げた。その後、アゾビスイソブチロニトリル(重合開始剤)0.14部を酢酸エチル10部に溶かした溶液を全量添加した。開始剤の添加した後1時間この温度で保持し、次いで内温を54〜56℃に保ちながら酢酸エチルを添加速度17.3部/hrで反応容器内へ連続的に加え、アクリル樹脂の濃度が35%となった時点で酢酸エチルの添加を止め、さらに酢酸エチルの添加開始から12時間経過するまでこの温度で保温した。最後に酢酸エチルを加えてアクリル樹脂の濃度が20%となるように調節し、アクリル樹脂の酢酸エチル溶液を調製した。得られたアクリル樹脂は、GPCによるポリスチレン換算の重量平均分子量Mwが147万、Mw/Mnが5.5であった。これをアクリル樹脂(A)とする。
(Example 5) Preparation of pressure-sensitive adhesive composition (1) <Preparation of acrylic resin>
[Polymerization Example 1]: Preparation of acrylic resin (A) 81.8 parts of ethyl acetate, 96 parts of butyl acrylate, acrylic acid as a solvent in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer. A mixed solution of 3 parts of 2-hydroxyethylmethyl and 1 part of acrylic acid was charged, and the internal temperature was raised to 55 ° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. Then, a total amount of a solution prepared by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. After the initiator was added, the temperature was maintained at this temperature for 1 hour, and then ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr while maintaining the internal temperature at 54 to 56 ° C. to concentrate the acrylic resin. The addition of ethyl acetate was stopped when the temperature reached 35%, and the temperature was kept at this temperature until 12 hours had passed from the start of addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, and an ethyl acetate solution of the acrylic resin was prepared. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1.47 million and Mw / Mn of 5.5 according to GPC. This is referred to as acrylic resin (A).

アクリル樹脂(A)の酢酸エチル溶液(樹脂濃度:20%)の固形分100部に対して、架橋剤(E)(東ソー株式会社製:商品名「コロネートL」、イソシアネート系化合物、固形分75%)0.3部、シラン化合物(F)(信越化学工業株式会社製:商品名「KBM3066」)0.28部、ラジカル硬化性成分(D)(新中村化学工業株式会社製:商品名「A−DPH−12E」、6官能(メタ)アクリレート化合物)10部、開始剤(C)(株式会社ADEKA社製:商品名「NCI−730」、オキシムエステル化合物である光ラジカル発生剤)0.3部、化合物(X)(式(UVA−1)で表される化合物)5部を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物(1)を得た。なお、上記架橋剤の配合量は、有効成分としての質量部数である。 A cross-linking agent (E) (manufactured by Toso Co., Ltd .: trade name "Coronate L", isocyanate compound, solid content 75) with respect to 100 parts of the solid content of the ethyl acetate solution (resin concentration: 20%) of the acrylic resin (A). %) 0.3 parts, silane compound (F) (manufactured by Shinetsu Chemical Industry Co., Ltd .: trade name "KBM3066") 0.28 parts, radical curable component (D) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: product name " A-DPH-12E ", 6 functional (meth) acrylate compound), initiator (C) (manufactured by ADEKA Co., Ltd .: trade name" NCI-730 ", photoradical generator which is an oxime ester compound) 0. 3 parts and 5 parts of compound (X) (compound represented by the formula (UVA-1)) are mixed, and ethyl acetate is further added so that the solid content concentration becomes 14% to prepare the pressure-sensitive adhesive composition (1). Got The blending amount of the above-mentioned cross-linking agent is the number of parts by mass as the active ingredient.

(実施例6〜12)及び(比較例1〜7)
表1及び表2に示すように各成分及び各成分の含有量を変えた以外は実施例5と同様にして粘着剤組成物(2)〜粘着剤組成物(15)を作製した。なお、架橋剤の配合量は有効成分としての質量部数であり、樹脂(A)は固形分の質量部数である。
(Examples 6 to 12) and (Comparative Examples 1 to 7)
The pressure-sensitive adhesive composition (2) to the pressure-sensitive adhesive composition (15) were prepared in the same manner as in Example 5 except that each component and the content of each component were changed as shown in Tables 1 and 2. The amount of the cross-linking agent blended is the number of parts by mass as the active ingredient, and the resin (A) is the number of parts by mass of the solid content.

