KR20240068585A - Triazine peroxide derivative and method for producing the same, polymerizable composition, and cured product and method for producing the same - Google Patents
Triazine peroxide derivative and method for producing the same, polymerizable composition, and cured product and method for producing the same Download PDFInfo
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- KR20240068585A KR20240068585A KR1020237038421A KR20237038421A KR20240068585A KR 20240068585 A KR20240068585 A KR 20240068585A KR 1020237038421 A KR1020237038421 A KR 1020237038421A KR 20237038421 A KR20237038421 A KR 20237038421A KR 20240068585 A KR20240068585 A KR 20240068585A
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- -1 Triazine peroxide Chemical class 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 79
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 45
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 61
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 53
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 125000000623 heterocyclic group Chemical group 0.000 claims description 20
- 125000002252 acyl group Chemical group 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 5
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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- Polymers & Plastics (AREA)
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- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
일반식 (1) 로 나타내는 트리아진퍼옥사이드 유도체.
(일반식 (1) 중, R1 및 R2 는 독립적으로 메틸기 또는 에틸기, R3 은 탄소수 1 ∼ 5 의 지방족 탄화수소기 등, R4 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기 등을 나타내고, Ar 은 하기 일반식 (2) : Ar1, Ar2, 또는 Ar3 으로 나타내는 아릴기이다)
그 트리아진퍼옥사이드 유도체는, 감도가 우수면서도, 고온 하에서도 양호한 장기 보존 안정성을 갖는 신규의 중합 개시제이다.A triazine peroxide derivative represented by general formula (1).
(In General Formula (1), R 1 and R 2 are independently a methyl group or an ethyl group, R 3 is an aliphatic hydrocarbon group with 1 to 5 carbon atoms, etc., and R 4 is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, etc. and Ar is an aryl group represented by the following general formula (2): Ar 1 , Ar 2 , or Ar 3 )
The triazine peroxide derivative is a novel polymerization initiator that has excellent sensitivity and good long-term storage stability even at high temperatures.
Description
본 발명은 트리아진퍼옥사이드 유도체 및 그 제조 방법, 중합성 조성물, 그리고 경화물 및 그 제조 방법에 관한 것이다.The present invention relates to triazine peroxide derivatives and methods for producing the same, polymerizable compositions, and cured products and methods for producing the same.
중합 개시제로서, 광 및 열 중합 개시제로서 이용할 수 있는, 트리아진퍼옥사이드 유도체가 알려져 있다 (특허문헌 1).As a polymerization initiator, a triazine peroxide derivative that can be used as a light and thermal polymerization initiator is known (Patent Document 1).
특허문헌 1 에서 개시된 트리아진퍼옥사이드 유도체는, 분자 내에 특정한 아릴기와 2 개의 과산화 결합을 갖고, 고압 수은 램프나 LED 등의 램프로부터 방출되는 파장 365 nm 등의 광을 효율적으로 흡수하여 라디칼을 발생할 수 있기 때문에, 감도가 우수하다. 그러나, 라디칼 중합성 화합물에 당해 화합물을 배합한 중합성 조성물에서는, 고온 하에 있어서의 장기 보존 안정성이 불충분해지는 경우가 있었다.The triazine peroxide derivative disclosed in Patent Document 1 has a specific aryl group and two peroxidation bonds in the molecule, and can generate radicals by efficiently absorbing light with a wavelength of 365 nm emitted from lamps such as high-pressure mercury lamps or LEDs. Because of this, the sensitivity is excellent. However, in polymerizable compositions obtained by mixing this compound with a radically polymerizable compound, long-term storage stability at high temperatures sometimes becomes insufficient.
이상과 같은 사정을 감안하여, 본 발명은, 감도가 우수하면서도, 고온 하에서도 양호한 장기 보존 안정성을 갖는 신규의 중합 개시제를 제공하는 것을 목적으로 한다.In view of the above circumstances, the purpose of the present invention is to provide a novel polymerization initiator that has excellent sensitivity and good long-term storage stability even at high temperatures.
즉, 본 발명은, 일반식 (1) :That is, the present invention has general formula (1):
[화학식 1][Formula 1]
((일반식 (1) 중, R1 및 R2 는 독립적으로 메틸기 또는 에틸기, R3 은 탄소수 1 ∼ 5 의 지방족 탄화수소기, 또는 알킬기를 가져도 되는 탄소수 6 ∼ 9 의 방향족 탄화수소기를 나타내고, R4 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다. Ar 은 하기 일반식 (2) : Ar1, Ar2, 또는 Ar3 으로 나타내는 아릴기이다.)((In General Formula (1), R 1 and R 2 independently represent a methyl group or an ethyl group, R 3 represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R 4 is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar 1 , Ar 2 , or Ar 3 . )
[화학식 2][Formula 2]
(일반식 (2) 중, m 은 0 내지 3 의 정수를 나타내고, R11 은 독립된 치환기로서, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다.)) 로 나타내는 트리아진퍼옥사이드 유도체에 관한 것이다.(In General Formula (2), m represents an integer of 0 to 3, and R 11 is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. , an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) ) relates to a triazine peroxide derivative represented by .
또한, 본 발명은, 상기 트리아진퍼옥사이드 유도체를 포함하는 (a) 중합 개시제, 및 (b) 라디칼 중합성 화합물을 함유하는 중합성 조성물에 관한 것이다.Additionally, the present invention relates to a polymerizable composition containing (a) a polymerization initiator containing the above triazine peroxide derivative, and (b) a radically polymerizable compound.
또한, 본 발명은, 상기 중합성 조성물로 형성되는 경화물, 및 상기 중합성 조성물을 활성 에너지선으로 조사하는 공정을 포함하는 경화물의 제조 방법에 관한 것이다.Additionally, the present invention relates to a cured product formed from the polymerizable composition and a method for producing the cured product including a step of irradiating the polymerizable composition with active energy rays.
본 발명의 트리아진퍼옥사이드 유도체는, 그 분자 내에 1 개의 과산화 결합밖에 갖지 않기 때문에, 당해 화합물의 분해에 의한 1 분자당 발생 라디칼수가, 상기의 특허문헌 1 에서 개시된 분자 내에 2 개의 과산화 결합을 갖는 트리아진퍼옥사이드 유도체보다 적지만, 특허문헌 1 에서 개시된 화합물과 동일한 정도의 감도를 갖는다는 특이한 효과를 갖는다. 한편, 본 발명의 트리아진퍼옥사이드 유도체는, 그 분자 내에 1 개의 과산화 결합밖에 갖지 않기 때문에, 상기한 특허문헌 1 에서 개시된 트리아진퍼옥사이드 유도체보다 고온 하에서의 장기 보존 안정성이 우수하다.Since the triazine peroxide derivative of the present invention has only one peroxidation bond in the molecule, the number of radicals generated per molecule by decomposition of the compound is that of the triazine peroxide derivative having two peroxidation bonds in the molecule disclosed in Patent Document 1 above. Although it is less than a triazine peroxide derivative, it has the unique effect of having the same level of sensitivity as the compound disclosed in Patent Document 1. On the other hand, since the triazine peroxide derivative of the present invention has only one peroxidation bond in its molecule, it is superior to the triazine peroxide derivative disclosed in Patent Document 1 above in long-term storage stability at high temperatures.
또한, 본 발명의 트리아진퍼옥사이드 유도체는, 감도가 우수하기 때문에, 카본 블랙 등의 차광성 안료를 포함하는 블랙 레지스트 등의 중합성 조성물의 중합 개시제로도 유용하다.In addition, since the triazine peroxide derivative of the present invention has excellent sensitivity, it is also useful as a polymerization initiator for polymerizable compositions such as black resist containing a light-shielding pigment such as carbon black.
본 발명의 트리아진퍼옥사이드 유도체는, 하기 일반식 (1) 로 나타낸다.The triazine peroxide derivative of the present invention is represented by the following general formula (1).
[화학식 3][Formula 3]
((일반식 (1) 중, R1 및 R2 는 독립적으로 메틸기 또는 에틸기, R3 은 탄소수 1 ∼ 5 의 지방족 탄화수소기, 또는 알킬기를 가져도 되는 탄소수 6 ∼ 9 의 방향족 탄화수소기를 나타내고, R4 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다. Ar 은 하기 일반식 (2) : Ar1, Ar2, 또는 Ar3 으로 나타내는 아릴기이다.)((In General Formula (1), R 1 and R 2 independently represent a methyl group or an ethyl group, R 3 represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R 4 is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar 1 , Ar 2 , or Ar 3 . )
[화학식 4][Formula 4]
(일반식 (2) 중, m 은 0 내지 3 의 정수를 나타내고, R11 은 독립된 치환기로서, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다.))(In General Formula (2), m represents an integer of 0 to 3, and R 11 is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. , an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) )
일반식 (1) 중, R1 및 R2 는 독립적으로 메틸기 또는 에틸기를 나타내고, 분해 온도가 높아, 중합성 조성물의 저장 안정성이 높아지는 관점에서, 메틸기가 바람직하다.In General Formula (1), R 1 and R 2 independently represent a methyl group or an ethyl group, and a methyl group is preferable from the viewpoint of high decomposition temperature and increased storage stability of the polymerizable composition.
일반식 (1) 중, R3 은 탄소수 1 ∼ 5 의 지방족 탄화수소기, 또는 알킬기를 가져도 되는 탄소수 6 ∼ 9 의 방향족 탄화수소기를 나타낸다. 상기 알킬기는, 직사슬이어도 되고, 분기사슬이어도 된다. R3 의 구체예로는 메틸기, 에틸기, 프로필기, 2,2-디메틸프로필기, 페닐기, 이소프로필페닐기 등을 들 수 있다. 이들 중에서도, 상기 트리아진퍼옥사이드 유도체의 합성이 용이한 관점에서, 메틸기, 에틸기, 프로필기, 2,2-디메틸프로필기, 페닐기인 것이 바람직하다. 상기 트리아진퍼옥사이드 유도체의 분해 온도가 높기 때문에 중합성 조성물의 저장 안정성이 높아지고, 광에 대한 감도가 높은 점에서, 메틸기, 에틸기인 것이 보다 바람직하다.In General Formula (1), R 3 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be straight chain or branched chain. Specific examples of R 3 include methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, phenyl group, and isopropylphenyl group. Among these, methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, and phenyl group are preferable from the viewpoint of ease of synthesis of the triazine peroxide derivative. Since the decomposition temperature of the triazine peroxide derivative is high, the storage stability of the polymerizable composition is high, and the sensitivity to light is high, it is more preferable that it is a methyl group or an ethyl group.
일반식 (1) 중, R4 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다. 상기의 R4 는 트리아진퍼옥사이드 유도체의 흡수 파장에 대한 영향이 작기 때문에, R4 가 상기의 광범위이더라도 양호한 감도를 발현한다. 또한, 상기의 「치환되어 있어도 되는」에 있어서의 「치환기」에는, 할로겐 원자, 탄소 골격 중에 에테르 결합이나 티오에테르 결합을 가져도 되는 지방족 탄화수소기, 방향족 탄화수소기, 복소 고리 함유기, 아실기, 시아노기, 니트로기, 카르복실기, 에폭시기, 수산기 등이 포함된다. 상기의 R4 는, 안정성이 높은 관점에서, 바람직하게는, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, 또는 -Y-R 이며, 합성이 용이한 관점에서, 보다 바람직하게는, -O-R 로서, R 은 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기이다.In general formula (1), R 4 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, An acyl group, -YR, or -N-RR' having 1 to 20 carbon atoms which may be substituted, where Y represents an oxygen atom or a sulfur atom, and R and R' are independently hydrogen atoms and 1 to 20 carbon atoms which may be substituted. It represents an aliphatic hydrocarbon group with 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms. Since the above R 4 has little influence on the absorption wavelength of the triazine peroxide derivative, good sensitivity is achieved even when R 4 is within the above wide range. In addition, the "substituent" in the above "may be substituted" includes a halogen atom, an aliphatic hydrocarbon group that may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic ring-containing group, an acyl group, Cyano group, nitro group, carboxyl group, epoxy group, hydroxyl group, etc. are included. From the viewpoint of high stability, the above R 4 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, or an optionally substituted aromatic hydrocarbon group having 2 to 20 carbon atoms. is a heterocyclic ring-containing group, an optionally substituted acyl group having 1 to 20 carbon atoms, or -YR. From the viewpoint of ease of synthesis, it is more preferably -OR, where R is an optionally substituted acyl group having 1 to 20 carbon atoms. These include an aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.
일반식 (2) 중, m 은 0 내지 3 의 정수를 나타내고, 합성이 용이한 관점에서, m 이 0 내지 2 인 것이 바람직하고, 광을 효율적으로 흡수하는 관점에서, m 이 1 인 것이 보다 바람직하다.In General Formula (2), m represents an integer of 0 to 3, and from the viewpoint of easy synthesis, m is preferably 0 to 2, and from the viewpoint of efficiently absorbing light, m is more preferably 1. do.
일반식 (2) 중, R11 은 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다. 상기의 R11 은 트리아진퍼옥사이드 유도체의 흡수 파장에 대한 영향이 작기 때문에, R11 이 상기의 광범위이더라도 양호한 감도를 발현한다. 또한, 상기의 「치환되어 있어도 되는」에 있어서의 「치환기」에는, 할로겐 원자, 탄소 골격 중에 에테르 결합이나 티오에테르 결합을 가져도 되는 지방족 탄화수소기, 방향족 탄화수소기, 복소 고리 함유기, 아실기, 시아노기, 니트로기, 카르복실기, 에폭시기, 수산기 등이 포함된다. 상기의 R11 은, 독립된 치환기로서, 탄소수 1 내지 20 의 알킬기, 일반식 (3) : R12-Y- 로 나타내는 치환기, 니트로기, 또는 시아노기를 나타내고, 상기 Y 는, 산소 원자 또는 황 원자를 나타내고, 상기 R12 는, 탄소 골격 중에, 에테르 결합, 티오에테르 결합, 및 말단에 수산기의 어느 1 개 이상을 갖고 있어도 되는 탄소수 1 ∼ 20 의 탄화수소기, 알킬기를 가져도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 또는 탄소수 1 ∼ 20 의 아실기여도 되고, 또 R11 은 인접하는 2 개의 상기 일반식 (3) : R12-Y- 에 의해 5 ∼ 6 원 (員) 고리를 형성하고 있어도 된다.In general formula (2), R 11 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, An acyl group, -YR, or -N-RR' having 1 to 20 carbon atoms which may be substituted, where Y represents an oxygen atom or a sulfur atom, and R and R' are independently hydrogen atoms and 1 to 20 carbon atoms which may be substituted. It represents an aliphatic hydrocarbon group of 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group of 2 to 20 carbon atoms. Since the above R 11 has little influence on the absorption wavelength of the triazine peroxide derivative, good sensitivity is achieved even if R 11 is within the above wide range. In addition, the "substituent" in the above "may be substituted" includes a halogen atom, an aliphatic hydrocarbon group that may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic ring-containing group, an acyl group, Cyano group, nitro group, carboxyl group, epoxy group, hydroxyl group, etc. are included. The above R 11 is an independent substituent and represents an alkyl group having 1 to 20 carbon atoms, a substituent represented by general formula (3): R 12 -Y-, a nitro group, or a cyano group, and Y is an oxygen atom or a sulfur atom. represents, and R 12 is a hydrocarbon group having 1 to 20 carbon atoms that may have one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton, or a hydrocarbon group having 6 to 20 carbon atoms that may have an alkyl group. It may be an aromatic hydrocarbon group or an acyl group having 1 to 20 carbon atoms, and R 11 may form a 5- to 6-membered ring by two adjacent general formulas (3): R 12 -Y-.
본 발명의 트리아진퍼옥사이드 유도체의 구체예를 이하에 나타내지만, 이들에 한정되지 않는다.Specific examples of the triazine peroxide derivative of the present invention are shown below, but are not limited to these.
[화학식 5][Formula 5]
본 발명의 트리아진퍼옥사이드 유도체로는, 화합물 19, 화합물 23, 화합물 25, 화합물 26, 화합물 27, 화합물 31, 화합물 32, 화합물 33, 화합물 35, 화합물 37, 화합물 38, 화합물 39, 화합물 43, 화합물 44, 화합물 45, 화합물 46, 화합물 47, 화합물 48, 화합물 49, 화합물 50, 화합물 51, 화합물 52, 화합물 53, 화합물 54, 화합물 55, 화합물 56, 화합물 57, 화합물 60, 화합물 61, 화합물 73, 화합물 77, 화합물 78, 화합물 79, 화합물 81 이 바람직하다.Triazine peroxide derivatives of the present invention include Compound 19, Compound 23, Compound 25, Compound 26, Compound 27, Compound 31, Compound 32, Compound 33, Compound 35, Compound 37, Compound 38, Compound 39, Compound 43, Compound 44, Compound 45, Compound 46, Compound 47, Compound 48, Compound 49, Compound 50, Compound 51, Compound 52, Compound 53, Compound 54, Compound 55, Compound 56, Compound 57, Compound 60, Compound 61, Compound 73 , Compound 77, Compound 78, Compound 79, and Compound 81 are preferred.
