KR102624940B1 - Fluorine-containing activated energy ray curable compositions and articles - Google Patents
Fluorine-containing activated energy ray curable compositions and articles Download PDFInfo
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- KR102624940B1 KR102624940B1 KR1020207023488A KR20207023488A KR102624940B1 KR 102624940 B1 KR102624940 B1 KR 102624940B1 KR 1020207023488 A KR1020207023488 A KR 1020207023488A KR 20207023488 A KR20207023488 A KR 20207023488A KR 102624940 B1 KR102624940 B1 KR 102624940B1
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- meth
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- acrylic
- fluorine
- compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 89
- 239000011737 fluorine Substances 0.000 title claims abstract description 85
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 83
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 100
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 72
- 125000005647 linker group Chemical group 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 13
- -1 acrylic compound Chemical class 0.000 claims description 88
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 7
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
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- 125000004122 cyclic group Chemical group 0.000 claims description 4
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- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
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- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
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- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
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- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
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- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
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- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- 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
- 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
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
Abstract
2가의 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 수산기와, 상기 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 (메타)아크릴기를, 각각 양쪽 말단의 시클로폴리실록산 구조의 어느 한쪽 또는 양쪽에 가지는 함불소 화합물 (A)를 함유하는 것을 특징으로 하는 함불소 활성 에너지선 경화성 조성물이 방오성, 특히는 우수한 발수발유성, 지문 부착 방지성, 지문 닦아냄성 및 마모 내구성을 부여할 수 있는 경화 피막을 제공하다.A cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group through a divalent linking group, a hydroxyl group is bonded to the cyclopolysiloxane structure through a divalent linking group, and ( A fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (A) having a meta)acrylic group on one or both ends of the cyclopolysiloxane structure, respectively, has antifouling properties, particularly excellent water and oil repellency, and fingerprint resistance. Provides a cured film that can provide anti-adhesion properties, fingerprint wiping properties, and wear resistance.
Description
본 발명은 자외선이나 전자선 등에 의해 경화되어, 우수한 방오성을 표면에 부여하는 함불소 활성 에너지선 경화성 조성물, 및 이 조성물의 경화물층을 기재 표면에 가지는 물품에 관한 것이다.The present invention relates to a fluorine-containing active energy ray-curable composition that is cured by ultraviolet rays, electron beams, etc. to impart excellent anti-fouling properties to the surface, and to an article having a layer of a cured product of this composition on the surface of a substrate.
종래, 수지 성형체 등의 표면을 보호하는 수단으로서 하드 코트 처리가 널리 일반적으로 사용되고 있다. 이것은 성형체의 표면에 경질의 경화 수지층(하드 코트층)을 형성하여, 상처 나기 어렵게 하는 것이다. 하드 코트층을 구성하는 재료로서는 열경화성 수지나 자외선 혹은 전자선 경화성 수지 등 활성 에너지선에 의한 경화성 조성물이 많이 사용되고 있다.Conventionally, hard coat treatment has been widely and generally used as a means to protect the surface of resin molded bodies and the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded body, making it difficult to scratch. As materials constituting the hard coat layer, compositions curable by active energy rays, such as thermosetting resins and ultraviolet rays or electron beam curable resins, are widely used.
한편, 수지 성형품의 이용 분야의 확대나 고부가가치화의 흐름에 따라, 경화 수지층(하드 코트층)에 대한 고기능화의 요망이 높아지고 있고, 그 하나로서 하드 코트층에 대한 방오성의 부여가 요구되고 있다. 이것은 하드 코트층의 표면에 발수성, 발유성 등의 성질을 부여함으로써, 더러워지기 어렵게, 또는 더러워져도 용이하게 제거할 수 있도록 하는 것이다.On the other hand, with the expansion of the field of use of resin molded products and the trend of increasing added value, the demand for higher functionality for the cured resin layer (hard coat layer) is increasing, and as one of them, imparting antifouling properties to the hard coat layer is required. This is to provide properties such as water repellency and oil repellency to the surface of the hard coat layer, making it difficult for it to become dirty or for easily removing it even if it becomes dirty.
하드 코트층에 방오성을 부여하는 방법으로서는 일단 형성된 하드 코트층 표면에 함불소 방오제를 도공 및/또는 정착시키는 방법이 널리 사용되고 있지만, 함불소 경화성 성분을 경화 전의 경화 수지 조성물에 첨가하고, 이것을 도포 경화시킴으로써 하드 코트층의 형성과 방오성의 부여를 동시에 행하는 방법에 대해서도 검토되어 왔다. 예를 들면, 일본 특개 평6-211945호 공보(특허문헌 1)에는, 아크릴계의 경화성 수지 조성물에 플루오로알킬아크릴레이트를 첨가, 경화시킴으로써 방오성을 부여한 하드 코트층의 제조가 개시되어 있다.As a method of imparting antifouling properties to the hard coat layer, a method of coating and/or fixing a fluorine-containing antifouling agent on the surface of the once formed hard coat layer is widely used. However, a fluorine-containing curable component is added to the cured resin composition before curing and then applied. A method of simultaneously forming a hard coat layer and imparting antifouling properties by curing has also been studied. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing it.
본 발명자는 이러한 경화성 수지 조성물에 방오성을 부여할 수 있는 불소 화합물로서 다양한 개발을 진행했으며, 예를 들면, 일본 특개 2010-53114호 공보(특허문헌 2), 일본 특개 2010-138112호 공보(특허문헌 3), 일본 특개 2010-285501호 공보(특허문헌 4)에 개시하는 광경화 가능한 불소 화합물을 제안했다.The present inventor has conducted various developments as fluorine compounds capable of imparting antifouling properties to such curable resin compositions, for example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 2), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 3), proposed a photocurable fluorine compound disclosed in Japanese Patent Application Laid-Open No. 2010-285501 (Patent Document 4).
한편, 하드 코트의 기능성 향상이 요구되고 있는 가운데, 사람이 맨손으로 접촉할 기회가 있는 장치, 예를 들면, 스마트폰, 태블릿 PC, 디지털 사이니지, 네비게이션 시스템이나 콘솔 등의 자동차의 차량 탑재 터치패널 디스플레이, 가정용 대형 TV, PC용 디스플레이의 용도에서는, 특히 방오성으로 총칭되는 중에서도, 지문의 부착이 눈에 띄지 않는 것, 지문의 닦아냄성이 우수한 것, 또한 하드 코트로서 마모의 내구성이 우수한 것과 같은 특성이 점점 강하게 요구되어 왔다. 이 때문에, 이들의 특징에 대해 종래로보다도 우수한 특성을 부여할 수 있는 활성 에너지선 경화성 조성물이 항상 요구되고 있다.Meanwhile, while there is a need to improve the functionality of hard courts, devices that people have the opportunity to touch with their bare hands, such as smartphones, tablet PCs, digital signage, and vehicle-mounted touch panels such as navigation systems and consoles, In applications such as displays, large TVs for home use, and displays for PCs, characteristics such as not being noticeable when fingerprints adhere, excellent wipeability of fingerprints, and excellent abrasion durability as a hard coat, among other general terms for anti-fouling properties. This has been increasingly demanded. For this reason, there is always a demand for an active energy ray-curable composition that can provide properties superior to those of the past with respect to these characteristics.
본 발명은 상기 사정을 감안하여 이루어진 것으로, 방오성, 특히는 우수한 발수발유성, 지문 부착 방지성, 지문 닦아냄성 및 마모 내구성을 부여할 수 있는 경화 피막을 공급하는 함불소 활성 에너지선 경화성 조성물, 및 이 조성물의 경화물층을 기재 표면에 가지는 물품을 제공하는 것을 목적으로 한다.The present invention has been made in consideration of the above circumstances, and provides a fluorine-containing active energy ray curable composition that supplies a cured film capable of providing antifouling properties, particularly excellent water and oil repellency, anti-fingerprint adhesion properties, fingerprint wiping properties, and abrasion durability, and The object is to provide an article having a layer of a cured product of this composition on the surface of a substrate.
본 발명자는 상기 목적을 달성하기 위해 예의 검토를 거듭한 결과, 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통한 수산기와, 상기 시클로폴리실록산 구조에 2가의 연결기를 통한 (메타)아크릴기가 각각 결합한 구조를 가지는 불소 화합물을 함유하는 함불소 활성 에너지선 경화성 조성물이 방오성으로 총칭되는 여러 특성 중에서도, 지문 부착의 시인 곤란성, 지문의 닦아냄성이 우수하고, 또한 하드 코트로서 마모의 내구성이 우수한 것을 발견하고, 본 발명을 이루게 되었다.The present inventor has conducted extensive studies to achieve the above object, and as a result, a cyclopolysiloxane structure is bonded to both ends of the perfluoropolyether group through a divalent linking group, and a hydroxyl group through a divalent linking group is attached to the cyclopolysiloxane structure. Among the various properties collectively referred to as antifouling properties, the fluorine-containing active energy ray-curable composition containing a fluorine compound having a structure in which a (meth)acrylic group is bonded to the cyclopolysiloxane structure through a divalent linking group, is difficult to see when fingerprints are attached, and It was discovered that it was excellent in wiping properties and had excellent abrasion durability as a hard coat, and the present invention was made.
