JPWO2014021023A1 - 潜在性添加剤及び該添加剤を含有する組成物 - Google Patents
潜在性添加剤及び該添加剤を含有する組成物 Download PDFInfo
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- JPWO2014021023A1 JPWO2014021023A1 JP2014528044A JP2014528044A JPWO2014021023A1 JP WO2014021023 A1 JPWO2014021023 A1 JP WO2014021023A1 JP 2014528044 A JP2014528044 A JP 2014528044A JP 2014528044 A JP2014528044 A JP 2014528044A JP WO2014021023 A1 JPWO2014021023 A1 JP WO2014021023A1
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Classifications
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- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
- C07C243/26—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C243/30—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C243/32—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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- C07D251/32—Cyanuric acid; Isocyanuric acid
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
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Abstract
Description
R1及びR2は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
R4は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R1、R2及びR4で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−S−CO−O−、−O−CO−S−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−又は−SO2−から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR2同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR2及びR4はそれぞれ同じでも異なっていてもよく、
nは、1〜10の整数を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
Xは、直接結合、窒素原子、酸素原子、硫黄原子、リン原子、下記〔化2〕で表される基、>P=O、>C=O、>NR10、>PR10、−OR10、−SR10、−NR10R11又は−PR10R11又はnと同数の価数を有する置換基を有していてもよい炭素原子数1〜120の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基、置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、R10及びR11は、水素原子、置換基を有していてもよい炭素原子数1〜35の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基又は置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素一炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−S−CO−O−、−O−CO−S−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、−SO2−又は窒素原子から選ばれた基の組み合わせで置き換わっていてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。但し、Xが窒素原子、リン原子又は下記〔化2〕で表される基の場合、nは3であり、Xが酸素原子又は硫黄原子の場合、nは2であり、Xが>C=O、−NH−CO−、−CO−NH−、>NR10又は>PR10の場合、nは2であり、Xが−OR10、−SR10、−NR10R11又は−PR10R11の場合、nが1であり、Xは、Aと一緒になって環を形成していてもよい。)
R201及びR202は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R204は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
該R201、R202及びR204で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR202同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR202及びR204はそれぞれ同じでも異なっていてもよく、