<트리아진퍼옥사이드 유도체의 제조 방법><Method for producing triazine peroxide derivatives>
상기 일반식 (1) 로 나타내는 트리아진퍼옥사이드 유도체의 제조 방법은, 염화시아누르 및/또는 그 유도체와, 하이드로퍼옥사이드를 원료로 하여 반응시키는 공정을 포함한다. 이와 같은 제조 방법으로는, 예를 들어, 하기 반응식과 같이, 염화시아누르 유도체를 얻는 공정 (이하, 공정 (A) 및 (B) 라고도 칭한다) 과, 계속해서, 얻어진 염화시아누르 유도체와, 하이드로퍼옥사이드를, 알칼리의 존재 하에서, 반응시키는 공정 (이하, 공정 (C) 라고도 칭한다) 을 포함하는 방법을 들 수 있다. 또한, 상기의 각 공정은, 순서가 한정되지 않고, 예를 들어, 염화시아누르 및 하이드로퍼옥사이드의 반응물에, 하기의 Ar-X 나 R4-X 를 반응시켜도 되고, 또, 각 공정은 동시에 실시해도 된다. 각 공정의 전후에는, 잉여의 원료 등을 감압 증류 제거 (제거) 하는 공정이나, 정제 공정을 포함해도 된다.The method for producing a triazine peroxide derivative represented by the general formula (1) includes a step of reacting cyanuric chloride and/or its derivative with hydroperoxide as a raw material. Such a production method includes, for example, a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as steps (A) and (B)) as shown in the following reaction formula, followed by the obtained cyanuric chloride derivative and A method including a step of reacting roperoxide in the presence of an alkali (hereinafter also referred to as step (C)) is included. In addition, the order of each of the above steps is not limited. For example, the reactants of cyanuric chloride and hydroperoxide may be reacted with Ar-X or R 4 -X below, and each step may be performed simultaneously. You can do it. Before and after each process, a process of vacuum distillation (removal) of excess raw materials, etc. or a purification process may be included.
[화학식 6][Formula 6]
(상기 반응식에 있어서, R1, R2, R3, R4 및 Ar 은 상기 일반식 (1) 과 동일하다)(In the above reaction formula, R 1 , R 2 , R 3 , R 4 and Ar are the same as the general formula (1))
상기 공정 (C) 에 있어서, 상기 염화시아누르 유도체는, 시판품을 이용할 수 있다. 또한, 시판품이 없는 경우, 상기 공정 (A) 및 (B) 에 있어서, 그리냐르 반응, 리튬화 반응, 스즈키 커플링 반응, 또는 프리델·크래프츠 반응, 알칼리 존재 하에서의 구핵 치환 반응 등의 공지된 합성법에 준하여 합성할 수 있다.In the step (C), a commercially available product can be used as the cyanuric chloride derivative. In addition, in the case where there is no commercially available product, in the above steps (A) and (B), known synthetic methods such as Grignard reaction, lithiation reaction, Suzuki coupling reaction, Friedel-Crafts reaction, nucleophilic substitution reaction in the presence of alkali, etc. It can be synthesized according to .
<그리냐르 반응에 의한 염화시아누르 유도체의 합성><Synthesis of cyanuric chloride derivatives by Grignard reaction>
상기 공정 (A) 및 (B) 에 있어서, 그리냐르 반응에 의해, 염화시아누르 유도체를 합성하는 경우, 일본 공개특허공보 평6-179661호 등에 기재된 공지된 합성법에 준하여 합성할 수 있다. 상기 공정 (A) 에 있어서의 Ar-X 및 상기 공정 (B) 에 있어서의 R4-X 의 X 가 염소 원자, 브롬 원자, 또는 요오드 원자로 나타내는 할로겐 화합물을 사용할 수 있다. 할로겐 화합물과 마그네슘을 반응시킴으로써 그리냐르 시약을 조제하고, 이어서 얻어진 그리냐르 시약을 염화시아누르와 반응시킴으로써 염화시아누르 유도체를 합성할 수 있다.In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by Grignard reaction, it can be synthesized according to a known synthesis method described in Japanese Patent Application Laid-Open No. 6-179661, etc. A halogen compound in which X of Ar-X in the step (A) and R 4 -X in the step (B) is represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A Grignard reagent can be prepared by reacting a halogen compound with magnesium, and then a cyanuric chloride derivative can be synthesized by reacting the obtained Grignard reagent with cyanuric chloride.
상기의 그리냐르 시약의 조제에 있어서, 마그네슘은, 할로겐 화합물 1 몰에 대하여, 0.8 내지 2.0 몰 사용하는 것이 바람직하고, 1 내지 1.5 몰 사용하는 것이 보다 바람직하다. 반응 개시제로서, 요오드, 브로모에탄, 디브로모에탄 등을 사용해도 되고, 할로겐 화합물 1 몰에 대하여, 0.0001 내지 0.01 몰 사용하는 것이 바람직하다. 반응 온도는 0 내지 70 ℃ 가 바람직하고, 10 내지 60 ℃ 가 보다 바람직하다. 반응 시간은 30 분 내지 20 시간이 바람직하고, 1 시간 내지 10 시간이 보다 바람직하다.In the preparation of the Grignard reagent, it is preferable to use 0.8 to 2.0 mol of magnesium, and more preferably 1 to 1.5 mol, per 1 mol of the halogen compound. As a reaction initiator, iodine, bromoethane, dibromoethane, etc. may be used, and it is preferably used in an amount of 0.0001 to 0.01 mol per 1 mol of the halogen compound. The reaction temperature is preferably 0 to 70°C, and more preferably 10 to 60°C. The reaction time is preferably 30 minutes to 20 hours, and more preferably 1 hour to 10 hours.
상기의 그리냐르 시약의 조제에 있어서, 예를 들어 테트라하이드로푸란 등의 에테르류 등의 용매를 사용할 수 있다.In preparing the Grignard reagent, solvents such as ethers such as tetrahydrofuran can be used.
또한, 상기 그리냐르 시약과 염화시아누르의 반응에 있어서, 염화시아누르는, 할로겐 화합물 1 몰에 대하여, 0.7 내지 1.5 몰 사용하는 것이 바람직하고, 0.8 내지 1.2 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -30 내지 70 ℃ 가 바람직하고, -10 내지 40 ℃ 가 보다 바람직하다. 반응 시간은 10 분 내지 20 시간이 바람직하고, 30 분 내지 15 시간인 것이 보다 바람직하다. 또한, 조제한 그리냐르 시약에 염화시아누르를 투입해도 되고, 염화시아누르의 용액에 그리냐르 시약을 투입해도 된다.Additionally, in the reaction between the Grignard reagent and cyanuric chloride, it is preferable to use 0.7 to 1.5 mole of cyanuric chloride, and more preferably 0.8 to 1.2 mole, per 1 mole of the halogen compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 20 hours, and more preferably 30 minutes to 15 hours. Additionally, cyanuric chloride may be added to the prepared Grignard reagent, or Grignard reagent may be added to a solution of cyanuric chloride.
상기의 그리냐르 시약과 염화시아누르의 반응에 있어서, 예를 들어 테트라하이드로푸란 등의 에테르류 등의 용매를 사용할 수 있다.In the reaction between the Grignard reagent and cyanuric chloride, solvents such as ethers such as tetrahydrofuran can be used, for example.
<리튬화 반응에 의한 염화시아누르 유도체의 합성><Synthesis of cyanuric chloride derivatives by lithiation reaction>
상기 공정 (A) 및 (B) 에 있어서, 리튬화 반응에 의해, 염화시아누르 유도체를 합성하는 경우, WO2012/096263 공보 등에 기재된 공지된 합성법에 준하여 합성할 수 있다. 상기 공정 (A) 에 있어서의 Ar-X 및 상기 공정 (B) 에 있어서의 R4-X 의 X 가 염소 원자, 브롬 원자, 또는 요오드 원자로 나타내는 할로겐 화합물을 사용할 수 있다. 할로겐 화합물과 리튬화제를 반응시킴으로써 리튬 화합물을 조제하고, 이어서 얻어진 리튬 화합물과 염화시아누르를 반응시킴으로써 염화시아누르 유도체를 합성할 수 있다.In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by lithiation reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 publication, etc. A halogen compound in which X of Ar-X in the step (A) and R 4 -X in the step (B) is represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A lithium compound can be prepared by reacting a halogen compound with a lithiating agent, and then a cyanuric chloride derivative can be synthesized by reacting the obtained lithium compound with cyanuric chloride.
상기 리튬화제로는 메틸리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬 등의 알킬리튬류 ; 페닐리튬 등의 아릴리튬류 ; 리튬디이소프로필아미드, 리튬비스(트리메틸실릴)아미드 등의 리튬아미드류를 들 수 있고, n-부틸리튬, s-부틸리튬, t-부틸리튬, 페닐리튬인 것이 바람직하다.Examples of the lithiating agent include alkyl lithium such as methyl lithium, n-butyl lithium, s-butyl lithium, and t-butyl lithium; Aryllithium such as phenyllithium; Examples of lithium amides include lithium diisopropylamide and lithium bis(trimethylsilyl)amide, and n-butyllithium, s-butyllithium, t-butyllithium, and phenyllithium are preferred.
상기의 리튬 화합물의 조제에 있어서, 리튬화제는, 할로겐 화합물 1 몰에 대하여, 0.8 내지 3.0 몰 사용하는 것이 바람직하고, 1.0 내지 2.2 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -100 내지 50 ℃ 가 바람직하고, -80 내지 0 ℃ 가 보다 바람직하다. 반응 시간은 0.2 내지 20 시간이 바람직하고, 0.5 내지 10 시간이 보다 바람직하다.In the preparation of the above lithium compound, the lithiating agent is preferably used in an amount of 0.8 to 3.0 mol, and more preferably in an amount of 1.0 to 2.2 mol, per 1 mol of the halogen compound. The reaction temperature is preferably -100 to 50°C, and more preferably -80 to 0°C. The reaction time is preferably 0.2 to 20 hours, and more preferably 0.5 to 10 hours.
상기의 리튬 화합물의 조제에 있어서, 예를 들면, 테트라하이드로푸란 등의 에테르류 등의 용매를 이용할 수 있다.In preparing the above lithium compound, solvents such as ethers such as tetrahydrofuran can be used, for example.
또한, 상기의 리튬 화합물과 염화시아누르의 반응에 있어서, 염화시아누르는, 할로겐 화합물 1 몰에 대하여, 0.7 내지 1.5 몰 사용하는 것이 바람직하고, 0.8 내지 1.2 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -30 내지 70 ℃ 가 바람직하고, -10 내지 40 ℃ 가 보다 바람직하다. 반응 시간은 10 분 내지 10 시간이 바람직하고, 30 분 내지 5 시간인 것이 보다 바람직하다. 또한, 조제한 리튬 화합물에 염화시아누르를 투입해도 되고, 염화시아누르의 용액에 리튬 화합물을 투입해도 된다.In addition, in the reaction between the above lithium compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mole of cyanuric chloride, and more preferably 0.8 to 1.2 mole per 1 mole of the halogen compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, cyanuric chloride may be added to the prepared lithium compound, or the lithium compound may be added to the solution of cyanuric chloride.
상기의 리튬 화합물과 염화시아누르의 반응에 있어서, 예를 들면 테트라하이드로푸란 등의 에테르류 등의 용매를 사용할 수 있다.In the reaction between the above lithium compound and cyanuric chloride, solvents such as ethers such as tetrahydrofuran can be used, for example.
<스즈키 커플링에 의한 염화시아누르 유도체의 합성><Synthesis of cyanuric chloride derivatives by Suzuki coupling>
상기 공정 (A) 및 (B) 에 있어서, 스즈키 커플링 반응에 의해, 염화시아누르 유도체를 합성하는 경우, WO2012/096263 공보 등에 기재된 공지된 합성법에 준하여 합성할 수 있다. 예를 들면, 전술한 리튬 화합물을 붕소 시약과 반응시킴으로써, 상기 공정 (A) 에 있어서의 Ar-X 및 상기 공정 (B) 에 있어서의 R4-X 의 X 가 보로닐기 또는 보론산으로 변환된 붕소 화합물을 합성할 수 있다. 이어서 얻어진 붕소 화합물을 염화시아누르와 반응시킴으로써 염화시아누르 유도체를 합성할 수 있다. 또한, 붕소 화합물의 시판품이 판매되고 있는 경우, 그대로 사용할 수 있다.In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by Suzuki coupling reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 publication, etc. For example, by reacting the above-mentioned lithium compound with a boron reagent, Ar-X in the above step (A) and Boron compounds can be synthesized. Cyanuric chloride derivatives can then be synthesized by reacting the obtained boron compound with cyanuric chloride. Additionally, if a commercial product of a boron compound is available, it can be used as is.
상기 붕소 시약으로는, 붕산트리메틸, 붕산트리이소프로필, 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보롤란 등을 들 수 있다.Examples of the boron reagent include trimethyl borate, triisopropyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the like.
상기한 붕소 화합물의 합성에 있어서, 붕소 시약은, 리튬 화합물 1 몰에 대하여 0.8 내지 3.0 몰 사용하는 것이 바람직하고, 1.0 내지 2.0 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -100 내지 50 ℃ 가 바람직하고, -80 내지 20 ℃ 가 보다 바람직하다. 반응 시간은 10 분 내지 20 시간이 바람직하고, 30 분 내지 10 시간이 보다 바람직하다.In the synthesis of the boron compound described above, it is preferable to use 0.8 to 3.0 mole of the boron reagent, and more preferably 1.0 to 2.0 mole per mole of the lithium compound. The reaction temperature is preferably -100 to 50°C, and more preferably -80 to 20°C. The reaction time is preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.
상기의 붕소 화합물의 합성에 있어서, 예를 들어 테트라하이드로푸란 등의 에테르류 등의 용매를 사용할 수 있다.In the synthesis of the above boron compound, solvents such as ethers such as tetrahydrofuran can be used.
또한, 상기 붕소 화합물과 염화시아누르의 반응에 있어서, 염화시아누르는 붕소 화합물 1 몰에 대하여 0.7 내지 1.5 몰 사용하는 것이 바람직하고, 0.8 내지 1.2 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -30 내지 70 ℃ 가 바람직하고, -10 내지 40 ℃ 가 보다 바람직하다. 반응 시간은 10 분 내지 10 시간이 바람직하고, 30 분 내지 5 시간인 것이 보다 바람직하다. 또한, 붕소 화합물에 염화시아누르를 투입해도 되고, 염화시아누르의 용액에 붕소 화합물을 투입해도 된다.In addition, in the reaction between the boron compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mol, and more preferably 0.8 to 1.2 mol, per 1 mol of boron compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, cyanuric chloride may be added to the boron compound, or the boron compound may be added to the solution of cyanuric chloride.
상기 붕소 화합물과 염화시아누르의 반응에 있어서, 팔라듐 촉매 및 알칼리를 사용하는 것이 바람직하고, 필요에 따라 배위자를 첨가해도 된다.In the reaction between the boron compound and cyanuric chloride, it is preferable to use a palladium catalyst and an alkali, and a ligand may be added as necessary.
상기 팔라듐 촉매로는, 아세트산팔라듐, 테트라키스트리페닐포스핀팔라듐, 비스(트리페닐포스핀)팔라듐디클로라이드, (비스(디페닐포스피노)페로센)팔라듐디클로라이드-염화메틸렌 착물 등을 들 수 있다.Examples of the palladium catalyst include palladium acetate, tetrakistriphenylphosphine palladium, bis(triphenylphosphine)palladium dichloride, (bis(diphenylphosphine)ferrocene)palladium dichloride-methylene chloride complex, etc. .
상기 알칼리로는, 탄산나트륨, 탄산수소나트륨, 아세트산나트륨, 아세트산칼륨, 인산칼륨 등의 알칼리 금속염 등의 무기 염기 ; 트리에틸아민 등의 유기 염기를 들 수 있다.Examples of the alkali include inorganic bases such as alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium acetate, potassium acetate, and potassium phosphate; Organic bases such as triethylamine can be mentioned.
상기 배위자로는, 트리페닐포스핀, 트리시클로헥실포스핀, 2,2'-비스(디페닐포스피노)-1,1'-비나프탈렌, 2-디시클로헥실포스피노-2,6'-디메톡시비페닐 등의 유기 인계 배위자 등을 들 수 있다.Examples of the ligand include triphenylphosphine, tricyclohexylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, 2-dicyclohexylphosphino-2,6'- Organophosphorous ligands such as dimethoxybiphenyl, etc. can be mentioned.
상기의 붕소 화합물과 염화시아누르의 반응에 있어서, 테트라하이드로푸란, 1,4-디옥산 등의 에테르류 ; 메탄올, 2-프로판올 등의 알코올류 ; 톨루엔, 자일렌 등의 방향족계 탄화수소류 ; N,N-디메틸포름아미드 등의 아미드류 등의 유기 용매를 사용할 수 있다. 상기 유기 용매는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다. 또한, 상기 유기 용매와 물의 혼합 용매를 사용할 수 있다.In the reaction between the boron compound and cyanuric chloride, ethers such as tetrahydrofuran and 1,4-dioxane; Alcohols such as methanol and 2-propanol; Aromatic hydrocarbons such as toluene and xylene; Organic solvents such as amides such as N,N-dimethylformamide can be used. The organic solvent may be used individually or two or more types may be used in combination. Additionally, a mixed solvent of the organic solvent and water may be used.