따라서, 본 발명은 하기의 함불소 활성 에너지선 경화성 조성물 및 이 조성물의 경화물층을 기재 표면에 가지는 물품을 제공한다.Accordingly, the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured layer of the composition on the surface of the substrate.
1.One.
2가의 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 수산기와, 상기 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 (메타)아크릴기를, 각각 양쪽 말단의 시클로폴리실록산 구조의 어느 한쪽 또는 양쪽에 가지는 함불소 화합물 (A)에 있어서, 하기 일반식 (1)
X1-Z-Rf-Z-X1 (1)
[식 중, Rf는 하기 식 (2)∼(5)
(식 중, Y는 서로 독립적으로 F 또는 CF3이고, r은 2∼6의 정수이고, m, n은 각각 0∼200의 정수이며, 단, m+n은 2∼200이고, s는 0∼6의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)
(식 중, j는 독립적으로 1∼3의 정수이며, k는 1∼200의 정수이다.)
(식 중, Y, j는 상기와 같고, p, q는 각각 0∼200의 정수이며, 단, p+q는 2∼200이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)
(식 중, t는 1∼100의 정수이다.)
로 표시되는 기로부터 선택되는 분자량 500∼30,000의 2가의 퍼플루오로폴리에테르기이며, X1은 서로 독립적으로, 하기 식 (6)
[식 중, Q1은 탄소수 3∼20의 에테르 결합, 에스테르 결합, 아미드 결합 및 우레탄 결합으로부터 선택되는 결합을 포함하고 있어도 되는 2가의 연결기이며, 도중 환상 구조나 분기 구조를 포함하고 있어도 되고, 각각 동일하여도 상이하여도 된다. R1은 하기 식 (7)
(식 중, R2는 독립적으로, 수소 원자 또는 메틸기이고, R3은 탄소수 1∼18의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가 혹은 3가의 연결기이며, c는 1 또는 2이다.)
로 표시되는 (메타)아크릴기 함유 기이고, a 및 b는 각각 0∼6의 정수이며, 단, a+b는 2∼11이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.]
으로 표시되는 기이며, 분자 중에 존재하는 X1 중의 a, b의 합계는 각각 2 이상이다. Z는 하기 식
중 어느 하나로 표시되는 2가의 유기기이다.]
로 표시되고, 상기 화합물 중에 포함되는 포함되는 수산기에 대한 (메타)아크릴기의 몰비[(메타)아크릴기(몰)/수산기(몰)]가 평균값으로서 0.1 이상 19 미만인 함불소 화합물 (A)를 함유하는 것을 특징으로 하는 함불소 활성 에너지선 경화성 조성물.A cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group through a divalent linking group, a hydroxyl group is bonded to the cyclopolysiloxane structure through a divalent linking group, and ( In the fluorine-containing compound (A) having a meth)acrylic group on one or both sides of the cyclopolysiloxane structure at both ends, the general formula (1)
X 1 -Z-Rf-ZX 1 (1)
[Wherein, Rf is represented by the following formulas (2) to (5)
(In the formula, Y is independently F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, provided that m+n is 2 to 200, and s is 0 It is an integer of ~6. Each repeating unit may be randomly combined.)
(In the formula, j is independently an integer from 1 to 3, and k is an integer from 1 to 200.)
(In the formula, Y and j are the same as above, p and q are each integers from 0 to 200, but p+q is from 2 to 200. Each repeating unit may be randomly combined.)
(In the formula, t is an integer from 1 to 100.)
is a divalent perfluoropolyether group with a molecular weight of 500 to 30,000 selected from groups represented by, and
[In the formula, Q 1 is a divalent linking group that may contain a bond selected from an ether bond, an ester bond, an amide bond, and a urethane bond having 3 to 20 carbon atoms, and may contain a cyclic structure or a branched structure, respectively. They may be the same or different. R 1 is given by the following formula (7)
(In the formula, R 2 is independently a hydrogen atom or a methyl group, R 3 is a divalent or trivalent linking group that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms, and c is 1 or 2. .)
It is a (meth)acrylic group-containing group represented by , and a and b are each integers of 0 to 6, provided that a+b is 2 to 11. Each repeating unit may be randomly combined.]
It is a group represented by , and the total of a and b among X 1 present in the molecule is each 2 or more. Z is the following expression
It is a divalent organic group represented by one of the following.]
A fluorine-containing compound (A), which is represented by and the molar ratio of the (meth)acrylic group to the hydroxyl group contained in the compound [(meth)acrylic group (mol)/hydroxyl group (mol)] is 0.1 or more and less than 19 as an average value. A fluorine-containing active energy ray-curable composition comprising:
2.2.
함불소 화합물 (A)에서, 함불소 화합물 (A) 중에 포함되는 수산기에 대한 (메타)아크릴기의 몰비[(메타)아크릴기(몰)/수산기(몰)]가 평균값으로서 0.1 이상 10 이하인 1에 기재된 함불소 활성 에너지선 경화성 조성물.In the fluorinated compound (A), the molar ratio of the (meth)acrylic group to the hydroxyl group contained in the fluorinated compound (A) [(meth)acrylic group (mol)/hydroxyl group (mol)] is 0.1 or more and 10 or less as an average value. The fluorine-containing active energy ray-curable composition described in .
3.3.
또한, 2가의 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 (메타)아크릴기를 가지고, 또한, 수산기를 가지지 않는 구조를 양쪽 말단에 가지는 함불소 화합물 (B)를 포함하는 것인 1 또는 2에 기재된 함불소 활성 에너지선 경화성 조성물.In addition, a cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group through a divalent linking group, has a (meth)acrylic group bonded to the cyclopolysiloxane structure through a divalent linking group, and does not have a hydroxyl group. The fluorine-containing active energy ray-curable composition according to 1 or 2, which contains a fluorine-containing compound (B) having a structure at both ends.
4.4.
조성물 전체에 포함되는 평균값으로서 조성물 중의 함불소 화합물 (A)에 포함되는 수산기에 대한 함불소 화합물 (A)에 포함되는 (메타)아크릴기와 함불소 화합물 (B)에 포함되는 (메타)아크릴기의 합계의 몰비[(메타)아크릴기의 합계(몰)/수산기(몰)]가 0.1 이상 25 이하인 3에 기재된 함불소 활성 에너지선 경화성 조성물.As an average value contained in the entire composition, the ratio of the (meth)acrylic group contained in the fluorinated compound (A) to the hydroxyl group contained in the fluorinated compound (A) in the composition and the (meth)acrylic group contained in the fluorinated compound (B) The fluorine-containing active energy ray-curable composition according to item 3, wherein the total molar ratio [sum of (meth)acrylic groups (mol)/hydroxyl group (mol)] is 0.1 or more and 25 or less.
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5.5.
함불소 화합물 (A), (B) 이외의 아크릴 화합물 (C)를 더 포함하는 3 또는 4 중 어느 하나에 기재된 함불소 활성 에너지선 경화성 조성물.The fluorine-containing active energy ray-curable composition according to any one of 3 or 4, further comprising an acrylic compound (C) other than the fluorine-containing compounds (A) and (B).
6.6.
아크릴 화합물 (C)가 1 분자 중에 3개 이상의 (메타)아크릴기를 가지고, 또한 분자 중에 수산기를 가지지 않는 비불소화 다작용 (메타)아크릴레이트인 5에 기재된 함불소 활성 에너지선 경화성 조성물.The fluorinated active energy ray-curable composition according to item 5, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth)acrylate having three or more (meth)acrylic groups in one molecule and no hydroxyl group in the molecule.
7.7.
아크릴 화합물 (C)가 1 분자 중에 3개 이상의 (메타)아크릴기와 1개 이상의 수산기를 가지는 비불소화 다작용 (메타)아크릴레이트인 5에 기재된 함불소 활성 에너지선 경화성 조성물.The fluorinated active energy ray-curable composition according to item 5, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth)acrylate having three or more (meth)acrylic groups and one or more hydroxyl groups in one molecule.
8.8.
아크릴 화합물 (C)가 분자 중에 우레탄 결합을 가지고, 1 분자 중에 6개 이상의 (메타)아크릴기를 가지는 비불소화 다작용 우레탄(메타)아크릴레이트인 5에 기재된 함불소 활성 에너지선 경화성 조성물.The fluorinated active energy ray-curable composition according to item 5, wherein the acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth)acrylate having a urethane bond in the molecule and 6 or more (meth)acrylic groups in one molecule.
9.9.
또한, (D) 광중합 개시제를 포함하는 1 또는 2에 기재된 함불소 활성 에너지선 경화성 조성물.Additionally, (D) the fluorine-containing active energy ray-curable composition according to 1 or 2, which contains a photopolymerization initiator.
10.10.
1 또는 2에 기재된 함불소 활성 에너지선 경화성 조성물의 경화 피막을 표면에 가지며, 수접촉각 105° 이상의 발수성 표면을 가지는 물품.An article having a cured film of the fluorine-containing active energy ray-curable composition according to 1 or 2 on the surface, and having a water-repellent surface with a water contact angle of 105° or more.
