TW202112747A - Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound - Google Patents

Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound Download PDF

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TW202112747A
TW202112747A TW109119445A TW109119445A TW202112747A TW 202112747 A TW202112747 A TW 202112747A TW 109119445 A TW109119445 A TW 109119445A TW 109119445 A TW109119445 A TW 109119445A TW 202112747 A TW202112747 A TW 202112747A
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hydrocarbon group
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友田和貴
大槻竜也
有吉智幸
岡田光裕
木村正樹
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日商艾迪科股份有限公司
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Abstract

The present invention addresses the problem of providing a compound having high photobase generation efficiency. The present invention is a carbamoyl oxime compound represented by general formula (I). (In the formula, R1 denotes a hydrogen atom, a cyano group or a hydrocarbon group having 1-20 carbon atoms. R2 denotes a hydrogen atom or a hydrocarbon group having 1-20 carbon atoms. R3, R4, R5, R6, R7, R8 and R9 each independently denote a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1-20 carbon atoms, a heterocyclic ring-containing group having 2-20 carbon atoms, or the like. At least one pair among R3 and R4, R6 and R7, R7 and R8, and R8 and R9 bond to each other to form a benzene ring. n is 0 or 1.).

Description

胺甲醯肟化合物以及含有該化合物之聚合起始劑及聚合性組合物Carbamethoxime compound and polymerization initiator and polymerizable composition containing the compound

本發明係關於一種胺甲醯肟化合物。The present invention relates to a carbamethoxime compound.

一般而言，感光性樹脂組合物等聚合性組合物係於感光性樹脂等聚合性化合物中添加光聚合起始劑而成者，可藉由照射能量線(光)進行聚合硬化或顯影，因此可用於光硬化性油墨、感光性印刷版、各種光阻劑、光硬化性接著劑等。Generally speaking, a polymerizable composition such as a photosensitive resin composition is formed by adding a photopolymerization initiator to a polymerizable compound such as a photosensitive resin, and can be polymerized and cured or developed by irradiating energy rays (light), so It can be used for photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc.

光聚合起始劑根據藉由照射能量線(光)而產生之活性種之差異而被分成光自由基產生劑、光產酸劑、光產鹼劑。光自由基產生劑具有硬化速度較快、硬化後不會殘存活性種等優點，但另一方面，存在如下缺點：由於會因氧氣而產生硬化阻礙，故而於薄膜之硬化中必須設置阻隔氧氣之層等。光產酸劑具有不會因氧氣而受到阻礙之優點，但另一方面，存在如下缺點：因活性種之酸殘存而腐蝕金屬基板或使硬化後之樹脂改性等。光產鹼劑由於不易產生上述由氧氣導致之硬化阻礙及由殘存活性種導致之腐蝕等問題而受到關注，但總體而言，存在與光產酸劑相比為低感度(低硬化性)之問題。光產鹼劑例如記載於專利文獻1及2中。 先前技術文獻 專利文獻The photopolymerization initiator is classified into a photoradical generator, a photoacid generator, and a photobase generator according to the difference in active species generated by irradiation of energy rays (light). The light radical generator has the advantages of faster curing speed and no survival of viable species after curing, but on the other hand, it has the following disadvantages: because the curing is hindered by oxygen, it is necessary to install an oxygen barrier during the curing of the film. Layers and so on. The photoacid generator has the advantage of not being hindered by oxygen, but on the other hand, it has the following disadvantages: the residual acid of the active species corrodes the metal substrate or modifies the hardened resin. Photobase generators have attracted attention because they are not easy to produce the above-mentioned hardening inhibition caused by oxygen and corrosion caused by surviving species. However, in general, there are low sensitivity (low hardening) compared with photoacid generators. problem. The photobase generator is described in Patent Documents 1 and 2, for example. Prior art literature Patent literature

專利文獻1：US9594302 專利文獻2：日本專利特開2013-163670號公報Patent Document 1: US9594302 Patent Document 2: Japanese Patent Laid-Open No. 2013-163670

然而，先前之光產鹼劑之產鹼效率較低，硬化感度並不充分。 因此，本發明之課題在於提供一種具有較高之光產鹼效率之化合物。However, the previous photoalkali generators have low alkali production efficiency and insufficient hardening sensitivity. Therefore, the subject of the present invention is to provide a compound with high photoalkali production efficiency.

本發明者進行努力研究，發現特定結構之化合物具有較高之光產鹼效率而作為聚合起始劑有用。 即，本發明係一種胺甲醯肟化合物，其以下述通式(I)表示。The inventors conducted diligent research and found that compounds with specific structures have higher photobase generation efficiency and are useful as polymerization initiators. That is, the present invention is a carbamate compound represented by the following general formula (I).

[化1]

Figure 02_image005
(式中，R1 表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R2 表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R3 、R4 、R5 、R6 、R7 、R8 及R9 分別獨立地表示氫原子、鹵素原子、氰基、硝基、-OR10 、-COOR10 、-CO-R10 、-SR10 、碳原子數1～20之烴基或碳原子數2～20之含雜環之基， R10 表示氫原子、碳原子數1～20之烴基、碳原子數2～20之含雜環之基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基，於分子中存在複數個R10 之情形時，其等可相同，亦可不同， X1 表示-NR21 R22 或下述通式(a)或者下述通式(b)所表示之基， R21 及R22 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R1 、R2 、R3 、R4 、R5 、R6 、R7 、R8 、R9 、R10 、R21 及R22 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR11 、-COOR11 、-CO-R11 或-SR11 而成之碳原子數1～20之基， R11 表示氫原子、碳原子數1～20之烴基、烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基或烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基或羥基而成之碳原子數1～20之基，於分子中存在複數個R11 之情形時，其等可相同，亦可不同， ＜群A＞為-O-、-CO-、-COO-、-NR12 -、-NR12 CO-及-S-， R12 表示氫原子或碳原子數1～20之烴基，於分子中存在複數個R12 之情形時，其等可相同，亦可不同， R3 與R4 、R6 與R7 、R7 與R8 及R8 與R9 可分別獨立地相互連結而形成包含氫原子及碳原子之碳原子數3～10之環， R3 與R4 、R6 與R7 、R7 與R8 及R8 與R9 中之至少1組相互連結而形成苯環， R21 與R22 可相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， n表示0或1)[化1]
Figure 02_image005
(In the formula, R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> R 2 represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> Formed into a group with 1-20 carbon atoms, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, and -OR 10 , -COOR 10 , -CO-R 10 , -SR 10 , a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic ring-containing group with 2 to 20 carbon atoms, R 10 represents a hydrogen atom, with 1 to 20 carbon atoms A hydrocarbon group, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group having 1 to 20 carbon atoms, When there are a plurality of R 10 in the molecule, they may be the same or different. X 1 represents -NR 21 R 22 or the group represented by the following general formula (a) or the following general formula (b), R 21 and R 22 each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group substituted with a divalent group selected from the following <Group A> with 1 to carbon atoms The group of 20, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 21 and R 22 can also be one of the hydrogen atoms in the hydrocarbon group Or two or more of them are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 11 , -COOR 11 , -CO-R 11 or -SR 11 and have 1 to 20 carbon atoms, and R 11 represents A hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group with 1 to 20 carbon atoms or hydrogen in the hydrocarbon group One or more of the atoms are substituted with halogen atoms, cyano groups, nitro groups, or hydroxy groups with 1 to 20 carbon atoms. When there are more than one R 11 in the molecule, they may be the same. It may be different. <Group A> is -O-, -CO-, -COO-, -NR 12 -, -NR 12 CO- and -S-, R 12 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms , When there are multiple R 12 in the molecule, they can be the same or different. R 3 and R 4 , R 6 and R 7 , R 7 and R 8, and R 8 and R 9 can be mutually independent Connected to form a ring with 3 to 10 carbon atoms containing hydrogen and carbon atoms , at least one of R 3 and R 4 , R 6 and R 7 , R 7 and R 8, and R 8 and R 9 are connected to each other. Form a benzene ring, R 21 and R 22 can be connected to each other to form a carbon atom containing hydrogen, nitrogen and carbon atoms 2 ～10 ring or 2～10 carbon ring containing hydrogen atom, oxygen atom, nitrogen atom and carbon atom, n represents 0 or 1)

[化2]

Figure 02_image007
(式中，R31 、R32 、R33 、R34 、R35 、R36 、R37 、R38 、R39 及R40 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群B＞中之二價基而成之碳原子數1～20之基， R31 、R32 、R33 、R34 、R35 、R36 、R37 、R38 、R39 及R40 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR41 、-COOR41 、-CO-R41 或-SR41 而成之碳原子數1～20之基， R41 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R41 之情形時，其等可相同，亦可不同， ＜群B＞為-O-、-CO-、-COO-、-NR42 -、-NR42 CO-及-S-， R42 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R42 之情形時，其等可相同，亦可不同， R31 與R32 、R33 與R34 、R35 與R36 、R37 與R38 、及R39 與R40 可分別獨立地相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， *表示鍵結鍵)[化2]
Figure 02_image007
(In the formula, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a hydrocarbon group The methylene group in is substituted with a group of 1 to 20 carbon atoms selected from the divalent group in the following <Group B>, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 may also be one or more of the hydrogen atoms in the hydrocarbyl group substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 41 , -COOR 41 ,- CO-R 41 or -SR 41 is a group with 1 to 20 carbon atoms. R 41 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R 41 in the group, they may be The same or different, <Group B> is -O-, -CO-, -COO-, -NR 42 -, -NR 42 CO- and -S-, R 42 represents a hydrogen atom or carbon number 1-20 When there are a plurality of R 42 in the base, they may be the same or different, R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R 38 , and R 39 and R 40 can be independently connected to each other to form a ring with 2-10 carbon atoms containing hydrogen, nitrogen and carbon atoms or 2-10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms The ring, * means bonding bond)

以下，對本發明詳細地進行說明。 本發明之胺甲醯肟化合物係上述通式(I)所表示者。上述通式(I)所表示之胺甲醯肟化合物中存在因肟之雙鍵而產生之幾何異構物，但不對該等進行區別。 即，於本說明書中，上述通式(I)所表示之胺甲醯肟化合物、以及下述作為該化合物之較佳形態之化合物及例示化合物表示異構物之混合物或其中任一者，並不限定於所示結構之異構物。 以下，將上述通式(I)所表示之胺甲醯肟化合物亦簡稱為「通式(I)所表示之化合物」或「本發明之化合物」。Hereinafter, the present invention will be described in detail. The aminomethoxime compound of the present invention is represented by the above general formula (I). There are geometric isomers due to the double bond of the oxime in the aminoformoxime compound represented by the above general formula (I), but these are not distinguished. That is, in this specification, the amine carboxamide compound represented by the above-mentioned general formula (I), and the following compounds and exemplified compounds which are preferred forms of the compound represent a mixture of isomers or any one of them, and It is not limited to the isomers of the structure shown. Hereinafter, the carboxime compound represented by the above general formula (I) is also simply referred to as "the compound represented by the general formula (I)" or "the compound of the present invention".

作為上述通式(I)、上述通式(a)及上述通式(b)中之鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。Examples of the halogen atom in the general formula (I), the general formula (a), and the general formula (b) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

作為上述通式(I)、上述通式(a)及上述通式(b)中之碳原子數1～20之烴基，可列舉：碳原子數1～20之脂肪族烴基及碳原子數6～20之芳香族烴基。Examples of the hydrocarbon group having 1 to 20 carbon atoms in the general formula (I), the general formula (a), and the general formula (b) include: aliphatic hydrocarbon groups having 1 to 20 carbon atoms and 6 carbon atoms ～20 aromatic hydrocarbon groups.

作為上述碳原子數1～20之脂肪族烴基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、十一烷基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基等烷基；環戊基、環己基等環烷基；及環己基甲基等環烷基烷基、以及作為將該等基之碳-碳單鍵取代為碳-碳雙鍵或碳-碳三鍵而成之結構之不飽和脂肪族烴基等。Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, Isopentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl , Dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and other alkyl groups; cyclopentyl, cyclohexyl and other cycloalkyl groups; and cyclohexyl methyl and other cycloalkyl alkanes A group, and an unsaturated aliphatic hydrocarbon group etc. which are a structure in which the carbon-carbon single bond of these groups is substituted with a carbon-carbon double bond or a carbon-carbon triple bond.

作為上述碳原子數6～20之芳香族烴基，例如可列舉：苯基、甲苯基、二甲苯基、2,4,6-三甲苯基、苄基、萘基、菲基、芘基及聯苯基等。As the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, for example, phenyl, tolyl, xylyl, 2,4,6- mesityl, benzyl, naphthyl, phenanthryl, pyrenyl and biphenyl can be mentioned. Phenyl and so on.

作為R1 ～R10 、R21 及R22 所表示之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR11 、-COOR11 、-CO-R11 或-SR11 而成之碳原子數1～20之基，可列舉為上述碳原子數1～20之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR11 、-COOR11 、-CO-R11 或-SR11 而成之結構且整體之碳原子數為1～20之基。又，作為R11 所表示之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基而成之碳原子數1～20之基，可列舉為上述碳原子數1～20之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基而成之結構且整體之碳原子數為1～20之基。One or more of the hydrogen atoms in the hydrocarbon groups represented by R 1 to R 10 , R 21 and R 22 are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 11 , -COOR 11 ,- CO-R 11 or -SR 11 is a group with 1 to 20 carbon atoms, and one or more of the hydrogen atoms in the above-mentioned hydrocarbon group with 1 to 20 carbon atoms are substituted with halogen atoms or cyanide. Group, nitro group, hydroxyl group, -OR 11 , -COOR 11 , -CO-R 11 or -SR 11 , and the whole group has 1 to 20 carbon atoms. In addition, as a group with 1 to 20 carbon atoms in which one or more of the hydrogen atoms in the hydrocarbon group represented by R 11 is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, the above-mentioned carbon may be exemplified A structure in which one or more of the hydrogen atoms in a hydrocarbon group having 1 to 20 atoms is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group, and the entire group has 1 to 20 carbon atoms.

作為R1 ～R11 、R21 及R22 所表示之烴基中之亞甲基被取代為選自上述＜群A＞中之二價基而成之碳原子數1～20之基，可列舉為上述碳原子數1～20之烴基中之亞甲基之1個或2個以上被取代為-O-、-CO-、-COO-、-NR12 -、-NR12 CO-或-S-而成之結構且整體之碳原子數為1～20之基。The methylene group in the hydrocarbon group represented by R 1 to R 11 , R 21 and R 22 is substituted with a group with 1 to 20 carbon atoms, which is a divalent group selected from the above-mentioned <Group A>, and examples thereof include One or more of the methylene groups in the above-mentioned hydrocarbon group with 1 to 20 carbon atoms are substituted with -O-, -CO-, -COO-, -NR 12 -, -NR 12 CO- or -S -It has a structure and the number of carbon atoms in the whole is a base of 1-20.