<프리델·크래프츠 반응에 의한 염화시아누르 유도체의 합성><Synthesis of cyanuric chloride derivatives by Friedel-Crafts reaction>
상기 공정 (A) 및 (B) 에 있어서, 프리델·크래프츠 반응에 의해, 염화시아누르 유도체를 합성하는 경우, US5322941 공보 등에 기재된 공지된 합성법에 준하여 합성할 수 있다. 상기 공정 (A) 에 있어서의 Ar-X 및 상기 공정 (B) 에 있어서의 R4-X 의 X 가 수소 원자로 나타내는 방향족 화합물을 사용할 수 있다. 염화알루미늄 등의 루이스산의 존재 하, 방향족 화합물과 염화시아누르를 반응시킴으로써 염화시아누르 유도체를 합성할 수 있다.In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by the Friedel-Crafts reaction, it can be synthesized according to a known synthesis method described in US5322941 publication, etc. An aromatic compound in which X of Ar-X in the step (A) and R 4 -X in the step (B) is represented by a hydrogen atom can be used. Cyanuric chloride derivatives can be synthesized by reacting an aromatic compound with cyanuric chloride in the presence of a Lewis acid such as aluminum chloride.
상기 루이스산으로는, 염화알루미늄, 브롬화알루미늄, 염화철 (III), 염화티탄 (IV), 염화주석 (IV), 염화아연, 비스무트 (III) 트리플레이트, 하프늄 (IV) 트리플레이트, 삼불화붕소디에틸에테르 착물 등을 사용할 수 있다.The Lewis acids include aluminum chloride, aluminum bromide, iron (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, and boron trifluoride. Ethyl ether complexes, etc. can be used.
상기의 방향족 화합물과 염화시아누르의 반응에 있어서, 염화시아누르는, 방향족 화합물 1 몰에 대하여, 0.7 내지 2.5 몰 사용하는 것이 바람직하고, 0.8 내지 1.5 몰 사용하는 것이 보다 바람직하다. 염화알루미늄은, 방향족 화합물 1 몰에 대하여, 1.0 내지 3.0 몰 사용하는 것이 바람직하고, 1.0 내지 2.0 몰 사용하는 것이 보다 바람직하다. 반응 온도는 -50 내지 60 ℃ 가 바람직하고, 0 내지 40 ℃ 가 보다 바람직하다. 반응 시간은 10 분 내지 10 시간이 바람직하고, 30 분 내지 5 시간인 것이 보다 바람직하다. 또한, 방향족 화합물과 염화시아누르의 용액에 염화알루미늄을 첨가해도 되고, 염화시아누르와 염화알루미늄의 용액에 방향족 화합물을 첨가해도 되고, 방향족 화합물과 염화알루미늄의 용액에 염화시아누르를 첨가해도 된다.In the reaction between the above aromatic compound and cyanuric chloride, it is preferable to use 0.7 to 2.5 mole of cyanuric chloride, and more preferably 0.8 to 1.5 mole per 1 mole of the aromatic compound. It is preferable to use 1.0 to 3.0 mol of aluminum chloride, and more preferably 1.0 to 2.0 mol per 1 mol of the aromatic compound. The reaction temperature is preferably -50 to 60°C, and more preferably 0 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, aluminum chloride may be added to a solution of an aromatic compound and cyanuric chloride, an aromatic compound may be added to a solution of cyanuric chloride and aluminum chloride, and cyanuric chloride may be added to a solution of an aromatic compound and aluminum chloride.
상기의 방향족 화합물과 염화시아누르의 반응에 있어서, 예를 들면 디클로로메탄, 1,2-디클로로에탄, 자일렌 등의 용매를 사용할 수 있다.In the reaction between the aromatic compound and cyanuric chloride, solvents such as dichloromethane, 1,2-dichloroethane, and xylene can be used, for example.
<트리아진퍼옥사이드 유도체의 합성><Synthesis of triazine peroxide derivatives>
상기 공정 (C) 에 있어서, 일반식 (1) 로 나타내는 트리아진퍼옥사이드 유도체의 제조 방법은, 특별히 한정되지 않지만, 일본 특허공보 소45-39468호 등에 기재된 공지된 트리아진퍼옥사이드의 합성법에 준하여 합성할 수 있다.In the above step (C), the method for producing the triazine peroxide derivative represented by general formula (1) is not particularly limited, but is performed according to the known synthesis method of triazine peroxide described in Japanese Patent Publication No. 45-39468, etc. It can be synthesized.
상기 공정 (A) 및 (B) 에서 얻어진 염화시아누르 유도체와, 하이드로퍼옥사이드를 알칼리의 존재 하에서, 반응시키는 공정 (C) 에 의해, 트리아진퍼옥사이드 유도체가 얻어진다.A triazine peroxide derivative is obtained through step (C) of reacting the cyanuric chloride derivative obtained in the above steps (A) and (B) with hydroperoxide in the presence of an alkali.
상기 공정 (C) 에 있어서, 하이드로퍼옥사이드는, 염화시아누르 유도체 1 몰에 대하여, 목적물의 수율성을 높이는 관점에서, 0.9 몰 이상 반응시키는 것이 바람직하고, 1.0 몰 이상 반응시키는 것이 보다 바람직하고, 그리고, 3.0 몰 이하 반응시키는 것이 바람직하고, 2.0 몰 이하 반응시키는 것이 보다 바람직하다. 또한, 하이드로퍼옥사이드는, 시판품을 이용할 수 있고, 시판품이 없는 경우, 일본 공개특허공보 소58-72557호 등에 기재된 공지의 합성법에 준하여 합성할 수 있다.In the above step (C), it is preferable to react 0.9 mol or more, and more preferably 1.0 mol or more of hydroperoxide per 1 mol of cyanuric chloride derivative, from the viewpoint of increasing the yield of the target product, And, it is preferable to react at 3.0 mol or less, and it is more preferable to react at 2.0 mol or less. In addition, hydroperoxide can be used as a commercial product, and if a commercial product is not available, it can be synthesized according to a known synthesis method described in Japanese Patent Application Laid-Open No. 58-72557, etc.
상기 공정 (C) 에 있어서, 반응 온도는, 목적물의 수율성을 높이는 관점에서, -10 ℃ 이상인 것이 바람직하고, 0 ℃ 이상인 것이 보다 바람직하고, 그리고, 50 ℃ 이하인 것이 바람직하고, 40 ℃ 이하인 것이 보다 바람직하다.In the above step (C), the reaction temperature is preferably -10°C or higher, more preferably 0°C or higher, and preferably 50°C or lower, and preferably 40°C or lower, from the viewpoint of increasing the yield of the target product. It is more desirable.
상기 공정 (C) 에 있어서, 반응 시간은, 원료나 반응 온도 등에 따라 상이하므로 일률적으로는 결정할 수 없지만, 통상, 목적물의 수율성을 높이는 관점에서, 10 분 내지 6 시간이 바람직하다.In the above step (C), the reaction time cannot be uniformly determined because it varies depending on the raw materials, reaction temperature, etc., but is usually preferably 10 minutes to 6 hours from the viewpoint of increasing the yield of the target product.
상기 공정 (C) 에 있어서, 사용하는 알칼리는, 특별히 제한은 없지만, 수산화나트륨, 수산화칼륨, 수산화리튬, 탄산칼륨, 탄산나트륨, 탄산수소나트륨, 피리딘, α-피콜린, γ-피콜린, 디메틸아미노피리딘, 트리에틸아민, 트리부틸아민, N,N-디이소프로필에틸아민, 1,5-디아자비시클로[4.3.0]-5-노넨 등을 들 수 있다. 알칼리는, 염화시아누르 유도체 1 몰에 대하여, 목적물의 수율성을 높이는 관점에서, 0.8 몰 이상 사용하는 것이 바람직하고, 1.0 몰 이상 사용하는 것이 보다 바람직하고, 그리고, 3.0 몰 이하 사용하는 것이 바람직하고, 2.0 몰 이하 사용하는 것이 보다 바람직하다.In the above step (C), the alkali used is not particularly limited, but is sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, α-picolin, γ-picolin, dimethylamino. Examples include pyridine, triethylamine, tributylamine, N,N-diisopropylethylamine, and 1,5-diazabicyclo[4.3.0]-5-nonene. From the viewpoint of increasing the yield of the target product, the alkali is preferably used at 0.8 mol or more, more preferably at least 1.0 mol, and preferably at most 3.0 mol per 1 mol of cyanuric chloride derivative. , it is more preferable to use 2.0 mol or less.
상기 공정 (C) 에서는, 염화시아누르 유도체가 액상인 경우에는, 유기 용매를 사용하지 않고 반응을 실시할 수 있다. 또한, 염화시아누르 유도체가 고체인 경우에는, 유기 용매를 사용하는 것이 바람직하다. 유기 용매로는, 염화시아누르 유도체의 종류에 따라 용해도가 상이하기 때문에, 특별히 한정되지 않지만, 예를 들어 톨루엔, 자일렌, 에틸벤젠 등의 방향족계 탄화수소류, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류, 테트라하이드로푸란, 디옥산 등의 에테르류, 아세트산에틸, 아세트산부틸 등의 에스테르류, 염화메틸렌, 클로로포름 등의 할로겐화 탄화수소류 등을 들 수 있다. 상기 유기 용매는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.In the above step (C), when the cyanuric chloride derivative is in a liquid state, the reaction can be carried out without using an organic solvent. Additionally, when the cyanuric chloride derivative is solid, it is preferable to use an organic solvent. The organic solvent is not particularly limited because the solubility varies depending on the type of cyanuric chloride derivative, but examples include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, acetone, methyl ethyl ketone, and methyl isobutyl. Examples include ketones such as ketones, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as methylene chloride and chloroform. The organic solvent may be used individually or two or more types may be used in combination.
상기 유기 용매의 사용량은, 통상, 원료의 합계량 100 질량부에 대하여 30 ∼ 1000 질량부 정도이다. 유기 용매는 공정 (C) 후에 증류 제거함으로써, 트리아진퍼옥사이드 유도체를 취출해도 되고, 취급성의 향상이나 열분해시의 위험성을 저감시키기 위해서, 트리아진퍼옥사이드 유도체를 유기 용매의 희석품으로서 사용해도 된다.The amount of the organic solvent used is usually about 30 to 1000 parts by mass based on 100 parts by mass of the total amount of raw materials. The organic solvent may be distilled off after step (C) to extract the triazine peroxide derivative, or in order to improve handling and reduce the risk of thermal decomposition, the triazine peroxide derivative may be used as a dilution of the organic solvent. .
상기 공정 (C) 는, 상압 하에서, 공기 하에서 실시할 수 있지만, 질소 기류 하 또는 질소 분위기 하에서 실시해도 된다.The above step (C) can be performed under normal pressure and air, but may also be performed under a nitrogen stream or nitrogen atmosphere.
상기 정제 공정으로는, 잉여의 원료나 부생물을 제거하기 위해서, 예를 들어, 탄산수소나트륨, 탄산수소칼륨, 탄산나트륨, 탄산칼륨, 수산화나트륨, 수산화칼륨, 아황산나트륨, 염화수소, 황산, 염화나트륨 등의 전해질 수용액이나, 이온 교환수를 사용하여 세정하고, 목적물을 정제하는 공정을 들 수 있다.In the above purification process, in order to remove excess raw materials and by-products, for example, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfite, hydrogen chloride, sulfuric acid, sodium chloride, etc. A step of washing using an aqueous electrolyte solution or ion-exchanged water and purifying the target product may be included.
<중합성 조성물><Polymerizable composition>
본 발명의 중합성 조성물은, (a) 중합 개시제 및 (b) 라디칼 중합성 화합물을 함유한다. 또한, 중합성 조성물은, (c) 알칼리 가용성 수지를 함유함으로써 현상성을 부여할 수 있다. 또한, 중합성 조성물은, 그 밖의 성분을 적절히 조합하여 함유시킬 수 있다.The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radically polymerizable compound. Additionally, the polymerizable composition can impart developability by containing (c) alkali-soluble resin. Additionally, the polymerizable composition may contain other components in appropriate combination.
<(a) 중합 개시제><(a) Polymerization initiator>
본 발명의 (a) 중합 개시제는, 상기 일반식 (1) 로 나타내는 트리아진퍼옥사이드 유도체를 함유한다. (a) 중합 개시제는, 활성 에너지선 또는 열에 의해 분해되고, 발생한 라디칼이 (b) 라디칼 중합성 화합물의 중합 (경화) 을 개시하는 작용을 갖는다. 트리아진퍼옥사이드 유도체는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.The polymerization initiator (a) of the present invention contains a triazine peroxide derivative represented by the general formula (1). (a) The polymerization initiator is decomposed by active energy rays or heat, and the generated radicals have the function of initiating polymerization (curing) of the (b) radically polymerizable compound. Triazine peroxide derivatives may be used individually or two or more types may be used in combination.
또한, 상기 (a) 중합 개시제는, 트리아진퍼옥사이드 유도체 이외의 중합 개시제 (이하, 다른 중합 개시제라고도 칭한다) 를 함유할 수 있다. 흡수대가 상이한 2 종류 이상의 트리아진퍼옥사이드 유도체나 다른 중합 개시제를 사용함으로써, 예를 들면, 고압 수은 램프 등의 복수의 파장의 광이 방사되는 램프에 대하여, 중합성 조성물의 고감도화를 도모할 수 있다. 또한, 중합성 조성물에 포함되는 (b) 라디칼 중합성 화합물의 중합성, 중합성 조성물에 포함되는 광을 흡수나 산란하는 안료 등의 종류, 경화물의 막두께 등을 고려하여, 다른 중합 개시제를 사용함으로써, 중합성 조성물의 표면 경화성이나 심부 경화성, 투명성 등을 개량할 수 있다.In addition, the polymerization initiator (a) may contain polymerization initiators other than triazine peroxide derivatives (hereinafter also referred to as other polymerization initiators). By using two or more triazine peroxide derivatives or other polymerization initiators with different absorption bands, it is possible to achieve higher sensitivity of the polymerizable composition to, for example, a lamp that emits light of multiple wavelengths, such as a high-pressure mercury lamp. there is. In addition, taking into account the polymerizability of (b) radically polymerizable compound contained in the polymerizable composition, the type of pigment etc. that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, etc., a different polymerization initiator may be used. By doing so, the surface hardenability, deep hardenability, transparency, etc. of the polymerizable composition can be improved.
상기 다른 중합 개시제로는, 공지된 것을 사용할 수 있고, 예를 들어, 1-하이드록시시클로헥실페닐케톤, 2-하이드록시-2-메틸-프로피오페논, 4'-(2-하이드록시에톡시)-2-하이드록시-2-메틸프로피오페논, 2-하이드록시-1-(4-(4-(2-하이드록시-2-메틸프로피오닐)벤질)페닐)-2-메틸프로판-1-온 등의 α-하이드록시아세토페논 유도체 ; 2-메틸-4'-메틸티오-2-모르폴리노프로피오페논, 2-벤질-2-(N,N-디메틸아미노)-1-(4-모르폴리노페닐)부탄-1-온, 2-(디메틸아미노)-2-(4-메틸벤질)-1-(4-모르폴리노페닐)부탄-1-온 등의 α-아미노아세토페논 유도체 ; 디페닐-2,4,6-트리메틸벤조일포스핀옥사이드, 페닐비스(2,4,6-트리메틸벤조일)포스핀옥사이드, 에틸(메시틸카르보닐)페닐포스피네이트 등의 아실포스핀옥사이드 유도체 ; 1-[4-(페닐티오)페닐]옥탄-1,2-디온-2-(O-벤조일옥심), 1-[({1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에틸리덴}아미노)옥시]에타논,], [8-[5-(2,4,6-트리메틸페닐)-11-(2-에틸헥실)-11H-벤조[a]카르바조일]][2-(2,2,3,3-테트라플루오로프로폭시)페닐]메타논-(O-아세틸옥심), 1-[4-[4-(2-벤조푸라닐카르보닐)페닐]티오]페닐-4-메틸-1-펜타논-1-(O-아세틸옥심) 등의 옥심에스테르 유도체 ; 2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(3,4-디메톡시스티릴)-4,6-비스(트리클로로메틸)1,3,5-트리아진, 2-(4-에톡시나프틸)-4,6-비스(트리클로로메틸)-1,3,5-트리아진 등의 할로메틸트리아진 유도체 ; 2,2-디메톡시-2-페닐아세토페논 등의 벤질케탈 유도체 ; 이소프로필티오크산톤 등의 티오크산톤 유도체, 4-(4-메틸페닐티오)벤조페논 등의 벤조페논 유도체 ; 3-벤조일-7-디에틸아미노쿠마린, 3,3'-카르보닐비스(7-디에틸아미노쿠마린) 등의 쿠마린 유도체 ; 2-(2-클로로페닐)-1-[2-(2-클로로페닐)-4,5-디페닐-1,3-디아졸-2-일]-4,5-디페닐이미다졸 등의 이미다졸 유도체 ; 3,3',4,4'-테트라키스(tert-부틸퍼옥시카르보닐)벤조페논, 2-(1-tert-부틸퍼옥시-1-메틸에틸)-9H-티오크산텐-9-온, 디벤조일퍼옥사이드 등의 유기 과산화물 ; 아조비스이소부티로니트릴 등의 아조 화합물 ; 캄파퀴논 등을 들 수 있다. 다른 중합 개시제는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.As the other polymerization initiators, known ones can be used, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy )-2-Hydroxy-2-methylpropiophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1 α-hydroxyacetophenone derivatives such as -one; 2-methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, α-aminoacetophenone derivatives such as 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; Acylphosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl(mesitylcarbonyl)phenylphosphinate; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]ethylidene}amino)oxy]ethanone,], [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[ a]carbazoyl]][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime), 1-[4-[4-(2-benzofura oxime ester derivatives such as nylcarbonyl)phenyl]thio]phenyl-4-methyl-1-pentanone-1-(O-acetyloxime); 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Halomethyltriazine derivatives such as romethyl)1,3,5-triazine and 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; Benzyl ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone; Thioxanthone derivatives such as isopropylthioxanthone, and benzophenone derivatives such as 4-(4-methylphenylthio)benzophenone; Coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole, etc. imidazole derivatives of; 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1-methylethyl)-9H-thioxanthen-9-one , organic peroxides such as dibenzoyl peroxide; Azo compounds such as azobisisobutyronitrile; Camphorquinone, etc. can be mentioned. Other polymerization initiators may be used individually or may be used in combination of two or more types.