본 발명의 함불소 활성 에너지선 경화성 조성물은 기재의 표면에 도공 경화시킴으로써, 발수성, 발유성, 방오성, 미끄럼성, 부착 지문의 저시인성, 지문의 닦아냄성, 내마모성을 부여할 수 있다.The fluorine-containing active energy ray-curable composition of the present invention can impart water repellency, oil repellency, antifouling properties, slipperiness, low visibility of attached fingerprints, wipeability of fingerprints, and abrasion resistance by applying and curing the surface of a substrate.
(발명을 실시하기 위한 형태)(Form for carrying out the invention)
본 발명의 함불소 활성 에너지선 경화성 조성물은 2가의 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 3가 이상(통상, 3∼12가, 바람직하게는 3∼8가, 보다 바람직하게는 3∼6가)의 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통한 수산기와, 상기 시클로폴리실록산 구조에 2가의 연결기를 통한 (메타)아크릴기가 양쪽 말단의 시클로폴리실록산 구조의 어느 한쪽 또는 양쪽에 각각 1개 이상 결합한 구조를 가지는 함불소 화합물 (A)를 함유하는 것을 특징으로 한다. 함불소 화합물 (A)에서, 상기 수산기를 가짐으로써 지문이 눈에 띄기 어려워진다고 하는 효과가 얻어지고, 상기 (메타)아크릴기를 가짐으로써 경화성이 얻어져, 표면에 방오성을 나타내는 불소 성분이 고정된다고 하는 효과가 얻어지는 것이다.The fluorinated active energy ray-curable composition of the present invention has a trivalent or higher (usually 3 to 12 valent, preferably 3 to 8 valent, more preferably 3 to 8 valent) group through a divalent linking group at both ends of the divalent perfluoropolyether group. is a 3 to 6 valent) cyclopolysiloxane structure bonded to the cyclopolysiloxane structure, and a hydroxyl group through a divalent linking group to the cyclopolysiloxane structure and a (meth)acrylic group through a divalent linking group to the cyclopolysiloxane structure are attached to any of the cyclopolysiloxane structures at both ends. It is characterized by containing a fluorine-containing compound (A) having a structure in which one or more compounds are bonded to one or both sides. In the fluorine-containing compound (A), by having the hydroxyl group, the effect of making fingerprints less noticeable is obtained, and by having the (meth)acrylic group, curability is obtained, and the fluorine component that exhibits antifouling properties is fixed to the surface. The effect is achieved.
함불소 화합물 (A) 중에 포함되는 (메타)아크릴기와 수산기의 비율은, 특히, 조성물 중에 포함되는 함불소 화합물 (A)의 평균값으로서 함불소 화합물 (A) 중에 포함되는 수산기에 대한 (메타)아크릴기의 몰비[(메타)아크릴기(몰)/수산기(몰)]가 0.1 이상 25 이하인 것이 바람직하고, 0.15 이상 19 이하인 것이 보다 바람직하고, 0.2 이상 10 이하인 것이 특히 바람직하고, 0.2 이상 5 이하인 것이 더욱 바람직하고, 0.2 이상 2.5 이하인 것이 가장 바람직하다. 이 몰비가 이것보다 커지면 함불소 화합물 (A) 중에 포함되는 수산기의 효과가 작아져, 수산기를 포함하지 않는 함불소 화합물과의 경화 후의 특성의 차이가 명확하지 않게 된다. 이 몰비가 이것보다 작아지면 함불소 화합물 (A) 중 (메타)아크릴기를 가지지 않는 분자의 함유량이 많아져, 비불소의 아크릴 화합물과의 용해성이 저하되어, 균일한 평면으로서 도공이 곤란하게 되거나, 경화 불량이 발생하거나 하는 경우가 있다.The ratio of the (meth)acrylic group and hydroxyl group contained in the fluorinated compound (A) is, in particular, the average value of the fluorinated compound (A) contained in the composition, and the ratio of the (meth)acrylic group to the hydroxyl group contained in the fluorinated compound (A) is the average value. The molar ratio of groups [(meth)acrylic group (mol)/hydroxyl group (mol)] is preferably 0.1 or more and 25 or less, more preferably 0.15 or more and 19 or less, particularly preferably 0.2 or more and 10 or less, and 0.2 or more and 5 or less. It is more preferable, and it is most preferable that it is 0.2 or more and 2.5 or less. If this molar ratio is larger than this, the effect of the hydroxyl group contained in the fluorine-containing compound (A) becomes small, and the difference in properties after curing with the fluorine-containing compound that does not contain a hydroxyl group becomes unclear. If this molar ratio is smaller than this, the content of molecules without a (meth)acrylic group in the fluorinated compound (A) increases, the solubility with the non-fluorinated acrylic compound decreases, and coating as a uniform plane becomes difficult, There may be cases where curing failure occurs.
함불소 화합물 (A)로서, 구체적으로는, 하기 일반식 (1)로 표시되는 구조를 가지는 화합물을 예시할 수 있다.As the fluorine-containing compound (A), a compound having a structure represented by the following general formula (1) can be specifically exemplified.
X1-Z-Rf-Z-X1 (1)X 1 -Z-Rf-ZX 1 (1)
식 (1) 중, Rf는 특히 주구조가 이하에 나타내는 반복단위군In formula (1), Rf is particularly a repeating unit group whose main structure is shown below.
-CF2O- -CF2O-
-CF2CF2O--CF 2 CF 2 O-
-CF2CF2CF2O--CF 2 CF 2 CF 2 O-
-CF(CF3)CF2O--CF(CF 3 )CF 2 O-
-CF2CF2CF2CF2O--CF 2 CF 2 CF 2 CF 2 O-
중 어느 하나 또는 복수의 조합으로 이루어지는 것이 바람직하다. 여기에서, 주구조에 해당하지 않는 부분으로서는 Z와의 결합 부분, 주쇄 구조 구축시의 개시제 단편이나 부생성 구조를 들 수 있다.It is preferable to use any one or a combination of a plurality of them. Here, the parts that do not correspond to the main structure include a bonding part with Z, an initiator fragment during construction of the main chain structure, and a by-product structure.
Rf로서는 그중에서도 하기 식 (2)∼(5)로 표시되는 기로부터 선택되는, 분자량 500∼30,000의 2가의 퍼플루오로폴리에테르기인 것이 바람직하다.As Rf, it is especially preferable that it is a divalent perfluoropolyether group with a molecular weight of 500 to 30,000 selected from groups represented by the following formulas (2) to (5).
(식 중, Y는 서로 독립적으로 F 또는 CF3이고, r은 2∼6의 정수이고, m, n은 각각 0∼200의 정수, 바람직하게는 1∼100의 정수, 보다 바람직하게는 4∼50의 정수이며, 단, m+n은 2∼200, 바람직하게는 8∼100이고, s는 0∼6의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)(In the formula, Y is independently F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably 4 to 100. It is an integer of 50, provided that m+n is 2 to 200, preferably 8 to 100, and s is an integer of 0 to 6. Each repeating unit may be randomly combined.)
(식 중, j는 독립적으로 1∼3의 정수이며, k는 1∼200의 정수, 바람직하게는 2∼100의 정수, 보다 바람직하게는 4∼50의 정수이다.)(In the formula, j is independently an integer of 1 to 3, and k is an integer of 1 to 200, preferably an integer of 2 to 100, and more preferably an integer of 4 to 50.)
(식 중, Y, j는 상기와 같고, p, q는 각각 0∼200의 정수, 바람직하게는 1∼100의 정수, 보다 바람직하게는 4∼50의 정수이며, 단, p+q는 2∼200, 바람직하게는 8∼100이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)(In the formula, Y and j are the same as above, and p and q are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, provided that p+q is 2 ~200, preferably 8 to 100. Each repeating unit may be randomly combined.)
(식 중, t는 1∼100의 정수, 바람직하게는 2∼60의 정수, 보다 바람직하게는 4∼40의 정수이다.)(In the formula, t is an integer of 1 to 100, preferably an integer of 2 to 60, more preferably an integer of 4 to 40.)
Rf로서는 그중에서도 식 (2) 및 (4)로 표시되는 구조가 바람직하다.As Rf, the structures represented by formulas (2) and (4) are particularly preferable.
또한, Rf는 분자량이 500∼30,000, 특히 1,500∼10,000인 것이 바람직하다. 분자량이 지나치게 작으면 조성물 중의 비불소화 성분과의 상용성이 지나치게 높아져, 도공 후의 경화물(도포막)의 표면에 (A) 성분이 모이지 않게 되는 경우가 있고, 지나치게 크면 조성물 중의 비불소화 성분과의 상용성이 지나치게 낮아져, 배합시의 탁함, 침전의 발생이나 도공 후의 경화물(도포막)의 헤이즈의 상승, 도포막의 결손 등, 평활성의 저하 등이 발생하는 경우가 있다. 또한, 분자량은, 예를 들면, 각종 함불소 용매를 전개 용매로 한 겔 퍼미에이션 크로마토그래피(GPC) 분석에 있어서의 폴리메틸메타크릴레이트 환산값으로서 구할 수 있고, 통상, 수량평균 분자량으로서 구하는 것이 적합하다(이하, 동일.).Additionally, Rf preferably has a molecular weight of 500 to 30,000, especially 1,500 to 10,000. If the molecular weight is too small, compatibility with the non-fluorinated components in the composition may become too high, and component (A) may not collect on the surface of the cured product (coated film) after coating. If the molecular weight is too large, it may cause compatibility with the non-fluorinated components in the composition. Compatibility may be too low, causing cloudiness and precipitation during mixing, an increase in haze of the cured product (coating film) after coating, defects in the coating film, etc., and a decrease in smoothness. In addition, the molecular weight can be determined, for example, as a polymethyl methacrylate conversion value in gel permeation chromatography (GPC) analysis using various fluorinated solvents as developing solvents, and is usually determined as the quantity average molecular weight. Suitable (hereinafter, same).