Figure 2021127336
Figure 2021127336

Figure 2021127336
Figure 2021127336

なお、表1及び表2における各略語は以下の意味を表す。
アクリル樹脂(A):重合例1で合成したアクリル樹脂(A)
式(UVA−1):実施例1で合成した式(UVA−1)で表される化合物
式(UVA−3):実施例3で合成した式(UVA−3)で表される化合物
式(UVA−4):実施例4で合成した式(UVA−4)で表される化合物
NCI−730:株式会社ADEKA社製、商品名:NCI−730、オキシムエステル化合物である光ラジカル発生剤
A−DPH−12E:新中村化学工業株式会社製、商品名;A−DPH−12E、6官能(メタ)アクリレート化合物
コロネートL:東ソー株式会社製、商品名:コロネートL、イソシアネート系架橋剤
KBM3066:信越化学工業株式会社製、商品名:KBM3066、シランカップリング剤
RUVA−93:大塚化学株式会社製、ベンゾトリアゾール系紫外線吸収剤、商品名:RUVA−93、極大吸収波長λmax=337nm
KB74:ケミプロ化成株式会社製、ベンゾトリアゾール系紫外線吸収剤、商品名:KEMSORB74、極大吸収波長λmax=342nm
SB107:シプロ化成株式会社製、ベンゾフェノン系紫外線吸収剤、商品名:SEESORB107、極大吸収波長λmax=350nm
SB707:シプロ化成株式会社製、ベンゾトリアゾール系紫外線吸収剤、商品名:SEESORB707、極大吸収波長λmax=343nm
UV3911:オリエント化学工業社製、インドール系紫外線吸収剤、商品名:BONASORB UA−3901 極大吸収波長λmax=393nm
式(a):下記式(a)で表される化合物(特開2019−089997号公報に記載の方法で合成)

Figure 2021127336
The abbreviations in Tables 1 and 2 have the following meanings.
Acrylic resin (A): Acrylic resin (A) synthesized in Polymerization Example 1
Formula (UVA-1): Compound represented by formula (UVA-1) synthesized in Example 1 Formula (UVA-3): Compound represented by formula (UVA-3) synthesized in Example 3 Formula (UVA-3) UVA-4): Compound represented by the formula (UVA-4) synthesized in Example 4 NCI-730: Manufactured by ADEKA Co., Ltd., trade name: NCI-730, photoradical generator A-, which is an oxime ester compound. DPH-12E: manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name; A-DPH-12E, hexafunctional (meth) acrylate compound Coronate L: manufactured by Toso Co., Ltd., trade name: coronate L, isocyanate-based cross-linking agent KBM3066: Shinetsu Chemical Co., Ltd. Industrial Co., Ltd., Product name: KBM3066, Silane coupling agent RUVA-93: Otsuka Chemical Co., Ltd., Benzotriazole-based ultraviolet absorber, Product name: RUVA-93, Maximum absorption wavelength λmax = 337 nm
KB74: Benzotriazole UV absorber manufactured by Chemipro Kasei Kaisha, trade name: KEMSORB74, maximum absorption wavelength λmax = 342nm
SB107: Benzophenone-based UV absorber manufactured by Cipro Kasei Co., Ltd., trade name: SEESORB107, maximum absorption wavelength λmax = 350 nm
SB707: Cipro Kasei Co., Ltd., Benzotriazole-based UV absorber, trade name: SEESORB707, maximum absorption wavelength λmax = 343 nm
UV3911: Indole-based UV absorber manufactured by Orient Chemical Industry Co., Ltd., trade name: BONASORB UA-3901 Maximum absorption wavelength λmax = 393 nm
Formula (a): Compound represented by the following formula (a) (synthesized by the method described in JP-A-2019-0899797)
Figure 2021127336

<粘着剤層の作製>
(実施例13)
上記で調製した粘着剤組成物(1)を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR−382190」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが5μmとなるように塗布し、温度100℃で1分間乾燥した。その後、セパレートフィルム側から紫外線照射装置(フュージョン UV システムズ社製「無電極UVランプシステム Hバルブ」)を用いてUV−A(波長320〜390nm)が照度500mW、積算光量が500mJになるよう調整し、紫外線照射することで粘着剤層(粘着剤シート)(1)を作製した。
<Preparation of adhesive layer>
(Example 13)
The pressure-sensitive adhesive composition (1) prepared above was applied to the release-treated surface of a separate film [trade name "PLR-382190" obtained from Lintec Corporation] made of a polyethylene terephthalate film that had been released-treated. The film was applied using an applicator so that the thickness after drying was 5 μm, and dried at a temperature of 100 ° C. for 1 minute. After that, from the separate film side, UV-A (wavelength 320 to 390 nm) was adjusted to an illuminance of 500 mW and an integrated light amount of 500 mJ using an ultraviolet irradiation device (“Fusion UV Systems Co., Ltd.“ Electrodeless UV lamp system H valve ”). , An adhesive layer (adhesive sheet) (1) was prepared by irradiating with ultraviolet rays.