X2は、酸素原子、硫黄原子、下記〔化4〕で表される基、>C=O、−NH−CO−、−CO−NH−、>NR12、>PR12又は下記一般式(3)、(4)あるいは下記[化10]の群で表されるいずれかの置換基を表し、R12は、水素原子、置換基を有していてもよい炭素原子数1〜35の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基又は置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素一炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2−から選ばれた基の組み合わせで置き換わっていてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。
X2は、Aと一緒になって環を形成していてもよい。)
R301及びR302は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R304は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R301、R302及びR304で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、−SO2−又は窒素原子から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR302同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR302及びR304はそれぞれ同じでも異なっていてもよく、
X3は、下記一般式(7)で表される置換基を表す。
X3は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
R401及びR402は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R404は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R401、R402及びR404で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR402同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR402及びR404はそれぞれ同じでも異なっていてもよく、
nは4〜6の数を表し、
X4は、n=4のとき下記一般式(9)で表される置換基を表し、n=5のとき下記一般式(10)で表される置換基を表し、n=6のとき下記一般式(11)で表される置換基を表す。
X4は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
潜在性添加剤とは、常温あるいは150℃以下のプリベーク工程では不活性であり、100〜250℃で加熱するか、あるいは酸/塩基触媒存在下で80〜200℃で加熱することにより保護基が脱離して活性となるものであり、具体的には、潜在性酸化防止剤、潜在性紫外線吸収剤等の潜在性樹脂添加剤;感熱紙用潜在性顕色剤;感熱紙用潜在性保存安定剤;潜在性硬化剤等が挙げられる。
R1及びR2で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、
R1、R2及びR4で表される炭素原子数1〜40のアルキル基としては、メチル、エチル、プロピル、iso−プロピル、ブチル、sec−ブチル、tert−ブチル、iso−ブチル、アミル、iso−アミル、tert−アミル、シクロペンチル、ヘキシル、2−ヘキシル、3−ヘキシル、シクロヘキシル、4−メチルシクロヘキシル、ヘプチル、2−ヘプチル、3−ヘプチル、iso−ヘプチル、tert−ヘプチル、1−オクチル、iso−オクチル、tert−オクチル、アダマンチル等が挙げられ、
R1及びR2で表される炭素原子数1〜8のアルコキシ基としては、メチルオキシ、エチルオキシ、iso−プロピルオキシ、ブチルオキシ、sec−ブチルオキシ、tert−ブチルオキシ、iso−ブチルオキシ、アミルオキシ、iso−アミルオキシ、tert−アミルオキシ、ヘキシルオキシ、2−ヘキシルオキシ、3−ヘキシルオキシ、シクロヘキシルオキシ、4−メチルシクロヘキシルオキシ、ヘプチルオキシ、2−ヘプチルオキシ、3−ヘプチルオキシ、iso−ヘプチルオキシ、tert−ヘプチルオキシ、1−オクチルオキシ、iso−オクチルオキシ、tert−オクチルオキシ等が挙げられ、
R1及びR2で表される炭素原子数1〜8のアルキル基及びアルコキシ基を置換する置換基としては、ビニル、アリル、アクリル、メタクリル等のエチレン性不飽和基;フッ素、塩素、臭素、ヨウ素等のハロゲン原子;アセチル、2−クロロアセチル、プロピオニル、オクタノイル、アクリロイル、メタクリロイル、フェニルカルボニル(ベンゾイル)、フタロイル、4−トリフルオロメチルベンゾイル、ピバロイル、サリチロイル、オキザロイル、ステアロイル、メトキシカルボニル、エトキシカルボニル、t−ブトキシカルボニル、n−オクタデシルオキシカルボニル、カルバモイル等のアシル基;アセチルオキシ、ベンゾイルオキシ等のアシルオキシ基;アミノ、エチルアミノ、ジメチルアミノ、ジエチルアミノ、ブチルアミノ、シクロペンチルアミノ、2−エチルヘキシルアミノ、ドデシルアミノ、アニリノ、クロロフェニルアミノ、トルイジノ、アニシジノ、N−メチル−アニリノ、ジフェニルアミノ,ナフチルアミノ、2−ピリジルアミノ、メトキシカルボニルアミノ、フェノキシカルボニルアミノ、アセチルアミノ、ベンゾイルアミノ、ホルミルアミノ、ピバロイルアミノ、ラウロイルアミノ、カルバモイルアミノ、N,N−ジメチルアミノカルボニルアミノ、N,N−ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ、メトキシカルボニルアミノ、エトキシカルボニルアミノ、t−ブトキシカルボニルアミノ、n−オクタデシルオキシカルボニルアミノ、N−メチル−メトキシカルボニルアミノ、フェノキシカルボニルアミノ、スルファモイルアミノ、N,N−ジメチルアミノスルホニルアミノ、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ等の置換アミノ基;スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基、ホスホン酸基、リン酸基又はカルボキシル基、スルホ基、ホスホン酸基、リン酸基の塩等が挙げられる。