일반식 (1)에 있어서, Z는 하기 식 중 어느 하나로 표시되는 2가의 유기기이다.In General Formula (1), Z is a divalent organic group represented by any of the following formulas.
Z로서는, 그중에서도,For Z, among others,
가 특히 바람직하다.is particularly preferable.
식 (1)에 있어서, X1은 서로 독립적으로, 하기 식 (6)으로 표시되는 기이다.In formula (1), X 1 is independently a group represented by the following formula (6).
[식 중, Q1은 탄소수 3∼20의 에테르 결합, 에스테르 결합, 아미드 결합 및 우레탄 결합으로부터 선택되는 결합을 포함하고 있어도 되는 2가의 연결기이며, 도중 환상 구조나 분기 구조를 포함하고 있어도 되고, 각각 동일하여도 상이하여도 된다. R1은 하기 식 (7)[In the formula, Q 1 is a divalent linking group that may contain a bond selected from an ether bond, an ester bond, an amide bond, and a urethane bond having 3 to 20 carbon atoms, and may contain a cyclic structure or a branched structure, respectively. They may be the same or different. R 1 is given by the following formula (7)
(식 중, R2는 독립적으로 수소 원자 또는 메틸기이고, R3은 탄소수 1∼18의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가 혹은 3가의 연결기이며, c는 1 또는 2이다.)(In the formula, R 2 is independently a hydrogen atom or a methyl group, R 3 is a divalent or trivalent linking group that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms, and c is 1 or 2. )
로 표시되는 (메타)아크릴기 함유 기이다. a 및 b는 각각 0∼6, 바람직하게는 1∼6, 보다 바람직하게는 2∼4의 정수이며, 단, a+b는 2∼11, 바람직하게는 2∼7, 보다 바람직하게는 2∼5이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다. 또한, 식 (1)에 있어서, 분자 중에 존재하는 X1 중의 a, b의 합계는 각각 2 이상이다.]It is a (meth)acrylic group-containing group represented by . a and b are each an integer of 0 to 6, preferably 1 to 6, more preferably 2 to 4, provided that a+b is 2 to 11, preferably 2 to 7, more preferably 2 to 4. It's 5. Each repeating unit may be randomly combined. Additionally, in formula (1), the sum of a and b among X 1 present in the molecule is each 2 or more.]
식 (6)에 있어서, Q1은 탄소수 3∼20의 에테르 결합, 에스테르 결합, 아미드 결합 및 우레탄 결합으로부터 선택되는 결합을 포함하고 있어도 되는 2가의 연결기이고, 바람직하게는 탄소수 3∼20, 특히 탄소수 3∼12의 에테르 결합, 에스테르 결합, 아미드 결합 및 우레탄 결합으로부터 선택되는 결합을 포함하고 있어도 되는 2가의 탄화수소기이며, 도중 환상 구조나 분기 구조를 포함하고 있어도 되고, 각각 동일하여도 상이하여도 된다.In formula (6), Q 1 is a divalent linking group that may contain a bond selected from ether bond, ester bond, amide bond and urethane bond having 3 to 20 carbon atoms, preferably 3 to 20 carbon atoms, especially carbon number. It is a divalent hydrocarbon group that may contain a bond selected from 3 to 12 ether bonds, ester bonds, amide bonds, and urethane bonds, and may contain a cyclic structure or branched structure, and may be the same or different. .
Q1로서는 그중에서도 이하의 어느 하나의 구조가 바람직하다.As Q 1 , any of the following structures is particularly preferable.
-CH2CH2CH2--CH 2 CH 2 CH 2 -
-CH2CH2CH2-O-CH2CH2--CH 2 CH 2 CH 2 -O-CH 2 CH 2 -
-CH2CH2CH2-O-CH2CH2-O-CH2CH2--CH 2 CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -
-CH2CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2--CH 2 CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -
-[CH2CH(CH3)O]z-CH2CH(CH3)--[CH 2 CH(CH 3 )O] z -CH 2 CH(CH 3 )-
(식 중, z는 0∼10의 정수이다.)(In the formula, z is an integer from 0 to 10.)
식 (6)에 있어서, R1은 하기 식 (7)로 표시되는 (메타)아크릴기 함유 기이다.In formula (6), R 1 is a (meth)acrylic group-containing group represented by the following formula (7).
(식 중, R2는 독립적으로 수소 원자 또는 메틸기이고, R3은 탄소수 1∼18의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가 혹은 3가의 연결기이며, c는 1 또는 2이다.)(In the formula, R 2 is independently a hydrogen atom or a methyl group, R 3 is a divalent or trivalent linking group that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms, and c is 1 or 2. )
식 (7)에 있어서, R2는 독립적으로, 수소 원자 또는 메틸기이다.In formula (7), R 2 is independently a hydrogen atom or a methyl group.
또한, R3은 탄소수 1∼18의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가 혹은 3가의 연결기이고, 바람직하게는 탄소수 1∼18, 특히 탄소수 2∼8의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가의 탄화수소기, 특히는 알킬렌기이며, 예를 들면, 하기 식으로 표시되는 것이 바람직하다.In addition, R 3 is a divalent or trivalent linking group that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms, and is preferably an ether bond and/or an ester bond having 1 to 18 carbon atoms, especially 2 to 8 carbon atoms. It is a divalent hydrocarbon group that may contain a bond, especially an alkylene group, and is preferably represented by the following formula, for example.
-CH2CH2--CH 2 CH 2 -
-CH2CH2CH2--CH 2 CH 2 CH 2 -
-CH2CH2CH2CH2--CH 2 CH 2 CH 2 CH 2 -
-CH2CH2CH2CH2CH2CH2--CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -
-CH2CH2OCH2CH2--CH 2 CH 2 OCH 2 CH 2 -
-CH2CH2OCH2CH2OCH2CH2--CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -
-CH2CH2OCH2CH2OCH2CH2--CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 -
c는 1 또는 2이며, 1이 바람직하다.c is 1 or 2, with 1 being preferred.
또한, 본 발명에 따른 함불소 화합물 (A)에서, 2가의 퍼플루오로폴리에테르기의 양쪽 말단에 연결하는 3가 이상(통상, 3∼12가, 바람직하게는 3∼8가, 보다 바람직하게는 3∼6가)의 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 수산기와, 이 시클로폴리실록산 구조에 2가의 연결기를 통하여 결합한 (메타)아크릴기는 이 양쪽 말단의 시클로폴리실록산 구조의 어느 한쪽 또는 양쪽에, 각각 독립적으로, 1개 이상, 바람직하게는 1∼6개, 보다 바람직하게는 2∼4개 가지는 것이며, 상기한 식 (1)에 있어서, 분자 중의 상기 (메타)아크릴기 수의 합계에 상당하는 a의 합계 (즉 양쪽 말단의 시클로폴리실록산 구조 중의 (메타)아크릴기 수의 합계)는 1 이상, 바람직하게는 1∼12, 보다 바람직하게는 2∼8, 더욱 바람직하게는 4∼6이며, 분자 중의 상기 수산기 수의 합계에 상당하는 b의 합계(즉 양쪽 말단의 시클로폴리실록산 구조 중의 수산기 수의 합계)는 1 이상, 바람직하게는 1∼12, 보다 바람직하게는 2∼8, 더욱 바람직하게는 4∼6이다.In addition, in the fluorinated compound (A) according to the present invention, trivalent or more (usually 3 to 12 valent, preferably 3 to 8 valent, more preferably 3 to 8 valent) groups are connected to both ends of the divalent perfluoropolyether group. A hydroxyl group bonded to a 3 to 6-valent cyclopolysiloxane structure through a divalent linking group, and a (meth)acrylic group bonded to this cyclopolysiloxane structure through a divalent linking group are attached to one or both ends of the cyclopolysiloxane structure at both ends, Each independently has at least 1, preferably 1 to 6, more preferably 2 to 4, and in the formula (1) above, corresponds to the sum of the number of (meth)acrylic groups in the molecule. The sum of a (i.e. the sum of the number of (meth)acrylic groups in the cyclopolysiloxane structure at both terminals) is 1 or more, preferably 1 to 12, more preferably 2 to 8, even more preferably 4 to 6, and the molecule The sum of b corresponding to the sum of the number of hydroxyl groups in the cyclopolysiloxane structure at both ends (i.e., the sum of the number of hydroxyl groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8, and even more preferably 4. It is ~6.