作為R31 ～R40 所表示之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR41 、-COOR41 、-CO-R41 或-SR41 而成之碳原子數1～20之基，可列舉為上述碳原子數1～20之烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR41 、-COOR41 、-CO-R41 或-SR41 而成之結構且整體之碳原子數為1～20之基。One or more of the hydrogen atoms in the hydrocarbon groups represented by R 31 to R 40 are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 41 , -COOR 41 , -CO-R 41 or- The group of 1-20 carbon atoms formed by SR 41 can be exemplified by one or more of the hydrogen atoms in the above-mentioned hydrocarbon group with 1-20 carbon atoms being substituted with halogen atoms, cyano groups, nitro groups, and hydroxyl groups. , -OR 41 , -COOR 41 , -CO-R 41 or -SR 41 , and the overall number of carbon atoms is 1-20.

作為R31 ～R40 所表示之烴基中之亞甲基被取代為選自上述＜群B＞中之二價基而成之碳原子數1～20之基，可列舉為上述碳原子數1～20之烴基中之亞甲基之1個或2個以上被取代為-O-、-CO-、-COO-、-NR42 -、-NR42 CO-或-S-而成之結構且整體之碳原子數為1～20之基。The methylene group in the hydrocarbon group represented by R 31 to R 40 is substituted with a divalent group selected from the above-mentioned <Group B>, and the group having 1 to 20 carbon atoms includes the above-mentioned carbon number 1 One or more of the methylene groups in the hydrocarbon group of ～20 are substituted with -O-, -CO-, -COO-, -NR 42 -, -NR 42 CO- or -S-, and The total number of carbon atoms is 1-20.

作為上述通式(I)中之碳原子數2～20之含雜環之基，例如可列舉：四氫呋喃基、二氧戊環基、四氫哌喃基、嗎啉基、呋喃基、噻吩基、甲基噻吩基、己基噻吩基、苯并噻吩基、吡咯基、吡咯啶基、咪唑基、咪唑啉基、咪唑啶基、吡唑啉基、吡唑啶基、哌啶基及哌嗪基等雜環基、以及含有該等基之基等。Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms in the general formula (I) include: tetrahydrofuranyl, dioxolane, tetrahydropiperanyl, morpholinyl, furanyl, and thienyl , Methylthienyl, hexylthienyl, benzothienyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolinyl, pyrazolidinyl, piperidinyl and piperazinyl And other heterocyclic groups, and groups containing such groups.

又，碳原子數2～20之含雜環之基可具有鹵素原子、氰基、硝基、羥基、-OR50 、-COOR50 、-CO-R50 或-SR50 等取代基，亦可包含-O-、-CO-、-COO-、-NR51 -、-NR51 CO-或-S-等結構。 此處，R50 及R51 分別獨立地表示氫原子或碳原子數1～20之烴基。R50 及R51 所表示之碳原子數1～20之烴基係與上述通式(I)、上述通式(a)及上述通式(b)中之碳原子數1～20之烴基相同。In addition, the heterocyclic ring-containing group having 2 to 20 carbon atoms may have a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 50 , -COOR 50 , -CO-R 50 or -SR 50 and other substituents. Contains -O-, -CO-, -COO-, -NR 51 -, -NR 51 CO- or -S- and other structures. Here, R 50 and R 51 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms represented by R 50 and R 51 is the same as the hydrocarbon group having 1 to 20 carbon atoms in the general formula (I), the general formula (a), and the general formula (b).

作為上述通式(I)中之R3 與R4 、R6 與R7 、R7 與R8 及R8 與R9 相互連結而形成之包含氫原子及碳原子之碳原子數3～10之環，可列舉：苯環、環己烯環、環己烷環、環戊二烯環、環戊烷環等。又，該等環亦可具有取代基，作為該情形時之取代基，可列舉上述碳原子數2～20之含雜環之基可具有之取代基。 As R 3 and R 4 , R 6 and R 7 , R 7 and R 8, and R 8 and R 9 in the above general formula (I) are connected to each other, the number of carbon atoms including hydrogen and carbon atoms is 3-10 Examples of the ring include benzene ring, cyclohexene ring, cyclohexane ring, cyclopentadiene ring, and cyclopentane ring. In addition, these rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

作為上述通式(I)、上述通式(a)及上述通式(b)中之R21 與R22 、R31 與R32 、R33 與R34 、R35 與R36 、R37 與R38 、及R39 與R40 相互連結而形成之包含氫原子、氮原子及碳原子之碳原子數2～10之環，作為包括所鍵結之氮原子在內之環，可列舉：吡咯環、吡咯啶環、咪唑環、咪唑啶環、咪唑啉環、吡唑環、吡唑啶環、哌啶環、哌𠯤環等。該等環亦可具有取代基，作為該情形時之取代基，可列舉上述碳原子數2～20之含雜環之基可具有之取代基。 As R 21 and R 22 , R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R in the above general formula (I), the above general formula (a) and the above general formula (b) R 38 , R 39 and R 40 are connected to each other to form a ring with 2 to 10 carbon atoms including hydrogen atom, nitrogen atom and carbon atom. Examples of the ring including the bonded nitrogen atom include: pyrrole Ring, pyrrolidine ring, imidazole ring, imidazole ring, imidazoline ring, pyrazole ring, pyrazole ring, piperidine ring, piperidine ring, etc. These rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

作為上述通式(I)、上述通式(a)及上述通式(b)中之R21 與R22 、R31 與R32 、R33 與R34 、R35 與R36 、R37 與R38 、及R39 與R40 相互連結而形成之包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環，作為包括所鍵結之氮原子在內之環，可列舉：嗎啉環、㗁唑環、㗁唑啉環、㗁二唑環等。該等環亦可具有取代基，作為該情形時之取代基，可列舉上述碳原子數2～20之含雜環之基可具有之取代基。 As R 21 and R 22 , R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R in the above general formula (I), the above general formula (a) and the above general formula (b) R 38 , R 39 and R 40 are connected to each other to form a ring with 2 to 10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms. As a ring including the bonded nitrogen atom, it can be Enumerated: morpholine ring, azole ring, oxazoline ring, oxadiazole ring and the like. These rings may have a substituent, and examples of the substituent in this case include the substituents that the heterocyclic ring-containing group having 2 to 20 carbon atoms may have.

通式(I)中之R1 為碳原子數6～20之芳香族烴基之胺甲醯肟化合物由於所獲得之聚合性組合物會於低曝光量下進行硬化，故而較佳，尤佳為通式(I)中之R1 為含有苯環之碳原子數6～20之芳香族烴基之胺甲醯肟化合物。又，上述R1 為碳原子數1～20之脂肪族烴基之情況亦由於所獲得之聚合性組合物會於低曝光量下進行硬化，故而較佳。 The amine methyl oxime compound in which R 1 in the general formula (I) is an aromatic hydrocarbon group with 6 to 20 carbon atoms is preferred because the polymerizable composition obtained will harden under a low exposure dose, and is particularly preferred. R 1 in the general formula (I) is an acarboxamide compound containing a benzene ring and an aromatic hydrocarbon group with 6 to 20 carbon atoms. In addition, the above-mentioned case where R 1 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms is also preferable because the obtained polymerizable composition will be cured under a low exposure amount.

於本發明中，就對溶劑之溶解性優異之方面而言，較佳為通式(I)中之R2 為碳原子數1～10之脂肪族烴基之胺甲醯肟化合物，尤佳為通式(I)中之R2 為碳原子數1～10之具有支鏈之烷基。In the present invention, in terms of excellent solubility in solvents, it is preferably an acarboxamide compound in which R 2 in the general formula (I) is an aliphatic hydrocarbon group with 1 to 10 carbon atoms, and particularly preferably R 2 in the general formula (I) is a branched alkyl group having 1 to 10 carbon atoms.

上述通式(I)中之R3 與R4 或R8 與R9 相互連結而形成苯環之胺甲醯肟化合物由於所獲得之聚合性組合物會於低曝光量下進行硬化，故而較佳。 The carbamethoxime compound in which R 3 and R 4 or R 8 and R 9 in the above general formula (I) are connected to each other to form a benzene ring is more difficult because the polymerizable composition obtained will harden under low exposure. good.

通式(I)中之X1 為-NR21 R22 且R21 與R22 相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環之胺甲醯肟化合物由於產鹼效率較高，故而較佳，更佳為形成包含氫原子、氮原子及碳原子之碳原子數2～6之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～6之環。 尤佳為R21 與R22 相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～6之環，進而較佳為形成哌啶環或吡咯啶環。 X 1 in the general formula (I) is -NR 21 R 22 and R 21 and R 22 are connected to each other to form a ring with 2 to 10 carbon atoms containing hydrogen, nitrogen and carbon atoms or containing hydrogen and oxygen atoms , Nitrogen and carbon atoms of the amine methyl oxime compound with a carbon atom number of 2 to 10 because of its higher alkali production efficiency, it is preferred, and it is more preferred to form a carbon atom containing hydrogen, nitrogen and carbon atoms 2 The ring of ~6 or a ring of 2 to 6 carbon atoms containing a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom. It is particularly preferable that R 21 and R 22 are linked to each other to form a carbon atom ring containing a hydrogen atom, a nitrogen atom, and a carbon atom, and it is more preferable to form a piperidine ring or a pyrrolidine ring.

又，於通式(I)中之X1 為-NR21 R22 之胺甲醯肟化合物中，R21 為氫原子且R22 為碳原子數6～20之芳香族烴基、以及R21 及R22 均為碳原子數1～20之脂肪族烴基亦由於產鹼效率較高，故而較佳。Furthermore, in the amine carboxamide compound in which X 1 in the general formula (I) is -NR 21 R 22 , R 21 is a hydrogen atom and R 22 is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 21 and R 22 is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, which is also preferred because of its higher alkali production efficiency.

R3 、R4 、R5 、R6 、R7 、R8 及R9 中之一個以上為-CO-R10 且R10 為碳原子數6～20之芳香族烴基之胺甲醯肟化合物由於所獲得之聚合性組合物會於低曝光量下進行硬化，故而較佳，尤佳為R7 為-CO-R10 且R10 為含有苯環之碳原子數6～20之芳香族烴基之胺甲醯肟化合物。One or more of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is -CO-R 10 and R 10 is an amine carboxamide compound having an aromatic hydrocarbon group with 6 to 20 carbon atoms Since the obtained polymerizable composition will be cured under low exposure, it is preferred. R 7 is -CO-R 10 and R 10 is an aromatic hydrocarbon group with 6 to 20 carbon atoms containing a benzene ring. The amine methyl oxime compound.

上述通式(I)中之n為0之胺甲醯肟化合物由於對熱之穩定性較高，故而較佳。 上述通式(I)中之n為1之胺甲醯肟化合物由於所獲得之聚合性組合物會於低曝光量下進行硬化，故而較佳。The aminomethoxime compound in which n is 0 in the above general formula (I) is preferred because of its higher stability to heat. The aminoformoxime compound in which n is 1 in the above general formula (I) is preferable because the obtained polymerizable composition will be cured under low exposure.

於本發明中，最佳為如下胺甲醯肟化合物，即通式(I)中之R1 為碳原子數6～20之芳香族烴基，R2 為碳原子數1～10之具有支鏈之烷基，R8 與R9 相互連結而形成苯環，X1 為-NR21 R22 且R21 與R22 相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環，R7 為-CO-R10 ，R10 為碳原子數6～20之芳香族烴基，n為0。In the present invention, the best carboxime compound is the following carbamate, that is, R 1 in the general formula (I) is an aromatic hydrocarbon group with 6 to 20 carbon atoms, and R 2 is a branched chain with 1 to 10 carbon atoms The alkyl group, R 8 and R 9 are connected to each other to form a benzene ring, X 1 is -NR 21 R 22 and R 21 and R 22 are connected to each other to form a hydrogen atom, a nitrogen atom and a carbon atom with 2 to 10 carbon atoms R 7 is -CO-R 10 , R 10 is an aromatic hydrocarbon group with 6 to 20 carbon atoms, and n is 0.

作為上述通式(I)所表示之胺甲醯肟化合物之具體例，可列舉以下化學式(1)～(52)所表示之化合物。但是，本發明並不受以下化合物任何限制。As specific examples of the aminomethoxime compound represented by the above general formula (I), the compounds represented by the following chemical formulas (1) to (52) can be cited. However, the present invention is not limited in any way by the following compounds.

[化3]

Figure 02_image009
[化3]
Figure 02_image009

[化4]

Figure 02_image011
[化4]
Figure 02_image011

[化5]

Figure 02_image013
[化5]
Figure 02_image013

[化6]

Figure 02_image015
[化6]
Figure 02_image015

[化7]

Figure 02_image017
[化7]
Figure 02_image017

[化8]

Figure 02_image019
[化8]
Figure 02_image019

上述通式(I)所表示之本發明之胺甲醯肟化合物之製造方法並無特別限定，例如於R8 與R9 相互連結而形成苯環且X1 為-NR21 R22 、n＝0之情形時，可依據下述反應式1並藉由以下方法來製造。 即，藉由使公知之酮化合物與鹽酸羥胺於吡啶等鹼之存在下進行反應而獲得肟化合物。繼而，使氯甲酸4-硝基苯酯與肟化合物反應，繼而使胺反應，藉此獲得本發明之胺甲醯肟化合物。The method for producing the aminomethoxime compound of the present invention represented by the above general formula (I) is not particularly limited, for example, when R 8 and R 9 are connected to each other to form a benzene ring, and X 1 is -NR 21 R 22 , n= In the case of 0, it can be produced by the following method according to the following reaction formula 1. That is, an oxime compound is obtained by reacting a known ketone compound and hydroxylamine hydrochloride in the presence of a base such as pyridine. Then, the 4-nitrophenyl chloroformate is reacted with the oxime compound, and then the amine is reacted, thereby obtaining the carboxamide oxime compound of the present invention.

[化9]

Figure 02_image021
(式中，R1 ～R7 、R21 及R22 係與上述通式(I)相同)[化9]
Figure 02_image021
(In the formula, R 1 to R 7 , R 21 and R 22 are the same as the above general formula (I))

上述反應式1表示X1 為-NR21 R22 之情形，但藉由變更所使用之胺，亦可製造X1 為上述通式(a)或上述通式(b)所表示之基之化合物。 肟化合物亦可利用日本專利第4223071號公報所記載之方法來製造。The above reaction formula 1 shows the case where X 1 is -NR 21 R 22 , but by changing the amine used, it is also possible to produce a compound in which X 1 is the group represented by the above general formula (a) or the above general formula (b) . The oxime compound can also be produced by the method described in Japanese Patent No. 4223071.