상기 (a) 중합 개시제의 함유량은, (b) 라디칼 중합성 화합물 100 질량부에 대하여, 0.1 내지 40 질량부인 것이 바람직하고, 0.5 내지 20 질량부인 것이 보다 바람직하고, 1 내지 15 질량부인 것이 더욱 바람직하다. (a) 중합 개시제의 함유량은, (b) 라디칼 중합성 화합물 100 질량부에 대하여, 0.1 질량부 미만에서는 경화 반응이 진행되지 않기 때문에 바람직하지 않다. 또, (a) 중합 개시제의 함유량은, (b) 라디칼 중합성 화합물 100 질량부에 대하여, 40 질량부보다 많은 경우, (b) 라디칼 중합성 화합물에 대한 용해도가 포화에 이르러, 중합성 조성물의 성막시에 (a) 중합 개시제의 결정이 석출되어, 피막 표면의 거침이 문제가 되는 경우나, (a) 중합 개시제의 분해 잔류물의 증가에 의해, 경화물의 도막의 강도가 저하되는 경우가 있기 때문에, 바람직하지 않다.The content of the polymerization initiator (a) is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b). do. The content of the polymerization initiator (a) is not preferable because the curing reaction does not proceed if it is less than 0.1 parts by mass based on 100 parts by mass of the radically polymerizable compound (b). Moreover, when the content of (a) the polymerization initiator is more than 40 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (b), the solubility of the radically polymerizable compound in (b) reaches saturation, and the polymerizable composition During film formation, (a) crystals of the polymerization initiator may precipitate, causing roughness of the film surface, or (a) the strength of the cured film may decrease due to an increase in the decomposition residue of the polymerization initiator. , is not desirable.
또한, 상기 (a) 중합 개시제에, 상기 다른 중합 개시제를 포함하는 경우, 다른 중합 개시제의 비율은, (a) 중합 개시제 중, 80 질량% 이하인 것이 바람직하고, 50 질량% 이하인 것이 더욱 바람직하다.In addition, when the other polymerization initiator is included in the polymerization initiator (a), the proportion of the other polymerization initiator is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the polymerization initiator (a).
<(b) 라디칼 중합성 화합물><(b) Radical polymerizable compound>
본 발명의 (b) 라디칼 중합성 화합물로는, 에틸렌성 불포화기를 갖는 화합물을 바람직하게 사용할 수 있다. (b) 라디칼 중합성 화합물로는, 예를 들어, (메트)아크릴산에스테르류, 스티렌류, 말레산에스테르류, 푸마르산에스테르류, 이타콘산에스테르류, 계피산에스테르류, 크로톤산에스테르류, 비닐에테르류, 비닐에스테르류, 비닐케톤류, 알릴에테르류, 알릴에스테르류, N-치환 말레이미드류, N-비닐 화합물류, 불포화 니트릴류, 올레핀류 등을 들 수 있다. 이들 중에서도, 반응성이 높은 (메트)아크릴산에스테르류를 포함하는 것이 바람직하다. (b) 라디칼 중합성 화합물은, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.As the (b) radically polymerizable compound of the present invention, a compound having an ethylenically unsaturated group can be preferably used. (b) Radically polymerizable compounds include, for example, (meth)acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, and vinyl ethers. , vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins, etc. Among these, those containing highly reactive (meth)acrylic acid esters are preferable. (b) The radically polymerizable compound may be used individually or may be used in combination of two or more types.
상기 (메트)아크릴산에스테르류는, 단관능 화합물 및 다관능 화합물을 사용할 수 있다. 단관능 화합물로는, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 스테아릴(메트)아크릴레이트 등의 알킬(메트)아크릴레이트; 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트, 2-에틸-2-아다만틸(메트)아크릴레이트 등의 (메트)아크릴산과 지환족 알코올의 에스테르 화합물 ; 페닐(메트)아크릴레이트, 벤질(메트)아크릴레이트 등의 아릴(메트)아크릴레이트 ; 2-하이드록시에틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 2-하이드록시-3-페녹시프로필(메트)아크릴레이트, 3-하이드록시-1-아다만틸(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트 등의 하이드록실기를 갖는 모노머 ; 메톡시에틸(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 2-페닐페녹시에틸(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, (2-메틸-2-에틸-1,3-디옥소란-4-일)메틸(메트)아크릴레이트, (3-에틸옥세탄-3-일)메틸(메트)아크릴레이트, 고리형 트리메틸올프로판포르말(메트)아크릴레이트 등의 사슬형 또는 고리형의 에테르 결합을 갖는 모노머 등 ; N,N-디메틸아미노에틸(메트)아크릴레이트, N,N-디메틸(메트)아크릴아미드, N-메틸올(메트)아크릴아미드, N-이소프로필(메트)아크릴아미드, N,N-디메틸아미노프로필(메트)아크릴아미드, 디아세톤(메트)아크릴아미드, (메트)아크릴로일모르폴린, N-(메트)아크릴로일옥시에틸헥사하이드로프탈이미드 등의 질소 원자를 갖는 모노머 ; 2-(메트)아크릴로일옥시에틸이소시아네이트 등의 이소시아네이트기를 갖는 모노머 ; 글리시딜(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트글리시딜에테르 등의 에폭시기를 갖는 모노머 ; 인산2-((메트)아크릴로일옥시)에틸 등의 인 원자를 갖는 모노머 ; 3-(메트)아크릴옥시프로필트리메톡시실란 등의 규소 원자를 갖는 모노머 ; 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3,3-펜타플루오로프로필(메트)아크릴레이트, 2-(퍼플루오로헥실)에틸(메트)아크릴레이트 등의 불소 원자를 갖는 모노머 ; (메트)아크릴산, 숙신산모노(2-(메트)아크릴로일옥시에틸), 프탈산모노(2-(메트)아크릴로일옥시에틸), 말레산모노(2-(메트)아크릴로일옥시에틸), ω-카르복시-폴리카프로락톤모노(메트)아크릴레이트 등의 카르복실기를 갖는 모노머 등을 들 수 있다.As the (meth)acrylic acid esters, monofunctional compounds and polyfunctional compounds can be used. Monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. ) Alkyl (meth)acrylates such as acrylate and stearyl (meth)acrylate; Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2- Ester compounds of (meth)acrylic acid and alicyclic alcohol, such as ethyl-2-adamantyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth) ) Monomers having a hydroxyl group such as acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; Methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate , (2-methyl-2-ethyl-1,3-dioxoran-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic trimethyl Monomers having chain-like or cyclic ether bonds, such as all-propane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylamino Monomers having a nitrogen atom such as propyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, and N-(meth)acryloyloxyethylhexahydrophthalimide; Monomers having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; Monomers having an epoxy group such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether; Monomers having a phosphorus atom such as 2-((meth)acryloyloxy)ethyl phosphoric acid; Monomers having silicon atoms such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate monomers having fluorine atoms, such as; (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, mono(2-(meth)acryloyloxyethyl) phthalate, mono(2-(meth)acryloyloxyethyl) maleate and monomers having a carboxyl group such as ω-carboxy-polycaprolactone mono(meth)acrylate.
상기 다관능 화합물로는, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 글리세린디(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 글리세린프로폭시트리(메트)아크릴레이트, 트리메틸올에탄트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 펜타에리트리톨디(메트)아크릴레이트모노스테아레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 하이드록시피발산네오펜틸글리콜디(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 2,2-비스(4-(메트)아크릴옥시에톡시페닐)프로판, 2,2-비스(4-(메트)아크릴옥시폴리에톡시페닐)프로판, 9,9-비스(4-(2-(메트)아크릴로일옥시에톡시)페닐)플루오렌, 9,9-비스(4-(2-(2-(메트)아크릴로일옥시에톡시)에톡시)페닐)플루오렌 등의 다가 알코올과 (메트)아크릴산의 에스테르 화합물 ; 비스(4-(메트)아크릴옥시페닐)술파이드, 비스(4-(메트)아크릴로일티오페닐)술파이드, 트리스(2-(메트)아크릴로일옥시에틸)이소시아누레이트, 에틸렌비스(메트)아크릴아미드, (메트)아크릴산아연, (메트)아크릴산지르코늄, 지방족 우레탄아크릴레이트, 방향족 우레탄아크릴레이트, 에폭시아크릴레이트, 폴리에스테르아크릴레이트 등을 들 수 있다.Examples of the multifunctional compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and 1,4-butanediol. Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin Propoxy tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate Erythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tricyclo Decane dimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9 ,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-(2-(meth)acryloyloxyethoxy) Ester compounds of polyhydric alcohols such as toxy)phenyl)fluorene and (meth)acrylic acid; Bis(4-(meth)acryloyloxyphenyl)sulfide, bis(4-(meth)acryloylthiophenyl)sulfide, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylenebis (meth)acrylamide, zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, polyester acrylate, etc.
상기 (메트)아크릴산에스테르류는, 중합성 조성물의 감도의 향상, 산소 저해의 저감이나, 경화물의 도막의 기계적 강도나 경도, 내열성, 내구성, 내약품성의 향상의 관점에서, 상기 다가 알코올과 (메트)아크릴산의 에스테르 화합물이 바람직하고, 특히, 트리메틸올에탄트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 펜타에리트리톨트리아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨펜타아크릴레이트, 디펜타에리트리톨헥사아크릴레이트가 바람직하다.The (meth)acrylic acid esters are a combination of the polyhydric alcohol and (meth)acrylic acid esters from the viewpoint of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, and improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product. ) Ester compounds of acrylic acid are preferable, especially trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythate. Litolhexaacrylate is preferred.
또한, 상기 중합성 조성물은, 상기 (b) 라디칼 중합성 화합물로부터 얻어진 공중합체를 첨가할 수 있다.Additionally, the polymerizable composition may contain a copolymer obtained from the radically polymerizable compound (b).
<(c) 알칼리 가용성 수지><(c) Alkali soluble resin>
상기 중합성 조성물은, 추가로 (c) 알칼리 가용성 수지를 배합함으로써, 네거티브형 레지스트로서 바람직하게 사용할 수 있다. (c) 알칼리 가용성 수지로는, 네거티브형 레지스트에 일반적으로 사용되는 것을 사용할 수 있고, 알칼리 수용액에 가용인 수지이면 특별히 한정되지 않지만, 카르복실기를 포함하는 수지인 것이 바람직하다. (c) 알칼리 가용성 수지는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.The polymerizable composition can be suitably used as a negative resist by further adding (c) an alkali-soluble resin. (c) The alkali-soluble resin can be one that is generally used in negative resists, and is not particularly limited as long as it is a resin that is soluble in aqueous alkali solution, but it is preferable that it is a resin containing a carboxyl group. (c) Alkali-soluble resin may be used individually or two or more types may be used in combination.
본 발명의 (c) 알칼리 가용성 수지에는, 예를 들어, 카르복실기 함유 (메트)아크릴산에스테르 공중합물, 카르복실기 함유 에폭시아크릴레이트 수지 등이 바람직하게 사용된다.For the (c) alkali-soluble resin of the present invention, for example, carboxyl group-containing (meth)acrylic acid ester copolymer, carboxyl group-containing epoxy acrylate resin, etc. are preferably used.
상기 카르복실기 함유 (메트)아크릴산에스테르 공중합물은, 전술한 (메트)아크릴산에스테르류의 단관능 화합물에서 선택되는 적어도 1 종 (단, 상기 카르복실기를 갖는 모노머를 제외한다) 과, (메트)아크릴산, (메트)아크릴산의 2 량체, 이타콘산, 크로톤산, 말레산, 푸마르산, 비닐벤조산, 계피산, 숙신산모노(2-(메트)아크릴로일옥시에틸), 프탈산모노(2-(메트)아크릴로일옥시에틸), 말레산모노(2-(메트)아크릴로일옥시에틸), ω-카르복시-폴리카프로락톤모노(메트)아크릴레이트, 및 그들의 산 무수물 등의 에틸렌성 불포화기 함유 카르복실산에서 선택되는 적어도 1 종을 포함하는 공중합물이다.The carboxyl group-containing (meth)acrylic acid ester copolymer includes at least one selected from the monofunctional compounds of the above-mentioned (meth)acrylic acid esters (however, excluding the monomer having the carboxyl group), (meth)acrylic acid, ( Dimer of meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylbenzoic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl) succinic acid, mono(2-(meth)acryloyloxy phthalate) ethyl), maleic acid mono(2-(meth)acryloyloxyethyl), ω-carboxy-polycaprolactone mono(meth)acrylate, and their acid anhydrides, etc. carboxylic acids containing ethylenically unsaturated groups. It is a copolymer containing at least one type.
상기 카르복실기 함유 (메트)아크릴산에스테르 공중합물로는, 예를 들어, 메틸메타크릴레이트와, 시클로헥실메타크릴레이트와, 메타크릴산의 공중합물 등을 들 수 있다. 또한 스티렌, α-메틸스티렌, N-비닐-2-피롤리돈, N-메틸말레이미드, N-페닐말레이미드, N-시클로헥실말레이미드, 푸마르산디에틸, 이타콘산디에틸 등이 공중합되어도 된다.Examples of the carboxyl group-containing (meth)acrylic acid ester copolymer include a copolymer of methyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Additionally, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diethyl fumarate, diethyl itaconate, etc. may be copolymerized. .
또, 상기 카르복실기 함유 (메트)아크릴산에스테르 공중합물은, 네거티브형 레지스트의 현상성과 내열성, 경도, 내약품성 등의 피막 특성을 양립시키는 관점에서, 에틸렌성 불포화기 등의 반응성기가 측사슬에 도입된 카르복실기 함유 (메트)아크릴산에스테르 공중합물도 바람직하게 사용된다. 상기의 측사슬에 에틸렌성 불포화기를 도입하는 방법으로서 예를 들어, 카르복실기 함유 (메트)아크릴산에스테르 공중합물의 카르복실기의 일부에, 글리시딜(메트)아크릴레이트 등의 분자 내에 에폭시기와 에틸렌성 불포화기를 갖는 화합물을 부가시키는 방법이나, 에폭시기 및 카르복실기 함유 (메트)아크릴산에스테르 공중합물에, 메타크릴산 등의 에틸렌성 불포화기 함유 모노카르복실산을 부가시키는 방법이나, 수산기 및 카르복실기 함유 (메트)아크릴산에스테르 공중합물에, 2-(메트)아크릴로일옥시에틸이소시아네이트 등의 분자 내에 이소시아네이트기와 에틸렌성 불포화기를 갖는 화합물을 부가시키는 방법 등을 들 수 있다.In addition, the carboxyl group-containing (meth)acrylic acid ester copolymer has a carboxyl group in which a reactive group such as an ethylenically unsaturated group is introduced into the side chain from the viewpoint of achieving both the developability of negative resist and film properties such as heat resistance, hardness, and chemical resistance. Containing (meth)acrylic acid ester copolymers are also preferably used. As a method of introducing an ethylenically unsaturated group into the above side chain, for example, a carboxyl group-containing (meth)acrylic acid ester copolymer having an epoxy group and an ethylenically unsaturated group in a molecule such as glycidyl (meth)acrylate is part of the carboxyl group. A method of adding a compound, a method of adding a monocarboxylic acid containing an ethylenically unsaturated group such as methacrylic acid to a (meth)acrylic acid ester copolymer containing an epoxy group and a carboxyl group, or a copolymerization of a (meth)acrylic acid ester containing a hydroxyl group and a carboxyl group. and a method of adding a compound having an isocyanate group and an ethylenically unsaturated group in the molecule, such as 2-(meth)acryloyloxyethyl isocyanate, to water.
상기 카르복실기 함유 에폭시아크릴레이트 수지로는, 에폭시 화합물과 상기 에틸렌성 불포화기 함유 카르복실산의 반응물인 에폭시아크릴레이트 수지에, 추가로 산 무수물을 반응시킨 화합물이 바람직하다.The carboxyl group-containing epoxy acrylate resin is preferably a compound obtained by reacting an epoxy acrylate resin, which is a reaction product of an epoxy compound and the ethylenically unsaturated group-containing carboxylic acid, with an acid anhydride.
상기 에폭시 수지로는, 예를 들어, (o, m, p-) 크레졸 노볼락형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 비스페놀 A 형 에폭시 수지, 비스페놀 F 형 에폭시 수지, 트리스페놀메탄형 에폭시 수지, 비스페닐플루오렌형 에폭시 수지 등을 들 수 있다. 에폭시 수지는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.Examples of the epoxy resin include (o, m, p-) cresol novolak-type epoxy resin, phenol novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and trisphenolmethane-type epoxy resin. , bisphenyl fluorene type epoxy resin, etc. Epoxy resins may be used individually or two or more types may be used in combination.