R4で表される炭素原子数6〜20のアリール基としては、フェニル、ナフチル、アントラセニル等が挙げられ、
R4で表される炭素原子数7〜20のアリールアルキル基としては、ベンジル、フルオレニル、インデニル、9−フルオレニルメチル基等が挙げられ、
R4で表される炭素原子数2〜20の複素環含有基としては、ピリジル、ピリミジル、ピリダジル、ピペリジル、ピラニル、ピラゾリル、トリアジル、ピロリル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、2−ピロリジノン−1−イル、2−ピペリドン−1−イル、2,4−ジオキシイミダゾリジン−3−イル、2,4−ジオキシオキサゾリジン−3−イル等が挙げられ、
R4で表されるトリアルキルシリル基としては、トリメチルシラン、トリエチルシラン、エチルジメチルシラン等が挙げられる。
R4の中でも、炭素原子数1〜8のアルキル基の酸素原子側の末端に−CO−O−が結合しているものが、潜在性添加剤として効率的に機能を発現するので好ましい。
置換基を有してもよい炭素原子数6〜35の一価の芳香環含有炭化水素基としては、ベンジル、フェネチル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等のアリールアルキル基;フェニル、ナフチル等のアリール基;フェノキシ、ナフチルオキシ等のアリールオキシ基;フェニルチオ、ナフチルチオ等のアリールチオ基等が挙げられ、
置換基を有してもよい炭素原子数2〜35の一価の複素環含有基としては、ピリジル、ピリミジル、ピリダジル、ピペリジル、ピラニル、ピラゾリル、トリアジル、ピロリル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、2−ピロリジノン−1−イル、2−ピペリドン−1−イル、2,4−ジオキシイミダゾリジン−3−イル、2,4−ジオキシオキサゾリジン−3−イル、ベンゾトリアゾイル等が挙げられる。
置換基としては、ビニル、アリル、アクリル、メタクリル等のエチレン性不飽和基;フッ素、塩素、臭素、ヨウ素等のハロゲン原子;アセチル、2−クロロアセチル、プロピオニル、オクタノイル、アクリロイル、メタクリロイル、フェニルカルボニル(ベンゾイル)、フタロイル、4−トリフルオロメチルベンゾイル、ピバロイル、サリチロイル、オキザロイル、ステアロイル、メトキシカルボニル、エトキシカルボニル、t−ブトキシカルボニル、n−オクタデシルオキシカルボニル、カルバモイル等のアシル基;アセチルオキシ、ベンゾイルオキシ等のアシルオキシ基;アミノ、エチルアミノ、ジメチルアミノ、ジエチルアミノ、ブチルアミノ、シクロペンチルアミノ、2−エチルヘキシルアミノ、ドデシルアミノ、アニリノ、クロロフェニルアミノ、トルイジノ、アニシジノ、N−メチル−アニリノ、ジフェニルアミノ,ナフチルアミノ、2−ピリジルアミノ、メトキシカルボニルアミノ、フェノキシカルボニルアミノ、アセチルアミノ、ベンゾイルアミノ、ホルミルアミノ、ピバロイルアミノ、ラウロイルアミノ、カルバモイルアミノ、N,N−ジメチルアミノカルボニルアミノ、N,N−ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ、メトキシカルボニルアミノ、エトキシカルボニルアミノ、t−ブトキシカルボニルアミノ、n−オクタデシルオキシカルボニルアミノ、N−メチル−メトキシカルボニルアミノ、フェノキシカルボニルアミノ、スルファモイルアミノ、N,N−ジメチルアミノスルホニルアミノ、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ等の置換アミノ基;スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基、ホスホン酸基、リン酸基又はカルボキシル基、スルホ基、ホスホン酸基、リン酸基の塩等が挙げられ、これらの基は更に置換されていてもよい。また、カルボキシル基及びスルホ基は塩を形成していてもよい。
二価の炭素原子数6〜35の芳香環含有炭化水素基としては、フェニレン、ナフチレン、ビフェニル等の基が、Z1及びZ2で置換された二価の基等が挙げられ、
二価の炭素原子数2〜35の複素環含有基としては、ピリジン、ピラジン、ピペリジン、ピペラジン、ピリミジン、ピリダジン、トリアジン、ヘキサヒドロトリアジン、フラン、テトラヒドロフラン、クロマン、キサンテン、チオフェン、チオラン等が、Z1及びZ2で置換された二価の基が挙げられる。
これらの基はハロゲン原子、シアノ基、ニトロ基又は炭素原子数1〜8のアルコキシ基でさらに置換されていてもよい。
炭素原子数6〜20のアリール基としては、フェニル、ナフチル、2−メチルフェニル、3−メチルフェニル、4−メチルフェニル、4−ビニルフェニル、3−iso−プロピルフェニル、4−iso−プロピルフェニル、4−ブチルフェニル、4−iso−ブチルフェニル、4−tert−ブチルフェニル、4−ヘキシルフェニル、4−シクロヘキシルフェニル、4−オクチルフェニル、4−(2−エチルヘキシル)フェニル、2,3−ジメチルフェニル、2,4−ジメチルフェニル、2,5−ジメチルフェニル、2,6−ジメチルフェニル、3,4−ジメチルフェニル、3,5−ジメチルフェニル、2,4−ジ−tert−ブチルフェニル、2,5−ジ−tert−ブチルフェニル、2,6−ジ−tert−ブチルフェニル、2,4−ジ−tert−ペンチルフェニル、2,5−ジ−tert−アミルフェニル、2,4,5−トリメチルフェニル等が挙げられ、
炭素原子数7〜20のアリールアルキル基としては、ベンジル、フェネチル、2−フェニルプロパン−2−イル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等が挙げられる。