또한, 상기한 식 (6)으로 표시되는 각 시클로폴리실록산 구조 중에서, a+b의 값은 각각 독립적으로, 통상, 2∼11, 바람직하게는 2∼7, 보다 바람직하게는 2∼5이며, 상기한 식 (1)에 있어서, 분자 중의 상기 (메타)아크릴기 수와 상기 수산기 수와의 합계에 상당하는 (a+b)값의 합계(즉 분자 중에 존재하는 2개의 X1기 중의 (메타)아크릴기 수와 상기 수산기 수와의 합계)는, 통상, 4∼22, 바람직하게는 6∼14, 보다 바람직하게는 6∼10이다.In addition, among each cyclopolysiloxane structure represented by the above formula (6), the value of a + b is each independently usually 2 to 11, preferably 2 to 7, more preferably 2 to 5, and In one formula (1), the sum of (a+b) values corresponding to the sum of the number of (meth)acrylic groups and the number of hydroxyl groups in the molecule (i.e., the ( meta ) of the two The total number of acrylic groups and the number of hydroxyl groups is usually 4 to 22, preferably 6 to 14, and more preferably 6 to 10.
또한, 함불소 화합물 (A)의 제조를 행할 때, 하기 일반식 (8)로 표시되는 구조를 갖는 화합물이 부생하는 경우가 있고, 이것들은 증류, 추출, 분취 크로마토그래피 등의 각종 수단에 의해 제거해도 되지만, 그대로 포함한 것도 사용할 수 있다.In addition, when producing the fluorinated compound (A), compounds having a structure represented by the following general formula (8) may be produced as by-products, and these are removed by various means such as distillation, extraction, and preparative chromatography. However, you can also use the one included as is.
X1-[Z-Rf-Z-X2]v-Z-Rf-Z-X1 (8)X 1 -[Z-Rf-ZX 2 ] v -Z-Rf-ZX 1 (8)
일반식 (8)에 있어서, X1, Z, Rf는 일반식 (1)과 같고, v는 1∼4의 정수이며, X2는 서로 독립적으로, 하기 식 (9)로 표시되는 기이다.In the general formula ( 8 ), X 1 , Z, and Rf are the same as in the general formula (1), v is an integer of 1 to 4, and
(식 중, Q1, R1은 상기한 바와 같고, d, e는 각각 0∼3의 정수, 바람직하게는 1∼3의 정수이며, 또한 d+e는 1∼10, 바람직하게는 1∼6의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)(Wherein, Q 1 and R 1 are as described above, d and e are each an integer of 0 to 3, preferably an integer of 1 to 3, and d+e is an integer of 1 to 10, preferably 1 to 3. It is an integer of 6. Each repeating unit may be randomly combined.)
함불소 화합물 (A)의 바람직한 구조로서, 구체적으로는, 이하의 것을 예시할 수 있다.As a preferable structure of the fluorine-containing compound (A), the following can be specifically exemplified.
[식 중, Rf'은 상기한 Rf와 동일한 것을 예시할 수 있고, 바람직하게는, -CF2O(CF2O)p'(CF2CF2O)q'CF2-(p',q'은 상기한 p, q와 동일한 것을 예시할 수 있다.)이다. R4는 수소 원자 또는 (메타)아크릴 함유 기이며, 분자 중에 포함되는 R4로서의 수소 원자의 수를 nH, (메타)아크릴 함유 기의 수를 nA로 했을 때, nH, nA는 각각 1∼5의 정수이며, 각각의 분자에 대하여 nH+nA=6이다.][In the formula, Rf' may exemplify the same as the above-mentioned Rf, preferably -CF 2 O(CF 2 O) p' (CF 2 CF 2 O) q' CF 2 -(p',q ' may exemplify the same thing as p and q described above.). R 4 is a hydrogen atom or a (meth)acrylic-containing group. When the number of hydrogen atoms as R 4 contained in the molecule is n H and the number of (meth)acrylic-containing groups is n A , n H and n A are Each is an integer from 1 to 5, and n H + n A = 6 for each molecule.]
여기에서, R4는 수소 원자 또는 (메타)아크릴 함유 기이며, (메타)아크릴 함유 기로서 바람직하게는 하기에 나타내는 것을 예시할 수 있다.Here, R 4 is a hydrogen atom or a (meth)acrylic-containing group, and examples of the (meth)acrylic-containing group are preferably those shown below.
CH2=CHCO-CH 2 =CHCO-
CH2=C(CH3)CO-CH 2 =C(CH 3 )CO-
CH2=CHCOOCH2CH2-NH-CO-CH 2 =CHCOOCH 2 CH 2 -NH-CO-
CH2=CCH3COOCH2CH2-NH-CO-CH 2 =CCH 3 COOCH 2 CH 2 -NH-CO-
CH2=CCH3COOCH2CH2OCH2CH2-NH-CO-CH 2 =CCH 3 COOCH 2 CH 2 OCH 2 CH 2 -NH-CO-
[CH2=CCH3COOCH2]2CH(CH3)-NH-CO-[CH 2 =CCH 3 COOCH 2 ] 2 CH(CH 3 )-NH-CO-
또한, 함불소 화합물 (A) 1 분자 중에 포함되는 R4로서의 수소 원자의 수를 nH, (메타)아크릴 함유 기의 수를 nA로 했을 때, nH, nA는 각각 1∼5의 정수이며, 각각의 분자에 대해 nH+nA=6이다.In addition, when the number of hydrogen atoms as R 4 contained in one molecule of the fluorinated compound (A) is n H and the number of (meth)acrylic-containing groups is n A , n H and n A are each 1 to 5. It is an integer, and n H + n A = 6 for each molecule.
본 발명에 따른 함불소 화합물 (A)는 어떠한 제조 방법을 사용해도 그 효과는 바뀌지 않지만, 예를 들면, 이하와 같은 방법으로 제조하는 것이 바람직하다. 즉 플루오로폴리에테르기의 양쪽 말단에 OH기(수산기)를 복수 가지는 화합물(함불소 알코올 화합물)의 수산기의 일부를, (메타)아크릴산 할라이드나, (메타)아크릴기를 함유하는 이소시아네이트 화합물 등의 (메타)아크릴기 도입 시약과 반응시켜, 이 수산기 부분에 (메타)아크릴기를 부분적으로 도입함으로써, 함불소 화합물 (A)를 얻을 수 있다.The effect of the fluorinated compound (A) according to the present invention does not change no matter what production method is used, but for example, it is preferable to produce it by the following method. That is, part of the hydroxyl group of a compound (fluorinated alcohol compound) having multiple OH groups (hydroxyl groups) at both ends of the fluoropolyether group can be replaced with (meth)acrylic acid halide or an isocyanate compound containing a (meth)acrylic group, etc. The fluorine-containing compound (A) can be obtained by reacting with a meth)acrylic group introduction reagent and partially introducing a (meth)acrylic group into the hydroxyl group portion.
여기에서, 함불소 화합물 (A)의 전구체가 되는 플루오로폴리에테르기의 양쪽 말단에 OH기를 복수 가지는 화합물(함불소 알코올 화합물)로서, 구체적으로는, 이하에 나타내는 것을 들 수 있다.Here, as a compound (fluorinated alcohol compound) having a plurality of OH groups at both ends of the fluoropolyether group that is the precursor of the fluorinated compound (A), the compounds shown below are specifically included.
(식 중, Rf'은 상기와 같다.)(Where Rf' is the same as above.)
(메타)아크릴기 도입 시약으로서는 아크릴산 클로리드, 메타크리르산 클로리드 등의 (메타)아크릴산 할라이드, 및 하기에 나타내는 (메타)아크릴기를 함유하는 이소시아네이트 화합물(이소시아네이트기를 가지는 아크릴산 유도체) 등을 예시할 수 있다.Examples of the (meth)acrylic group introduction reagent include (meth)acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and isocyanate compounds (acrylic acid derivatives having an isocyanate group) containing a (meth)acrylic group shown below. there is.
CH2=CHCOOCH2CH2-N=C=OCH 2 =CHCOOCH 2 CH 2 -N=C=O
CH2=CCH3COOCH2CH2-N=C=OCH 2 =CCH 3 COOCH 2 CH 2 -N=C=O
CH2=CCH3COOCH2CH2OCH2CH2-N=C=OCH 2 =CCH 3 COOCH 2 CH 2 OCH 2 CH 2 -N=C=O
[CH2=CCH3COOCH2]2CH(CH3)-N=C=O[CH 2 =CCH 3 COOCH 2 ] 2 CH(CH 3 )-N=C=O
이들 (메타)아크릴산 할라이드 혹은 (메타)아크릴기를 함유하는 이소시아네이트 화합물은 함불소 알코올 화합물의 수산기량의 합계에 대하여 과잉으로 되지 않는 필요량을 장입하고, 반응시키는 방법이 바람직하다. 구체적으로는, 반응계 중의, 함불소 알코올 화합물의 수산기량의 합계를 x몰로 한 경우, (메타)아크릴산 할라이드 혹은 (메타)아크릴기를 함유하는 이소시아네이트 화합물의 할로겐 원자 혹은 이소시아네이트기량을 y몰로 한 경우, 바람직하게는 0.1≤y/(x-y)≤25, 보다 바람직하게는 0.15≤y/(x-y)≤19, 특히 바람직하게는 0.2≤y/(x-y)≤10, 더욱 바람직하게는 0.2≤y/(x-y)≤5, 가장 바람직하게는 0.2≤y/(x-y)≤2.5가 되는 비율로 장입하고, 이것을 모두 또는 바람직한 양으로 반응시키면 된다. 또한, 상기 비율을 y/(x-y)>25로 하여 장입하고, 반응을 완결시키지 않고 정지시키는 방법도 사용할 수 있지만, 이 경우에는 반응 촉매의 제거 등에 의해 반응을 확실하게 정지시킬 필요가 있다.It is preferable to charge these (meth)acrylic acid halide or isocyanate compounds containing a (meth)acrylic group in the required amount that is not excessive relative to the total amount of hydroxyl groups of the fluorinated alcohol compound, and then react. Specifically, when the total amount of hydroxyl groups of the fluorinated alcohol compounds in the reaction system is set to x mole, and the amount of halogen atoms or isocyanate groups of the (meth)acrylic acid halide or isocyanate compound containing a (meth)acrylic group is set to y moles, it is preferable. Preferably 0.1≤y/(x-y)≤25, more preferably 0.15≤y/(x-y)≤19, particularly preferably 0.2≤y/(x-y)≤10, more preferably 0.2≤y/(x-y ) ≤ 5, most preferably 0.2 ≤ y/(x-y) ≤ 2.5, and react all or a desired amount. In addition, a method of charging at the above ratio of y/(x-y)>25 and stopping the reaction without completing it can also be used, but in this case, it is necessary to surely stop the reaction by removing the reaction catalyst, etc.