상기 산 무수물로는, 예를 들어, 무수 말레산, 무수 숙신산, 무수 프탈산, 테트라하이드로 무수 프탈산, 헥사하이드로 무수 프탈산, 4-메틸헥사하이드로 무수 프탈산, 엔도메틸렌테트라하이드로 무수 프탈산, 무수 클로렌드산, 무수 트리멜리트산, 무수 피로멜리트산, 벤조페논테트라카르복실산 2 무수물, 비페닐테트라카르복실산 2 무수물, 무수 이타콘산 등을 들 수 있다.Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and itaconic anhydride can be mentioned.
또한 카르복실기 함유 에폭시아크릴레이트 수지의 합성시에, 필요에 따라, 무수 트리멜리트산 등의 트리카르복실산 무수물을 사용하고, 반응 후에 남은 산 무수물기를 가수분해함으로써, 카르복실기를 늘릴 수 있다. 또, 에틸렌성 불포화기 함유의 무수 말레산을 사용하여, 더욱 에틸렌성 이중 결합을 늘릴 수도 있다.Additionally, when synthesizing a carboxyl group-containing epoxy acrylate resin, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride can be used and the acid anhydride group remaining after the reaction can be hydrolyzed to increase the carboxyl group. Additionally, the ethylenic double bond can be further increased by using maleic anhydride containing an ethylenically unsaturated group.
상기 (c) 알칼리 가용성 수지의 산가는, 20 내지 300 ㎎KOH/g 인 것이 바람직하고, 40 내지 180 ㎎KOH/g 인 것이 더욱 바람직하다. 산가가 20 ㎎KOH/g 보다 적은 경우, 알칼리 수용액에 대한 용해성이 부족하기 때문에, 미노광부의 현상이 곤란해지기 때문에 바람직하지 않다. 또, 산가가 300 ㎎KOH/g 보다 많은 경우, 현상시에 노광부도 기재로부터 탈리되기 쉬운 경향이 있기 때문에 바람직하지 않다.The acid value of the alkali-soluble resin (c) is preferably 20 to 300 mgKOH/g, and more preferably 40 to 180 mgKOH/g. When the acid value is less than 20 mgKOH/g, it is not preferable because the solubility in aqueous alkaline solution is insufficient and development of unexposed areas becomes difficult. Additionally, if the acid value is more than 300 mgKOH/g, the exposed portion tends to be easily detached from the substrate during development, which is not preferable.
상기 (c) 알칼리 가용성 수지의 중량 평균 분자량은, 1,000 내지 100,000 인 것이 바람직하고, 1,500 내지 30,000 인 것이 바람직하다. 중량 평균 분자량이 1,000 보다 작은 경우, 노광부의 내열성이나 경도 등이 부족하기 때문에, 바람직하지 않다. 중량 평균 분자량이 100,000 보다 큰 경우에는, 미노광부의 현상이 곤란해지는 경우가 있기 때문에, 바람직하지 않다. 또한, 상기 중량 평균 분자량은, 겔 침투 크로마토그래피 (GPC) 법에 의해 측정할 수 있다. 일례로서, GPC 장치로서 HLC-8220GPC (토소사 제조), 칼럼으로서 3 개의 TSKgelHZM-M (토소사 제조) 을 사용하고, 전개 용매로서 테트라하이드로푸란, 칼럼 온도 40 ℃, 유속 0.3 밀리리터/분, RI 검출기, 시료 주입 농도 0.5 질량%, 주입량 10 마이크로리터의 조건 하, 크로마토그래피를 실시하여, 폴리스티렌 환산의 중량 평균 분자량으로서 구할 수 있다.The weight average molecular weight of the alkali-soluble resin (c) is preferably 1,000 to 100,000, and preferably 1,500 to 30,000. If the weight average molecular weight is less than 1,000, it is not preferable because the heat resistance and hardness of the exposed area are insufficient. When the weight average molecular weight is greater than 100,000, it is not preferable because development of unexposed areas may become difficult. Additionally, the weight average molecular weight can be measured by gel permeation chromatography (GPC). As an example, HLC-8220GPC (manufactured by Tosoh Corporation) was used as a GPC device, three TSKgelHZM-M (manufactured by Tosoh Corporation) were used as columns, tetrahydrofuran was used as a developing solvent, column temperature was 40°C, flow rate was 0.3 milliliter/min, RI Chromatography can be performed under the conditions of a detector, a sample injection concentration of 0.5% by mass, and an injection amount of 10 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.
또, (c) 알칼리 가용성 수지의 비율은, 중합성 조성물의 전체 고형분 중, 10 내지 70 질량% 인 것이 바람직하고, 15 내지 60 질량% 인 것이 보다 바람직하다. 상기 비율이 10 질량% 보다 적은 경우, 현상성이 부족하기 때문에, 바람직하지 않다. 상기 비율이 70 질량% 보다 많은 경우, 패턴 형상의 재현성이나 내열성이 저하되기 때문에, 바람직하지 않다.Moreover, the proportion of (c) alkali-soluble resin is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, based on the total solid content of the polymerizable composition. When the above ratio is less than 10% by mass, developability is insufficient, so it is not preferable. When the above ratio is more than 70% by mass, the reproducibility of the pattern shape and heat resistance decrease, so it is not preferable.
또한, 상기 (c) 알칼리 가용성 수지는, 합성 반응 후에 유효 성분인 알칼리 가용성 수지를 단리 정제한 것을 사용할 수 있는 것 외에, 합성 반응에 의해 얻어진 반응 용액, 그 건조물 등을 그대로 사용할 수도 있다.In addition, the alkali-soluble resin (c) above can be obtained by isolating and purifying the alkali-soluble resin, which is an active ingredient, after the synthesis reaction. In addition, the reaction solution obtained through the synthesis reaction, its dried product, etc. can also be used as is.
<그 밖의 성분><Other ingredients>
상기 그 밖의 성분으로서, 경화 촉진제를 사용함으로써, 중합성 조성물의 가열에 의한 경화를 저온에서 실시할 수도 있다. 경화 촉진제로는, 예를 들어, 아민 화합물, 티오우레아 화합물, 2-메르캅토벤즈이미다졸계 화합물, 오르토벤조익술피미드, 제 4 주기 천이 금속 화합물 등을 사용할 수 있다. 경화 촉진제는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.By using a curing accelerator as the other component, the polymerizable composition can be cured by heating at a low temperature. As the curing accelerator, for example, amine compounds, thiourea compounds, 2-mercaptobenzimidazole-based compounds, orthobenzoixulfimide, fourth-period transition metal compounds, etc. can be used. A hardening accelerator may be used individually, or two or more types may be used together.
상기 아민 화합물로는, 제 3 급 아민이 바람직하고, 예를 들어, N,N-디메틸아닐린, N,N-디메틸톨루이딘, N,N-디에틸아닐린, N,N-비스(2-하이드록시에틸)-p-톨루이딘, 4-(디메틸아미노)벤조산에틸, 4-디메틸아미노벤조산(2-메타크릴로일옥시)에틸 등을 들 수 있다.The amine compound is preferably a tertiary amine, for example, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-bis(2-hydroxy Ethyl)-p-toluidine, 4-(dimethylamino)ethyl benzoate, 4-dimethylaminobenzoate (2-methacryloyloxy)ethyl, etc. are mentioned.
상기 티오우레아로는, 예를 들어, 아세틸티오우레아, N,N'디부틸티오우레아 등을 들 수 있다.Examples of the thiourea include acetylthiourea, N,N'dibutylthiourea, and the like.
상기 2-메르캅토벤즈이미다졸계 화합물로는, 예를 들어, 2-메르캅토벤즈이미다졸, 2-메르캅토메틸벤즈이미다졸, 2-메르캅토메톡시벤즈이미다졸 등을 들 수 있다.Examples of the 2-mercaptobenzimidazole-based compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and 2-mercaptomethoxybenzimidazole.
상기 제 4 주기 천이 금속 화합물로는, 바나듐, 코발트, 구리 등의 유기산염 또는 금속 킬레이트 화합물에서 선택할 수 있고, 예를 들어, 옥틸산코발트, 나프텐산코발트, 나프텐산구리, 나프텐산바나듐, 구리아세틸아세토네이트, 망간아세틸아세토네이트, 바나딜아세틸아세토네이트 등을 들 수 있다.The fourth period transition metal compound may be selected from organic acid salts or metal chelate compounds such as vanadium, cobalt, and copper, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, and copper acetyl. Acetonate, manganese acetylacetonate, vanadyl acetylacetonate, etc. can be mentioned.
상기 경화 촉진제는, 중합성 조성물을 사용하기 직전에 배합하는 것이 바람직하다. 경화 촉진제의 함유량은, (b) 라디칼 중합성 화합물 100 질량부에 대하여, 0.1 내지 20 질량부인 것이 바람직하고, 0.2 내지 10 질량부인 것이 보다 바람직하다.The curing accelerator is preferably mixed immediately before using the polymerizable composition. The content of the curing accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b).
상기 그 밖의 성분으로서, 중합성 조성물에는, 코팅제나 도료, 인쇄 잉크, 감광성 인쇄판, 접착제, 컬러 레지스트나 블랙 레지스트 등의 각종 포토레지스트 등의 용도로 일반적으로 사용되고 있는 첨가제를 배합할 수 있다. 첨가제로는, 예를 들어, 증감제 (이소프로필티오크산톤, 디에틸티오크산톤, 4,4'-비스(디에틸아미노)벤조페논, 9,10-디부톡시안트라센, 쿠마린, 케토쿠마린, 아크리딘 오렌지, 캄파퀴논 등), 중합 금지제 (p-메톡시페놀, 하이드로퀴논, 2,6-디-t-부틸-4-메틸페놀, 페노티아진 등), 자외선 흡수제, 적외선 흡수제, 연쇄 이동제, 광 안정제, 산화 방지제, 레벨링제, 표면 조정제, 계면 활성제, 증점제, 소포제, 접착 촉진제, 가소제, 에폭시 화합물, 티올 화합물, 에틸렌성 불포화 결합을 갖는 수지, 포화 수지, 착색 염료, 형광 염료, 안료 (유기 안료, 무기 안료), 탄소계 재료 (탄소 섬유, 카본 블랙, 흑연, 흑연화 카본 블랙, 활성탄, 카본 나노 튜브, 플러렌, 그래핀, 카본 마이크로 코일, 카본 나노 혼, 카본 에어로겔 등), 금속 산화물 (산화티탄, 산화이리듐, 산화아연, 알루미나, 실리카 등), 금속 (은, 구리 등), 무기 화합물 (유리 분말, 층상 점도 광물, 마이카, 탤크, 탄산칼슘 등), 분산제, 난연제 등을 들 수 있다. 첨가제는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.As the other components mentioned above, the polymerizable composition can be blended with additives that are generally used for applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, and various photoresists such as color resists and black resists. Additives include, for example, sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin) , acridine orange, camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorber, infrared absorber , chain transfer agents, light stabilizers, antioxidants, leveling agents, surface conditioners, surfactants, thickeners, anti-foaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, colored dyes, fluorescent dyes. , pigments (organic pigments, inorganic pigments), carbon-based materials (carbon fiber, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoil, carbon nanohorn, carbon airgel, etc.) , metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, layered viscosity minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants, etc. can be mentioned. Additives may be used individually or two or more types may be used in combination.
상기 첨가제의 함유량은, 사용 목적에 따라 적절히 선택되고, 특별히 제한되는 것은 아니지만, 통상, (b) 라디칼 중합성 화합물 100 질량부에 대하여, 500 질량부 이하인 것이 바람직하고, 100 질량부 이하인 것이 보다 바람직하다.The content of the additive is appropriately selected depending on the purpose of use and is not particularly limited, but is usually preferably 500 parts by mass or less, and more preferably 100 parts by mass or less, with respect to 100 parts by mass of the radically polymerizable compound (b). do.
상기 중합성 조성물에는, 점도나 도장성, 경화막의 평활성의 개량을 위해, 추가로 용매를 첨가할 수도 있다. 용매는, 상기 (a) 중합 개시제, 상기 (b) 라디칼 중합성 화합물, 상기 (c) 알칼리 가용성 수지, 상기 그 밖의 성분을, 용해 또는 분산시킬 수 있는 것이고, 건조 온도에 있어서 휘발되는 용매이면, 특별히 제한되는 것은 아니다.A solvent may be further added to the polymerizable composition to improve viscosity, paintability, and smoothness of the cured film. The solvent is capable of dissolving or dispersing the (a) polymerization initiator, (b) the radically polymerizable compound, (c) the alkali-soluble resin, and the other components, and is a solvent that volatilizes at a drying temperature, There is no particular limitation.
상기 용매로는, 예를 들어, 물, 알코올계 용매, 카르비톨계 용매, 에스테르계 용매, 케톤계 용매, 에테르계 용매, 락톤계 용매, 불포화 탄화수소계 용매, 셀로솔브아세테이트계 용매, 카르비톨아세테이트계 용매나 프로필렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜디메틸에테르 등을 들 수 있다. 용매는, 단독으로 사용해도 되고 2 종류 이상을 병용해도 된다.Examples of the solvent include water, alcohol-based solvent, carbitol-based solvent, ester-based solvent, ketone-based solvent, ether-based solvent, lactone-based solvent, unsaturated hydrocarbon-based solvent, cellosolve acetate-based solvent, and carbitol acetate. Examples include solvents such as propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether. Solvents may be used individually or two or more types may be used in combination.
상기 용매의 사용량은, 중합성 조성물의 고형분 100 질량부에 대하여, 10 내지 1000 질량부인 것이 바람직하고, 20 내지 500 질량부인 것이 보다 바람직하다.The amount of the solvent used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of solid content of the polymerizable composition.
<중합성 조성물의 조제 방법><Method for preparing polymerizable composition>
상기 중합성 조성물을 조제하는 경우에는, 수납 용기 내에 상기 (a) 중합 개시제, 상기 (b) 라디칼 중합성 화합물, 필요에 따라, 상기 (c) 알칼리 가용성 수지나 상기 그 밖의 성분을 투입하고, 페인트 쉐이커, 비드 밀, 샌드 그라인드 밀, 볼 밀, 어트리터 밀, 2 본 롤 밀, 3 본 롤 밀 등을 사용하여, 통상적인 방법에 따라 용해 또는 분산시키면 된다. 또, 필요에 따라, 메시 또는 멤브레인 필터 등을 통해서도 여과해도 된다.When preparing the polymerizable composition, the polymerization initiator (a), the radical polymerizable compound (b), and, if necessary, the alkali-soluble resin (c) and the other components are added into a storage container, and then painted. It may be dissolved or dispersed according to a conventional method using a shaker, bead mill, sand grind mill, ball mill, attritor mill, two-bone roll mill, three-bone roll mill, etc. Additionally, if necessary, filtration may be performed through a mesh or membrane filter, etc.
또한, 상기 중합성 조성물의 조제에 있어서, 상기 (a) 중합 개시제는, 중합성 조성물에 최초부터 첨가해 두어도 되지만, 중합성 조성물을 비교적 장시간 보존하는 경우에는, 사용 직전에 (a) 중합 개시제를 (b) 라디칼 중합성 화합물을 포함하는 조성물 중에 용해 또는 분산시키는 것이 바람직하다.In addition, in the preparation of the polymerizable composition, the polymerization initiator (a) may be added to the polymerizable composition from the beginning, but when the polymerizable composition is stored for a relatively long time, the polymerization initiator (a) is added immediately before use. (b) It is preferable to dissolve or disperse in a composition containing a radically polymerizable compound.
<경화물의 제조 방법><Method for producing hardened product>
본 발명의 경화물은, 상기 중합성 조성물로 형성되는 것이다. 경화물의 제조 방법은, 중합성 조성물을 기판 상에 도포 후, 당해 중합성 조성물을 활성 에너지선으로 조사하는 공정, 및 당해 중합성 조성물을 가열하는 공정 중 어느 공정을 포함하는 제조 방법이다. 또, 상기 활성 에너지선으로 조사하는 공정과 상기 가열하는 공정의 양방을 포함하는 공정을, 듀얼 큐어 공정이라고도 한다.The cured product of the present invention is formed from the polymerizable composition. The method for producing a cured product is a production method that includes any of the steps of applying the polymerizable composition to a substrate and then irradiating the polymerizable composition with active energy rays and heating the polymerizable composition. Additionally, a process including both the step of irradiating with the active energy ray and the step of heating is also called a dual cure process.
상기 도포 방법으로는, 예를 들어, 스핀 코트법, 바 코트법, 스프레이 코트법, 딥 코트법, 플로우 코트법, 슬릿 코트법, 닥터 블레이드 코트법, 그라비아 코트법, 스크린 인쇄법, 오프셋 인쇄법, 잉크젯 인쇄법, 디스펜서 인쇄법 등의 여러 가지 방법을 들 수 있다. 또, 상기 기판은, 예를 들어, 유리, 실리콘 웨이퍼, 금속, 플라스틱 등의 필름이나 시트, 및 입체 형상의 성형품 등을 들 수 있고, 기판의 형상이 제한되는 일은 없다.Examples of the application method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, and offset printing. , inkjet printing, and dispenser printing. Additionally, the substrate may be, for example, a film or sheet made of glass, silicon wafer, metal, or plastic, or a three-dimensional molded product, and the shape of the substrate is not limited.
상기의 중합성 조성물을 활성 에너지선으로 조사하는 공정은, 전자선, 자외선, 가시광선, 방사선 등의 활성 에너지선의 조사에 의해, (a) 중합 개시제를 분해시키고, (b) 라디칼 중합성 화합물을 중합시킴으로써, 경화물을 얻을 수 있는 것이다.The step of irradiating the polymerizable composition with active energy rays includes (a) decomposing the polymerization initiator and (b) polymerizing the radically polymerizable compound by irradiating the polymerizable composition with active energy rays such as electron beams, ultraviolet rays, visible rays, and radiation. By doing so, a cured product can be obtained.