(実施例14〜23)及び(比較例8〜13)
表3に示すように、使用する粘着剤組成物、形成される粘着剤層の厚みを変化させる以外は実施例13と同様にして、粘着剤層(2)〜粘着剤層(17)を作製した。
(Examples 14 to 23) and (Comparative Examples 8 to 13)
As shown in Table 3, the pressure-sensitive adhesive layer (2) to the pressure-sensitive adhesive layer (17) are prepared in the same manner as in Example 13 except that the pressure-sensitive adhesive composition used and the thickness of the pressure-sensitive adhesive layer formed are changed. bottom.

(比較例14)
上記で調整した粘着剤組成物(15)を離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR−382190」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが5μmとなるように塗布し、温度100℃で1分間乾燥して粘着剤層(18)を作製した。
得られた粘着剤層(18)をラミネーターにより、23μmのシクロオレフィンフィルム(日本ゼオン株式会社製ZF−14)に張り合わせた後、温度23℃、相対湿度65%の条件で7日間養生し、粘着剤シート(18)を得た。
(Comparative Example 14)
An applicator is applied to the release-treated surface of a separate film [trade name "PLR-382190" obtained from Lintec Co., Ltd.] made of a polyethylene terephthalate film that has been released from the pressure-sensitive adhesive composition (15) prepared above. Was applied so that the thickness after drying was 5 μm, and the film was dried at a temperature of 100 ° C. for 1 minute to prepare an adhesive layer (18).
The obtained pressure-sensitive adhesive layer (18) was bonded to a 23 μm cycloolefin film (ZF-14 manufactured by Nippon Zeon Corporation) with a laminator, and then cured under the conditions of a temperature of 23 ° C. and a relative humidity of 65% for 7 days to adhere. An agent sheet (18) was obtained.

<粘着剤シートの吸光度測定>
得られた粘着剤層(1)〜粘着剤層(17)をそれぞれ無アルカリガラスに貼合し、セパレートフィルムを剥離した後、粘着剤層にシクロオレフィンポリマー(COP)フィルム(日本ゼオン株式会社製ZF−14)を貼合し、COPフィルム/粘着剤層/ガラスの構成を有する積層体を作製した。
また、得られた粘着剤シート(18)のセパレートフィルムを剥離し、無アルカリガラスに貼合してCOPフィルム/粘着剤層/ガラスの構成を有する積層体を作製した。
作製した積層体を分光光度計UV−2450(株式会社島津製作所製)にセットし、ダブルビーム法により1nmステップ300〜800nmの波長範囲で吸光度を測定した。作製した粘着剤層の波長330nm、波長400nm及び波長420nmにおける吸光度(Abs)を表3に示す。なお、波長330nm、波長400nm及び波長420nmにおける、無アルカリガラスの吸光度及びCOPフィルムの吸光度はいずれも0である。
<Measurement of absorbance of adhesive sheet>
The obtained pressure-sensitive adhesive layers (1) to pressure-sensitive adhesive layers (17) are respectively bonded to non-alkali glass, the separate film is peeled off, and then a cycloolefin polymer (COP) film (manufactured by Nippon Zeon Co., Ltd.) is applied to the pressure-sensitive adhesive layer. ZF-14) was laminated to prepare a laminate having a composition of COP film / adhesive layer / glass.
Further, the separate film of the obtained pressure-sensitive adhesive sheet (18) was peeled off and bonded to non-alkali glass to prepare a laminate having a composition of COP film / pressure-sensitive adhesive layer / glass.
The prepared laminate was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance was measured in the wavelength range of 1 nm step 300 to 800 nm by the double beam method. Table 3 shows the absorbances (Abs) of the prepared pressure-sensitive adhesive layer at a wavelength of 330 nm, a wavelength of 400 nm, and a wavelength of 420 nm. The absorbance of the non-alkali glass and the absorbance of the COP film at a wavelength of 330 nm, a wavelength of 400 nm and a wavelength of 420 nm are all 0.

吸光度測定後のサンプルを、温度63℃、相対湿度50%の条件でサンシャインウェザーメーター(スガ試験機株式会社製)に200時間投入し、耐候性試験を実施した。取り出したサンプルの吸光度を上記と同様の方法で測定した。測定した吸光度から、下記式に基づき、波長400nmにおけるサンプルの吸光度保持率を求めた。結果を表3に示す。
吸光度保持率(%)
=(耐久試験後のA(400)/耐久試験前のA(400))×100
[式中、A(400)は、波長400nmにおけるサンプルの吸光度を表す。]
The sample after the absorbance measurement was put into a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) under the conditions of a temperature of 63 ° C. and a relative humidity of 50% for 200 hours to carry out a weather resistance test. The absorbance of the taken-out sample was measured by the same method as described above. From the measured absorbance, the absorbance retention rate of the sample at a wavelength of 400 nm was determined based on the following formula. The results are shown in Table 3.
Absorbance retention rate (%)
= (A (400) after endurance test / A (400) before endurance test) x 100
[In the formula, A (400) represents the absorbance of the sample at a wavelength of 400 nm. ]