R22で表される炭素原子数1〜10のアルキル基、炭素原子数1〜10のアルコキシ基及びハロゲン原子としては、上記一般式(1)の説明で例示したアルキル基、アルコキシ基及びハロゲン原子等が挙げられ、
炭素原子数2〜10のアルケニル基としては、ビニル、アリル、1−プロペニル、イソプロペニル、2−ブテニル、1,3−ブタジエニル、2−ペンテニル、2−オクテニル等が挙げられ、
上記R22におけるアルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、その置換位置は制限されない。
炭素原子数6〜20のアリールオキシ基としては、フェニルオキシ、ナフチルオキシ、2−メチルフェニルオキシ、3−メチルフェニルオキシ、4−メチルフェニルオキシ、4−ビニルフェニル二オキシ、3−iso−プロピルフェニルオキシ、4−iso−プロピルフェニルオキシ、4−ブチルフェニルオキシ、4−tert−ブチルフェニルオキシ、4−へキシルフェニルオキシ、4−シクロヘキシルフェニルオキシ、4−オクチルフェニルオキシ、4−(2−エチルヘキシル)フェニルオキシ、2,3−ジメチルフェニルオキシ、2,4−ジメチルフェニルオキシ、2,5−ジメチルフェニルオキシ、2.6−ジメチルフェニルオキシ、3.4−ジメチルフェニルオキシ、3.5−ジメチルフェニルオキシ、2,4−ジーtert−ブチルフェニルオキシ、2,5−ジーtert−ブチルフェニルオキシ、2,6−ジーtert−ブチルフェニルオキシ、2.4−ジーtert−ペンチルフェニルオキシ、2,5−tert−アミルフェニルオキシ、4−シクロへキシルフェニルオキシ、2,4,5−トリメチルフェニルオキシ、フェロセニルオキシ等の基及びこれらの基がハロゲン原子で置換された基が奉げられ、
炭素原子数6〜20のアリールチオ基としては、上記ハロゲン原子で置換されていてもよい炭素原子数6〜20のアリールオキシ基の酸素原子を硫黄原子に置換した基等が奉げられ、
炭素原子数8〜20のアリールアルケニル基としては、上記ハロゲン原子で置換されていてもよい炭素原子数6−20のアリールオキシ基の酸素原子をビニル、アリル、1−プロペニル、イソプロペニル、2−ブテニル、1,3−ブタジエニル、2−ペンテニル、2−オクテニル等のアルケニル基で置換した基等が挙げられ、
炭素原子数2−20の複素環含有基としては、ピリジン、ピラジン、ピペリジン、ピペラジン、ピリミジン、ピリダジン、トリアジン、ヘキサヒドロトリアジン、フラン、テトラヒドロフラン、クロマン、キサンテン、チオフェン、チオフラン等の基及びこれらの基がハロゲン原子で置換された基等が挙げられる。
三価の炭素原子数6〜35の芳香環含有炭化水素基としては、上記一般式(12)におけるX1の説明で例示した芳香環含有炭化水素基が、Z1、Z2及びZ3で置換された三価の基が挙げられ、
三価の炭素原子数2〜35の複素環含有基としては、上記一般式(12)におけるX1の説明で例示した複素環含有基が、Z1、Z2及びZ3で置換された三価の基が挙げられる。
四価の炭素原子数6〜35の芳香環含有炭化水素基としては、上記一般式(2)におけるX1の説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3及びZ4で置換された四価の基が挙げられ、
四価の炭素原子数2〜35の複素環含有基としては、上記一般式(2)におけるX1の説明で例示した複素環含有基が、Z1、Z2、Z3及びZ4で置換された四価の基が挙げられる。
五価の炭素原子数6〜35の芳香環含有炭化水素基としては、上記一般式(12)におけるX1の説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3、Z4及びZ5で置換された五価の基が挙げられ、
五価の炭素原子数2〜35の複素環含有基としては、上記一般式(12)におけるX1で説明で例示した複素環含有基が、Z1、Z2、Z3、Z4及びZ5で置換された五価の基が挙げられる。
六価の炭素原子数6〜35の芳香環含有炭化水素基としては、上記一般式(12)におけるX1で説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3、Z4、Z5及びZ6で置換された六価の基が挙げられ、
六価の炭素原子数2〜35の複素環含有基としては、上記一般式(12)におけるX1の説明で例示した複素環含有基が、Z1、Z2、Z3、Z4、Z5及びZ6で置換された六価の基が挙げられる。
本発明の潜在性添加剤は、潜在性酸化防止剤あるいは潜在性紫外線吸収剤として光硬化性組成物、熱硬化性組成物、感光性組成物あるいは重合性組成物に用いられる他、潜在性顕色剤として感熱材料にも用いられる。
上記光硬化性組成物において、本発明の潜在性添加剤の含有量は、0.001〜20質量%が好ましく、0.005〜5質量%がより好ましい。
上記熱硬化性組成物において、本発明の潜在性添加剤の含有量は、0.001〜20質量%が好ましく、0.005〜5質量%がより好ましい。
上記感光性組成物において、本発明の潜在性添加剤の含有量は、0.001〜20質量%が好ましく、0.005〜5質量%がより好ましい。
上記重合性組成物において、本発明の潜在性添加剤の含有量は、0.001〜20質量%が好ましく、0.005〜5質量%がより好ましい。
該光ラジカル硬化性組成物は、本発明の潜在性添加剤を潜在性酸化防止剤として含む他、ラジカル重合性有機物質及び光ラジカル重合開始剤を必須成分とする。
、配合して使用することができる。なお、ラジカル重合性有機物質のうち50質量%以上
が、分子中に(メタ)アクリル基を有する化合物であることが好ましい。
該熱ラジカル硬化性組成物は、本発明の潜在性添加剤を潜在性酸化防止剤として含む他、上記ラジカル重合性有機物質及び熱ラジカル重合開始剤を必須成分とする。