활성 에너지선은, 활성 에너지선의 파장이 250 내지 450 nm 의 광인 것이 바람직하고, 경화를 신속하게 실시할 수 있는 관점에서, 350 내지 410 nm 의 광인 것이 보다 바람직하다.The active energy ray is preferably light with a wavelength of 250 to 450 nm, and more preferably 350 to 410 nm from the viewpoint of rapid curing.
상기 광의 조사의 광원으로는, 저압 수은 램프, 고압 수은 램프, 초고압 수은 램프, 메탈 할라이드 램프, 자외선 무전극 램프, 발광 다이오드 (LED), 크세논 아크 램프, 카본 아크 램프, 태양광, YAG 레이저 등의 고체 레이저, 반도체 레이저, 아르곤 레이저 등의 가스 레이저 등을 사용할 수 있다. 또한, (a) 중합 개시제의 흡수가 적은 가시광으로부터 적외광의 광을 사용하는 경우에는, 상기 첨가제로서, 그 광을 흡수하는 증감제를 사용함으로써 경화를 실시할 수 있다.Light sources for the irradiation of the light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet electrodeless lamps, light-emitting diodes (LEDs), xenon arc lamps, carbon arc lamps, sunlight, YAG lasers, etc. Solid-state lasers, semiconductor lasers, gas lasers such as argon lasers, etc. can be used. In addition, (a) when using light from visible light to infrared light, which is less absorbed by the polymerization initiator, curing can be performed by using a sensitizer that absorbs the light as the additive.
상기 활성 에너지선의 노광량은, 활성 에너지선의 파장이나 강도, 중합성 조성물의 조성에 따라 적절히 설정해야 한다. 일례로서, UV-A 영역에서의 노광량은, 10 내지 5,000 mJ/cm2 인 것이 바람직하고, 30 내지 1,000 mJ/cm2 인 것이 보다 바람직하다. 또한, 상기의 경화물의 제조 방법으로서, 듀얼 큐어 공정을 적용하고, 또한 상기 활성 에너지선으로 조사하는 공정 후에, 가열하는 공정을 실시하는 경우, (a) 중합 개시제가 활성 에너지선에 의해 완전히 분해되어 버리지 않게, 노광량을 적절히 설정해야 한다.The exposure amount of the active energy ray must be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably 10 to 5,000 mJ/cm 2 , and more preferably 30 to 1,000 mJ/cm 2 . In addition, as a method for producing the cured product described above, when a dual cure process is applied and a heating process is performed after the process of irradiating with active energy rays, (a) the polymerization initiator is completely decomposed by the active energy rays, To avoid wasting it, the exposure amount must be set appropriately.
상기의 중합성 조성물을 가열하는 공정은, 열에 의해 (a) 중합 개시제를 분해시키고, (b) 라디칼 중합성 화합물을 중합시킴으로써, 경화물을 얻을 수 있는 것이다.In the step of heating the polymerizable composition described above, a cured product can be obtained by (a) decomposing the polymerization initiator and (b) polymerizing the radically polymerizable compound by heat.
상기 중합성 조성물을 가열하는 공정에 있어서, 가열하는 수법은, 예를 들어, 가열, 통풍 가열 등을 들 수 있다. 가열의 방식으로는, 특별히 제한되지 않지만, 예를 들어, 오븐, 핫 플레이트, 적외선 조사, 전자파 조사 등을 들 수 있다. 또, 통풍 가열의 방식으로는, 예를 들어, 송풍식 건조 오븐 등을 들 수 있다.In the step of heating the polymerizable composition, examples of heating methods include heating, ventilation heating, and the like. The heating method is not particularly limited, and examples include oven, hot plate, infrared irradiation, and electromagnetic wave irradiation. In addition, examples of ventilation heating methods include a blowing drying oven and the like.
상기 중합성 조성물을 가열하는 공정에 있어서, 가열 온도는 높을수록, (a) 중합 개시제의 분해 속도는 가속된다. 그러나, 분해 속도가 지나치게 빠르면, (b) 라디칼 중합성 화합물의 분해 잔류물이 많아지는 경우를 갖는다. 한편, 가열 온도는 낮을수록, (a) 중합 개시제의 분해 속도는 느리기 때문에, 경화에 장시간을 필요로 한다. 따라서, 가열 온도와 가열 시간은, 상기 중합성 조성물의 조성에 의해 적절히 설정해야 한다. 일례로서, 가열 온도는, 50 내지 230 ℃ 인 것이 바람직하고, 100 내지 160 ℃ 인 것이 보다 바람직하다. 또, 상기 중합성 조성물에, 상기 경화 촉진제를 배합하는 경우에는, 그 종류나 배합량에 의해, 가열 온도는 실온 내지 160 ℃ 에서 임의로 조정할 수 있다. 한편, 가열 시간은 1 내지 180 분인 것이 바람직하고, 5 내지 120 분인 것이 더욱 바람직하다.In the process of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of (a) the polymerization initiator. However, if the decomposition rate is too fast, the decomposition residue of the (b) radically polymerizable compound may increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of the polymerization initiator (a), so curing requires a longer time. Therefore, the heating temperature and heating time must be appropriately set depending on the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230°C, and more preferably 100 to 160°C. In addition, when blending the curing accelerator in the polymerizable composition, the heating temperature can be arbitrarily adjusted from room temperature to 160°C depending on the type or blending amount. Meanwhile, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.
상기 경화물의 제조 방법으로서, 상기 듀얼 큐어 공정을 적용하는 경우, 특히, 중합성 조성물을 활성 에너지선으로 조사하는 공정 후에, 가열하는 공정을 실시하는 것이, 광을 흡수나 산란하는 착색 안료를 고농도로 포함하는 중합 조성물의 도막의 심부나, 광이 차광되어 광이 닿지 않는 지점의 경화를 효율적으로 실시할 수 있기 때문에, 바람직하다.As a method for producing the cured product, when applying the dual cure process, in particular, a heating process is performed after the process of irradiating the polymerizable composition with active energy rays to increase the coloring pigment that absorbs or scatters light at a high concentration. This is preferable because curing can be carried out efficiently in the deep part of the coating film of the polymer composition containing it or in points where light does not reach due to shading.
또, 상기 중합 조성물에 상기 용매를 포함하는 경우, 상기 경화물의 제조 방법은, 건조 공정을 포함할 수 있다. 특히, 중합성 조성물을 기판 상에 도포 후에, 계속해서, 상기 활성 에너지선으로 조사하는 공정을 적용하는 경우, 당해 활성 에너지선으로 조사하는 공정 전에, 건조 공정을 형성하는 것이 바람직하다.In addition, when the polymer composition includes the solvent, the method for producing the cured product may include a drying process. In particular, when applying the step of applying the polymerizable composition to a substrate and subsequently irradiating it with the active energy ray, it is preferable to provide a drying step before the step of irradiating the polymerizable composition with the active energy ray.
상기 건조 공정에 있어서, 용매를 건조시키는 수법은, 예를 들어, 가열 건조, 통풍 가열 건조, 감압 건조 등을 들 수 있다. 가열 건조의 방식으로는, 특별히 제한되지 않지만, 예를 들어, 오븐, 핫 플레이트, 적외선 조사, 전자파 조사 등을 들 수 있다. 또, 통풍 가열 건조의 방식으로는, 예를 들어, 송풍식 건조 오븐 등을 들 수 있다.In the drying process, examples of methods for drying the solvent include heat drying, ventilation heat drying, and reduced pressure drying. The method of heat drying is not particularly limited, and examples include oven, hot plate, infrared irradiation, and electromagnetic wave irradiation. Moreover, as a method of ventilation heating drying, a ventilation type drying oven etc. are mentioned, for example.
또, 상기 건조 공정에 있어서, 중합성 조성물의 온도는, 용매의 증발 잠열에 의해, 건조의 설정 온도보다 낮아지기 때문에, 중합성 조성물이 겔화될 때까지의 시간을 길게 확보할 수 있다. 이 겔화될 때까지의 시간은, 건조 수법이나 막두께 등에도 영향을 미치기 때문에, 용매의 선정을 포함하여 건조 온도와 시간은 적절히 설정해야 한다. 일례로서, 건조 온도는, 20 내지 120 ℃ 인 것이 바람직하고, 40 내지 100 ℃ 인 것이 보다 바람직하다. 건조 시간은 1 내지 60 분인 것이 바람직하고, 1 내지 30 분인 것이 보다 바람직하다. 또, 상기 중합 금지제를 사용함으로써, 겔화까지의 시간을 길게 확보할 수도 있다. 또한, 상기 트리아진퍼옥사이드 유도체는 열에 의해 분해되지만, 80 ℃ 에서 5 분 가열했을 때의 당해 화합물의 분해율은 0.1 % 정도이기 때문에, 이 정도의 조건이면 중합성 조성물이 증점이나 겔화되는 일은 그다지 없다.In addition, in the drying process, the temperature of the polymerizable composition is lowered than the set temperature for drying due to the latent heat of evaporation of the solvent, so a long time until the polymerizable composition gels can be ensured. Since the time until gelation also affects the drying method and film thickness, the drying temperature and time, including the selection of solvent, must be set appropriately. As an example, the drying temperature is preferably 20 to 120°C, and more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. Additionally, by using the polymerization inhibitor, a longer time until gelation can be ensured. In addition, the triazine peroxide derivative is decomposed by heat, but the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%, so under these conditions, the polymerizable composition is unlikely to thicken or gel. .
상기 중합성 조성물의 건조 막두께 (경화물의 막두께) 는, 용도에 따라 적절히 설정되지만, 0.05 내지 300 ㎛ 인 것이 바람직하고, 0.1 내지 100 ㎛ 인 것이 보다 바람직하다.The dry film thickness (film thickness of the cured product) of the polymerizable composition is appropriately set depending on the application, but is preferably 0.05 to 300 μm, and more preferably 0.1 to 100 μm.
<패턴 형성 방법><Pattern formation method>
상기 중합성 조성물이 (c) 알칼리 가용성 수지를 포함하는 경우, 포토리소그래피법에 의해 패턴을 형성할 수 있다. 전술과 동일하게 하여 중합성 조성물을 기재에 도포하고, 필요에 따라, 건조시켜 건조 피막을 형성한다. 그리고, 건조 피막에 마스크를 개재하여 활성 에너지선을 조사함으로써, 노광부에서는 (b) 라디칼 중합성 화합물이 중합함으로써 경화막이 된다. 한편, 레이저를 사용한 직접 묘화에 의해, 마스크를 개재하지 않고 고정밀한 패턴 형상을 제조할 수도 있다.When the polymerizable composition includes (c) an alkali-soluble resin, a pattern can be formed by photolithography. In the same manner as above, the polymerizable composition is applied to the substrate and, if necessary, dried to form a dry film. Then, by irradiating the dried film with active energy rays through a mask, the radically polymerizable compound (b) polymerizes in the exposed area to form a cured film. On the other hand, a high-precision pattern shape can also be manufactured without a mask through direct drawing using a laser.
상기의 노광 후, 미노광부는, 예를 들어, 0.3 에서 3 질량% 의 탄산나트륨 수용액 등의 알칼리 현상액에 의해 현상 제거되고, 패턴화된 경화막이 얻어진다. 또한 경화막과 기재의 밀착성을 높이는 것 등을 목적으로, 후건조로서 180 내지 250 ℃, 20 내지 90 분에서의 포스트베이크가 실시된다. 이와 같이 하여, 경화막에 기초하는 원하는 패턴이 형성된다.After the above exposure, the unexposed portion is developed and removed with an alkaline developer such as a 0.3 to 3% by mass aqueous sodium carbonate solution, and a patterned cured film is obtained. Additionally, for the purpose of improving the adhesion between the cured film and the substrate, post-drying is performed at 180 to 250°C for 20 to 90 minutes. In this way, the desired pattern based on the cured film is formed.
본 발명의 중합성 조성물은, 하드 코트제, 광 디스크용 코트제, 광 파이버용 코트제, 모바일 단말용 도료, 가전용 도료, 화장품 용기용 도료, 광학 소자용 내면 반사 방지 도료, 고·저굴절률 코트제, 차열 코트제, 방열 코트제, 방담제 등의 도료·코팅제 ; 오프셋 인쇄 잉크, 그라비아 인쇄 잉크, 스크린 인쇄 잉크, 잉크젯 인쇄 잉크, 도전성 잉크, 절연성 잉크, 도광판용 잉크 등의 인쇄 잉크 ; 감광성 인쇄판 ; 나노 임프린트 재료 ; 3D 프린터용 수지 ; 홀로그래피 기록 재료 ; 치과용 재료 ; 도파로용 재료 ; 렌즈 시트용 블랙 스트라이프 ; 콘덴서용 그린 시트 및 전극 재료 ; FPD 용 접착제, HDD 용 접착제, 광 픽업용 접착제, 이미지 센서용 접착제, 유기 EL 용 시일제, 터치 패널용 OCA, 터치 패널용 OCR 등의 접착제·시일제 ; 컬러 레지스트, 블랙 레지스트, 컬러 필터용 보호막, 포토 스페이서, 블랙 칼럼 스페이서, 프레임 레지스트, TFT 배선용 포토레지스트, 층간 절연막 등의 FPD 용 레지스트 ; 액상 솔더 레지스트, 드라이 필름 레지스트 등의 프린트 기판용 레지스트 ; 반도체 레지스트, 버퍼 코트막 등의 반도체용 재료 등의 각종 용도에 사용할 수 있고, 그 용도에 특별히 제한은 없다.The polymerizable composition of the present invention is a hard coat agent, a coating agent for optical disks, a coating agent for optical fibers, a paint for mobile terminals, a paint for home appliances, a paint for cosmetic containers, an inner anti-reflection paint for optical elements, and a high/low refractive index. Paints and coating agents such as coating agents, heat-insulating coating agents, heat-dissipating coating agents, and anti-fog agents; Printing inks such as offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, conductive ink, insulating ink, and light guide plate ink; photosensitive printing plate; nano imprint material; Resin for 3D printers; Holographic recording material; Dental materials; Materials for waveguides; Black stripe for lens seat; Green sheets and electrode materials for condensers; Adhesives and sealants such as adhesives for FPDs, adhesives for HDDs, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch panels, and OCR for touch panels; Resists for FPD, such as color resist, black resist, protective film for color filters, photo spacer, black column spacer, frame resist, photoresist for TFT wiring, and interlayer insulation film; Resists for printed circuit boards, such as liquid solder resist and dry film resist; It can be used for various purposes such as semiconductor materials such as semiconductor resists and buffer coat films, and there are no particular restrictions on its use.
실시예Example
<합성예 1-8><Synthesis Example 1-8>
(1) 트리아진퍼옥사이드 유도체의 합성(1) Synthesis of triazine peroxide derivatives
[합성예 1 : 화합물 19 의 합성][Synthesis Example 1: Synthesis of Compound 19]
100 mL 가지형 플라스크에 디페닐술파이드 3.03 g (16.3 mmol), 탈수 디클로로메탄 30 mL 를 첨가하고, 0 ℃ 까지 냉각하였다. 여기에 염화시아누르 3.00 g (16.3 mmol) 을 첨가한 후, 염화알루미늄 2.39 g (17.9 mmol) 을 10 분에 걸쳐 첨가하고, 0 ℃ 에서 3 시간 반응시켰다. 반응 종료 후, 반응액을 빙랭 1 M 염산 50 mL 에 부어 교반하고, 수상을 분액하였다. 유상을 포화 식염수 50 mL 로 세정하고, 무수 황산나트륨으로 탈수하였다. 여과 후, 감압 농축하여, 조체 (粗體) 를 얻었다. 조체를 실리카겔 칼럼 크로마토그래피 (n-헥산/아세트산에틸 = 4/1 내지 2/1) 로 정제하여, 5.03 g (수율 92.6 %) 의 2,4-디클로로-6-(4-페닐티오-1-페닐)-1,3,5-트리아진을 얻었다.3.03 g (16.3 mmol) of diphenyl sulfide and 30 mL of dehydrated dichloromethane were added to a 100 mL eggplant flask, and cooled to 0°C. After adding 3.00 g (16.3 mmol) of cyanuric chloride, 2.39 g (17.9 mmol) of aluminum chloride was added over 10 minutes, and reaction was performed at 0°C for 3 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure to obtain a crude body. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 4/1 to 2/1) to obtain 5.03 g (yield 92.6%) of 2,4-dichloro-6-(4-phenylthio-1- Phenyl)-1,3,5-triazine was obtained.