<粘着剤層の耐ブリード性評価>
得られた粘着剤層の面にさらにセパレートフィルムを積層させて両面セパレートフィルム付き粘着剤層を得た。得られた両面セパレートフィルム付き粘着剤層を温度23〜25℃の空気下で1ヶ月保管した。保管後の両面セパレートフィルム付き粘着剤層を顕微鏡を用いて面内の化合物の結晶析出有無を確認した。結晶析出がないと「〇」とし、結晶析出があると「×」とした。評価結果を表3に示す。
<Evaluation of bleed resistance of adhesive layer>
A separate film was further laminated on the surface of the obtained pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive layer with a double-sided separate film. The obtained pressure-sensitive adhesive layer with a double-sided separate film was stored in air at a temperature of 23 to 25 ° C. for 1 month. After storage, the pressure-sensitive adhesive layer with the double-sided separate film was checked for crystal precipitation of the compound in the plane using a microscope. If there was no crystal precipitation, it was evaluated as "○", and if there was crystal precipitation, it was evaluated as "x". The evaluation results are shown in Table 3.

Figure 2021127336
Figure 2021127336

本発明のメロシアニン骨格を有する新規化合物は長波紫外線〜近紫外線の領域に対して高い吸収選択性を有し、かつ、良好な耐候性を有し、本発明の新規化合物を含む組成物から形成された層を薄膜にしたとしても、化合物が析出せず良好な耐ブリード性を有する。 The novel compound having the merocyanine skeleton of the present invention has high absorption selectivity in the region of long-wave ultraviolet rays to near-ultraviolet rays, has good weather resistance, and is formed from a composition containing the novel compound of the present invention. Even if the layer is made into a thin film, the compound does not precipitate and has good bleed resistance.

Claims (40)

重合性基と下記式(X)で表される部分構造とを有する化合物。
Figure 2021127336

[式(X)中、環Wは、環の構成要素として二重結合を有し、かつ芳香族性を有さない環構造を表し、環Wは置換基を有していてもよい。
は、1価の置換基を表す。]
A compound having a polymerizable group and a partial structure represented by the following formula (X).
Figure 2021127336

[In formula (X), ring W 1 represents a ring structure having a double bond as a component of the ring and having no aromaticity, and ring W 1 may have a substituent. ..
R 3 represents a monovalent substituent. ]
重合性基と式(X)で表される部分構造とを有する化合物が、式(I)で表される化合物〜式(IX)で表される化合物のいずれかである請求項1に記載の化合物。
Figure 2021127336