ルグリシジルエーテル、フェニルグリシジルエーテル、p−メトキシグリシジルエーテル、p−ブチルフェノールグリシジルエーテル、クレジルグリシジルエーテル、2−メチルクレジルグリシジルエーテル、4−ノニルフェニルグリシジルエーテル、ベンジルグリシジルエーテル、p−クミルフェニルグリシジルエーテル、トリチルグリシジルエーテル、2,3−エポキシプロピルメタクリレート、エポキシ化大豆油、エポキシ化アマニ油、グリシジルブチレート、ビニルシクロヘキサンモノオキシド、1,2−エポキシ−4−ビニルシクロヘキサン、スチレンオキシド、ピネンオキシド、メチルスチレンオキシド、シクロヘキセンオキシド、プロピレンオキシド、等が挙げられる。
その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールAノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物;3,4−エポキシ−6−メチルシクロヘキシルメチル−3,4−エポキシ−6−メチルシクロヘキサンカルボキシレート、3,4−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート、1−エポキシエチル−3,4−エポキシシクロヘキサン等の脂環式エポキシ化合物;フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類;テトラグリシジルジアミノジフェニルメタン、トリグリシジル−p−アミノフェノール、N,N−ジグリシジルアニリン等のグリシジルアミン類;1,3−ジグリシジル−5,5−ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物;ジシクロペンタジエンジオキシド等のジオキシド化合物;ナフタレン型エポキシ化合物、トリフェニルメタン型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物等を用いることもできる。
上記着色感光性組成物において、着色剤の添加量は、0.01〜50質量%が好ましく、0.1〜30質量%がより好ましい。
染料としては、380〜1200nmに吸収を有する化合物であれば特に限定されないが、例えば、アゾ化合物、アントラキノン化合物、インジゴイド化合物、トリアリールメタン化合物、キサンテン化合物、アリザリン化合物、アクリジン化合物、スチルベン化合物、チアゾール化合物、ナフトール化合物、キノリン化合物、ニトロ化合物、インダミン化合物、オキサジン化合物、フタロシアニン化合物、シアニン化合物、ジインモニウム化合物、シアノエテニル化合物、ジシアノスチレン化合物、ローダミン化合物、ペリレン化合物、ポリエンナフトラクタム化合物、クマリン化合物、スクアリリウム化合物、クロコニウム化合物、スピロピラン化合物、スピロオキサジン化合物、メロシアニン化合物、オキソノール化合物、スチリル化合物、ピリリウム化合物、ローダニン化合物、オキサゾロン化合物、フタルイミド化合物、シンノリン化合物、ナフトキノン化合物、アザアントラキノン化合物、ポルフィリン化合物、アザポルフィリン化合物、ピロメテン化合物、キナクリドン化合物、ジケトピロロピロール化合物、インジゴ化合物、アクリジン化合物、アジン化合物、アゾメチン化合物、アニリン化合物、キナクリドン化合物、キノフタロン化合物、キノンイミン化合物、イリジウム錯体化合物、ユーロピウム錯体化合物等の染料等が挙げられ、これらは複数を混合して用いてもよい。
ルキルエーテル化された化合物を挙げることができる。ここで、アルキルエーテルを構成するアルキル基としては、メチル基、エチル基又はブチル基が挙げられ、互いに同一であってもよいし、異なっていてもよい。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果オリゴマー成分が形成されていてもよい。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。これらのなかでも、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。
R201及びR202は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R204は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
該R201、R202及びR204で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR202同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR202及びR204はそれぞれ同じでも異なっていてもよく、
X2は、酸素原子、硫黄原子、下記〔化4〕で表される基、>C=O、−NH−CO−、−CO−NH−、>NR12、>PR12又は下記一般式(3)、(4)あるいは下記[化10]の群で表されるいずれかの置換基を表し、R12は、水素原子、置換基を有していてもよい炭素原子数1〜35の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基又は置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素一炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2−から選ばれた基の組み合わせで置き換わっていてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。
X2は、Aと一緒になって環を形成していてもよい。)
R301及びR302は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R304は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R301、R302及びR304で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、−SO2−又は窒素原子から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR302同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR302及びR304はそれぞれ同じでも異なっていてもよく、