本發明之胺甲醯肟化合物由於藉由紫外線等光照射或加熱而有效率地產生鹼及自由基，故而作為潛在性產鹼劑及聚合起始劑有用，尤其是作為聚合起始劑有用。The amine oxime compound of the present invention efficiently generates bases and free radicals by light irradiation such as ultraviolet rays or heating, and is therefore useful as a latent base generator and polymerization initiator, and is particularly useful as a polymerization initiator.

所謂本發明之潛在性產鹼劑，意指含有如下化合物之組成物，該化合物具有藉由照射紫外線等光而高效率地產生鹼之功能，作為該組成物之用途，可列舉pH值調整劑、利用鹼之觸媒等。The latent alkali generator of the present invention means a composition containing a compound that has the function of efficiently generating alkali by irradiating light such as ultraviolet rays, and the use of the composition includes a pH adjusting agent , The use of alkali catalysts, etc.

又，本發明之胺甲醯肟化合物由於在上述聚合起始劑之中，藉由光照射所帶來之鹼及自由基之產生效率較高，故而作為光產鹼劑及光自由基聚合起始劑有用，且由於產鹼效率非常高，故而尤其是作為光產鹼劑有用。In addition, the aminomethoxime compound of the present invention has a higher efficiency in generating bases and free radicals caused by light irradiation among the above-mentioned polymerization initiators, so it functions as a photobase generator and photoradical polymerization. The starter is useful, and because the alkali production efficiency is very high, it is especially useful as a photoalkali generator.

本發明之聚合起始劑含有至少1種上述通式(I)所表示之胺甲醯肟化合物。作為可與上述通式(I)所表示之胺甲醯肟化合物併用之聚合起始劑，並無特別限制，可列舉先前已知之光產鹼劑及光自由基聚合起始劑。The polymerization initiator of the present invention contains at least one carboxime compound represented by the above-mentioned general formula (I). The polymerization initiator that can be used in combination with the aminoformoxime compound represented by the above general formula (I) is not particularly limited, and the previously known photobase generators and photoradical polymerization initiators can be cited.

關於上述聚合起始劑中之上述通式(I)所表示之化合物之含量，就所獲得之聚合性組合物會於低曝光量下進行硬化之方面而言，較佳為1～100質量%，更佳為50～100質量%。Regarding the content of the compound represented by the general formula (I) in the polymerization initiator, it is preferably 1-100% by mass in terms of the obtained polymerizable composition curing under low exposure. , More preferably 50-100% by mass.

本發明之聚合性組合物含有具有至少1種上述通式(I)所表示之胺甲醯肟化合物之聚合起始劑(A)、及聚合性化合物(B)。 關於聚合起始劑(A)之含量，就所獲得之聚合性組合物會於低曝光量下進行硬化之方面而言，相對於聚合性化合物(B)100質量份較佳為1～20質量份，更佳為1～10質量份。藉由使聚合起始劑(A)之含量為1質量份以上，容易防止由硬化感度不足所導致之硬化不良，故而較佳，藉由設為20質量份以下，可抑制光照射時或加熱時之揮發物，故而較佳。The polymerizable composition of the present invention contains a polymerization initiator (A) and a polymerizable compound (B) having at least one type of amine oxime compound represented by the above-mentioned general formula (I). Regarding the content of the polymerization initiator (A), it is preferably 1-20 mass parts relative to 100 mass parts of the polymerizable compound (B) in terms of the obtained polymerizable composition curing at a low exposure dose Parts, more preferably 1-10 parts by mass. By setting the content of the polymerization initiator (A) to 1 part by mass or more, it is easy to prevent poor curing caused by insufficient curing sensitivity. Therefore, it is preferably set to 20 parts by mass or less to suppress light irradiation or heating The volatile matter of time is better.

作為本發明中所使用之聚合性化合物(B)，可列舉：具有陰離子聚合性官能基之化合物、藉由鹼作為觸媒發揮作用之反應或鹼所加成之反應而硬化之化合物、及自由基聚合性化合物，就所獲得之聚合性組合物會於低曝光量下進行硬化之方面而言，較佳為藉由照射紫外線等能量線而進行聚合並硬化之感光性樹脂或硬化溫度低溫化之硬化樹脂。所謂上述陰離子聚合性官能基，意指可藉由利用紫外線等活性能量線而自光產鹼劑產生之鹼進行聚合之官能基，例如可列舉：環氧基、環硫化物基、環狀單體(σ-戊內酯、ε-己內醯胺)、丙二酸酯等。作為鹼作為觸媒發揮作用之反應或鹼所加成之反應，可列舉：藉由異氰酸酯與醇所進行之胺基甲酸酯鍵形成反應、含有環氧樹脂與羥基之化合物之加成反應、含有環氧樹脂與羧酸基之化合物之加成反應、環氧樹脂與硫醇化合物之加成反應、(甲基)丙烯酸基之麥可加成反應、聚醯胺酸之脫水縮合反應、烷氧基矽烷之水解/縮聚反應等。Examples of the polymerizable compound (B) used in the present invention include: a compound having an anionic polymerizable functional group, a compound that is cured by a reaction in which a base acts as a catalyst or a reaction in which the base is added, and free The base polymerizable compound is preferably a photosensitive resin that is polymerized and cured by irradiating energy rays such as ultraviolet rays, or the curing temperature is lowered from the viewpoint that the obtained polymerizable composition will be cured under low exposure. The hardening resin. The aforementioned anionic polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator using active energy rays such as ultraviolet rays, and examples include epoxy groups, episulfide groups, and cyclic monomers. Body (σ-valerolactone, ε-caprolactone), malonate, etc. As a reaction in which a base acts as a catalyst or a reaction in which a base is added, examples include: urethane bond formation reaction by isocyanate and alcohol, addition reaction of a compound containing epoxy resin and hydroxyl group, Addition reaction of compounds containing epoxy resin and carboxylic acid group, addition reaction of epoxy resin and thiol compound, Michael addition reaction of (meth)acrylic acid group, dehydration condensation reaction of polyamide acid, alkane Hydrolysis/condensation reaction of oxysilane, etc.

作為具有陰離子聚合性官能基之化合物，例如可列舉：環氧樹脂、氧雜環丁烷樹脂、環硫樹脂、環狀醯胺(內醯胺系化合物)、環狀酯(內酯系化合物)、環狀碳酸酯系化合物、丙二酸酯等。作為藉由鹼作為觸媒發揮作用之反應或鹼所加成之反應而硬化之化合物，例如可列舉：聚醯胺樹脂(藉由脫水環化進行之聚醯亞胺化反應)、環氧基・羥基系(開環加成反應)、環氧基・羧酸系(開環加成反應)、環氧基・硫醇系(開環加成反應)、環氧基・酸酐系(開環縮聚)、氰酸酯(三𠯤環化反應)、氰酸酯・環氧系(環化反應)、氰酸酯・馬來醯亞胺系(交聯共聚)、氧雜環丁烷・羥基系(開環加成反應)、氧雜環丁烷・羧酸系(開環加成反應)、氧雜環丁烷・硫醇系(開環加成反應)、氧雜環丁烷・酸酐系(開環縮聚)、環硫化物・羥基系(開環加成反應)、環硫化物・羧酸系(開環加成反應)、環硫化物・硫醇系(開環加成反應)、環硫化物・酸酐系(開環縮聚)、丙烯酸・硫醇系(麥可加成反應)、甲基丙烯酸・硫醇系(麥可加成反應)、丙烯酸・胺系(麥可加成反應)、甲基丙烯酸・胺系(麥可加成反應)、羧酸・羥基系(聚酯化反應)、羧酸・胺系(聚醯胺化反應)、異氰酸酯・羥基系(聚胺基甲酸酯化反應)、異氰酸酯・硫醇系(多硫胺基甲酸酯化反應)、烷氧基矽烷系(水解・縮聚)等。作為藉由自由基進行聚合之化合物，可列舉乙烯性不飽和化合物。就反應性較高之方面而言，較佳為使用進行自由基聚合之化合物。該等樹脂可單獨使用，亦可將2種以上併用。作為較佳組合，就反應快速進行或接著性良好之方面而言，可列舉環氧樹脂與酚樹脂之組合，就低溫硬化性優異之方面而言，可列舉環氧樹脂與硫醇化合物之組合，就反應性較高之方面而言，可列舉乙烯性不飽和化合物與硫醇化合物之組合。Examples of compounds having anionic polymerizable functional groups include epoxy resins, oxetane resins, episulfide resins, cyclic amides (lactone compounds), and cyclic esters (lactone compounds) , Cyclic carbonate-based compounds, malonic acid esters, etc. Examples of compounds that are cured by a reaction in which a base acts as a catalyst or a reaction in which the base is added include: polyamide resin (polyimination reaction by dehydration and cyclization), epoxy・Hydroxy group (ring-opening addition reaction), epoxy group, carboxylic acid system (ring-opening addition reaction), epoxy group, mercaptan system (ring-opening addition reaction), epoxy group, acid anhydride system (ring-opening Polycondensation), cyanate ester (tricyclic cyclization reaction), cyanate ester, epoxy type (cyclization reaction), cyanate ester, maleimide type (crosslinked copolymerization), oxetane, hydroxyl System (ring-opening addition reaction), oxetane, carboxylic acid system (ring-opening addition reaction), oxetane, mercaptan system (ring-opening addition reaction), oxetane, acid anhydride System (ring-opening polycondensation), episulfide, hydroxyl system (ring-opening addition reaction), episulfide, carboxylic acid system (ring-opening addition reaction), episulfide, mercaptan system (ring-opening addition reaction) , Episulfide and acid anhydride series (ring-opening polycondensation), acrylic acid and mercaptan series (Miccan addition reaction), methacrylic acid and mercaptan series (Miccan addition reaction), acrylic acid and amine series (Miccan addition reaction) Reaction), methacrylic acid, amine system (Miccan addition reaction), carboxylic acid, hydroxyl system (polyesterification reaction), carboxylic acid, amine system (polyamide reaction), isocyanate, hydroxyl system (polyamine Formate reaction), isocyanate/thiol series (polythiocarbamation reaction), alkoxysilane series (hydrolysis and polycondensation), etc. Examples of the compound that undergoes radical polymerization include ethylenically unsaturated compounds. In terms of higher reactivity, it is preferable to use a compound that undergoes radical polymerization. These resins may be used alone or in combination of two or more kinds. As a preferred combination, in terms of rapid reaction progress or good adhesion, a combination of epoxy resin and phenol resin can be cited, and a combination of epoxy resin and thiol compound in terms of excellent low-temperature curability In terms of higher reactivity, a combination of ethylenically unsaturated compounds and thiol compounds can be cited.

上述環氧樹脂只要具有環氧基即可，但本發明之胺甲醯肟化合物除外。作為環氧樹脂，例如可列舉：對苯二酚、間苯二酚、鄰苯二酚、間苯三酚等單核多酚化合物之聚縮水甘油醚化合物；二羥基萘、聯苯酚、亞甲基雙酚(雙酚F)、亞甲基雙(鄰甲酚)、亞乙基雙酚、亞異丙基雙酚(雙酚A)、4,4'-二羥基二苯甲酮、亞異丙基雙(鄰甲酚)、四溴雙酚A、1,3-雙(4-羥基異丙苯基苯)、1,4-雙(4-羥基異丙苯基苯)、1,1,3-三(4-羥基苯基)丁烷、1,1,2,2-四(4-羥基苯基)乙烷、硫代雙酚、磺基雙酚、氧基雙酚、酚系酚醛清漆、鄰甲酚酚醛清漆、乙基酚系酚醛清漆、丁基酚系酚醛清漆、辛基酚系酚醛清漆、間苯二酚酚醛清漆、萜酚等多核多酚化合物之聚縮水甘油醚化合物；乙二醇、丙二醇、丁二醇、己二醇、聚二醇、硫代雙乙醇、甘油、三羥甲基丙烷、季戊四醇、山梨糖醇、雙酚A-環氧乙烷加成物等多元醇類之聚縮水甘油醚；順丁烯二酸、反丁烯二酸、伊康酸、琥珀酸、戊二酸、辛二酸、己二酸、壬二酸、癸二酸、二聚酸、三聚物酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三甲酸、均苯三酸、均苯四甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸等脂肪族、芳香族或脂環族多元酸之縮水甘油酯類、及甲基丙烯酸縮水甘油酯之均聚物或共聚物；N,N-二縮水甘油基苯胺、雙(4-(N-甲基-N-縮水甘油基胺基)苯基)甲烷、二縮水甘油基鄰甲苯胺等具有縮水甘油基胺基之環氧化合物；乙烯基環己烯二環氧化物、二環戊二烯二環氧化物、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、3,4-環氧-6-甲基環己基甲基-6-甲基環己烷羧酸酯、己二酸雙(3,4-環氧-6-甲基環己基甲基)酯等環狀烯烴化合物之環氧化物；環氧化聚丁二烯、環氧化丙烯腈-丁二烯共聚物、環氧化苯乙烯-丁二烯共聚物等環氧化共軛二烯聚合物、三縮水甘油基異氰尿酸酯等雜環化合物。又，該等環氧樹脂亦可為藉由封端異氰酸酯之預聚物進行內部交聯而成者或利用多元活性氫化合物(多酚、聚胺、含羰基之化合物、聚磷酸酯等)進行高分子量化而成者。 上述環氧樹脂之中，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為具有縮水甘油基者，更佳為具有2官能以上之縮水甘油基者。The above-mentioned epoxy resin only needs to have an epoxy group, except for the carbamate compound of the present invention. Examples of epoxy resins include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, catechol, and phloroglucinol; dihydroxy naphthalene, biphenol, methylene Bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, sub Isopropyl bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1, 1,3-Tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol Polyglycidyl ether of polynuclear polyphenol compounds such as novolac, o-cresol novolac, ethyl phenol novolac, butylphenol novolac, octylphenol novolak, resorcinol novolak, terpene phenol and other polynuclear polyphenol compounds Compounds; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyglycol, thiodiethanol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Polyglycidyl ether such as polyols; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, two Polyacid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid Glycidyl esters of aliphatic, aromatic or cycloaliphatic polybasic acids such as formic acid and endomethylene tetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N,N-di Glycidyl aniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl o-toluidine and other epoxy compounds with glycidyl amino groups; vinyl ring Hexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6- The epoxides of cyclic olefin compounds such as methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene-butadiene copolymer, and heterocyclic rings such as triglycidyl isocyanurate Compound. In addition, these epoxy resins may also be formed by internal crosslinking of prepolymers of blocked isocyanates, or may be formed by using multiple active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.) High molecular weight. Among the above-mentioned epoxy resins, in terms of excellent curability of the obtained polymerizable composition, those having a glycidyl group are preferred, and those having a glycidyl group having a bifunctional or more are more preferred.