Figure 2021127336

[式(I)〜式(IX)中、環W及びRは、前記と同じ意味を表す。
環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、それぞれ独立して、環の構成要素として少なくとも1つの二重結合を有する環構造を表す。環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13は、置換基を有していてもよい。
環W111は、構成要素として窒素原子を2つ有する複素環を表す。
環W112、環W113及び環W114は、それぞれ独立して、構成要素として窒素原子を1つ有する複素環を表す。
、R41、R51、R61、R91、R101、R111、R、R12、R42、R52、R62、R72、R82、R92、R102及びR112は、それぞれ独立して、水素原子、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−NR12A−、−SO−、−CO−、−O−、−COO−、−OCO−、−CONR13A−、−NR14A−CO−、−S−、−SO−、−SO−、−CF−又は−CHF−に置換されていてもよい。
13、R23、R33、R43、R53、R63、R73、R83、R93、R103、R113及びR123は、それぞれ独立して、複素環基、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、チオール基、カルボキシ基、−SF、−SF、−SOH、−SOH、重合性基を含む基、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表し、該脂肪族炭化水素基又は芳香族炭化水素基に含まれる−CH−及び−CH=は、それぞれ独立して、−O−、−S−、−NR1A−、−CO−、−CO−O−、−O−CO−、−O−CO−O−、−CONR2A−、−O−CO−NR3A−、−NR4A−CO−、−NR5A−CO−O−、−NR6A−CO−NR7A−、−CO−S−、−S−CO−S−、−S−CO−NR8A−、−NR9A−CO−S−、−CS−、−O−CS−、−CS−O−、−NR10A−CS−、−NR11A−CS−S−、−S−CS−、−CS−S−、−S−CS−S−、−SO−又は−SO−に置換されていてもよい。
1A、R2A、R3A、R4A、R5A、R6A、R7A、R8A、R9A、R10A、R11A、R12A、R13A及びR14Aは、それぞれ独立して、水素原子又は炭素数1〜6のアルキル基を表す。
、R14、R24、R34、R44、R54、R64、R74、R84、R94、R104、R114、R124、R、R15、R25、R35、R75、R85及びR125は、それぞれ独立して、電子求引性基又は重合性基を含む基を表す。
及びRは互いに結合して環を形成してもよい。
41及びR42は互いに結合して環を形成してもよい。
51及びR52は互いに結合して環を形成してもよい。
61及びR62は互いに結合して環を形成してもよい。
91及びR92は互いに結合して環を形成してもよい。
101及びR102は互いに結合して環を形成してもよい。
111及びR112は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
12及びR13は互いに結合して環を形成してもよい。
42及びR43は互いに結合して環を形成してもよい。
52及びR53は互いに結合して環を形成してもよい。
62及びR63は互いに結合して環を形成してもよい。
72及びR73は互いに結合して環を形成してもよい。
82及びR83は互いに結合して環を形成してもよい。
92及びR93は互いに結合して環を形成してもよい。
102及びR103は互いに結合して環を形成してもよい。
112及びR113は互いに結合して環を形成してもよい。
及びRは互いに結合して環を形成してもよい。
14及びR15は互いに結合して環を形成してもよい。
24及びR25は互いに結合して環を形成してもよい。
34及びR35は互いに結合して環を形成してもよい。
74及びR85は互いに結合して環を形成してもよい。
84及びR85は互いに結合して環を形成してもよい。
124及びR125は互いに結合して環を形成してもよい。
及びRは、それぞれ独立して、2価の連結基を表す。
及びR126は、それぞれ独立して、単結合又は2価の連結基を表す。
及びR10は、それぞれ独立して、3価の連結基を表す。
11は、4価の連結基を表す。
ただし、式(I)においては、R、R、R及びRのうち少なくとも一つは重合性基を含む基を表す。
式(II)においては、R、R、R、R12、R13、R14及びR15のうち少なくとも一つは重合性基を含む基を表す。
式(III)のおいては、R、R、R23、R24及びR25のうち少なくとも一つは重合性基を含む基を表す。
式(IV)においては、R、R、R33、R34及びR35のうち少なくとも一つは重合性基を含む基を表す。
式(V)においては、R、R、R、R41、R42、R43及びR44のうち少なくとも一つは重合性基を含む基を表す。
式(VI)においては、R、R、R、R51、R52、R53、R54、R61、R62、R63及びR64のうち少なくとも一つは重合性基を含む基を表す。
式(VII)においては、R、R、R、R72、R73、R74、R75、R82、R83、R84及びR85のうち少なくとも一つは重合性基を含む基を表す。
式(VIII)においては、R、R、R、R91、R92、R93、R94、R101、R102、R103、R104、R111、R112、R113及びR114のうち少なくとも一つは重合性基を含む基を表す。
式(IX)においては、R、R、R、R123、R124及びR125のうち少なくとも一つは重合性基を含む基を表す。]
The compound according to claim 1, wherein the compound having a polymerizable group and a partial structure represented by the formula (X) is any one of a compound represented by the formula (I) to a compound represented by the formula (IX). Compound.
Figure 2021127336