X3は、下記一般式(7)で表される置換基を表す。
X3は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
R401及びR402は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R404は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R401、R402及びR404で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR402同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR402及びR404はそれぞれ同じでも異なっていてもよく、
nは4〜6の数を表し、
X4は、n=4のとき下記一般式(9)で表される置換基を表し、n=5のとき下記一般式(10)で表される置換基を表し、n=6のとき下記一般式(11)で表される置換基を表す。
X4は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
フェノール化合物0.01mol、二炭酸ジ−tert−ブチル0.05mol及びピリジン30gを混合し、窒素雰囲気下、室温で4−ジメチルアミノピリジン0.025molを加え、60℃で3時間撹拌した。室温まで冷却後、反応液をイオン交換水150gに注ぎ、クロロホルム200gを加えて油水分離を行った。有機層を無水硫酸ナトリウムで乾燥後、溶媒を留去し、残渣にメタノール100gを加えて晶析を行った。得られた白色粉状結晶を60℃で3時間減圧乾燥させ、目的物を得た。得られた白色粉状結晶が目的物であることは1H−NMR、IRにて確認した。また、融点を測定した。結果を[表1]〜[表3]に示す。
製造例1−1と同様にして、化合物No.2〜No.10を合成した。
50ml四つ口フラスコに、メタクリル酸メチル2.97g及びアゾイソブチロニトリ ル0.03gを入れ、化合物No.1(実施例2)又は比較化合物No.1を0.01 gとトルエン7.00gを加え、80℃で2時間撹拌した。GPCを測定し重合物の分 子量を測定した。結果を〔表4〕に示す。
<ステップ1>感光性組成物No.1〜No.8及び比較感光性組成物No.1〜No.8の調製
SPC−1000(昭和電工社製、固形分29%のPGMEA溶液)50.9g、アロニックスM−450(東亜合成社製)11.9g、OXE−01(BASF社製)1.04g、PGMEA34.0g、FZ2122(東レ・ダウコーニング社製、固形分1%のPGMEA溶液)2.9g及び[表5]記載の潜在性添加剤0.81gを混合し、不溶物が無くなるまで撹拌し、感光性組成物No.1〜No.8及び比較感光性組成物No.1〜No.8を得た。
着色剤0.10gに、PGMEA1.90gを加え、撹拌して溶解させた。
ステップ1で得られた感光性組成物No.1〜No.8及び比較感光性組成物No.1〜No.8を2.50gとステップ2で得られた着色剤溶液No.1〜No.8の1.00gとを[表5]記載のように混合して均一になるまで撹拌し、着色感光性組成物No.1〜No.8及び比較着色感光性組成物No.1〜No.8を得た。
SPC−1000(昭和電工社製、固形分29%のPGMEA溶液)50.9g、アロニックスM−450(東亜合成社製)11.9g、NCI−930(ADEKA社製)0.3g、PGMEA34.0g、FZ2122(東レ・ダウコーニング社製、固形分1%のPGMEA溶液)2.9g及び[表6]記載の添加剤0.81gを混合し、不溶物が無くなるまで撹拌し、感光性組成物No.9及び比較感光性組成物No.9〜No.10を得た。
[表7]の配合に従って樹脂及び添加剤を混合し、50℃で300〜400rpmの撹拌速度で1時間撹拌して均一に溶解させた。熱開始剤としてCP−66(ADEKA社製)0.75gを加えて撹拌速度400〜500rpmで1時間撹拌した。尚、数値は質量部を表す。
<ステップ1>光硬化性組成物No.1及び比較光硬化性組成物No.1〜No.2の調製
SPC−1000(昭和電工社製、固形分29%のPGMEA溶液)49.6g、アロニックスM−450(東亜合成社製)11.5g、OXE−01(BASF社製)1.0g、PGMEA35.0g、FZ2122(東レ・ダウコーニング社製、固形分1%のPGMEA溶液)2.9g及び[表8]記載の添加剤2.0gを混合し、光硬化性組成物No.1及び比較光硬化性組成物No.1〜No.2を得た。
上記で得られた着色感光性組成物No.1〜No.8並びに比較着色感光性組成物No.1〜No.8をガラス基板に410rpm×7secの条件で塗工し、ホットプレートで乾燥(90℃、90sec)させた。得られた塗膜に超高圧水銀ランプで露光(150mJ/cm2)した。露光後の塗膜を、230℃×30minの条件で焼成した。用いた着色剤の極大吸収波長(λmax)における焼成前(露光後)の塗膜の吸光度と焼成後の塗膜の吸光度を測定し、焼成前(露光後)の塗膜の吸光度を100としたときの相対強度として評価した。尚、焼成後の塗膜の吸光度が100に近いほど耐熱性が高いことを示す。結果を[表9]に示す。
実施例3−1〜3−3で調製した着色感光性組成物No.1〜No.3並びに比較例3−1〜3−3で調製した比較着色感光性組成物No.1〜No.3、及び、比較着色感光性組成物No.1〜No.3にそれぞれ比較化合物No.2の0.81gを加えた比較着色感光性組成物No.4〜No.6を、それぞれガラス基板に410rpm×7secの条件で塗工し、ホットプレートで乾燥(90℃、90sec)させた。得られた塗膜に20μmのギャップをおいたマスクを介し超高圧水銀ランプで露光(50mJ/cm2〜270mJ/cm2まで30mJ/cm2おき8分割)した。露光後の塗膜を、アルカリ現像液で現像を行った後、230℃×30minの条件で焼成した。マスク開口20μmにおいて各露光量での線幅をプロットし、線幅が20μmになる露光量を線幅感度とした。結果を[表10]に示す。尚、値が小さいほど感度が高いと言える。