이들 반응은 필요에 따라 적당한 용제로 희석하여 반응을 행해도 된다. 이러한 용제로서는 함불소 알코올 화합물의 수산기, (메타)아크릴산 할라이드의 할로겐 원자, (메타)아크릴기를 함유하는 이소시아네이트 화합물의 이소시아네이트기와 반응하지 않는 용제이면 특별히 제한 없이 사용할 수 있고, 구체적으로는, 톨루엔, 크실렌, 이소옥탄 등의 탄화수소계 용제, 테트라히드로푸란, 디이소프로필에테르, 디부틸에테르 등의 에테르계 용제, 아세톤, 메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 시클로헥산온 등의 케톤계 용제, m-크실렌헥사플루오라이드, 벤조트리플루오라이드 등의 불소 변성 방향족 탄화수소계 용제, 메틸퍼플루오로부틸에테르 등의 불소 변성 에테르계 용제 등을 들 수 있다. 이 용제는, 반응 후에 감압 증류 제거 등의 공지의 수법으로 제거해도 되고, 원하는 용도에 따라 그대로 희석 용액으로서 사용해도 된다. 용제의 사용량은 특별히 한정되지 않지만, 반응 성분의 전체 합계 질량에 대하여 10배 이하가 바람직하다. 용매의 사용량이 지나치게 많으면, 반응속도가 대폭 저하될 위험이 있다.These reactions may be carried out by diluting with an appropriate solvent as needed. Such a solvent can be used without particular limitation as long as it does not react with the hydroxyl group of a fluorinated alcohol compound, the halogen atom of a (meth)acrylic acid halide, or the isocyanate group of an isocyanate compound containing a (meth)acrylic group. Specifically, toluene and xylene are used. , hydrocarbon solvents such as isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether, and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclohexanone, Fluorine-modified aromatic hydrocarbon-based solvents such as m-xylenehexafluoride and benzotrifluoride, and fluorine-modified ether-based solvents such as methyl perfluorobutyl ether. This solvent may be removed after the reaction by a known method such as distillation under reduced pressure, or may be used as is as a diluted solution depending on the desired use. The amount of solvent used is not particularly limited, but is preferably 10 times or less relative to the total mass of all reaction components. If the amount of solvent used is too large, there is a risk that the reaction rate will significantly decrease.
또한, 반응 시에는, 필요에 따라 중합금지제를 첨가해도 된다. 중합금지제로서는 특별히 제한은 없지만, 통상, 아크릴 화합물의 중합금지제로서 사용되는 것을 사용할 수 있다. 구체적으로는, 히드로퀴논, 히드로퀴논 모노메틸에테르, 4-tert-부틸카테콜, 디부틸히드록시톨루엔 등을 들 수 있다. 중합금지제의 사용량은 반응 조건, 반응 후의 정제 조건, 최종적인 사용 조건으로부터 결정하면 되고, 특별히 제한은 되지 않지만, 통상, 반응 성분의 전체 합계 질량에 대하여 0.01∼5,000ppm, 특히 바람직하게는 0.1∼500ppm이다.Additionally, during the reaction, a polymerization inhibitor may be added as needed. There are no particular restrictions on the polymerization inhibitor, but those normally used as polymerization inhibitors for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. are mentioned. The amount of the polymerization inhibitor used may be determined from the reaction conditions, purification conditions after the reaction, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000 ppm, particularly preferably 0.1 to 5,000 ppm, based on the total mass of the reaction components. It is 500ppm.
함불소 알코올 화합물에, (메타)아크릴산 할라이드를 반응시키는 경우, 특히 아크릴산 클로리드, 메타크리르산 클로리드를 반응시켜, 에스테르를 생성하는 것이 바람직하다. 이 에스테르 생성 반응은 상기 반응중간체(함불소 알코올 화합물), 수산제를 혼합 교반하면서 (메타)아크릴산 할라이드를 적하하여 행한다. 수산제는 트리에틸아민, 피리딘, 요소 등을 사용할 수 있다. 수산제의 사용량은 (메타)아크릴산 할라이드의 장입 몰수에 대하여 0.9∼3배 정도가 바람직하다. 지나치게 적으면 트랩되지 않는 산이 많이 잔존하게 되고, 지나치게 많으면 잉여가 되는 수산제의 제거가 곤란하게 된다.When reacting a (meth)acrylic acid halide with a fluorinated alcohol compound, it is particularly preferable to react with acrylic acid chloride or methacrylic acid chloride to produce an ester. This ester formation reaction is carried out by dropping a (meth)acrylic acid halide while mixing and stirring the reaction intermediate (fluorinated alcohol compound) and the oxalic acid agent. Hydroxide agents include triethylamine, pyridine, and urea. The amount of acid used is preferably about 0.9 to 3 times the number of moles of (meth)acrylic acid halide charged. If it is too small, a lot of untrapped acid will remain, and if it is too large, it will be difficult to remove the excess oxalic acid.
(메타)아크릴산 할라이드의 적하는 반응 혼합물의 온도를 0∼35℃로 유지하고, 20∼60분 걸쳐서 행한다. 그 후, 또한 30분∼10시간 교반을 계속한다. 반응 종료 후, 미반응의 (메타)아크릴산 할라이드, 반응에 의해 발생한 염 및 반응 용매 등을 증류 제거, 흡착, 여과 세정 등의 방법으로 제거함으로써, 본 발명에 따른 함불소 화합물 (A)를 얻을 수 있다.The dropwise addition of (meth)acrylic acid halide is carried out over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35°C. After that, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by methods such as distillation, adsorption, filtration and washing to obtain the fluorinated compound (A) according to the present invention. there is.
또한, 반응 정지 시에, 메탄올, 에탄올 등의 알코올 화합물을 계 내에 첨가하고, 미반응의 (메타)아크릴산 할라이드를 에스테르화해도 된다. 생성한 (메타)아크릴산 에스테르류는 미반응의 (메타)아크릴산 할라이드 제거와 동일한 방법으로 제거할 수 있지만, 잔존시킨 채 사용할 수도 있다.Additionally, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The produced (meth)acrylic acid esters can be removed by the same method as removing unreacted (meth)acrylic acid halides, but can also be used while remaining.
함불소 알코올 화합물에, (메타)아크릴기를 함유하는 이소시아네이트 화합물을 반응시키는 경우에는, 함불소 알코올 화합물과 (메타)아크릴기를 함유하는 이소시아네이트 화합물을 필요에 따라 용매와 함께 교반하고, 반응을 진행시킨다.When reacting an isocyanate compound containing a (meth)acrylic group with a fluorinated alcohol compound, the fluorinated alcohol compound and the isocyanate compound containing a (meth)acryl group are stirred with a solvent as necessary to allow the reaction to proceed.
이 반응에 있어서, 반응의 속도를 증가하기 위해 적절한 촉매를 첨가해도 된다. 촉매로서는, 예를 들면, 디부틸주석디아세테이트, 디부틸주석디라우레이트, 디부틸주석디옥토에이트, 디옥틸주석디아세테이트, 디옥틸주석디라우레이트, 디옥틸주석디옥테이트, 디옥탄산 제1주석 등의 알킬주석에스테르 화합물, 테트라이소프로폭시티탄, 테트라n-부톡시티탄, 테트라키스(2-에틸헥속시)티탄, 디프로폭시비스(아세틸아세토네이토)티탄, 티타늄이소프로폭시옥틸렌글리콜 등의 티탄산 에스테르 또는 티탄 킬레이트 화합물, 지르코늄테트라아세틸아세토네이트, 지르코늄트리부톡시모노아세틸아세토네이트, 지르코늄모노부톡시아세틸아세토네이트비스(에틸아세토아세테이트), 지르코늄디부톡시비스(에틸아세토아세테이트), 지르코늄테트라아세틸아세토네이트, 지르코늄 킬레이트 화합물 등이 예시된다. 이것들은 그 1종에 한정되지 않고, 2종 혹은 그 이상의 혼합물로서 사용할 수 있지만, 특히 환경에 대한 영향이 낮은 티탄 화합물, 지르코늄 화합물의 사용이 바람직하다. 이들 촉매를, 함불소 알코올 화합물과 (메타)아크릴기를 함유하는 이소시아네이트 화합물의 총질량에 대하여, 0.01∼5질량%, 바람직하게는 0.05∼3질량% 첨가함으로써, 반응속도를 증가시킬 수 있다.In this reaction, an appropriate catalyst may be added to increase the rate of reaction. Catalysts include, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and dioctanoic acid 1. Alkyl tin ester compounds such as tin, tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctylene. Titanium ester or titanium chelate compounds such as glycol, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium Examples include tetraacetylacetonate and zirconium chelate compounds. These are not limited to one type and can be used as a mixture of two or more types, but the use of titanium compounds and zirconium compounds, which have a low impact on the environment, is particularly preferable. The reaction rate can be increased by adding 0.01 to 5% by mass, preferably 0.05 to 3% by mass, of these catalysts relative to the total mass of the fluorinated alcohol compound and the isocyanate compound containing a (meth)acrylic group.