100 mL 가지형 플라스크에 2,4-디클로로-6-(4-페닐티오-1-페닐)-1,3,5-트라이아진 3.00 g (8.98 mmol), 메틸에틸케톤 30 mL 를 첨가하고, 40 ℃ 로 가온시켰다. 이온 교환수 4.67 g, 25 질량% 수산화나트륨 수용액 4.31 g (26.9 mmol) 을 첨가한 후, 메탄올 0.32 g (9.87 mmol) 을 10 분에 걸쳐 적하하고, 40 ℃ 에서 2 시간 반응시켰다. 40 ℃ 이하에서 69 질량% tert-부틸하이드로퍼옥사이드 수용액 1.29 g (9.87 mmol) 을 10 분에 걸쳐 적하하고, 40 ℃ 에서 1 시간 반응시켰다. 반응 종료 후, 수상을 분액하고, 유상을 얼음물 50 mL 에 투입하였다. 석출한 결정을 여과하고, 이온 교환수로 세정하고, 감압 하에서 건조시켜, 2.60 g (수율 75.5 %) 으로 본 발명의 화합물 19 를 얻었다. 얻어진 화합물 19 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Add 3.00 g (8.98 mmol) of 2,4-dichloro-6-(4-phenylthio-1-phenyl)-1,3,5-triazine and 30 mL of methyl ethyl ketone to a 100 mL eggplant flask, and add 40 mL of methyl ethyl ketone. Warmed to ℃. After adding 4.67 g of ion-exchanged water and 4.31 g (26.9 mmol) of 25% by mass aqueous sodium hydroxide solution, 0.32 g (9.87 mmol) of methanol was added dropwise over 10 minutes, and reaction was performed at 40°C for 2 hours. 1.29 g (9.87 mmol) of a 69% by mass tert-butylhydroperoxide aqueous solution was added dropwise over 10 minutes at 40°C or lower, and reacted at 40°C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 2.60 g (yield 75.5%) of Compound 19 of the present invention. The results of analysis of the obtained compound 19 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 2 : 화합물 25 의 합성][Synthesis Example 2: Synthesis of Compound 25]
본 발명의 화합물 25 는, 합성예 1 에 기재된 디페닐술파이드를 1-메톡시나프탈렌으로 변경한 것 이외에는, 합성예 1 에 기재된 방법에 준하여 합성하였다. 얻어진 화합물 25 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Compound 25 of the present invention was synthesized according to the method described in Synthesis Example 1, except that the diphenyl sulfide described in Synthesis Example 1 was changed to 1-methoxynaphthalene. The results of analysis of the obtained compound 25 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 3 : 화합물 35 의 합성][Synthesis Example 3: Synthesis of Compound 35]
히트 드라이 건조시킨 100 mL 3 구 플라스크에, 마그네슘 0.44 g (17.1 mmol), 탈수 테트라하이드로푸란 15 mL, 촉매량의 요오드를 넣고, 실온 하에서 교반하였다. 4-브로모-4'-메톡시비페닐 4.29 g (16.3 mmol) 과 탈수 테트라하이드로푸란 15 mL 의 혼합 용액을 적하한 후, 1 시간 환류 교반시켰다. 별도의 100 mL 3 구 플라스크에 염화시아누르 3.00 g (16.3 mmol), 탈수 테트라하이드로푸란 15 mL 를 첨가하고, 0 ℃ 까지 냉각하였다. 여기에, 앞서 조제한 혼합 용액을, 30 분에 걸쳐 적하하고, 실온으로 올려, 15 시간 교반하였다. 반응액을 빙욕으로 냉각하고, 1 M 염산을 첨가하여 교반하고, 포화 탄산수소나트륨 수용액으로 pH 를 8 로 조정하였다. 이어서, 아세트산에틸로 추출하였다. 유상을 포화 식염수로 1 회 세정한 후, 황산마그네슘으로 탈수하였다. 여과 후, 유상을 감압 하에서 농축하여, 조체를 얻었다. 조체를 실리카겔 칼럼 크로마토그래피 (n-헥산/아세트산에틸 = 3/1 내지 1/1) 로 정제하여, 2.07 g (수율 38.2 %) 의 2,4-디클로로-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진을 얻었다.In a heat-dried 100 mL three-necked flask, 0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and stirred at room temperature. A mixed solution of 4.29 g (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and 15 mL of dehydrated tetrahydrofuran was added dropwise, followed by refluxing and stirring for 1 hour. 3.00 g (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added to a separate 100 mL three-necked flask, and cooled to 0°C. The mixed solution prepared previously was added dropwise over 30 minutes, raised to room temperature, and stirred for 15 hours. The reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added, stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. The oil phase was washed once with saturated saline solution and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1), and 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxy) was obtained. Cibiphenyl)]-1,3,5-triazine was obtained.
50 mL 가지형 플라스크에 2,4-디클로로-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진 1.20 g (3.62 mmol), 메틸에틸케톤 10 mL 를 첨가하고, 40 ℃ 로 가온시켰다. 이온 교환수 1.88 g, 25 질량% 수산화나트륨 수용액 1.74 g (10.9 mmol) 을 첨가한 후, 메탄올 0.13 g (3.98 mmol) 을 5 분에 걸쳐 적하하고, 40 ℃ 에서 2 시간 반응시켰다. 40 ℃ 이하에서 69 질량% tert-부틸하이드로퍼옥사이드 수용액 0.52 g (3.98 mmol) 을 5 분에 걸쳐 적하하고, 40 ℃ 에서 1 시간 반응시켰다. 반응 종료 후, 수상을 분액하고, 유상을 얼음물 50 mL 에 투입하였다. 석출한 결정을 여과하고, 이온 교환수로 세정하고, 감압 하에서 건조시켜, 1.04 g (수율 75.0 %) 으로 본 발명의 화합물 35 를 얻었다. 얻어진 화합물 35 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Add 1.20 g (3.62 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine and 10 mL of methyl ethyl ketone to a 50 mL eggplant flask. , warmed to 40°C. After adding 1.88 g of ion-exchanged water and 1.74 g (10.9 mmol) of a 25% by mass aqueous sodium hydroxide solution, 0.13 g (3.98 mmol) of methanol was added dropwise over 5 minutes, and the mixture was allowed to react at 40°C for 2 hours. 0.52 g (3.98 mmol) of a 69% by mass tert-butylhydroperoxide aqueous solution was added dropwise over 5 minutes at 40°C or lower, and reaction was performed at 40°C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 1.04 g (yield 75.0%) of compound 35 of the present invention. The results of analysis of the obtained compound 35 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 4 : 화합물 48 의 합성][Synthesis Example 4: Synthesis of Compound 48]
본 발명의 화합물 48 은, 합성예 3 에 기재된 메탄올을 에탄올로, 및 69 질량% tert-부틸하이드로퍼옥사이드 수용액을 85 질량% tert-아밀하이드로퍼옥사이드 용액으로 변경한 것 이외에는, 합성예 3 에 기재된 방법에 준하여 합성하였다. 얻어진 화합물 48 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Compound 48 of the present invention is the same as described in Synthesis Example 3, except that methanol as described in Synthesis Example 3 is changed to ethanol, and the 69 mass% tert-butylhydroperoxide aqueous solution is changed to an 85 mass% tert-amylhydroperoxide solution. It was synthesized according to the method. The results of analysis of the obtained compound 48 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 5 : 화합물 53 의 합성][Synthesis Example 5: Synthesis of Compound 53]
본 발명의 화합물 53 은, 합성예 3 에 기재된 메탄올을 이소프로필알코올로, 및 69 질량% tert-부틸하이드로퍼옥사이드 수용액을 90 질량% tert-헥실하이드로퍼옥사이드 용액으로 변경한 것 이외에는, 합성예 3 에 기재된 방법에 준하여 합성하였다. 얻어진 화합물 53 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Compound 53 of the present invention was prepared according to Synthesis Example 3, except that methanol as described in Synthesis Example 3 was changed to isopropyl alcohol, and the 69 mass% tert-butylhydroperoxide aqueous solution was changed to a 90 mass% tert-hexylhydroperoxide solution. It was synthesized according to the method described in . The results of analysis of the obtained compound 53 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 6 : 화합물 56 의 합성][Synthesis Example 6: Synthesis of Compound 56]
본 발명의 화합물 6 은, 합성예 3 에 기재된 메탄올을 tert-부틸알코올로, 및 69 질량% tert-부틸하이드로퍼옥사이드 수용액을 80 질량% 쿠멘하이드로퍼옥사이드 용액으로 변경한 것 이외에는, 합성예 3 에 기재된 방법에 준하여 합성하였다. 얻어진 화합물 56 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.Compound 6 of the present invention was prepared in Synthesis Example 3, except that the methanol described in Synthesis Example 3 was changed to tert-butyl alcohol, and the 69 mass% tert-butylhydroperoxide aqueous solution was changed to 80 mass% cumene hydroperoxide solution. It was synthesized according to the described method. The results of analysis of the obtained compound 56 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 7 : 화합물 77 의 합성][Synthesis Example 7: Synthesis of Compound 77]
히트 드라이 건조시킨 100 mL 3 구 플라스크에, 마그네슘 0.44 g (17.1 mmol), 탈수 테트라하이드로푸란 15 mL, 촉매량의 요오드를 넣고, 실온 하에서 교반하였다. 4-브로모-4'-메톡시비페닐 4.29 g (16.3 mmol) 과 탈수 테트라하이드로푸란 15 mL 의 혼합 용액을 적하한 후, 1 시간 환류 교반시켰다. 별도의 100 mL 3 구 플라스크에 염화시아누르 3.00 g (16.3 mmol), 탈수 테트라하이드로푸란 15 mL 를 첨가하고, 0 ℃ 까지 냉각하였다. 여기에, 앞서 조제한 혼합 용액을, 30 분에 걸쳐 적하하고, 실온으로 올려, 15 시간 교반하였다. 반응액을 빙욕으로 냉각하고, 1 M 염산을 첨가하여 교반하고, 포화 탄산수소나트륨 수용액으로 pH 를 8 로 조정하였다. 이어서, 아세트산에틸로 추출하였다. 유상을 포화 식염수로 1 회 세정한 후, 황산마그네슘으로 탈수하였다. 여과 후, 유상을 감압 하에서 농축하여, 조체를 얻었다. 조체를 실리카겔 칼럼 크로마토그래피 (n-헥산/아세트산에틸 = 3/1 내지 1/1) 로 정제하여, 2.07 g (수율 38.2 %) 의 2,4-디클로로-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진을 얻었다.In a heat-dried 100 mL three-necked flask, 0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and stirred at room temperature. A mixed solution of 4.29 g (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and 15 mL of dehydrated tetrahydrofuran was added dropwise, followed by refluxing and stirring for 1 hour. 3.00 g (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added to a separate 100 mL three-necked flask, and cooled to 0°C. The mixed solution prepared previously was added dropwise over 30 minutes, raised to room temperature, and stirred for 15 hours. The reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added, stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. The oil phase was washed once with saturated saline solution and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1), and 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxy) was obtained. Cibiphenyl)]-1,3,5-triazine was obtained.
100 mL 가지형 플라스크에, 아니솔 3.03 g (16.3 mmol), 탈수 디클로로메탄 30 mL 를 첨가하고, 0 ℃ 까지 냉각하였다. 여기에, 2,4-디클로로-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진 3.00 g (16.3 mmol) 을 첨가한 후, 염화알루미늄 2.39 g (17.9 mmol) 을 10 분에 걸쳐 첨가하고, 0 ℃ 에서 3 시간 반응시켰다. 반응 종료 후, 반응액을 빙랭 1 M 염산 50 mL 에 부어 교반하고, 수상을 분액하였다. 유상을 포화 식염수 50 mL 로 세정하고, 무수 황산나트륨으로 탈수하였다. 여과 후, 감압 농축하여, 조체를 얻었다. 조체를 실리카겔 칼럼 크로마토그래피 (n-헥산/아세트산에틸 = 4/1 내지 2/1) 로 정제하여, 5.03 g (수율 92.6 %) 의 2-클로로-4-(4-메톡시페닐)-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진을 얻었다.In a 100 mL eggplant flask, 3.03 g (16.3 mmol) of anisole and 30 mL of dehydrated dichloromethane were added, and the mixture was cooled to 0°C. Here, 3.00 g (16.3 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine was added, and then 2.39 g (17.9 mmol) of aluminum chloride was added. ) was added over 10 minutes and reacted at 0°C for 3 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, the product was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 4/1 to 2/1) to obtain 5.03 g (yield 92.6%) of 2-chloro-4-(4-methoxyphenyl)-6-. [4-(4'-methoxybiphenyl)]-1,3,5-triazine was obtained.
50 mL 가지형 플라스크에 이온 교환수 1.88 g, 25 질량% 수산화나트륨 수용액 1.74 g (10.9 mmol) 을 첨가하고, 30 ℃ 이하에서 69 질량% tert-부틸하이드로퍼옥사이드 수용액 0.52 g (3.98 mmol) 을 서서히 첨가하였다. 여기에, 2-클로로-4-(4-메톡시페닐)-6-[4-(4'-메톡시비페닐)]-1,3,5-트리아진 1.20 g (3.62 mmol) 과 테트라하이드로푸란 10 mL 의 혼합 용액을 10 ℃ 에서 10 분에 걸쳐 적하하고, 20 ℃ 에서 3 시간 반응시켰다. 반응 종료 후, 디클로로메탄 10 mL 를 첨가하고, 수상을 분액하였다. 유상을 이온 교환수로 세정하고, 0 ℃ 에서 무수 황산마그네슘으로 건조시켰다. 여과 후, 유상을 감압 하에서 농축하여, 1.04 g (수율 75.0 %) 으로 본 발명의 화합물 77 을 얻었다. 얻어진 화합물 77 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.To a 50 mL eggplant-shaped flask, 1.88 g of ion-exchanged water and 1.74 g (10.9 mmol) of a 25 mass% sodium hydroxide aqueous solution were added, and 0.52 g (3.98 mmol) of a 69 mass% tert-butylhydroperoxide aqueous solution was slowly added at 30°C or lower. Added. Here, 1.20 g (3.62 mmol) of 2-chloro-4-(4-methoxyphenyl)-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine and tetrahydrofuran 10 mL of the mixed solution was added dropwise at 10°C over 10 minutes and reacted at 20°C for 3 hours. After completion of the reaction, 10 mL of dichloromethane was added, and the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0°C. After filtration, the oil phase was concentrated under reduced pressure to obtain 1.04 g (yield 75.0%) of compound 77 of the present invention. The results of analysis of the obtained compound 77 by EI-MS and 1 H-NMR are shown in Table 1.
[합성예 8 : 화합물 81 의 합성][Synthesis Example 8: Synthesis of Compound 81]
100 mL 가지형 플라스크에, 염화시아누르 3.00 g (16.3 mmol), 탈수 디클로로메탄 30 mL, 염화알루미늄 4.35 g (32.6 mmol) 을 첨가하고, 20 ℃ 까지 냉각하였다. 여기에, 1-메톡시나프탈렌 5.16 g (32.6 mmol) 을 15 분에 걸쳐 첨가하고, 20 ℃ 에서 3 시간 반응시켰다. 반응 종료 후, 반응액을 0 ℃ 까지 냉각하고, 빙랭 1 M 염산 50 mL 를 첨가하여 교반하고, 수상을 분액하였다. 유상을 포화 식염수 50 mL 로 세정하고, 무수 황산나트륨으로 탈수하였다. 여과 후, 감압 농축하여, 5.48 g (수율 78.6 %) 의 2-클로로-4,6-비스(4-메톡시-1-나프탈레닐)-1,3,5-트리아진의 조체를 얻었다.In a 100 mL eggplant flask, 3.00 g (16.3 mmol) of cyanuric chloride, 30 mL of dehydrated dichloromethane, and 4.35 g (32.6 mmol) of aluminum chloride were added and cooled to 20°C. Here, 5.16 g (32.6 mmol) of 1-methoxynaphthalene was added over 15 minutes, and reaction was performed at 20°C for 3 hours. After completion of the reaction, the reaction solution was cooled to 0°C, 50 mL of ice-cooled 1 M hydrochloric acid was added, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, the product was concentrated under reduced pressure to obtain 5.48 g (78.6% yield) of crude 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine.
100 mL 가지형 플라스크에 2-클로로-4,6-비스(4-메톡시-1-나프탈레닐)-1,3,5-트리아진의 조체 3.00 g (5.45 mmol), 테트라하이드로푸란 30 mL 를 첨가하고, 40 ℃ 로 가온시켰다. 여기에, 20 질량% 수산화나트륨 수용액 2.18 g (10.9 mmol) 과 69 질량% tert-부틸하이드로퍼옥사이드 수용액 1.42 g (10.9 mmol) 의 혼합액을 10 분에 걸쳐 적하하고, 40 ℃ 에서 4 시간 반응시켰다. 반응 종료 후, 디클로로메탄 50 mL 를 첨가하고, 수상을 분액하였다. 유상을 이온 교환수로 세정하고, 0 ℃ 에서 무수 황산마그네슘으로 건조시켰다. 여과 후, 감압 하에서 농축하여, 조체를 얻었다. 조체를 실리카젤 칼럼 크로마토그래피 (디클로로메탄 사용) 로 정제하여, 1.63 g (수율 62.3 %) 으로 본 발명의 화합물 81 을 얻었다. 얻어진 화합물 81 의 EI-MS 및 1H-NMR 에 의한 분석 결과를 표 1 에 나타낸다.3.00 g (5.45 mmol) of crude 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine and 30 mL of tetrahydrofuran in a 100 mL eggplant flask. was added and warmed to 40°C. A mixture of 2.18 g (10.9 mmol) of 20 mass% sodium hydroxide aqueous solution and 1.42 g (10.9 mmol) of 69 mass% tert-butylhydroperoxide aqueous solution was added dropwise over 10 minutes and allowed to react at 40°C for 4 hours. After completion of the reaction, 50 mL of dichloromethane was added, and the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0°C. After filtration, it was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (using dichloromethane) to obtain 1.63 g (yield 62.3%) of compound 81 of the present invention. The results of analysis of the obtained compound 81 by EI-MS and 1 H-NMR are shown in Table 1.