上記で得られた感光性組成物No.9並びに比較感光性組成物No.9〜No.10について、上記評価例1と同様に耐熱性評価を行った。結果を[表11]に示す。
上記で得られた感光性組成物No.9並びに比較感光性組成物No.9〜No.10をガラス基板に410rpm×7secの条件で塗工し、ホットプレートで乾燥(90℃、90sec)させた。得られた塗膜に超高圧水銀ランプで露光(150mJ/cm2)した。露光後の塗膜を、230℃×90minの条件で焼成した。焼成後の塗膜の透過率を測定して評価した。尚、焼成後の塗膜の透過率が100に近いほど耐熱性が高いことを示す。結果を[表11]に示す。
上記で得られた感光性組成物No.9並びに比較感光性組成物No.9〜No.10について、上記評価例1と同様に線幅感度の測定を行った。結果を[表12]に示す。
未処理のPETフィルムを貼り付けたガラス基板に、0.5〜1.0mm厚のフッ素樹脂スペーサー(間隙部材)を設け、このスペーサーを介して離型処理を施したガラス基板を重ね、上記で得られた熱硬化性組成物No.1及び比較熱硬化性組成物No.1〜No.2を注入した。オーブン中150℃で1時間加熱し、ポストキュアを行った。冷却後にガラス基板から取り出し、ガラス基板から樹脂硬化膜を剥離した。硬化物を200℃/1hで加熱して耐熱性試験を行い、耐熱性試験前後の硬化物の透過率を吸光光度計で測定した。結果を[表13]に示す。
上記で得られた熱硬化性組成物No.1及び比較熱硬化性組成物No.1について、冷暗所に放置して、粘度が30%増加するまでの日数を数えてポットライフ評価とした。結果を[表14]に示す。
上記で得られた光硬化性組成物No.1並びに比較光硬化性組成物No.2をガラス基板に410rpm×7secの条件で塗工し、ホットプレートで乾燥(90℃、90sec)させた。得られた塗膜に超高圧水銀ランプで露光(150mJ/cm2)した。露光後の塗膜を、230℃×30minの条件で焼成した。焼成前(露光後)の塗膜の透過率と焼成後の塗膜の365nmにおける透過率を測定した。尚、比較光硬化性組成物No.1は、溶解せず白濁したため評価を行わなかった。結果を[表15]に示す。
化合物No.1を5mg測りとり、熱質量測定装置にて室温から230℃まで昇温(10℃/min)した後、30分間230℃で加熱下においたところ、26質量%の減少が見られた。すなわち、この減少分はt−ブトキシカルボニル基に相当し、加熱により脱保護が行われたことを示唆している。また、1H−NMR、IR測定を行い、フェノールが生成していることを確認した。
Claims (7)
- 下記一般式(1)で表される潜在性添加剤。
R1及びR2は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
R4は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R1、R2及びR4で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−S−CO−O−、−O−CO−S−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−又は−SO2−から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR2同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR2及びR4はそれぞれ同じでも異なっていてもよく、
nは、1〜10の整数を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
Xは、直接結合、窒素原子、酸素原子、硫黄原子、リン原子、下記〔化2〕で表される基、>P=O、>C=O、>NR10、>PR10、−OR10、−SR10、−NR10R11又は−PR10R11又はnと同数の価数を有する置換基を有していてもよい炭素原子数1〜120の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基、置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、R10及びR11は、水素原子、置換基を有していてもよい炭素原子数1〜35の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基又は置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素一炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−S−CO−O−、−O−CO−S−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、−SO2−又は窒素原子から選ばれた基の組み合わせで置き換わっていてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。但し、Xが窒素原子、リン原子又は下記〔化2〕で表される基の場合、nは3であり、Xが酸素原子又は硫黄原子の場合、nは2であり、Xが>C=O、−NH−CO−、−CO−NH−、>NR10又は>PR10の場合、nは2であり、Xが−OR10、−SR10、−NR10R11又は−PR10R11の場合、nが1であり、Xは、Aと一緒になって環を形成していてもよい。)
- 上記一般式(1)中、Aがベンゼン環であることを特徴とする請求項1に記載の潜在性添加剤。
- 上記一般式(1)中、R4が炭素原子数2〜9のアルコキシカルボニル基であることを特徴とする請求項1又は2に記載の潜在性添加剤。
- 請求項1〜3のいずれか1項に記載の潜在性添加剤を含有する組成物。
- 下記一般式(2)で表される化合物。
R201及びR202は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R204は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