上述酚樹脂只要具有酚性羥基即可，但上述胺甲醯肟化合物及環氧樹脂除外。作為酚樹脂，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為1分子中具有2個以上羥基之酚樹脂，通常可使用公知者。作為酚樹脂，例如可列舉：雙酚A型酚樹脂、雙酚E型酚樹脂、雙酚F型酚樹脂、雙酚S型酚樹脂、酚系酚醛清漆型樹脂、雙酚A酚醛清漆型酚樹脂、縮水甘油酯型酚樹脂、芳烷基酚醛清漆型酚樹脂、聯苯基芳烷基型酚樹脂、甲酚酚醛清漆型酚樹脂、多官能酚樹脂、萘酚樹脂、萘酚酚醛清漆樹脂、多官能萘酚樹脂、蒽型酚樹脂、萘骨架改性酚醛清漆型酚樹脂、苯酚芳烷基型酚樹脂、萘酚芳烷基型酚樹脂、二環戊二烯型酚樹脂、聯苯型酚樹脂、脂環式酚樹脂、多元醇型酚樹脂、含磷之酚樹脂、含聚合性不飽和烴基之酚樹脂及含羥基之聚矽氧樹脂類，並無特別限制。該等酚樹脂可單獨使用1種或將2種以上組合使用。The said phenol resin should just have a phenolic hydroxyl group, but the said carbamate compound and epoxy resin are excluded. As the phenol resin, in terms of excellent curability of the obtained polymerizable composition, a phenol resin having two or more hydroxyl groups per molecule is preferred, and generally known ones can be used. Examples of phenol resins include: bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak type resin, bisphenol A novolak type phenol Resin, glycidyl ester type phenol resin, aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, multifunctional phenol resin, naphthol resin, naphthol novolak resin , Multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl Type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, polymerizable unsaturated hydrocarbon group-containing phenol resins, and hydroxyl group-containing silicone resins are not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

上述硫醇化合物只要具有硫醇基即可，但上述胺甲醯肟化合物、環氧樹脂及酚樹脂除外。硫醇化合物之中，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為1分子中具有2個以上硫醇基者。 作為硫醇化合物之較佳具體例，為雙(2-巰基乙基)硫醚、2,5-二巰基甲基-1,4-二噻烷、1,3-雙(巰基甲基)苯、1,4-雙(巰基甲基)苯、4-巰基甲基-1,8-二巰基-3,6-二噻辛烷、4,8-二巰基甲基-1,11-二巰基-3,6,9-三噻十一烷、4,7-二巰基甲基-1,11-二巰基-3,6,9-三噻十一烷、5,7-二巰基甲基-1,11-二巰基-3,6,9-三噻十一烷、1,2,6,7-四巰基-4-噻庚烷、季戊四醇、1,1,3,3-四(巰基甲基硫基)丙烷、季戊四醇四巰基丙酸酯、季戊四醇四巰基乙醇酸酯、三羥甲基丙烷巰基乙醇酸酯、及三羥甲基丙烷三巰基丙酸酯，更佳為列舉：1,2,6,7-四巰基-4-噻庚烷、季戊四醇、雙(2-巰基乙基)硫醚、2,5-雙(2-巰基甲基)-1,4-二噻烷、4-巰基甲基-1,8-二巰基-3,6-二噻辛烷、1,3-雙(巰基甲基)苯、季戊四醇四巰基丙酸酯、及季戊四醇四巰基乙醇酸酯。 尤佳之化合物為1,2,6,7-四巰基-4-噻庚烷、季戊四醇、雙(2-巰基乙基)硫醚、2,5-二巰基甲基-1,4-二噻烷、及4-巰基甲基-1,8-二巰基-3,6-二噻辛烷。 硫醇化合物可單獨使用1種或將2種以上組合使用。The above-mentioned thiol compound should just have a thiol group, except for the above-mentioned carbamate compound, epoxy resin, and phenol resin. Among the thiol compounds, those having two or more thiol groups in one molecule are preferable in terms of excellent curability of the obtained polymerizable composition. As preferred specific examples of the thiol compound, bis(2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis(mercaptomethyl)benzene , 1,4-bis(mercaptomethyl)benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto -3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl- 1,11-Dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-tetra(mercaptomethyl Thiol) propane, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoglycolate, trimethylolpropane mercaptoglycolate, and trimethylolpropane trimercaptopropionate, more preferably listed: 1,2 ,6,7-Tetramercapto-4-thiaheptane, pentaerythritol, bis(2-mercaptoethyl)sulfide, 2,5-bis(2-mercaptomethyl)-1,4-dithiane, 4- Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,3-bis(mercaptomethyl)benzene, pentaerythritol tetramercaptopropionate, and pentaerythritol tetramercaptoglycolate. Particularly preferred compounds are 1,2,6,7-tetramercapto-4-thiaheptane, pentaerythritol, bis(2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiol Alkanes, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. A thiol compound can be used individually by 1 type or in combination of 2 or more types.

作為上述聚醯胺樹脂，可列舉以作為酸二酐之伸乙基四羧酸二酐、1,2,3,4-苯四羧酸二酐、1,2,3,4-環己烷四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2,3,3-聯苯基四羧酸酐、1,4,5,8-萘四羧酸二酐等作為原料且以作為二胺之(鄰、間或者對)苯二胺、(3,3'-或者4,4'-)二胺基二苯醚、二胺基二苯甲酮、(3,3'-或者4,4'-)二胺基二苯甲烷等作為原料之樹脂。Examples of the polyamide resin include ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexane, which are acid dianhydrides. Tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, etc. as raw materials and used as diamines (ortho, meta or p) phenylenediamine, (3,3'- or 4,4'-) diamino diphenyl ether, diamino diphenyl Methyl ketone, (3,3'- or 4,4'-) diaminodiphenylmethane and other resins are used as raw materials.

作為上述聚胺基甲酸酯樹脂，可列舉以甲苯二異氰酸酯、六亞甲基二異氰酸酯、二苯甲烷二異氰酸酯、異佛酮二異氰酸酯等多官能異氰酸酯與聚醚多元醇、聚酯聚醇、聚碳酸酯多元醇等多元醇(多官能醇)作為原料之樹脂等。 又，作為上述尼龍樹脂，可列舉以ε-己內醯胺、十二內醯胺等環狀單體作為原料之樹脂等。 又，作為上述聚酯樹脂，可列舉以δ-戊內酯、β-丙內酯等環狀單體作為原料之樹脂等。Examples of the polyurethane resin include polyfunctional isocyanates such as toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and polyether polyols, polyester polyols, etc. Polycarbonate polyols and other polyols (polyfunctional alcohols) are used as raw materials for resins, etc. Moreover, as said nylon resin, the resin etc. which use cyclic monomers, such as ε-caprolactam and dodecanolide as a raw material, are mentioned. Moreover, as the said polyester resin, resin etc. which use cyclic monomers, such as delta-valerolactone and beta-propiolactone, as a raw material, etc. are mentioned.

上述乙烯性不飽和化合物只要具有乙烯性不飽和鍵即可，但上述胺甲醯肟化合物、環氧樹脂、酚樹脂及硫醇化合物除外。作為乙烯性不飽和化合物，例如可列舉：乙烯、丙烯、丁烯、異丁烯、氯乙烯、偏二氯乙烯、偏二氟乙烯、四氟乙烯等不飽和脂肪族烴；(甲基)丙烯酸、α-氯丙烯酸、伊康酸、順丁烯二酸、檸康酸、反丁烯二酸、雙環庚烯二甲酸、丁烯酸、異丁烯酸、乙酸乙烯酯、乙酸烯丙酯、桂皮酸、山梨酸、中康酸、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等兩末端具有羧基及羥基之聚合物之單(甲基)丙烯酸酯；(甲基)丙烯酸羥乙酯・順丁烯二酸酯、(甲基)丙烯酸羥丙酯・順丁烯二酸酯、二環戊二烯・順丁烯二酸酯或具有1個羧基及2個以上(甲基)丙烯醯基之多官能(甲基)丙烯酸酯等不飽和多元酸；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸二甲基胺基甲酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸二甲基胺基丙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸聚(乙氧基)乙酯、(甲基)丙烯酸丁氧基乙氧基乙酯、(甲基)丙烯酸乙酯己酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三環癸烷二羥甲基二(甲基)丙烯酸酯、異氰尿酸三[(甲基)丙烯醯基乙基]酯、聚酯(甲基)丙烯酸酯低聚物等不飽和一元酸及多元醇或多酚之酯；(甲基)丙烯酸鋅、(甲基)丙烯酸鎂等不飽和多元酸之金屬鹽；順丁烯二酸酐、伊康酸酐、檸康酸酐、甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、三烷基四氫鄰苯二甲酸酐、5-(2,5-二側氧四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、三烷基四氫鄰苯二甲酸酐-順丁烯二酸酐加成物、十二烯基琥珀酸酐、甲基雙環庚烯二甲酸酐等不飽和多元酸之酸酐；(甲基)丙烯醯胺、亞甲基雙-(甲基)丙烯醯胺、二伸乙基三胺三(甲基)丙烯醯胺、苯二甲基雙(甲基)丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基(甲基)丙烯醯胺等不飽和一元酸及多元胺之醯胺；丙烯醛等不飽和醛；(甲基)丙烯腈、α-氯丙烯腈、二氰亞乙烯、氰化烯丙基等不飽和腈；苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-甲氧基苯乙烯、4-羥基苯乙烯、4-氯苯乙烯、二乙烯苯、乙烯基甲苯、乙烯基苯甲酸、乙烯基苯酚、乙烯基磺酸、4-乙烯基苯磺酸、乙烯基苄基甲醚、乙烯基苄基縮水甘油醚等不飽和芳香族化合物；甲基乙烯基酮等不飽和酮；乙烯胺、烯丙胺、N-乙烯基吡咯啶酮、乙烯基哌啶等不飽和胺化合物；烯丙醇、巴豆醇等乙烯醇；乙烯基甲醚、乙烯基***、正丁基乙烯醚、異丁基乙烯醚、烯丙基縮水甘油醚等乙烯醚；順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等不飽和醯亞胺類；茚、1-甲基茚等茚類；1,3-丁二烯、異戊二烯、氯丁二烯等脂肪族共軛二烯類；聚苯乙烯、聚(甲基)丙烯酸甲酯、聚-(甲基)丙烯酸正丁酯、聚矽氧烷等於聚合物分子鏈之末端具有單(甲基)丙烯醯基之巨單體類；氯乙烯、偏二氯乙烯、丁二酸二乙烯酯、鄰苯二甲酸二烯丙酯、磷酸三烯丙酯、異氰尿酸三烯丙酯、乙烯基硫醚、乙烯基咪唑、乙烯基㗁唑啉、乙烯基咔唑、乙烯基吡咯啶酮、乙烯基吡啶、含羥基之乙烯基單體及聚異氰酸酯化合物之胺基甲酸乙烯酯化合物、含羥基之乙烯基單體及聚環氧化合物之乙烯基環氧化合物。 乙烯性不飽和化合物可單獨使用或將2種以上混合使用。The above-mentioned ethylenically unsaturated compound may have an ethylenically unsaturated bond, except for the above-mentioned carbamate compounds, epoxy resins, phenol resins, and thiol compounds. Examples of ethylenically unsaturated compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid Acid, mesaconic acid, mono[2-(meth)acryloxyethyl] succinate, mono[2-(meth)acryloxyethyl] phthalate, ω-carboxyl poly Caprolactone mono(meth)acrylate and other mono(meth)acrylates of polymers with carboxyl and hydroxyl groups at both ends; hydroxyethyl (meth)acrylate maleate, (meth)acrylic acid Hydroxypropyl, maleate, dicyclopentadiene, maleate, or multifunctional (meth)acrylate with one carboxyl group and two or more (meth)acrylic acid groups, etc. Saturated polybasic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate , Isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth) ) Isononyl acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, (methyl) )Dimethylaminoethyl acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(meth)acrylate (Ethoxy) ethyl, butoxy ethoxy ethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate , Vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, three Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, two Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, isocyanurate tri ((former) Ethyl) acryloyl ethyl) ester, polyester (meth)acrylate oligomer and other unsaturated monobasic acid and polyol or polyphenol ester; zinc (meth)acrylate, magnesium (meth)acrylate, etc. Metal salts of saturated polybasic acids; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)- 3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl bicycloheptane Anhydrides of unsaturated polybasic acids such as enedicarboxylic acid anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, benzene Unsaturated monobasic acids such as methylbis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide, and amides of polyamines; unsaturated aldehydes such as acrolein ; (Meth) acrylonitrile, α-chloroacrylonitrile, dicyandiene, allyl cyanide and other unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxy Vinyl styrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl Unsaturated aromatic compounds such as methyl ether and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine ; Vinyl alcohol such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide, Unsaturated imines such as N-phenyl maleimide and N-cyclohexyl maleimide; indene such as indene and 1-methylindene; 1,3-butadiene, Aliphatic conjugated dienes such as isoprene and chloroprene; polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxane are equal to polymer molecules Macromonomers with mono(meth)acrylic acid groups at the end of the chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, isocyanide Triallyl urate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and amine groups of polyisocyanate compounds Vinyl epoxy compounds of vinyl formate compounds, hydroxyl-containing vinyl monomers and polyepoxy compounds. The ethylenically unsaturated compound can be used alone or in combination of two or more kinds.

作為上述乙烯性不飽和化合物，亦可使用市售品，例如可列舉：Kayarad DPHA、DPEA-12、PEG400DA、THE-330、RP-1040、NPGDA、PET30、R-684(以上由日本化藥製造)；ARONIX M-215、M-350(以上由東亞合成製造)；NK ESTER A-DPH、A-TMPT、A-DCP、A-HD-N、TMPT、DCP、NPG及HD-N(以上由新中村化學工業製造)；SPC-1000、SPC-3000(以上由昭和電工製造)等。As the above-mentioned ethylenically unsaturated compounds, commercially available products can also be used, for example: Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (the above are manufactured by Nippon Kayaku ); ARONIX M-215, M-350 (manufactured by Toagosei above); NK ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (the above are made by Shinnakamura Chemical Industry Co., Ltd.); SPC-1000, SPC-3000 (manufactured by Showa Denko), etc.