상기 반응은 0∼120℃, 바람직하게는 10∼70℃의 온도에서, 1분∼500시간, 바람직하게는 10분∼48시간 행한다. 반응 온도가 지나치게 낮으면 반응속도가 지나치게 늦어지는 경우가 있고, 반응 온도가 지나치게 높으면 부반응으로서 (메타)아크릴기의 중합이 일어나버릴 가능성이 있다. 반응 종료 후, 미반응의 이소시아네이트 화합물 및 반응 용매 등을 증류 제거, 흡착, 여과 세정 등의 방법으로 제거함으로써 본 발명에 따른 함불소 화합물 (A)를 얻을 수 있다.The reaction is carried out at a temperature of 0 to 120°C, preferably 10 to 70°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of the (meth)acrylic group may occur as a side reaction. After completion of the reaction, the unreacted isocyanate compound and reaction solvent can be removed by methods such as distillation, adsorption, filtration and washing to obtain the fluorinated compound (A) according to the present invention.
또 반응 정지 시에, 메탄올, 에탄올 등의 알코올 화합물을 계 내에 첨가하고, 미반응의 이소시아네이트 화합물과 우레탄 결합을 형성시켜도 된다. 생성한 우레탄(메타)아크릴레이트류는 미반응의 이소시아네이트 화합물과 동일한 방법으로 제거할 수 있지만, 잔존시킨 채 사용할 수도 있다.Additionally, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane (meth)acrylates can be removed in the same manner as the unreacted isocyanate compound, but can also be used while remaining.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물에 있어서, 함불소 화합물 (A)의 제조에서 부생하는, (메타)아크릴기의 도입 비율 등의 요인에 의해, 전구체 미반응의 플루오로폴리에테르기의 양쪽 말단에 복수의 알코올을 가지는 화합물이 잔존할 가능성이 있지만, 이것을 함유하고 있어도 된다. 또한 수산기에 모두 (메타)아크릴기가 도입된 화합물도 발생할 가능성이 있지만, 이것에 대해서는 후술하는 함불소 화합물 (B)에 상당한다고 생각해도 된다.In addition, in the fluorine-containing active energy ray-curable composition of the present invention, unreacted precursor fluoropolyether groups are formed due to factors such as the introduction ratio of (meth)acrylic groups, which are by-produced in the production of the fluorine-containing compound (A). There is a possibility that a compound having a plurality of alcohols remains at both ends of the , but it may be contained. In addition, there is a possibility that a compound in which (meth)acrylic groups are introduced into both hydroxyl groups may also occur, but this may be considered to correspond to the fluorine-containing compound (B) described later.
본 발명의 함불소 활성 에너지선 경화성 조성물의 또 하나의 구성법으로서 함불소 화합물 (A), 및 퍼플루오로폴리에테르기의 양쪽 말단에 2가의 연결기를 통하여 시클로폴리실록산 구조가 결합하고, 상기 시클로폴리실록산 구조에 2가의 연결기를 통한 (메타)아크릴기가 결합하고, 수산기를 포함하지 않는 구조를 가지는 함불소 화합물 (B)를 포함하는 함불소 활성 에너지선 경화성 조성물을 나타낼 수 있다.As another method of constituting the fluorinated active energy ray-curable composition of the present invention, a cyclopolysiloxane structure is bonded to both ends of a fluorinated compound (A) and a perfluoropolyether group through a divalent linking group, and the cyclopolysiloxane structure A fluorine-containing active energy ray-curable composition containing a fluorine-containing compound (B) to which a (meth)acrylic group is bonded through a divalent linking group and has a structure that does not contain a hydroxyl group can be shown.
함불소 화합물 (B)로서, 구체적으로는, 하기 일반식 (10)으로 표시되는 구조를 가지는 화합물을 예시할 수 있다.As the fluorine-containing compound (B), a compound having a structure represented by the following general formula (10) can be specifically exemplified.
X3-Z-Rf-Z-X3 (10)X 3 -Z-Rf-ZX 3 (10)
[식 중, Rf, Z는 상기와 같다. X3은 서로 독립적으로 하기 식 (11)[Where Rf and Z are as above. X 3 are independently of each other in the following equation (11)
(식 중, Q1, R1은 상기와 같다. f는 2∼11의 정수, 바람직하게는 2∼7의 정수, 보다 바람직하게는 2∼5의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)(In the formula, Q 1 and R 1 are the same as above. f is an integer of 2 to 11, preferably an integer of 2 to 7, more preferably an integer of 2 to 5. Each repeating unit is randomly combined You can have it.)
로 표시되는 기이다.]It is a group indicated by .]
또한, 함불소 화합물 (B)의 제조를 행할 때, 하기 일반식 (12)로 표시되는 구조를 가지는 화합물이 부생하는 경우가 있고, 이것들은 증류, 추출, 분취 크로마토그래프 등의 각종의 수단에 의해 제거해도 되지만, 그대로 포함한 것도 사용할 수 있다.In addition, when producing the fluorine-containing compound (B), compounds having a structure represented by the following general formula (12) may be produced as by-products, and these may be produced by various means such as distillation, extraction, and preparative chromatography. You can remove it, but you can also use the one included as is.
X3-[Z-Rf-Z-X4]w-Z-Rf-Z-X3 (12)X 3 -[Z-Rf-ZX 4 ] w -Z-Rf-ZX 3 (12)
일반식 (12)에 있어서, Rf, Z, X3은 일반식 (10)과 동일하고, w는 0∼5의 정수이며, X4는 서로 독립적으로, 하기 식 (13)으로 표시되는 기이다.In the general formula (12 ) , Rf, Z , and .
(식 중, Q1, R1은 상기와 같고, g는 1 이상의 정수, 바람직하게는 1∼7의 정수, 보다 바람직하게는 2∼3의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)(Wherein, Q 1 and R 1 are the same as above, and g is an integer of 1 or more, preferably an integer of 1 to 7, more preferably an integer of 2 to 3. Each repeating unit may be randomly combined. .)
즉 함불소 화합물 (B)는 일반식 (1)로 표시되는 화합물 중, X1에서 b=0인 화합물을 나타낼 수 있다.That is, the fluorine-containing compound (B) may represent a compound where b=0 in X 1 among the compounds represented by general formula (1).
함불소 화합물 (B)의 바람직한 구조로서, 구체적으로는, 이하의 것을 예시할 수 있다.As a preferable structure of the fluorine-containing compound (B), the following can be specifically exemplified.
(식 중, Rf'은 상기와 같고, R5는 (메타)아크릴 함유 기이다.)(Wherein, Rf' is the same as above, and R 5 is a (meth)acrylic-containing group.)
여기에서, R5의 (메타)아크릴 함유 기로서는 R4에서 예시한 (메타)아크릴 함유 기와 동일한 것을 예시할 수 있다.Here, the (meth)acryl-containing group of R 5 may be the same as the (meth)acryl-containing group exemplified for R 4 .
이러한 함불소 화합물 (B)는, 앞에 예시한 함불소 화합물 (A)의 합성법에서, 함불소 알코올 화합물의 수산기량의 합계 x몰에 대한 (메타)아크릴기 도입 시약의 할로겐 원자 혹은 이소시아네이트기량 y몰을 x<y가 되는 비율로 장입하고, 수산기를 모두 반응시킴으로써 얻을 수 있다.In the synthesis method of the fluorinated compound (A) exemplified above, this fluorinated compound (B) is the amount of y moles of halogen atoms or isocyanate groups of the (meth)acrylic group-introducing reagent relative to the total amount of x moles of hydroxyl groups of the fluorinated alcohol compound. It can be obtained by charging in a ratio such that x<y and reacting all the hydroxyl groups.