Figure 2021127336

[In formulas (I) to (IX), rings W 1 and R 3 have the same meanings as described above.
Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. Independently, it represents a ring structure having at least one double bond as a component of the ring. Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12 and Ring W 13 are replaced. It may have a group.
Ring W 111 represents a heterocycle having two nitrogen atoms as a component.
Ring W 112 , ring W 113, and ring W 114 each independently represent a heterocycle having one nitrogen atom as a component.
R 1 , R 41 , R 51 , R 61 , R 91 , R 101 , R 111 , R 2 , R 12 , R 42 , R 52 , R 62 , R 72 , R 82 , R 92 , R 102 and R 112. Independently, hydrogen atom, heterocyclic group, halogen atom, nitro group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, Represents a group containing a polymerizable group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. -CH 2- and -CH = contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group are independently -NR 12A- , -SO 2- , -CO-, -O-,-, respectively. COO -, - OCO -, - CONR 13A -, - NR 14A -CO -, - S -, - SO -, - SO 2 -, - CF 2 - or may be substituted in -CHF-.
R 13 , R 23 , R 33 , R 43 , R 53 , R 63 , R 73 , R 83 , R 93 , R 103 , R 113 and R 123 are independently heterocyclic groups, halogen atoms and nitros, respectively. Group, cyano group, hydroxy group, thiol group, carboxy group, -SF 5 , -SF 3 , -SO 3 H, -SO 2 H, group containing polymerizable group, carbon number which may have substituent Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have 1 to 25 aliphatic hydrocarbon groups or substituents, and is contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group -CH. 2- and -CH = are independently -O-, -S-, -NR 1A- , -CO-, -CO-O-, -O-CO-, -O-CO-O-, respectively. -CONR 2A- , -O-CO-NR 3A- , -NR 4A- CO-, -NR 5A- CO-O-, -NR 6A- CO-NR 7A- , -CO-S-, -S-CO -S-, -S-CO-NR 8A- , -NR 9A -CO-S-, -CS-, -O -CS-, -CS-O-, -NR 10A -CS-, -NR 11A-CS It may be substituted with -S-, -S-CS-, -CS-S-, -S-CS-S-, -SO- or -SO 2-.
R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A and R 14A are independent hydrogen atoms, respectively. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.
R 4 , R 14 , R 24 , R 34 , R 44 , R 54 , R 64 , R 74 , R 84 , R 94 , R 104 , R 114 , R 124 , R 5 , R 15 , R 25 , R 35. , R 75 , R 85 and R 125 each independently represent a group containing an electron-attracting group or a polymerizable group.
R 1 and R 2 may be combined with each other to form a ring.
R 41 and R 42 may be combined with each other to form a ring.
R 51 and R 52 may be combined with each other to form a ring.
R 61 and R 62 may be combined with each other to form a ring.
R 91 and R 92 may be combined with each other to form a ring.
R 101 and R 102 may be combined with each other to form a ring.
R 111 and R 112 may be combined with each other to form a ring.
R 2 and R 3 may be combined with each other to form a ring.
R 12 and R 13 may be combined with each other to form a ring.
R 42 and R 43 may be combined with each other to form a ring.
R 52 and R 53 may be combined with each other to form a ring.
R 62 and R 63 may be combined with each other to form a ring.
R 72 and R 73 may be combined with each other to form a ring.
R 82 and R 83 may be combined with each other to form a ring.
R 92 and R 93 may be combined with each other to form a ring.
R 102 and R 103 may be combined with each other to form a ring.
R 112 and R 113 may be combined with each other to form a ring.
R 4 and R 5 may be combined with each other to form a ring.
R 14 and R 15 may be combined with each other to form a ring.
R 24 and R 25 may be combined with each other to form a ring.
R 34 and R 35 may be combined with each other to form a ring.
R 74 and R 85 may be combined with each other to form a ring.
R 84 and R 85 may be combined with each other to form a ring.
R 124 and R 125 may be combined with each other to form a ring.
R 6 and R 8 each independently represent a divalent linking group.
R 7 and R 126 each independently represent a single bond or a divalent linking group.
R 9 and R 10 each independently represent a trivalent linking group.
R 11 represents a tetravalent linking group.
However, in the formula (I), at least one of R 1 , R 2 , R 4 and R 5 represents a group containing a polymerizable group.
In formula (II), at least one of R 2 , R 4 , R 5 , R 12 , R 13 , R 14 and R 15 represents a group containing a polymerizable group.
In formula (III), at least one of R 4 , R 5 , R 23 , R 24 and R 25 represents a group containing a polymerizable group.
In formula (IV), at least one of R 4 , R 5 , R 33 , R 34 and R 35 represents a group containing a polymerizable group.
In formula (V), at least one of R 1 , R 2 , R 4 , R 41 , R 42 , R 43 and R 44 represents a group containing a polymerizable group.