聚合性組合物(B)之含量只要為適合其使用目的之量即可，為了防止硬化不良，較佳為以於聚合性組合物中之固形物成分(溶劑以外之總成分)中成為50質量份以上之方式含有，更佳為60質量份以上，尤佳為70質量份以上。The content of the polymerizable composition (B) only needs to be an amount suitable for the purpose of use. In order to prevent poor curing, it is preferably 50% by mass in the solid content (total components other than the solvent) in the polymerizable composition. It is contained in the form of more than 60 parts by mass, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

本發明之聚合性組合物可使用無機化合物、色料、潛在性環氧硬化劑、鏈轉移劑、增感劑、溶劑等添加劑作為任意成分。The polymerizable composition of the present invention may use additives such as inorganic compounds, colorants, latent epoxy hardeners, chain transfer agents, sensitizers, solvents, etc., as optional components.

作為上述無機化合物，例如可列舉：氧化鎳、氧化鐵、氧化銥、氧化鈦、氧化鋅、氧化鎂、氧化鈣、氧化鉀、二氧化矽、氧化鋁等金屬氧化物；層狀黏土礦物、米洛麗藍、碳酸鈣、碳酸鎂、鈷系、錳系、玻璃粉末(尤其是玻璃漿料)、雲母、滑石、高嶺土、亞鐵氰化物、各種金屬硫酸鹽、硫化物、硒化物、矽酸鋁、矽酸鈣、氫氧化鋁、鉑、金、銀、銅等。該等無機化合物例如可用作填充劑、抗反射劑、導電材、穩定劑、阻燃劑、機械強度改善劑、特殊波長吸收劑、發墨劑等。Examples of the above-mentioned inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide; layered clay minerals, rice Lori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder (especially glass paste), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, silicic acid Aluminum, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds can be used as fillers, anti-reflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink-generating agents, etc., for example.

作為上述色料，可列舉：顏料、染料、天然色素等。該等色料可單獨使用或將2種以上混合使用。Examples of the aforementioned colorants include pigments, dyes, natural pigments, and the like. These color materials can be used alone or in a mixture of two or more.

作為上述顏料，例如可使用：亞硝基化合物；硝基化合物；偶氮化合物；二偶氮化合物；𠮿

Figure 109119445-A0304-12-01
化合物；喹啉化合物；蒽醌化合物；香豆素化合物；酞菁化合物；異吲哚啉酮化合物；異吲哚啉化合物；喹吖啶酮化合物；蒽締蒽酮化合物；芘酮化合物；苝化合物；吡咯并吡咯二酮化合物；硫靛化合物；二㗁𠯤化合物；三苯甲烷化合物；喹酞酮化合物；萘四羧酸；偶氮染料、花青染料之金屬錯合物化合物；色澱顏料；藉由爐排法、導槽法或熱分析法所獲得之碳黑或乙炔黑、科琴黑或燈黑等碳黑；利用環氧樹脂對上述碳黑進行調整或被覆而成者、預先於溶劑中利用樹脂對上述碳黑進行分散處理而使之吸附20～200 mg/g之樹脂而成者、對上述碳黑進行酸性或鹼性表面處理而成者、平均粒徑為8 nm以上且DBP(Dibutyl Phthalate，鄰苯二甲酸二丁酯)吸油量為90 ml/100 g以下之碳黑、表面積每100 m2 根據950℃下之揮發成分中之CO及CO2 算出之總氧氣量為9 mg以上之碳黑；石墨、石墨化碳黑、活性碳、碳纖維、奈米碳管、螺旋碳纖維、碳奈米角、碳氣凝膠、富勒烯；苯胺黑、顏料黑7、鈦黑；氧化鉻綠、米洛麗藍、鈷綠、鈷青、錳系、亞鐵氰化物、磷酸鹽群青、鐵藍、群青、天藍、濃綠色、翡翠綠、硫酸鉛、黃丹、鋅黃、鐵丹(紅色氧化鐵(III))、鎘紅、合成鐵黑、棕土等有機或無機顏料。該等顏料可單獨使用或將複數種混合使用。As the above-mentioned pigments, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds; 𠮿
Figure 109119445-A0304-12-01
Compounds; Quinoline Compounds; Anthraquinone Compounds; Coumarin Compounds; Phthalocyanine Compounds; Isoindolinone Compounds; Isoindoline Compounds; Quinacridone Compounds; Anthroneanthone Compounds; Pyrene Compounds; Perylene Compounds ; Dione pyrrolopyrrole compound; thioindigo compound; diphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; metal complex compound of azo dye and cyanine dye; lake pigment; Carbon black, acetylene black, Ketjen black, or lamp black obtained by grate method, channel method or thermal analysis method; the carbon black is adjusted or coated with epoxy resin, and the above-mentioned carbon black is adjusted or coated in advance. It is obtained by dispersing the above-mentioned carbon black with resin in a solvent to adsorb 20-200 mg/g of resin, or after performing acidic or alkaline surface treatment on the above-mentioned carbon black, with an average particle size of 8 nm or more and DBP (Dibutyl Phthalate, dibutyl phthalate) carbon black with an oil absorption of 90 ml/100 g or less, the total oxygen content calculated from the CO and CO 2 in the volatile components at 950℃ per 100 m 2 of surface area is Carbon black above 9 mg; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black ; Chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, iron blue, ultramarine, sky blue, dark green, emerald green, lead sulfate, yellow red, zinc yellow, Iron red (red iron oxide (III)), cadmium red, synthetic iron black, umber and other organic or inorganic pigments. These pigments can be used alone or in a mixture of plural kinds.

作為上述顏料，亦可使用市售之顏料，例如可列舉：顏料紅1、2、3、9、10、14、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254；顏料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71；顏料黃1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185；顏料綠7、10、36；顏料藍15、15：1、15：2、15：3、15：4、15：5、15：6、22、24、56、60、61、62、64；顏料紫1、19、23、27、29、30、32、37、40、50等。As the above-mentioned pigments, commercially available pigments can also be used, for example: Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

作為上述染料，可列舉：偶氮染料、蒽醌染料、靛屬染料、三芳基甲烷染料、𠮿

Figure 109119445-A0304-12-01
染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁𠯤染料、酞菁染料、花青染料等染料等；該等亦可混合複數種使用。Examples of the above-mentioned dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, and
Figure 109119445-A0304-12-01
Dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, alizarin dyes, phthalocyanine dyes, cyanine dyes, etc.; Multiple types can also be mixed for use.

作為上述潛在性環氧硬化劑，例如可列舉：雙氰胺、改性聚胺、醯肼類、4,4'-二胺基二苯基碸、三氟化硼胺錯鹽、咪唑類、胍胺類、咪唑類、脲類及三聚氰胺等。Examples of the above-mentioned latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazines, 4,4'-diaminodiphenyl sulfides, boron trifluoride amine complex salts, imidazoles, Guanamines, imidazoles, ureas, melamine, etc.

作為上述鏈轉移劑或增感劑，通常可使用含硫原子之化合物。例如可列舉：硫代乙醇酸、硫代蘋果酸、硫代水楊酸、2-巰基丙酸、3-巰基丙酸、3-巰基丁酸、N-(2-巰基丙醯基)甘胺酸、2-巰基菸鹼酸、3-[N-(2-巰基乙基)胺甲醯基]丙酸、3-[N-(2-巰基乙基)胺基]丙酸、N-(3-巰基丙醯基)丙胺酸、2-巰基乙磺酸、3-巰基丙磺酸、4-巰基丁磺酸、十二烷基(4-甲基硫基)苯醚、2-巰基乙醇、3-巰基-1,2-丙二醇、1-巰基-2-丙醇、3-巰基-2-丁醇、巰基苯酚、2-巰基乙基胺、2-巰基咪唑、2-巰基苯并咪唑、2-巰基-3-羥基吡啶、2-巰基苯并噻唑、巰基乙酸、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)等巰基化合物、使該巰基化合物氧化所獲得之二硫醚化合物、碘乙酸、碘丙酸、2-碘乙醇、2-碘乙磺酸、3-碘丙磺酸等碘化烷基化合物、三羥甲基丙烷三(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、己二硫醇、癸二硫醇、1,4-二甲基巰基苯、丁二醇雙巰基丙酸酯、丁二醇雙巰基乙醇酸酯、乙二醇雙巰基乙醇酸酯、三羥甲基丙烷三巰基乙醇酸酯、丁二醇雙巰基丙酸酯、三羥甲基丙烷三巰基丙酸酯、三羥甲基丙烷三巰基乙醇酸酯、季戊四醇四巰基丙酸酯、季戊四醇四巰基乙醇酸酯、三羥基乙基三巰基丙酸酯、二乙基9-氧硫𠮿

Figure 109119445-A0304-12-01
、二異丙基9-氧硫𠮿
Figure 109119445-A0304-12-01
、下述化合物No.C1、三巰基丙酸三(2-羥基乙基)異氰尿酸酯等脂肪族多官能硫醇化合物、昭和電工公司製造之Karenz MT BD1、PE1、NR1等。As the above-mentioned chain transfer agent or sensitizer, a sulfur atom-containing compound can usually be used. Examples include: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycamine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminomethanyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylsulfanyl) phenyl ether, 2-mercaptoethanol , 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole , 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate) and other mercapto compounds, make The disulfide compound obtained by oxidation of the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane three (3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexamethylene dithiol, decane dithiol, 1,4-dimethylmercaptobenzene, butanediol dimercaptopropane Esters, butanediol bismercaptoglycolate, ethylene glycol bismercaptoglycolate, trimethylolpropane trimercaptoglycolate, butanediol bismercaptopropionate, trimethylolpropane trimercaptopropionic acid Esters, trimethylolpropane trimercaptoglycolate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoglycolate, trihydroxyethyl trimercaptopropionate, diethyl 9-oxythio𠮿
Figure 109119445-A0304-12-01
, Diisopropyl 9-oxysulfur 𠮿
Figure 109119445-A0304-12-01
, The following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

[化10] 化合物No.C1

Figure 02_image023
[化10] Compound No.C1
Figure 02_image023

作為上述溶劑，通常可使用：可使上述各成分(聚合起始劑(A)及聚合性化合物(B)等)溶解或分散之溶劑、例如甲基乙基酮、甲基戊基酮、二乙基酮、丙酮、甲基異丙基酮、甲基異丁基酮、環己酮、2-庚酮等酮類；***、二㗁烷、四氫呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、二丙二醇二甲醚等醚系溶劑；乙酸甲酯、乙酸乙酯、乙酸-正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸環己酯、乳酸乙酯、琥珀酸二甲酯、TEXANOL等酯系溶劑；γ-己內酯、δ-己內酯、γ-丁內酯等內酯系溶劑；乙二醇單甲醚、乙二醇單***等溶纖素系溶劑；甲醇、乙醇、異或正丙醇、異或正丁醇、戊醇等醇系溶劑；乙二醇單甲基乙酸酯、乙二醇單乙基乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、二丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯、丙酸乙氧基乙酯等醚酯系溶劑；苯、甲苯、二甲苯等BTX系溶劑；己烷、庚烷、辛烷、環己烷等脂肪族烴系溶劑；松節油、D-檸檬烯、蒎烯等萜烯系烴油；礦油精、Swazol#310(科斯莫松山石油(股))、Solvesso#100(Exxon Chemical(股))等烷烴系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2-二氯乙烷等鹵化脂肪族烴系溶劑；氯苯等鹵化芳香族烴系溶劑；卡必醇系溶劑；苯胺；三乙胺；吡啶；乙酸；乙腈；二硫化碳；N,N-二甲基甲醯胺；N,N-二甲基乙醯胺；N-甲基吡咯啶酮；二甲基亞碸；水等；該等溶劑可使用1種或以2種以上之混合溶劑之形式來使用。 該等之中，就鹼性顯影性、製圖性、製膜性、溶解性之方面而言，可較佳地使用酮類或醚酯系溶劑、尤其是丙二醇-1-單甲醚-2-乙酸酯(以下，亦稱為「PGMEA」)或環己酮。 於本發明之聚合性組合物中，溶劑之含量並無特別限制，只要為使各成分均勻地分散或溶解且使本發明之聚合性組合物呈適合各用途之液狀或糊狀之量即可，通常於本發明之聚合性組合物中之固形物成分(溶劑以外之總成分)之量成為10～90質量%之範圍內含有溶劑能夠獲得均勻之硬化物，故而較佳。As the above-mentioned solvent, it is usually possible to use: solvents that can dissolve or disperse the above-mentioned components (polymerization initiator (A) and polymerizable compound (B), etc.), such as methyl ethyl ketone, methyl amyl ketone, di Ethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; diethyl ether, diethane, tetrahydrofuran, 1,2-dimethoxyethane , 1,2-diethoxyethane, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate , Ethyl lactate, dimethyl succinate, TEXANOL and other ester solvents; γ-caprolactone, δ-caprolactone, γ-butyrolactone and other ester solvents; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether; alcohol solvents such as methanol, ethanol, iso-or n-propanol, iso-or n-butanol, pentanol, etc.; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetic acid Ester, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate and other ether ester solvents; benzene, toluene , Xylene and other BTX solvents; hexane, heptane, octane, cyclohexane and other aliphatic hydrocarbon solvents; turpentine, D-limonene, pinene and other terpene hydrocarbon oils; mineral spirits, Swazol#310( Cosmo Songshan Petroleum (stock)), Solvesso#100 (Exxon Chemical (stock)) and other alkane solvents; carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane and other halogenated fats Group hydrocarbon solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N- Dimethyl acetamide; N-methyl pyrrolidone; dimethyl sulfide; water, etc.; these solvents can be used in the form of one kind or a mixed solvent of two or more kinds. Among them, ketone or ether ester solvents, especially propylene glycol-1-monomethyl ether-2-one can be preferably used in terms of alkali developability, graphics, film-forming properties, and solubility. Acetate (hereinafter, also referred to as "PGMEA") or cyclohexanone. In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, as long as the amount of the solvent is such that the components are uniformly dispersed or dissolved and the polymerizable composition of the present invention is in a liquid or paste state suitable for each application. However, it is generally preferable that the amount of the solid content (total components other than the solvent) in the polymerizable composition of the present invention is within the range of 10 to 90% by mass to obtain a uniform cured product.

又，本發明之聚合性組合物亦可藉由使用有機聚合物來改善硬化物之特性。作為該有機聚合物，例如可列舉：聚苯乙烯、聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯酸乙酯共聚物、聚(甲基)丙烯酸、苯乙烯-(甲基)丙烯酸共聚物、(甲基)丙烯酸-甲基丙烯酸甲酯共聚物、乙烯-氯乙烯共聚物、乙烯-乙烯基共聚物、聚氯乙烯樹脂、ABS(Acrylonitrile Butadiene Styrene，丙烯腈-丁二烯-苯乙烯)樹脂、尼龍6、尼龍66、尼龍12、胺基甲酸酯樹脂、聚碳酸酯聚乙烯醇縮丁醛、纖維素酯、聚丙烯醯胺、飽和聚酯、酚樹脂、苯氧基樹脂等。 於使用上述有機聚合物之情形時，就所獲得之聚合性組合物之硬化性優異之方面而言，其含量相對於聚合性化合物(B)100質量份，較佳為10～500質量份。In addition, the polymerizable composition of the present invention can also improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene) Resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, etc. In the case of using the above-mentioned organic polymer, the content is preferably 10 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound (B) in terms of excellent curability of the obtained polymerizable composition.