該R201、R202及びR204で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR202同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR202及びR204はそれぞれ同じでも異なっていてもよく、
X2は、酸素原子、硫黄原子、下記〔化4〕で表される基、>C=O、−NH−CO−、−CO−NH−、>NR12、>PR12又は下記一般式(3)、(4)あるいは下記[化10]の群で表されるいずれかの置換基を表し、R12は、水素原子、置換基を有していてもよい炭素原子数1〜35の脂肪族炭化水素基、置換基を有していてもよい炭素原子数6〜35の芳香環含有炭化水素基又は置換基を有していてもよい炭素原子数2〜35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素一炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2−から選ばれた基の組み合わせで置き換わっていてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。
X2は、Aと一緒になって環を形成していてもよい。)
- 下記一般式(6)で表される化合物。
R301及びR302は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R304は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R301、R302及びR304で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、−SO2−又は窒素原子から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR302同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR302及びR304はそれぞれ同じでも異なっていてもよく、
X3は、下記一般式(7)で表される置換基を表す。
X3は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
- 下記一般式(8)で表される化合物。
R401及びR402は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数1〜40のアルキル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基又は炭素原子数2〜20の複素環含有基を表し、
dは、1〜3の整数を表し、
kは、1〜3の整数を表し、
R404は、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基、炭素原子数7〜20のアリールアルキル基、炭素原子数2〜20の複素環含有基又はトリアルキルシリル基を表し、
R401、R402及びR404で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−O−、−S−、−CO−、−O−CO−、−CO−O−、−O−CO−O−、−O−CO−O−、−S−CO−、−CO−S−、−O−CO−S−、−S−CO−O−、−CO−NH−、−NH−CO−、−NH−CO−O−、−NR'−、>P=O、−S−S−、又は−SO2から選ばれた基の組み合わせで置き換わっていてもよく、R’は、水素原子又は炭素原子数1〜8のアルキル基を表し、
複数のR402同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
複数のR402及びR404はそれぞれ同じでも異なっていてもよく、
nは4〜6の数を表し、
X4は、n=4のとき下記一般式(9)で表される置換基を表し、n=5のとき下記一般式(10)で表される置換基を表し、n=6のとき下記一般式(11)で表される置換基を表す。
X4は、Aと一緒になって環を形成していてもよく、上記芳香環又は複素環は、他の環と縮合されていてもよい。)
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CN107817650A (zh) | 2018-03-20 |
US9777138B2 (en) | 2017-10-03 |
JP6312259B2 (ja) | 2018-04-18 |
JP6741711B2 (ja) | 2020-08-19 |
US20150291772A1 (en) | 2015-10-15 |
TW201407276A (zh) | 2014-02-16 |
KR102171002B1 (ko) | 2020-10-28 |
EP2881450A1 (en) | 2015-06-10 |
WO2014021023A1 (ja) | 2014-02-06 |
CN104334684B (zh) | 2019-08-27 |
CN104334684A (zh) | 2015-02-04 |
TWI598684B (zh) | 2017-09-11 |
KR20200125749A (ko) | 2020-11-04 |
EP2881450A4 (en) | 2016-02-10 |
KR102398814B1 (ko) | 2022-05-17 |
JP2018150301A (ja) | 2018-09-27 |
KR20150040797A (ko) | 2015-04-15 |
EP3753997A1 (en) | 2020-12-23 |
EP2881450B1 (en) | 2020-09-09 |
CN107817650B (zh) | 2024-07-02 |
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