In formula (VI), at least one of R 1 , R 2 , R 4 , R 51 , R 52 , R 53 , R 54 , R 61 , R 62 , R 63 and R 64 contains a polymerizable group. Represents a group.
In formula (VII), at least one of R 2 , R 4 , R 5 , R 72 , R 73 , R 74 , R 75 , R 82 , R 83 , R 84 and R 85 contains a polymerizable group. Represents a group.
In formula (VIII), R 1 , R 2 , R 4 , R 91 , R 92 , R 93 , R 94 , R 101 , R 102 , R 103 , R 104 , R 111 , R 112 , R 113 and R. At least one of 114 represents a group containing a polymerizable group.
In formula (IX), at least one of R 2 , R 4 , R 5 , R 123 , R 124 and R 125 represents a group containing a polymerizable group. ]
及びRからなる群から選ばれる少なくとも一方が、ニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基、フルオロアリール基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である請求項2に記載の化合物。 At least one selected from the group consisting of R 4 and R 5 is a nitro group, a cyano group, a halogen atom, -OCF 3 , -SCF 3 , -SF 5 , -SF 3 , fluoroalkyl group, fluoroaryl group, -CO. -O-R 222 or -SO 2- R 222 (R 222 may have a hydrogen atom, a substituent and may have an alkyl group or a substituent having 1 to 25 carbon atoms. 6 carbon atoms. The compound according to claim 2, which represents the aromatic hydrocarbon group of ~ 18). 及びRからなる群から選ばれる少なくとも一方が、ニトロ基、シアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である請求項2又は3に記載の化合物。 At least one selected from the group consisting of R 4 and R 5 is a nitro group, a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO-O-R 222 or -SO 2. -R 222 (R 222 is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. The compound according to claim 2 or 3. 及びRからなる群から選ばれる少なくとも一方が、シアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である請求項2〜4のいずれかに記載の化合物。 At least one selected from the group consisting of R 4 and R 5 is a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 is a carbon which may have a hydrogen atom and a substituent. The compound according to any one of claims 2 to 4 which is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have an alkyl group of 1 to 25 or a substituent. 及びRからなる群から選ばれる少なくとも一方が、シアノ基である請求項2〜5のいずれかに記載の化合物。 The compound according to any one of claims 2 to 5, wherein at least one selected from the group consisting of R 4 and R 5 is a cyano group. がシアノ基であり、
がシアノ基、−CO−O−R222又は−SO−R222(R222は、水素原子、置換基を有していてもよい炭素数1〜25のアルキル基又は置換基を有していてもよい炭素数6〜18の芳香族炭化水素基を表す。)である請求項2〜6のいずれかに記載の化合物。
R 4 is a cyano group
R 5 has a cyano group, -CO-O-R 222 or -SO 2- R 222 (R 222 has a hydrogen atom, an alkyl group or substituent having 1 to 25 carbon atoms which may have a substituent. The compound according to any one of claims 2 to 6, which represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be used.
及びRがともにシアノ基である請求項2〜7のいずれかに記載の化合物。 The compound according to any one of claims 2 to 7, wherein both R 4 and R 5 are cyano groups. 及びRが、それぞれ独立して、置換基を有していてもよい炭素数1〜25の脂肪族炭化水素基である請求項2〜8のいずれかに記載の化合物。 The compound according to any one of claims 2 to 8, wherein R 1 and R 2 are aliphatic hydrocarbon groups having 1 to 25 carbon atoms, which may independently have a substituent. 及びRが互いに連結して環を形成する請求項2〜8のいずれかに記載の化合物。 The compound according to any one of claims 2 to 8, wherein R 1 and R 2 are linked to each other to form a ring. 及びRが互いに連結して形成する環が、脂肪族複素環である請求項10に記載の化合物。 The compound according to claim 10, wherein the ring formed by connecting R 1 and R 2 to each other is an aliphatic heterocycle. 及びRからなる群から選ばれる少なくとも一方が、重合性基を含む基である請求項2〜9のいずれかに記載の化合物。 The compound according to any one of claims 2 to 9, wherein at least one selected from the group consisting of R 1 and R 2 is a group containing a polymerizable group. 及びRが互いに連結して環を形成し、かつ、R及びRが互いに連結した環が重合性基を有する請求項2〜8のいずれかに記載の化合物。 Linked R 1 and R 2 together form a ring, and A compound according to any one of claims 2-8 wherein the ring to which R 1 and R 2 are linked to each other has a polymerizable group. 環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、芳香族性を有さない環である請求項2〜13のいずれかに記載の化合物。 Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. The compound according to any one of claims 2 to 13, which is an independently non-aromatic ring. 環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、5〜7員環構造である請求項2〜14のいずれかに記載の化合物。 Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. The compound according to any one of claims 2 to 14, which independently has a 5 to 7-membered ring structure. 環W、環W、環W、環W、環W、環W、環W、環W、環W10、環W11、環W12及び環W13が、それぞれ独立して、6員環構造である請求項15に記載の化合物。 Ring W 2 , Ring W 3 , Ring W 4 , Ring W 5 , Ring W 6 , Ring W 7 , Ring W 8 , Ring W 9 , Ring W 10 , Ring W 11 , Ring W 12, and Ring W 13 , respectively. The compound according to claim 15, which independently has a 6-membered ring structure. がニトロ基、シアノ基、ハロゲン原子、−OCF、−SCF、−SF、−SF、フルオロアルキル基、フルオロアリール基、−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)である請求項1〜16のいずれかに記載の化合物。 