本發明之聚合性組合物可進而併用界面活性劑、矽烷偶合劑、三聚氰胺化合物等。The polymerizable composition of the present invention may further use a surfactant, a silane coupling agent, a melamine compound, and the like in combination.

作為上述界面活性劑，可使用：全氟烷基磷酸酯、全氟烷基羧酸鹽等氟系界面活性劑；高級脂肪酸鹼鹽、烷基磺酸鹽、烷基硫酸鹽等陰離子系界面活性劑；高級胺鹵酸鹽、四級銨鹽等陽離子系界面活性劑；聚乙二醇烷基醚、聚乙二醇脂肪酸酯、山梨糖醇酐脂肪酸酯、單甘油脂肪酸酯等非離子界面活性劑；兩性界面活性劑；聚矽氧系界面活性劑等界面活性劑；該等亦可組合使用。As the above-mentioned surfactants, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; and anionic interfaces such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates can be used. Active agent; cationic surfactants such as higher amine halide, quaternary ammonium salt; polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, monoglycerin fatty acid ester, etc. Nonionic surfactants; amphoteric surfactants; surfactants such as silicone surfactants; these can also be used in combination.

作為上述矽烷偶合劑，例如可使用信越化學公司製造之矽烷偶合劑，其中可較佳地使用KBE-9007、KBM-502、KBE-403等具有異氰酸基、甲基丙烯醯基或環氧基之矽烷偶合劑。As the above-mentioned silane coupling agent, for example, the silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc. having isocyanate groups, methacrylic groups or epoxy groups can be preferably used. Base silane coupling agent.

作為上述三聚氰胺化合物，可列舉(聚)羥甲基三聚氰胺、(聚)羥甲基甘脲、(聚)羥甲基苯胍𠯤、(聚)羥甲基脲等氮化合物中之活性羥甲基(CH2 OH基)之全部或一部分(至少2個)經烷基醚化而成之化合物等。 此處，作為構成烷基醚之烷基，可列舉：甲基、乙基或丁基；相互可相同亦可不同。又，未經烷基醚化之羥甲基可於一分子中自我縮合，亦可於兩分子間縮合，結果形成低聚物成分。 具體而言，可使用六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、四甲氧基甲基甘脲、四丁氧基甲基甘脲等。 該等之中，就對溶劑之溶解性、不易自聚合性組合物析出結晶之方面而言，較佳為六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺等經烷基醚化之三聚氰胺。Examples of the above-mentioned melamine compound include (poly)methylol melamine, (poly)methylol glycoluril, (poly)methylol benzoguanidine, (poly)methylolurea and other nitrogen compounds, which are active methylol groups. (CH 2 OH group) All or a part (at least 2) of the compound is etherified with an alkyl group, etc. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, or a butyl group; they may be the same or different from each other. In addition, the methylol group that has not been etherified with alkyl can condense itself in one molecule, or it can condense between two molecules, resulting in the formation of oligomer components. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among them, in terms of solubility in solvents and difficulty in crystallizing from polymerizable compositions, melamine etherified with alkyl groups such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred. .

於本發明之聚合性組合物中，聚合起始劑(A)及聚合性化合物(B)以外之任意成分(其中，無機化合物、色料、及溶劑除外)之含量視其使用目的來適當選擇，並無特別限制，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為相對於聚合性化合物(B)100質量份設為合計50質量份以下。In the polymerizable composition of the present invention, the content of any components other than the polymerization initiator (A) and the polymerizable compound (B) (excluding inorganic compounds, colorants, and solvents) is appropriately selected depending on the purpose of use There is no particular limitation. In terms of excellent curability of the obtained polymerizable composition, it is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the polymerizable compound (B).

本發明之聚合性組合物可照射能量線而製成硬化物。該硬化物形成為與用途對應之適當形狀。例如於形成膜狀硬化物之情形時，本發明之聚合性組合物可利用旋轉塗佈機、輥式塗佈機、棒式塗佈機、模嘴塗佈機、簾幕式塗佈機、各種印刷、浸漬等公知之機構應用於鈉玻璃、石英玻璃、半導體基板、金屬、紙、塑膠等支持基體上。又，亦可暫時於膜等支持基體上實施後轉印至其他支持基體上，其應用方法並無限制。The polymerizable composition of the present invention can be irradiated with energy rays to form a cured product. The hardened product is formed into an appropriate shape corresponding to the application. For example, in the case of forming a film-like cured product, the polymerizable composition of the present invention can be used with a spin coater, roll coater, bar coater, die nozzle coater, curtain coater, Various known mechanisms such as printing and dipping are applied to support substrates such as soda glass, quartz glass, semiconductor substrate, metal, paper, and plastic. In addition, it may be temporarily performed on a supporting substrate such as a film and then transferred to another supporting substrate, and the application method is not limited.

作為使本發明之聚合性組合物硬化時可使用之能量線之光源，可利用自超高壓水銀燈、高壓水銀燈、中壓水銀燈、低壓水銀燈、水銀蒸氣弧燈、氙弧燈、碳弧燈、金屬鹵化物燈、螢光燈、鎢燈、準分子燈、殺菌燈、發光二極體、CRT光源等獲得之具有2000埃～7000埃之波長之電磁波能量或電子束、X射線、放射線等高能量線，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為可使用發出波長300～450 nm之光之超高壓水銀燈、水銀蒸氣弧燈、碳弧燈、氙弧燈等。As a light source of energy rays that can be used to harden the polymerizable composition of the present invention, it can be used from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, and metal Halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. obtain electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms or high energy such as electron beams, X-rays, and radiation In terms of the excellent curability of the obtained polymerizable composition, it is preferable to use an ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc lamp, etc. that emit light with a wavelength of 300 to 450 nm. .

進而，藉由使曝光光源使用雷射光，不使用遮罩而根據電腦等數位資訊直接形成圖像之雷射直接描繪法不僅會提高生產性，亦會提高解像性或位置精度等，故而有用，作為該雷射光，可較佳地使用340～430 nm之波長之光，亦可使用準分子雷射、氮雷射、氬離子雷射、氦鎘雷射、氦氖雷射、氪離子雷射、各種半導體雷射及YAG(Yttrium Aluminum Garnet，釔-鋁-石榴石)雷射等發出可見至紅外區域之光者。於使用該等雷射光之情形時，就所獲得之聚合性組合物之硬化性優異之方面而言，較佳為添加於可見至紅外之相關區域進行吸收之增感色素。Furthermore, by using laser light as the exposure light source, the direct laser drawing method that directly forms an image based on digital information such as a computer without using a mask will not only improve productivity, but also improve resolution or position accuracy, which is useful. As the laser light, light with a wavelength of 340 to 430 nm can be preferably used, and excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers can also be used Lasers, various semiconductor lasers and YAG (Yttrium Aluminum Garnet, Yttrium Aluminum Garnet) lasers that emit light in the visible to infrared range. In the case of using these laser lights, it is preferable to add a sensitizing dye that absorbs in the visible to infrared region in terms of the excellent curability of the obtained polymerizable composition.

又，於本發明之聚合性組合物之硬化時，通常必須於上述能量線之照射後進行加熱，就硬化率之方面而言，較佳為40～150℃左右之加熱。In addition, when the polymerizable composition of the present invention is cured, it is usually necessary to heat it after the above-mentioned energy rays are irradiated. In terms of the curing rate, heating at about 40 to 150°C is preferred.

本發明之聚合性組合物可使用於如下等各種用途：光硬化性塗料或清漆；光硬化性接著劑；金屬用塗佈劑；印刷基板；彩色電視、PC(Personal Computer，個人電腦)監視器、便攜型資訊終端、數位相機等彩色顯示之液晶顯示元件中之彩色濾光片；CCD(CCD，電荷耦合元件)影像感測器之彩色濾光片；電漿顯示面板用之電極材料；粉末塗佈；印刷油墨；印刷版；接著劑；牙科用組合物；凝膠塗層；電子工程用之光阻劑；電鍍抗蝕劑；蝕刻抗蝕劑；乾膜；焊料抗蝕劑；用以製造各種顯示用途用之彩色濾光片或者用以於電漿顯示面板、電發光顯示裝置、及LCD(Liquid Crystal Display，液晶顯示裝置)之製造步驟中形成其等構造之抗蝕劑；用以封入電氣及電子零件之組合物；阻焊劑；磁記錄材料；微小機械零件；光波導；光開關；鍍覆用遮罩；蝕刻遮罩；彩色試驗系統；玻璃纖維電纜塗層；網版印刷用模板；用以藉由立體光刻製造三維物體之材料；全像術記錄用材料；圖像記錄材料；微細電子電路；脫色材料；用於圖像記錄材料之脫色材料；使用微膠囊之圖像記錄材料用之脫色材料；印刷配線板用光阻材料；UV(ultraviolet，紫外線)及可見光雷射直接圖像系統用之光阻劑材料；印刷電路基板之逐次積層中之介電體層形成所使用之光阻劑材料或保護膜，其用途並無特別限制。The polymerizable composition of the present invention can be used in various applications such as the following: photocurable paints or varnishes; photocurable adhesives; coating agents for metals; printed circuit boards; color televisions, PC (Personal Computer) monitors , Color filters in liquid crystal display elements for color displays such as portable information terminals and digital cameras; color filters in CCD (CCD, charge coupled device) image sensors; electrode materials for plasma display panels; powder Coating; Printing Ink; Printing Plate; Adhesive; Dental Composition; Gel Coating; Photoresist for Electronic Engineering; Electroplating Resist; Etching Resist; Dry Film; Solder Resist; Manufacture of color filters for various display purposes or resists for forming their structures in the manufacturing steps of plasma display panels, electroluminescent display devices, and LCD (Liquid Crystal Display, liquid crystal display devices); Encapsulation of electrical and electronic components; solder resist; magnetic recording materials; small mechanical parts; optical waveguides; optical switches; masks for plating; etching masks; color test systems; glass fiber cable coatings; for screen printing Template; materials used to produce three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; microelectronic circuits; decolorizing materials; decolorizing materials for image recording materials; images using microcapsules Decolorizing materials for recording materials; photoresist materials for printed wiring boards; photoresist materials for UV (ultraviolet) and visible light laser direct imaging systems; used for the formation of dielectric layers in the sequential build-up of printed circuit boards The use of the photoresist material or protective film is not particularly limited.

本發明之聚合性組合物亦可用於形成液晶顯示面板用間隔件及用於形成垂直配向型液晶顯示元件用突起。尤其是作為用以同時形成垂直配向型液晶顯示元件用之突起與間隔件之感光性樹脂組合物有用。The polymerizable composition of the present invention can also be used to form spacers for liquid crystal display panels and to form protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertical alignment type liquid crystal display elements.

上述液晶顯示面板用間隔件係藉由如下步驟而較佳地形成：(1)於基板上形成本發明之聚合性組合物之塗膜之步驟；(2)隔著具有特定圖案形狀之遮罩對該塗膜照射能量線(光)之步驟；(3)曝光後之烘烤步驟；(4)使曝光後之覆膜顯影之步驟；及(5)對顯影後之該覆膜進行加熱之步驟。The above-mentioned spacers for liquid crystal display panels are preferably formed by the following steps: (1) a step of forming a coating film of the polymerizable composition of the present invention on a substrate; (2) a mask having a specific pattern shape is interposed The step of irradiating the coating with energy rays (light); (3) the baking step after exposure; (4) the step of developing the exposed coating; and (5) the step of heating the developed coating step.

添加有色料之本發明之聚合性組合物可較佳地用作構成彩色濾光片中之RGB(Red-Green-Blue，紅-綠-藍)等各像素之抗蝕劑或形成各像素之間隔壁之黑矩陣用抗蝕劑。進而，於添加撥墨劑之黑矩陣用抗蝕劑之情形時，可較佳地用於分佈角為50°以上之噴墨方式彩色濾光片用間隔壁。作為該撥墨劑，可較佳地使用氟系界面活性劑及含有氟系界面活性劑之組合物。The polymerizable composition of the present invention added with a colorant can be preferably used as a resist for each pixel such as RGB (Red-Green-Blue, red-green-blue) in a color filter or as a resist for forming each pixel Resist for the black matrix of the partition wall. Furthermore, when the black matrix resist of the ink repellent is added, it can be preferably used as a partition wall for an inkjet type color filter with a distribution angle of 50° or more. As the ink repellent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant can be preferably used.

於用於上述噴墨方式彩色濾光片用間隔壁之情形時，藉由如下方法來製造光學元件：於被轉印體上劃分由本發明之聚合性組合物形成之間隔壁，藉由噴墨法對經劃分之被轉印體上之凹部賦予液滴而形成圖像區域。此時，較佳為上述液滴含有著色劑而使上述圖像區域著色，於該情形時，藉由上述製造方法所製作之光學元件於基板上至少具有包含複數個著色區域之像素群及將該像素群之各著色區域隔開之間隔壁。In the case of using the above-mentioned inkjet type color filter partition wall, the optical element is manufactured by the following method: the partition wall formed of the polymerizable composition of the present invention is divided on the to-be-transferred body, and the partition wall is formed by inkjet The method applies droplets to the divided recesses on the transferred body to form an image area. In this case, it is preferable that the droplet contains a coloring agent to color the image area. In this case, the optical element produced by the above-mentioned manufacturing method has at least a pixel group including a plurality of colored areas on the substrate and will The partition wall separating each colored area of the pixel group.

本發明之聚合性組合物亦可用作保護膜或絕緣膜用組合物。於該情形時，可含有紫外線吸收劑、烷基化改性三聚氰胺及/或丙烯酸改性三聚氰胺、分子中含有醇性羥基之1或2官能之(甲基)丙烯酸酯單體及/或矽溶膠。The polymerizable composition of the present invention can also be used as a composition for a protective film or an insulating film. In this case, it may contain ultraviolet absorbers, alkylated modified melamine and/or acrylic modified melamine, 1 or 2 functional (meth)acrylate monomers containing alcoholic hydroxyl groups in the molecule, and/or silica sol .