<실시예 1 ∼ 8, 비교예 1><Examples 1 to 8, Comparative Example 1>
<중합성 조성물 (A) 의 조제><Preparation of polymerizable composition (A)>
표 2 에 나타내는 양의 라디칼 중합성 화합물, 알칼리 가용성 수지, 그 밖의 성분을 혼합 교반하고, 중합 개시제를 첨가하여 잘 교반하여, 실시예 1 ∼ 8 및 비교예 1 의 중합성 조성물 (A) 를 조제하였다. 또한, 비교예 1 에는 중합 개시제로서, 하기 식으로 나타내는 화합물 R1 을 사용하였다.The amounts of the radically polymerizable compound, alkali-soluble resin, and other components shown in Table 2 were mixed and stirred, a polymerization initiator was added, and the mixture was stirred well to prepare the polymerizable composition (A) of Examples 1 to 8 and Comparative Example 1. did. In addition, in Comparative Example 1, compound R1 represented by the following formula was used as a polymerization initiator.
[화학식 7][Formula 7]
상기 표 2 및 하기 표 4, 표 6 중, DPHA 는, 디펜타에리스리톨펜타아크릴레이트 및 디펜타에리스리톨헥사아크릴레이트의 혼합물 (상품명 : 아로닉스 M-402, 토아 합성사 제조) ;In Table 2 above and Table 4 and Table 6 below, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (brand name: Aronix M-402, manufactured by Toa Synthetic Company);
RD200 은, 메타크릴산메틸/메타크릴산/시클로헥실말레이미드 (질량% : 61/14/25) 공중합물, 중량 평균 분자량 : 17,000, 산가 : 90 (합성품) ;RD200 is a copolymer of methyl methacrylate/methacrylic acid/cyclohexylmaleimide (mass%: 61/14/25), weight average molecular weight: 17,000, acid value: 90 (synthetic product);
F-477 은, 불소계 레벨링제 (상품명 : 메가팍 F-477, DIC 사 제조) ;F-477 silver, fluorine-based leveling agent (brand name: Megapak F-477, manufactured by DIC);
PGMEA 는, 프로필렌글리콜모노메틸에테르아세테이트 ; 를 나타낸다.PGMEA is propylene glycol monomethyl ether acetate; represents.
(1) 감도의 평가(1) Evaluation of sensitivity
상기에서 조제한 중합성 조성물 (A) 를, 스핀 코터를 사용하여, 알루미늄 기판 상에 도포하였다. 도포 후, 알루미늄 기판을 90 ℃ 의 클린 오븐 중에서 2.5 분간 건조 처리에 의해 용매를 건조시켜, 두께 1.5 ㎛ 의 균일한 도포막을 제조하였다. 이어서, 초고압 수은등을 광원으로 하는 프록시미티 노광기를 사용하여, 마스크 패턴을 개재하여 10 내지 1000 mJ/cm2 의 범위에서, 단계 노광을 실시하였다. 노광 후의 알루미늄 기판을 1.0 질량% 의 탄산나트륨 수용액에 23 ℃ 에서 60 초간 침지하여, 현상에 의한 미노광부의 제거를 실시하였다. 계속해서 순수로 30 초간 세정을 실시하여, 레지스트 패턴을 얻었다. 레지스트 패턴이 형성되는 최저 노광량을 「감도」로서 평가하였다. 최저 노광량의 값이 작을수록, 소량의 광으로 패턴을 형성 가능하고, 200 mJ/cm2 이하는 고감도인 것을 나타낸다. 결과를 표 3 에 나타낸다.The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After application, the aluminum substrate was dried in a clean oven at 90°C for 2.5 minutes to dry the solvent, thereby producing a uniform coating film with a thickness of 1.5 μm. Next, step exposure was performed in the range of 10 to 1000 mJ/cm 2 through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The aluminum substrate after exposure was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The lowest exposure amount at which a resist pattern is formed was evaluated as “sensitivity.” The smaller the value of the minimum exposure amount, the more it is possible to form a pattern with a small amount of light, and 200 mJ/cm 2 or less indicates high sensitivity. The results are shown in Table 3.
(2) 장기 보존 안정성의 평가(2) Evaluation of long-term storage stability
상기에서 조제한 중합성 조성물 (A) 를, 갈색의 유리병 안에 넣고, 알루미늄 호일로 차광시킨 후에, 50 ℃ 로 설정한 정온 항온기 내에 정치하였다. 겔화에 필요한 일수가 60 일 이상을 ○, 60 일 미만을 × 로 하였다. 결과를 표 3 에 나타낸다.The polymerizable composition (A) prepared above was placed in a brown glass bottle, shielded from light with aluminum foil, and left to stand in a constant temperature thermostat set at 50°C. The number of days required for gelation was designated as ○ if it was 60 days or more, and × if it was less than 60 days. The results are shown in Table 3.
<실시예 9 ∼ 16, 비교예 2><Examples 9 to 16, Comparative Example 2>
<중합성 조성물 (B) 의 조제><Preparation of polymerizable composition (B)>
표 4 에 나타내는 양의 라디칼 중합성 화합물, 알칼리 가용성 수지, 흑색 안료, 그 밖의 성분을 혼합 교반하고, 중합 개시제를 첨가하여 잘 교반하여, 실시예 9 ∼ 16 및 비교예 2 의 중합성 조성물 (B) 를 조제하였다. 또한, 비교예 2 에는 중합 개시제로서, 상기 식으로 나타내는 화합물 R1 을 사용하였다.The amounts of the radically polymerizable compound, alkali-soluble resin, black pigment, and other components shown in Table 4 were mixed and stirred, a polymerization initiator was added, and the polymerizable compositions of Examples 9 to 16 and Comparative Example 2 (B) were stirred well. ) was prepared. Additionally, in Comparative Example 2, compound R1 represented by the above formula was used as a polymerization initiator.
상기 표 4 중, TSG-BK133 은, 카본 블랙 분산액 (다이세이 화공사 제조) 을 나타낸다.In Table 4 above, TSG-BK133 represents a carbon black dispersion (manufactured by Taisei Chemical Co., Ltd.).
(3) 해상도의 평가(3) Evaluation of resolution
상기에서 조제한 중합성 조성물 (B) 를, 스핀 코터를 사용하여 유리 기판 상에 도포하였다. 도포 후, 유리 기판을 90 ℃ 의 클린 오븐 중에서 2.5 분간 건조 처리에 의해 용매를 건조시켜, 두께 1.5 ㎛ 의 균일한 도포막을 제조하였다. 이어서, 초고압 수은등을 광원으로 하는 프록시미티 노광기를 사용하여, 마스크 패턴을 개재하여 200 mJ/cm2 노광을 실시하였다. 노광 후의 유리 기판을 1.0 질량% 의 탄산나트륨 수용액에 23 ℃ 에서 60 초간 침지하여, 현상에 의한 미노광부의 제거를 실시하였다. 계속해서 순수로 30 초간 세정을 실시하여, 레지스트 패턴을 얻었다. 얻어진 패턴을 현미경으로 관찰하여, 최소 패턴 치수가 10 ㎛ 이하인 것을 ◎, 10 ㎛ 를 초과하고 20 ㎛ 이하인 것을 ○, 20 ㎛ 를 초과하고 30 ㎛ 이하인 것을 △, 30 ㎛ 를 초과하는 것을 × 로 하였다. 결과를 표 5 에 나타낸다.The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After application, the solvent was dried by drying the glass substrate in a clean oven at 90°C for 2.5 minutes to produce a uniform coating film with a thickness of 1.5 μm. Next, 200 mJ/cm 2 exposure was performed through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The glass substrate after exposure was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The obtained pattern was observed under a microscope, and those with a minimum pattern dimension of 10 ㎛ or less were designated ◎, those with a minimum pattern dimension of more than 10 ㎛ and 20 ㎛ or less as ○, those with a minimum pattern dimension of more than 20 ㎛ and 30 ㎛ or less as △, and those with a minimum pattern dimension of more than 30 ㎛ as ×. The results are shown in Table 5.
<실시예 17 ∼ 24, 비교예 3><Examples 17 to 24, Comparative Example 3>
<중합성 조성물 (C) 의 조제><Preparation of polymerizable composition (C)>
표 6 에 나타내는 양의 라디칼 중합성 화합물, 알칼리 가용성 수지, 녹색 안료, 그 밖의 성분을 혼합 교반하고, 중합 개시제를 첨가하여 잘 교반하여, 실시예 17 ∼ 24 및 비교예 3 의 중합성 조성물 (C) 를 조제하였다. 또한, 비교예 3 에는 중합 개시제로서, 상기 식으로 나타내는 화합물 R1 을 사용하였다.The radically polymerizable compound, alkali-soluble resin, green pigment, and other components in the amounts shown in Table 6 were mixed and stirred, a polymerization initiator was added, and the polymerizable composition (C) of Examples 17 to 24 and Comparative Example 3 was stirred well. ) was prepared. Additionally, in Comparative Example 3, compound R1 represented by the above formula was used as a polymerization initiator.
상기 표 6 중, SG036 은, 녹색 안료 분산액 (다이세이 화공사 제조) 을 나타낸다.In Table 6 above, SG036 represents a green pigment dispersion (manufactured by Taisei Chemical Co., Ltd.).
(4) 언더 컷의 평가(4) Evaluation of undercut
상기에서 조제한 중합성 조성물 (C) 를, 스핀 코터를 사용하여 유리 기판 상에 도포하였다. 도포 후, 유리 기판을 90 ℃ 의 클린 오븐 중에서 2.5 분간 건조 처리에 의해 용매를 건조시켜, 두께 1.5 ㎛ 의 균일한 도포막을 제조하였다. 이어서, 초고압 수은등을 광원으로 하는 프록시미티 노광기를 사용하여, 마스크 패턴을 개재하여 150 mJ/cm2 노광을 실시하였다. 노광 후의 유리 기판을 1.0 질량% 의 탄산나트륨 수용액에 23 ℃ 에서 60 초간 침지하여, 현상에 의한 미노광부의 제거를 실시하였다. 계속해서 순수로 30 초간 세정을 실시하여, 레지스트 패턴을 얻었다. 얻어진 패턴 중, 개구 폭이 15 ㎛ 인 라인상 개구부에 대응하는 패턴의 단면을 현미경으로 관찰하고, 기판 표면에 평행한 패턴 폭 중 최대폭과 최소폭의 차에 의해 라인상 패턴의 언더 컷을 평가하였다. 최대폭과 최소폭의 차가 작을수록 언더 컷이 억제되는 것을 나타내고, 1.5 ㎛ 이하인 것을 ○, 1.5 ㎛ 를 초과하고 2.5 ㎛ 이하인 것을 △, 2.5 ㎛ 를 초과하는 것을 × 로 하였다. 결과를 표 7 에 나타낸다.The polymerizable composition (C) prepared above was applied onto a glass substrate using a spin coater. After application, the solvent was dried by drying the glass substrate in a clean oven at 90°C for 2.5 minutes to produce a uniform coating film with a thickness of 1.5 μm. Next, 150 mJ/cm 2 exposure was performed through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The glass substrate after exposure was immersed in a 1.0% by mass aqueous solution of sodium carbonate at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. Among the obtained patterns, the cross section of the pattern corresponding to the line-shaped opening with an opening width of 15 μm was observed under a microscope, and the undercut of the line-shaped pattern was evaluated by the difference between the maximum and minimum widths among the pattern widths parallel to the substrate surface. . The smaller the difference between the maximum width and the minimum width, the more suppressed the undercut is. 1.5 ㎛ or less was designated as ○, greater than 1.5 ㎛ and 2.5 ㎛ or less was designated as △, and greater than 2.5 ㎛ was designated as ×. The results are shown in Table 7.
<실시예 25 ∼ 32, 비교예 4><Examples 25 to 32, Comparative Example 4>
<중합성 조성물 (D) 의 조제><Preparation of polymerizable composition (D)>
표 8 에 나타내는 양의 라디칼 중합성 화합물, 중합 개시제, 경화 촉진제, 용매를 첨가하여 잘 교반하여, 실시예 25 ∼ 32 및 비교예 4 의 중합성 조성물 (D) 를 조제하였다. 또한, 비교예 4 에는 중합 개시제로서, 상기 식으로 나타내는 화합물 R1 을 사용하였다.The amounts of the radically polymerizable compound, polymerization initiator, curing accelerator, and solvent shown in Table 8 were added and stirred well to prepare the polymerizable composition (D) of Examples 25 to 32 and Comparative Example 4. Additionally, in Comparative Example 4, compound R1 represented by the above formula was used as a polymerization initiator.
(5) 경화성의 평가(5) Evaluation of hardenability
상기에서 조제한 중합성 조성물 (D) 를, 유리 기판 상에 바 코터를 이용하여 두께 100 ㎛ 로 도포하였다. 도포 후 90 ℃ 의 오븐에서 2.5 분간 건조시킨 후, 고압 수은 램프가 설치된 컨베이어식 UV 조사 장치를 사용하여 30 mJ/cm2 의 조사를 실시하였다. 이어서, 150 ℃ 의 오븐 중에서 30 분간 가열하여, 경화막을 얻었다. 얻어진 경화막의 중합 전화율을 측정하고, 경화성을 이하의 기준으로 평가하였다. 또한, 중합 전화율은, 감쇠 전반사 적외 분광법 (ATR-IR) 으로 측정하고, 그 때, 이중 결합기 유래의 흡수 스펙트럼 (810 cm-1) 의 피크 면적 A 및 노광 전후에서 변화가 없는 카르보닐기 유래의 흡수 스펙트럼 (1740 cm-1) 의 피크 면적 B 를 사용하여, 이하의 식에 기초하여 중합 전화율을 산출하였다. 결과를 표 9 에 나타낸다.The polymerizable composition (D) prepared above was applied to a thickness of 100 μm on a glass substrate using a bar coater. After application, it was dried in an oven at 90°C for 2.5 minutes, and then irradiated at 30 mJ/cm 2 using a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp. Next, it was heated in a 150 degreeC oven for 30 minutes, and the cured film was obtained. The polymerization conversion rate of the obtained cured film was measured, and curability was evaluated based on the following standards. In addition, the polymerization conversion rate was measured by attenuated total reflection infrared spectroscopy (ATR-IR), and the peak area A of the absorption spectrum (810 cm -1 ) derived from the double bond group and the absorption spectrum derived from the carbonyl group that did not change before and after exposure were measured. Using the peak area B of (1740 cm -1 ), the polymerization conversion rate was calculated based on the following formula. The results are shown in Table 9.
중합 전화율 = (1-(경화 후의 A/B)/(경화 전의 A/B))×100Polymerization conversion rate = (1-(A/B after curing)/(A/B before curing))×100
○ : 중합 전화율이 80 % 이상○: Polymerization conversion rate is 80% or more
△ : 중합 전화율이 60 % 이상 80 % 미만△: Polymerization conversion ratio is 60% or more and less than 80%
× : 중합 전환율이 60 % 미만×: Polymerization conversion rate is less than 60%
상기 표 8 중, TMPTA 는, 트리메틸올프로판트리아크릴레이트 (신나카무라 화학 공업 제조) ;In Table 8 above, TMPTA is trimethylolpropane triacrylate (manufactured by Shinnakamura Chemical Industry);
PE4A 는, 펜타에리트리톨테트라아크릴레이트 (후지 필름 와코 순약 시약) ; 를 나타낸다.PE4A is pentaerythritol tetraacrylate (Fujifilm Wako Pure Chemical Reagent); represents.
Claims (6)
((일반식 (1) 중, R1 및 R2 는 독립적으로 메틸기 또는 에틸기, R3 은 탄소수 1 ∼ 5 의 지방족 탄화수소기, 또는 알킬기를 가져도 되는 탄소수 6 ∼ 9 의 방향족 탄화수소기를 나타내고, R4 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다. Ar 은 하기 일반식 (2) : Ar1, Ar2, 또는 Ar3 으로 나타내는 아릴기이다.)
(일반식 (2) 중, m 은 0 내지 3 의 정수를 나타내고, R11 은 독립된 치환기로서, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 아실기, -Y-R, 또는 -N-RR’로서, Y 는 산소 원자 또는 황 원자를 나타내고, R 및 R’는 독립적으로 수소 원자, 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기, 치환되어 있어도 되는 탄소수 6 ∼ 20 의 방향족 탄화수소기, 치환되어 있어도 되는 탄소수 2 ∼ 20 의 복소 고리 함유기를 나타낸다.)) 로 나타내는 것을 특징으로 하는 트리아진퍼옥사이드 유도체.General formula (1):
((In General Formula (1), R 1 and R 2 independently represent a methyl group or an ethyl group, R 3 represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R 4 is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar 1 , Ar 2 , or Ar 3 . )
(In General Formula (2), m represents an integer of 0 to 3, and R 11 is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. , an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) ) A triazine peroxide derivative characterized by being represented by .
추가로 (c) 알칼리 가용성 수지를 함유하는 것을 특징으로 하는 중합성 조성물.According to claim 2,
A polymerizable composition further comprising (c) an alkali-soluble resin.
염화시아누르 및/또는 그 유도체와, 하이드로퍼옥사이드를 원료로 하여 반응시키는 공정을 포함하는 것을 특징으로 하는 트리아진퍼옥사이드 유도체의 제조 방법.A method for producing the triazine peroxide derivative according to claim 1, comprising:
A method for producing a triazine peroxide derivative, comprising the step of reacting cyanuric chloride and/or its derivatives with hydroperoxide as a raw material.
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