R 3 is a nitro group, a cyano group, a halogen atom, -OCF 3, -SCF 3, -SF 5, -SF 3, fluoroalkyl group, fluoroaryl group, -CO-O-R 111A or -SO 2 -R 112A (R 111A and R 112A each independently represent an alkyl group having 1 to 24 carbon atoms which may have a halogen atom.) The compound according to any one of claims 1 to 16. がシアノ基、フッ素原子、塩素原子、−OCF、−SCF、フルオロアルキル基、−CO−O−R111A又は−SO−R112A(R111A及びR112Aは、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1〜24のアルキル基を表す。)である請求項1〜17のいずれかに記載の化合物。 R 3 is a cyano group, a fluorine atom, a chlorine atom, -OCF 3 , -SCF 3 , a fluoroalkyl group, -CO-O-R 111A or -SO 2- R 112A (R 111A and R 112A are independent of each other. , The compound according to any one of claims 1 to 17, which represents an alkyl group having 1 to 24 carbon atoms which may have a halogen atom. がシアノ基である請求項1〜18のいずれかに記載の化合物。 The compound according to any one of claims 1 to 18, wherein R 3 is a cyano group. 環Wが5〜7員環である請求項1〜19のいずれかに記載の化合物。 The compound according to any one of claims 1 to 19, wherein the ring W 1 is a 5 to 7-membered ring. 環Wが6員環である請求項20に記載の化合物。 The compound according to claim 20, wherein the ring W 1 is a 6-membered ring. 極大吸収波長におけるグラム吸光係数εが50L/(g・cm)以上である請求項1〜21のいずれかに記載の化合物。 The compound according to any one of claims 1 to 21, wherein the gram absorption coefficient ε at the maximum absorption wavelength is 50 L / (g · cm) or more. ε(λmax)/ε(λmax+30nm)≧5である請求項1〜22のいずれかに記載の化合物。
[ε(λmax)は、重合性基と式(X)で表される部分構造とを有する化合物における極大吸収波長におけるグラム吸光係数を表す。
ε(λmax+30nm)は、重合性基と式(X)で表される部分構造とを有する化合物の(極大吸収波長+30nm)におけるグラム吸光係数を表す。
グラム吸光係数の単位は、L/(g・cm)である。]
The compound according to any one of claims 1 to 22, wherein ε (λmax) / ε (λmax + 30 nm) ≧ 5.
[Ε (λmax) represents the gram absorption coefficient at the maximum absorption wavelength in a compound having a polymerizable group and a partial structure represented by the formula (X).
ε (λmax + 30 nm) represents the gram absorption coefficient at (maximum absorption wavelength + 30 nm) of a compound having a polymerizable group and a partial structure represented by the formula (X).
The unit of the gram extinction coefficient is L / (g · cm). ]
請求項1〜23のいずれかに記載の化合物を含む組成物。 A composition comprising the compound according to any one of claims 1 to 23. さらに開始剤を含む請求項24に記載の組成物。 The composition according to claim 24, further comprising an initiator. 前記開始剤がラジカル重合開始剤である請求項25に記載の組成物。 The composition according to claim 25, wherein the initiator is a radical polymerization initiator. 前記開始剤が光ラジカル重合開始剤である請求項26に記載の組成物。 The composition according to claim 26, wherein the initiator is a photoradical polymerization initiator. さらにラジカル重合性成分を含む請求項24〜27のいずれかに記載の組成物。 The composition according to any one of claims 24 to 27, further comprising a radically polymerizable component. 前記ラジカル重合性成分が(メタ)アクリレート化合物である請求項28に記載の組成物。 The composition according to claim 28, wherein the radically polymerizable component is a (meth) acrylate compound. 前記ラジカル重合性成分が多官能(メタ)アクリレート化合物である請求項29に記載の組成物。 The composition according to claim 29, wherein the radically polymerizable component is a polyfunctional (meth) acrylate compound. さらに、樹脂(A)を含む請求項24〜30のいずれかに記載の組成物。 The composition according to any one of claims 24 to 30, further comprising the resin (A). 前記樹脂(A)は、ガラス転移温度が40℃以下の樹脂である請求項31に記載の組成物。 The composition according to claim 31, wherein the resin (A) is a resin having a glass transition temperature of 40 ° C. or lower. 前記ガラス転移温度が40℃以下の樹脂が、(メタ)アクリル系樹脂である請求項32に記載の組成物。 The composition according to claim 32, wherein the resin having a glass transition temperature of 40 ° C. or lower is a (meth) acrylic resin. さらに、架橋剤(E)を含む請求項31〜33のいずれかに記載の組成物。 The composition according to any one of claims 31 to 33, further comprising a cross-linking agent (E). 前記架橋剤(E)が、イソシアネート架橋剤である請求項34に記載の組成物。 The composition according to claim 34, wherein the cross-linking agent (E) is an isocyanate cross-linking agent. 請求項24〜30のいずれかに記載の組成物から形成されるハードコート層。 A hard coat layer formed from the composition according to any one of claims 24 to 30. 請求項31〜35のいずれかに記載の組成物からなる粘着剤層。 A pressure-sensitive adhesive layer comprising the composition according to any one of claims 31 to 35. 請求項24に記載の組成物から形成される成形物。 A molded product formed from the composition according to claim 24. 式(X)で表される部分構造を有する樹脂。
Figure 2021127336

[式(X)中、環Wは、環の構成要素として二重結合を有し、かつ芳香族性を有さない環構造を表し、環Wは置換基を有していてもよい。
は、1価の置換基を表す。]
A resin having a partial structure represented by the formula (X).
Figure 2021127336

[In formula (X), ring W 1 represents a ring structure having a double bond as a component of the ring and having no aromaticity, and ring W 1 may have a substituent. ..
R 3 represents a monovalent substituent. ]
請求項39に記載の樹脂を含む組成物。 The composition containing the resin according to claim 39.
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