上述絕緣膜可用於在能夠剝離之支持基材上設置有絕緣樹脂層之積層體中之該絕緣樹脂層，該積層體係藉由鹼性水溶液能夠顯影者，絕緣樹脂層之膜厚較佳為10～100 μm。The above-mentioned insulating film can be used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a support base that can be peeled. If the laminate system can be developed by an alkaline aqueous solution, the thickness of the insulating resin layer is preferably 10 ~100 μm.

本發明之聚合性組合物可藉由含有無機化合物而用作感光性漿料組合物。該感光性漿料組合物可用於形成電漿顯示器面板之間隔壁圖案、介電體圖案、電極圖案及黑矩陣圖案等焙燒物圖案。 [實施例]The polymerizable composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used to form fired product patterns such as partition wall patterns, dielectric patterns, electrode patterns, and black matrix patterns of plasma display panels. [Example]

以下，列舉實施例及比較例對本發明進一步詳細地進行說明，但本發明並不限定於該等實施例等。Hereinafter, the present invention will be described in further detail with examples and comparative examples, but the present invention is not limited to these examples and the like.

[實施例1] 依據以下所示之方案合成化合物1。[Example 1] Compound 1 was synthesized according to the scheme shown below.

[化11]

Figure 02_image025
[化11]
Figure 02_image025

向100 ml四口燒瓶中添加肟體1 1.0 eq.、二氯甲烷(理論產量之600重量%)、三乙胺3.0 eq.，於冰浴上以5℃進行攪拌。向其中滴加添加使氯甲酸4-硝基苯酯1.1 eq.溶解於二氯甲烷中而成者。滴加結束後，於冰浴上冷卻至0℃，滴加添加哌啶1.1 eq.。將混合液於室溫下攪拌1.5小時，於減壓下將溶劑蒸餾去除。使濃縮後之殘渣溶解於乙酸乙酯中，利用1質量%NaOH水溶液洗淨2次後，進而藉由離子交換水洗淨3次。藉由硫酸鎂使有機層乾燥、濃縮。藉由矽膠管柱層析法(溶離劑＝乙酸乙酯：己烷＝1：4→1：3)對有機層進行精製，以產率41%獲得了作為淡褐色粉狀化合物之目標物。將1 H-NMR(Nuclear Magnetic Resonance，核磁共振)測定結果示於表1。To a 100 ml four-necked flask were added 1.0 eq. of oxime 1, dichloromethane (600% by weight of theoretical output), and 3.0 eq. of triethylamine, and stirred at 5°C on an ice bath. What was obtained by dissolving 1.1 eq. of 4-nitrophenyl chloroformate in dichloromethane was added dropwise. After the dropwise addition, it was cooled to 0°C on an ice bath, and 1.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 1.5 hours, and the solvent was distilled off under reduced pressure. The concentrated residue was dissolved in ethyl acetate, washed twice with a 1% by mass NaOH aqueous solution, and further washed with ion-exchanged water three times. The organic layer was dried and concentrated with magnesium sulfate. The organic layer was purified by silica gel column chromatography (eluent=ethyl acetate:hexane=1:4→1:3), and the target compound was obtained as a light brown powdery compound with a yield of 41%. Table 1 shows the 1 H-NMR (Nuclear Magnetic Resonance) measurement results.

[表1]    化學位移/ppm(多重性、質子數) 化合物1 (CDCl3 、400 MHz) 9.51 (d, 1H), 8.63 (d, 1H), 8.48 (s, 1H), 8.37 (s, 1H), 7.6 - 7.8 (m, 2H), 7.4 - 7.5 (m, 2H), 7.3 - 7.4 (m, 1H), 7.2 - 7.3 (m, 1H), 7.1 - 7.2 (m, 1H), 6.99 (d, 1H), 6.94 (s, 2H), 4.71 (m, 2H), 4.28 (m, 2H), 3.3 - 3.5 (m, 2H), 2.9 - 3.1 (m, 2H), 2.38 (s, 3H), 2.19 (s, 6H), 1.1 - 1.7 (m, 15H), 0.87 (t, 3H), 0.80 (t, 3H) [Table 1] Chemical shift/ppm (multiplicity, number of protons) Compound 1 (CDCl 3 , 400 MHz) 9.51 (d, 1H), 8.63 (d, 1H), 8.48 (s, 1H), 8.37 (s, 1H), 7.6-7.8 (m, 2H), 7.4-7.5 (m, 2H), 7.3-7.4 ( m, 1H), 7.2-7.3 (m, 1H), 7.1-7.2 (m, 1H), 6.99 (d, 1H), 6.94 (s, 2H), 4.71 (m, 2H), 4.28 (m, 2H) , 3.3-3.5 (m, 2H), 2.9-3.1 (m, 2H), 2.38 (s, 3H), 2.19 (s, 6H), 1.1-1.7 (m, 15H), 0.87 (t, 3H), 0.80 (t, 3H)

[實施例2及比較例1]聚合性組合物之製備 進行表2所記載之調配，獲得聚合性組合物1及比較聚合性組合物1。再者，表中之調配數值表示質量份。 又，表中之各成分之符號表示下述成分。 A-1：化合物1 A'-2：比較化合物1 B-1：EPPN-201(酚系酚醛清漆型環氧樹脂、環氧當量193 g/ eq.、日本化藥公司製造) B-2：H-3M(酚樹脂、羥基當量105～109 g/ eq.、明和化成公司製造) C-1：FZ-2122(聚醚改性聚矽氧烷、東麗道康寧公司製造、1重量%PGMEA溶液) D-1：環戊酮(溶劑)[Example 2 and Comparative Example 1] Preparation of polymerizable composition The formulations described in Table 2 were performed to obtain polymerizable composition 1 and comparative polymerizable composition 1. Furthermore, the blending values in the table represent parts by mass. In addition, the symbols of each component in the table indicate the following components. A-1: Compound 1 A'-2: Comparative compound 1 B-1: EPPN-201 (phenol novolac epoxy resin, epoxy equivalent 193 g/eq., manufactured by Nippon Kayaku Co., Ltd.) B-2: H-3M (phenol resin, hydroxyl equivalent 105～109 g/eq., manufactured by Meiwa Chemical Co., Ltd.) C-1: FZ-2122 (polyether modified polysiloxane, manufactured by Toray Dow Corning, 1% by weight PGMEA solution) D-1: Cyclopentanone (solvent)

[表2]    實施例2 比較例1 聚合性組合物 聚合性組合物1 比較聚合性組合物1 A-1 1.5 - A'-2 - 1.5 B-1 23.6 23.6 B-2 14.8 14.8 C-1 7.3 7.3 D-1 52.8 52.8 合計 100 100 [Table 2] Example 2 Comparative example 1 Polymerizable composition Polymerizable composition 1 Comparative polymerizable composition 1 A-1 1.5 - A'-2 - 1.5 B-1 23.6 23.6 B-2 14.8 14.8 C-1 7.3 7.3 D-1 52.8 52.8 total 100 100

[化12]

Figure 02_image027
[化12]
Figure 02_image027

[評價例1以及比較評價例1] 針對聚合性組合物1及比較聚合性組合物1之硬化物，按下述順序確認有無殘膜。將結果示於表4。 使用旋轉塗佈機將聚合性組合物1及比較聚合性組合物1分別塗佈(500 rpm×2秒→1000 rpm×10秒→斜度×0.5秒、塗佈量約2 mL)於玻璃基材(10 cm×10 cm)，於烘箱中進行預烘烤(90℃×90秒)而製膜。 針對各膜，遮蔽具有透過率連續變化之灰階之階段式曝光表(33段型、OD值0～3、表3)，使用UV-LED(365 nm)照射特定量之紫外線光(照度20 mW/cm2 、曝光時間150秒、累計曝光量3000 mJ/cm2 )。 曝光後，於烘箱中進行後烘烤(100℃×20分鐘)，並進行顯影(PGMEA、30秒)及沖洗(異丙醇、10秒)。 針對所獲得之硬化膜樣品，藉由目視確認剩餘階數。所謂剩餘階數，意指硬化膜殘存之最大階數。根據剩餘階數並根據表3來確定透過率，藉由使用下述式算出換算感度。 換算感度(mJ/cm2 )＝累計曝光量(3000 mJ/cm2 )×透過率(%) 將剩餘階數與換算感度示於表4。[Evaluation Example 1 and Comparative Evaluation Example 1] Regarding the cured products of the polymerizable composition 1 and the comparative polymerizable composition 1, the presence or absence of residual film was confirmed in the following order. The results are shown in Table 4. Use a spin coater to coat polymerizable composition 1 and comparative polymerizable composition 1 (500 rpm×2 seconds→1000 rpm×10 seconds→inclination×0.5 seconds, coating amount about 2 mL) on the glass substrate. The material (10 cm×10 cm) is pre-baked (90°C×90 seconds) in an oven to form a film. For each film, shield the step-type exposure meter (33-segment type, OD value 0~3, Table 3) with gray levels with continuous changes in transmittance, and use UV-LED (365 nm) to irradiate a specific amount of ultraviolet light (illuminance 20 mW/cm 2 , exposure time 150 seconds, cumulative exposure 3000 mJ/cm 2 ). After exposure, post-baking (100°C×20 minutes) in an oven, and developing (PGMEA, 30 seconds) and washing (isopropanol, 10 seconds). With regard to the obtained cured film sample, visually confirm the remaining order. The so-called remaining order refers to the maximum order remaining in the cured film. Determine the transmittance according to the remaining order and according to Table 3, and calculate the conversion sensitivity by using the following formula. Conversion sensitivity (mJ/cm 2 )=cumulative exposure (3000 mJ/cm 2 )×transmittance (%) Table 4 shows the remaining steps and conversion sensitivity.

[表3] 階數 OD值 透過率(%) 0 0 100.000 1 0.06 87.096 2 0.15 70.795 3 0.24 57.544 4 0.35 44.668 5 0.44 36.308 6 0.54 28.840 7 0.64 22.909 8 0.74 18.197 9 0.84 14.454 10 0.94 11.482 11 1.05 8.913 12 1.15 7.079 13 1.25 5.623 14 1.35 4.467 15 1.44 3.631 16 1.54 2.884 17 1.64 2.291 18 1.74 1.820 19 1.84 1.445 20 1.94 1.148 21 2.04 0.912 22 2.14 0.724 23 2.24 0.575 24 2.34 0.457 25 2.44 0.363 26 2.54 0.288 27 2.65 0.224 28 2.75 0.178 29 2.84 0.145 30 2.93 0.117 31 2.95 0.112 32 2.97 0.107 33 3.00 0.100 [table 3] Order OD value Transmittance (%) 0 0 100.000 1 0.06 87.096 2 0.15 70.795 3 0.24 57.544 4 0.35 44.668 5 0.44 36.308 6 0.54 28.840 7 0.64 22.909 8 0.74 18.197 9 0.84 14.454 10 0.94 11.482 11 1.05 8.913 12 1.15 7.079 13 1.25 5.623 14 1.35 4.467 15 1.44 3.631 16 1.54 2.884 17 1.64 2.291 18 1.74 1.820 19 1.84 1.445 20 1.94 1.148 twenty one 2.04 0.912 twenty two 2.14 0.724 twenty three 2.24 0.575 twenty four 2.34 0.457 25 2.44 0.363 26 2.54 0.288 27 2.65 0.224 28 2.75 0.178 29 2.84 0.145 30 2.93 0.117 31 2.95 0.112 32 2.97 0.107 33 3.00 0.100

[表4]    聚合性組合物1 比較聚合性組合物1 剩餘階數(階) 2 0 換算感度(mJ/cm2 ) 2124 ＞3000 [Table 4] Polymerizable composition 1 Comparative polymerizable composition 1 Remaining order (order) 2 0 Conversion sensitivity (mJ/cm 2 ) 2124 ＞3000

根據上述表4之結果，含有本發明之胺甲醯肟化合物之聚合性組合物與比較聚合性組合物相比，剩餘階數較多(硬化性較高)，因此光產鹼效率較高，於低曝光量下能夠硬化且對於UV-LED光源呈高感度。因此，明確本發明之化合物作為聚合起始劑優異。According to the results in Table 4 above, the polymerizable composition containing the carbamethoxime compound of the present invention has more remaining stages (higher curability) than the comparative polymerizable composition, so the photobase generation efficiency is higher. It can be cured under low exposure and has high sensitivity to UV-LED light source. Therefore, it is clear that the compound of the present invention is excellent as a polymerization initiator.

[實施例3] 依據以下所示之方案合成化合物2。[Example 3] Compound 2 was synthesized according to the scheme shown below.

[化13]

Figure 02_image029
[化13]
Figure 02_image029

(肟體2之合成) 向燒瓶中添加8-(3-環戊基丙基)-11-(2-乙基己基)-11H-苯并[a]咔唑1.0 eq.，使之溶解於二甲基甲醯胺(理論產量之500重量%)中。向溶液中添加氯化羥基銨2.2 eq.及吡啶2.2 eq.。將反應混合物於60℃下加熱攪拌9小時後，添加離子交換水，利用氯仿進行萃取。利用離子交換水將有機層洗淨2次，藉由硫酸鎂進行乾燥、濃縮。藉由矽膠管柱層析法(溶離劑＝己烷：乙酸乙酯＝94：6)對殘渣進行精製，以產率28%獲得了作為白色粉狀化合物之目標物。(Synthesis of oxime 2) Add 8-(3-cyclopentylpropyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazole 1.0 eq. to the flask and dissolve it in dimethylformamide ( 500% by weight of theoretical output). Add 2.2 eq. of hydroxyammonium chloride and 2.2 eq. of pyridine to the solution. After the reaction mixture was heated and stirred at 60°C for 9 hours, ion-exchanged water was added, and extraction was performed with chloroform. The organic layer was washed twice with ion-exchanged water, and dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent = hexane: ethyl acetate = 94: 6), and the target product as a white powdery compound was obtained with a yield of 28%.

(化合物2之合成) 向燒瓶中添加肟體2 1.0 eq.、氯仿(理論產量之500重量%)、三乙胺2.0 eq.，於冰浴上以5℃下進行攪拌。向其中滴加添加使氯甲酸4-硝基苯酯1.1 eq.溶解於氯仿(理論產量之500重量%)中而成者。滴加結束後於室溫下攪拌1小時。再次於冰浴上冷卻至5℃後，滴加添加苯胺1.1 eq.。於室溫下攪拌2小時後，利用1質量%氫氧化鈉水溶液洗淨3次，利用離子交換水洗淨3次，藉由硫酸鎂使有機層乾燥、濃縮。藉由矽膠管柱層析法(溶離劑＝己烷：乙酸乙酯＝94：6)對殘渣進行精製，以產率35%獲得了作為黃色不定形固體化合物之目標物。將所獲得之化合物之1 H-NMR測定結果示於表5。(Synthesis of Compound 2) 1.0 eq. of oxime body 2, chloroform (500% by weight of the theoretical yield), and 2.0 eq. of triethylamine were added to the flask, and the mixture was stirred at 5°C on an ice bath. What was obtained by dissolving 1.1 eq. of 4-nitrophenyl chloroformate in chloroform (500% by weight of the theoretical output) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. After cooling to 5°C on an ice bath again, 1.1 eq. of aniline was added dropwise. After stirring at room temperature for 2 hours, it was washed 3 times with a 1% by mass aqueous sodium hydroxide solution and 3 times with ion-exchanged water, and the organic layer was dried and concentrated with magnesium sulfate. The residue was purified by silica gel column chromatography (eluent = hexane: ethyl acetate = 94: 6), and the target product as a yellow amorphous solid compound was obtained with a yield of 35%. Table 5 shows the 1 H-NMR measurement results of the obtained compound.

[實施例4] 依據以下所示之方案合成化合物3。[Example 4] Compound 3 was synthesized according to the scheme shown below.

[化14]

Figure 02_image031
[化14]
Figure 02_image031

(肟體3之合成) 向燒瓶中添加1-(11-(2-乙基己基)-11H-苯并[a]咔唑-8-基)辛烷-1-酮1.0 eq.，使之溶解於二甲基甲醯胺(理論產量之400重量%)中。向其中添加4M・HCl-乙酸乙酯1.1 eq.及亞硝酸異丁酯1.1 eq.，並於45℃下攪拌1小時。向反應液中添加氯仿，利用離子交換水洗淨4次，藉由硫酸鎂使有機層乾燥後進行濃縮。藉由矽膠管柱層析法(溶離劑＝己烷：乙酸乙酯＝91：9)對殘渣進行精製，以產率18%獲得了作為白色粉狀化合物之目標物。(Synthesis of oxime 3) Add 1.0 eq. of 1-(11-(2-ethylhexyl)-11H-benzo[a]carbazol-8-yl)octane-1-one to the flask and dissolve it in dimethylformamide Amine (400% by weight of theoretical output). 1.1 eq. of 4M·HCl-ethyl acetate and 1.1 eq. of isobutyl nitrite were added thereto, and the mixture was stirred at 45°C for 1 hour. Chloroform was added to the reaction liquid, washed with ion-exchanged water 4 times, and the organic layer was dried with magnesium sulfate and then concentrated. The residue was purified by silica gel column chromatography (eluent = hexane: ethyl acetate = 91: 9), and the target product as a white powdery compound was obtained with a yield of 18%.

(化合物3之合成) 將實施例3之肟體2變更為肟體3，除此以外，以相同順序進行至水洗後之濃縮。藉由矽膠管柱層析法(溶離劑＝己烷：乙酸乙酯＝95：5)對殘渣進行精製，以產率27%獲得了作為黃色不定形固體化合物之化合物2。將所獲得之化合物之1 H-NMR測定結果示於表5。(Synthesis of Compound 3) Except for changing the oxime body 2 of Example 3 to the oxime body 3, the same procedure was followed until the concentration after washing with water. The residue was purified by silica gel column chromatography (eluent = hexane: ethyl acetate = 95: 5) to obtain Compound 2 as a yellow amorphous solid compound with a yield of 27%. Table 5 shows the 1 H-NMR measurement results of the obtained compound.

[表5]    化學位移/ppm(多重性、質子數) 化合物2 (CDCl3 、400 MHz) 8.62 - 8.50 (m, 2H), 8.45 (s, 1H), 8.22 (d, 1H), 8.06 (d, 1H), 7.85 (d, 1H), 7.73 (d, 1H), 7.66 - 7.50 (m, 5H), 7.37 (t, 2H), 7.13 (t, 1H), 4.71 (t, 2H), 3.16 - 3.08 (m, 2H), 2.37 - 2.20 (m, 1H), 2.04 - 1.13 (m, 19H), 0.90 (t, 3H), 0.83 (t, 3H) 化合物3 (CDCl3 、400 MHz) 9.07 (d, 1H), 8.50 (d, 1H), 8.36 (dd, 1H), 8.25 (d, 1H), 8.03 (dd, 1H), 7.72 (d, 1H), 7.65 - 7.50 (m, 3H), 4.77 - 4.59 (m, 2H), 3.45 - 3.25 (m, 4H), 2.83 (t, 2H), 2.33 - 2.20 (m, 1H), 1.73 - 1.15 (m, 24H), 1.05 - 0.78 (m, 15H) [產業上之可利用性][table 5] Chemical shift/ppm (multiplicity, number of protons) Compound 2 (CDCl 3 , 400 MHz) 8.62-8.50 (m, 2H), 8.45 (s, 1H), 8.22 (d, 1H), 8.06 (d, 1H), 7.85 (d, 1H), 7.73 (d, 1H), 7.66-7.50 (m, 5H), 7.37 (t, 2H), 7.13 (t, 1H), 4.71 (t, 2H), 3.16-3.08 (m, 2H), 2.37-2.20 (m, 1H), 2.04-1.13 (m, 19H) , 0.90 (t, 3H), 0.83 (t, 3H) Compound 3 (CDCl 3 , 400 MHz) 9.07 (d, 1H), 8.50 (d, 1H), 8.36 (dd, 1H), 8.25 (d, 1H), 8.03 (dd, 1H), 7.72 (d, 1H), 7.65-7.50 (m, 3H) , 4.77-4.59 (m, 2H), 3.45-3.25 (m, 4H), 2.83 (t, 2H), 2.33-2.20 (m, 1H), 1.73-1.15 (m, 24H), 1.05-0.78 (m, 15H) [Industrial availability]

本發明之胺甲醯肟化合物具有較高之光產鹼效率，於用作聚合起始劑之情形時，可較先前之光產鹼劑更有效率地產生鹼，因此即便於低曝光量下亦可使聚合性化合物硬化。尤其是於用於含有環氧樹脂或酚樹脂之硬化性樹脂組合物之情形時顯示出較高之硬化性。The amine methyl oxime compound of the present invention has a higher photobase generation efficiency. When used as a polymerization initiator, it can generate bases more efficiently than the previous photobase generators, so it can be used even under low exposure. Harden the polymerizable compound. Especially when used in a curable resin composition containing an epoxy resin or a phenol resin, it exhibits high curability.

Figure 109119445-A0101-11-0001-2
Figure 109119445-A0101-11-0001-2

Claims (10)

一種胺甲醯肟化合物，其以下述通式(I)表示， [化1]
Figure 03_image033
(式中，R1 表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R2 表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R3 、R4 、R5 、R6 、R7 、R8 及R9 分別獨立地表示氫原子、鹵素原子、氰基、硝基、-OR10 、-COOR10 、-CO-R10 、-SR10 、碳原子數1～20之烴基或碳原子數2～20之含雜環之基， R10 表示氫原子、碳原子數1～20之烴基、碳原子數2～20之含雜環之基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基，於分子中存在複數個R10 之情形時，其等可相同，亦可不同， X1 表示-NR21 R22 或下述通式(a)或者下述通式(b)所表示之基， R21 及R22 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基， R1 、R2 、R3 、R4 、R5 、R6 、R7 、R8 、R9 、R10 、R21 及R22 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR11 、-COOR11 、-CO-R11 或-SR11 而成之碳原子數1～20之基， R11 表示氫原子、碳原子數1～20之烴基、烴基中之亞甲基被取代為選自下述＜群A＞中之二價基而成之碳原子數1～20之基或烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基或羥基而成之碳原子數1～20之基，於分子中存在複數個R11 之情形時，其等可相同，亦可不同， ＜群A＞為-O-、-CO-、-COO-、-NR12 -、-NR12 CO-及-S-， R12 表示氫原子或碳原子數1～20之烴基，於分子中存在複數個R12 之情形時，其等可相同，亦可不同， R3 與R4 、R6 與R7 、R7 與R8 及R8 與R9 可分別獨立地相互連結而形成包含氫原子及碳原子之碳原子數3～10之環， R3 與R4 、R6 與R7 、R7 與R8 及R8 與R9 中之至少1組相互連結而形成苯環， R21 與R22 可相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， n表示0或1) [化2]
Figure 03_image035
(式中，R31 、R32 、R33 、R34 、R35 、R36 、R37 、R38 、R39 及R40 分別獨立地表示氫原子、碳原子數1～20之烴基或烴基中之亞甲基被取代為選自下述＜群B＞中之二價基而成之碳原子數1～20之基， R31 、R32 、R33 、R34 、R35 、R36 、R37 、R38 、R39 及R40 亦可為烴基中之氫原子之1個或2個以上被取代為鹵素原子、氰基、硝基、羥基、-OR41 、-COOR41 、-CO-R41 或-SR41 而成之碳原子數1～20之基， R41 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R41 之情形時，其等可相同，亦可不同， ＜群B＞為-O-、-CO-、-COO-、-NR42 -、-NR42 CO-及-S-， R42 表示氫原子或碳原子數1～20之烴基，於基中存在複數個R42 之情形時，其等可相同，亦可不同， R31 與R32 、R33 與R34 、R35 與R36 、R37 與R38 、及R39 與R40 可分別獨立地相互連結而形成包含氫原子、氮原子及碳原子之碳原子數2～10之環或包含氫原子、氧原子、氮原子及碳原子之碳原子數2～10之環， *表示鍵結鍵)。A carboxime compound, which is represented by the following general formula (I), [化1]
Figure 03_image033
(In the formula, R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> R 2 represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> Formed into a group with 1-20 carbon atoms, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, and -OR 10 , -COOR 10 , -CO-R 10 , -SR 10 , a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic ring-containing group with 2 to 20 carbon atoms, R 10 represents a hydrogen atom, with 1 to 20 carbon atoms A hydrocarbon group, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group having 1 to 20 carbon atoms, When there are a plurality of R 10 in the molecule, they may be the same or different. X 1 represents -NR 21 R 22 or the group represented by the following general formula (a) or the following general formula (b), R 21 and R 22 each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a methylene group in the hydrocarbon group substituted with a divalent group selected from the following <Group A> with 1 to carbon atoms The group of 20, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 21 and R 22 can also be one of the hydrogen atoms in the hydrocarbon group Or two or more of them are substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 11 , -COOR 11 , -CO-R 11 or -SR 11 and have 1 to 20 carbon atoms, and R 11 represents A hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, the methylene group in the hydrocarbon group is substituted with a divalent group selected from the following <Group A> to form a group with 1 to 20 carbon atoms or hydrogen in the hydrocarbon group One or more of the atoms are substituted with halogen atoms, cyano groups, nitro groups, or hydroxy groups with 1 to 20 carbon atoms. When there are more than one R 11 in the molecule, they may be the same. It may be different. <Group A> is -O-, -CO-, -COO-, -NR 12 -, -NR 12 CO- and -S-, R 12 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms , When there are multiple R 12 in the molecule, they can be the same or different. R 3 and R 4 , R 6 and R 7 , R 7 and R 8, and R 8 and R 9 can be mutually independent Connected to form a ring with 3 to 10 carbon atoms containing hydrogen and carbon atoms , at least one of R 3 and R 4 , R 6 and R 7 , R 7 and R 8, and R 8 and R 9 are connected to each other. Form a benzene ring, R 21 and R 22 can be connected to each other to form a carbon atom containing hydrogen, nitrogen and carbon atoms 2 ～10 ring or 2～10 carbon ring containing hydrogen atom, oxygen atom, nitrogen atom and carbon atom, n represents 0 or 1) [化2]
Figure 03_image035
(In the formula, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a hydrocarbon group The methylene group in is substituted with a group of 1 to 20 carbon atoms selected from the divalent group in the following <Group B>, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 may also be one or more of the hydrogen atoms in the hydrocarbyl group substituted with halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 41 , -COOR 41 ,- CO-R 41 or -SR 41 is a group with 1 to 20 carbon atoms. R 41 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. When there are more than one R 41 in the group, they may be The same or different, <Group B> is -O-, -CO-, -COO-, -NR 42 -, -NR 42 CO- and -S-, R 42 represents a hydrogen atom or carbon number 1-20 When there are a plurality of R 42 in the base, they may be the same or different, R 31 and R 32 , R 33 and R 34 , R 35 and R 36 , R 37 and R 38 , and R 39 and R 40 can be independently connected to each other to form a ring with 2-10 carbon atoms containing hydrogen, nitrogen and carbon atoms or 2-10 carbon atoms containing hydrogen, oxygen, nitrogen and carbon atoms The ring, * means bonding bond). 如請求項1之胺甲醯肟化合物，其中通式(I)中之R3 與R4 或R8 與R9 相互連結而形成苯環。The carboxime compound of claim 1, wherein R 3 and R 4 or R 8 and R 9 in the general formula (I) are connected to each other to form a benzene ring. 如請求項1之胺甲醯肟化合物，其中通式(I)中之X1 為-NR21 R22 。The carboxime compound of claim 1, wherein X 1 in the general formula (I) is -NR 21 R 22 . 如請求項1之胺甲醯肟化合物，其中通式(I)中之R2 為碳原子數1～10之脂肪族烴基。The amine carboxamide compound of claim 1, wherein R 2 in the general formula (I) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms. 一種潛在性產鹼劑，其含有如請求項1至4中任一項之胺甲醯肟化合物。A potential alkali generator, which contains the carbamate compound according to any one of claims 1 to 4. 一種聚合起始劑，其含有如請求項1至4中任一項之胺甲醯肟化合物。A polymerization initiator containing the carboxamide oxime compound according to any one of claims 1 to 4. 一種聚合性組合物，其含有如請求項1至4中任一項之胺甲醯肟化合物及聚合性化合物。A polymerizable composition containing the carbamate compound and polymerizable compound according to any one of claims 1 to 4. 如請求項7之聚合性組合物，其中上述聚合性化合物為環氧樹脂或者乙烯性不飽和化合物、或包含環氧樹脂與酚樹脂之混合物、包含環氧樹脂與硫醇化合物之混合物、或者包含乙烯性不飽和化合物與硫醇化合物之混合物。The polymerizable composition of claim 7, wherein the polymerizable compound is an epoxy resin or an ethylenically unsaturated compound, or a mixture containing an epoxy resin and a phenol resin, a mixture containing an epoxy resin and a thiol compound, or A mixture of ethylenically unsaturated compounds and mercaptan compounds. 一種硬化物，其係如請求項7之聚合性組合物之硬化物。A cured product, which is a cured product of the polymerizable composition of claim 7. 一種硬化物之製造方法，其具有對如請求項7之聚合性組合物照射能量線之步驟。A method for manufacturing a hardened product, which has the step of irradiating the polymerizable composition according to claim 7 with energy rays.
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