본 발명에 있어서의 함불소 화합물 (A)와 함불소 화합물 (B)를 병용하는 형태에서는, 함불소 화합물 (A)와 함불소 화합물 (B)의 함유율을 조정함으로써, 함불소 화합물 (A) 단체에서 (메타)아크릴기와 수산기의 비율을 변화시키는 것과 동일한 효과를 얻을 수 있다. 이 경우, 조성물 중에 포함되는 함불소 화합물 (A), 함불소 화합물 (B) 전체의 평균값으로서 조성물 중의 함불소 화합물 (A)에 포함되는 수산기에 대한 함불소 화합물 (A) 중에 포함되는 (메타)아크릴기와 함불소 화합물 (B) 중에 포함되는 (메타)아크릴기의 합계의 몰비[(메타)아크릴기의 합계(몰)/수산기(몰)]가 0.2 이상 19 이하인 것이 바람직하고, 0.3 이상 10 이하인 것이 보다 바람직하고, 0.4 이상 5 이하인 것이 더욱 바람직하다. 즉 계 내에 포함되는 함불소 화합물 (A)에 포함되는 (메타)아크릴기의 합계 몰수를 NaA, 수산기의 합계 몰수를 NaH, 함불소 화합물 (B)에 포함되는 (메타)아크릴기의 합계 몰수를 NbA로 했을 때, 0.2≤(NaA+NbA)/NaH≤19인 것이 바람직하다.In the form of using the fluorinated compound (A) and the fluorinated compound (B) together in the present invention, by adjusting the content ratio of the fluorinated compound (A) and the fluorinated compound (B), the fluorinated compound (A) alone The same effect can be obtained by changing the ratio of (meth)acrylic groups and hydroxyl groups. In this case, as the average value of all the fluorinated compound (A) and fluorinated compound (B) contained in the composition, the (meta) contained in the fluorinated compound (A) relative to the hydroxyl group contained in the fluorinated compound (A) in the composition The molar ratio of the total of the acrylic group and the (meth)acrylic group contained in the fluorinated compound (B) [sum of (meth)acrylic groups (mol)/hydroxyl group (mol)] is preferably 0.2 or more and 19 or less, and 0.3 or more and 10 or less. It is more preferable that it is 0.4 or more and 5 or less. That is, the total number of moles of (meth)acrylic groups contained in the fluorine-containing compound (A) contained in the system is N aA , the total number of moles of hydroxyl groups is N aH , and the total number of moles of (meth)acrylic groups contained in the fluorine-containing compound (B) is N aH. When the number of moles is N bA , it is preferable that 0.2≤(N aA +N bA )/N aH≤19 .
이것보다 커지면 함불소 화합물 (B) 단체와의 특성의 차이가 명확하지 않게 되고, 이것보다 작아지면 비불소의 아크릴 화합물과의 용해성이 저하되어, 특성의 발현에 필요한 농도에서의 균일한 도공이 곤란하게 된다.If it is larger than this, the difference in characteristics from the fluorinated compound (B) alone will not be clear, and if it is smaller than this, the solubility with the non-fluorinated acrylic compound will decrease, making uniform coating at the concentration necessary for expression of the properties difficult. I do it.
함불소 활성 에너지선 경화성 조성물은 함불소 화합물 (A) 단체, 및 함불소 화합물 (A)와 함불소 화합물 (B)의 혼합물만으로서도 사용할 수 있지만, 함불소 화합물 (A) 및 함불소 화합물 (B)와 혼합, 경화 가능하면, 어떠한 것이어도 사용할 수 있다. 이러한 배합물로서, 구체적으로는, 함불소 화합물 (A), (B)에 해당하지 않는, 바람직하게는 분자 중에 불소 원자를 함유하지 않는 (비불소화의), 분자 중에 우레탄 결합을 함유 또는 비함유한, 아크릴 화합물 (C)를 들 수 있다. 이 아크릴 화합물 (C)로서는, 예를 들면, 1,6-헥산디올디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 이소시아누르산 에틸렌옥시드 변성 디(메타)아크릴레이트, 이소시아누르산 EO 변성 트리(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 트리스(메타)아크릴로일옥시에틸포스페이트, 프탈산 수소-(2,2,2-트리-(메타)아크릴로일옥시메틸)에틸, 글리세롤트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 소르비톨헥사(메타)아크릴레이트 등의 2∼6 작용의 (메타)아크릴 화합물, 이들 (메타)아크릴 화합물의 에틸렌옥시드, 프로필렌옥시드, 에피클로로히드린, 지방산, 알킬 변성품, 에폭시 수지에 (메타)아크릴산을 부가시켜 얻어지는 에폭시(메타)아크릴레이트류, 및 아크릴산 에스테르 공중합체의 측쇄에 (메타)아크릴로일기를 도입한 공중합체 등을 포함하는 것을 들 수 있다.The fluorinated active energy ray-curable composition can be used as a single fluorinated compound (A) or as a mixture of the fluorinated compound (A) and the fluorinated compound (B). Any material can be used as long as it can be mixed and hardened. As such a combination, specifically, it does not correspond to the fluorinated compounds (A) and (B), preferably does not contain a fluorine atom in the molecule (non-fluorinated), and contains or does not contain a urethane bond in the molecule. , acrylic compound (C). Examples of this acrylic compound (C) include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, and ethylene oxide isocyanurate. Seed-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, Tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acryl 2 to 6-functional (such as ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc.) Meth)acrylic compounds, ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl modified products of these (meth)acrylic compounds, epoxy (meth)acrylates obtained by adding (meth)acrylic acid to epoxy resin, and copolymers in which a (meth)acryloyl group is introduced into the side chain of an acrylic acid ester copolymer.
또한, 우레탄(메타)아크릴레이트류, 폴리이소시아네이트에 수산기를 가지는 (메타)아크릴레이트를 반응시켜 얻어지는 것, 폴리이소시아네이트와 말단 디올의 폴리에스테르에 수산기를 가지는 (메타)아크릴레이트를 반응시켜 얻어지는 것, 폴리올에 과잉의 디이소시아네이트와 반응시켜 얻어지는 폴리이소시아네이트에, 수산기를 가지는 (메타)아크릴레이트를 반응시켜 얻어지는 것을 사용할 수도 있다. 그중에서도, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시-3-아크릴로일옥시프로필메타크릴레이트, 및 펜타에리트리톨트리(메타)아크릴레이트로부터 선택되는 수산기를 가지는 (메타)아크릴레이트와, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 톨릴렌디이소시아네이트, 리신디이소시아네이트, 노르보르난디이소시아네이트, 1,3-비스(이소시아네이토메틸)시클로헥산, 메틸렌비스(4-시클로헥실이소시아네이트), 2-메틸-1,3-디이소시아네이토시클로헥산, 2-메틸-1,5-디이소시아네이토시클로헥산 및 디페닐메탄디이소시아네이트로부터 선택되는 폴리이소시아네이트를 반응시킨 우레탄(메타)아크릴레이트류가 바람직하다.In addition, urethane (meth)acrylates, those obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate, those obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate and a polyester of a terminal diol, What is obtained by reacting polyisocyanate obtained by reacting polyol with excess diisocyanate and (meth)acrylate having a hydroxyl group can also be used. Among them, (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol tri(meth)acrylate. and, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexylisocyanate), Urethane (meth)acrylates obtained by reacting a polyisocyanate selected from 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate. is desirable.
그중에서도 특히, 1 분자 중에 3개 이상의 (메타)아크릴기를 가지며, 또한 분자 중에 수산기를 가지지 않는, 우레탄 결합 함유 또는 비함유의, 비불소화 다작용 (메타)아크릴레이트, 1 분자 중에 3개 이상의 (메타)아크릴기와 1개 이상의 수산기를 가지는 우레탄 결합 함유 또는 비함유의, 비불소화 다작용 (메타)아크릴레이트, 및 분자 중에 우레탄 결합을 가지고, 1 분자 중에 6개 이상의 (메타)아크릴기를 가지는 비불소화 다작용 우레탄(메타)아크릴레이트의 어느 하나 또는 2종류 이상의 조합을 포함한 것이 바람직하다.Among them, in particular, non-fluorinated polyfunctional (meth)acrylates containing or not containing urethane bonds, having 3 or more (meth)acrylic groups in 1 molecule and no hydroxyl groups in 1 molecule, 3 or more (meth)acrylates in 1 molecule ) Non-fluorinated polyfunctional (meth)acrylates containing or not containing a urethane bond having an acrylic group and one or more hydroxyl groups, and non-fluorinated polyfunctional (meth)acrylates having a urethane bond in the molecule and having six or more (meth)acrylic groups in one molecule. It is preferable to include one or a combination of two or more functional urethane (meth)acrylates.
(C) 성분은 1종 단독으로 사용해도 2종 이상을 병용해도 된다. 또 조성물의 물성 조정을 위해 불소화, 비불소화의 1 작용의 (메타)아크릴레이트류를 배합해도 된다.(C) Component may be used individually or in combination of two or more types. Additionally, in order to adjust the physical properties of the composition, fluorinated or non-fluorinated monofunctional (meth)acrylates may be added.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물은 (D) 성분으로서 광중합 개시제를 함유함으로써, 활성 에너지선 중에서도 자외선에 의해 경화하기 쉬운 경화성 조성물로 할 수 있다. (D) 성분의 광중합 개시제는 자외선 조사에 의해 아크릴 화합물을 경화시킬 수 있는 것이면 특별히 한정되지 않지만, 바람직하게는, 예를 들면, 아세토페논, 벤조페논, 2,2-디메톡시-1,2-디페닐에탄-1-온, 1-히드록시-시클로헥실-페닐-케톤, 2-히드록시-2-메틸-1-페닐-프로판-1-온, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄온-1,2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부탄온, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 1,2-옥탄디온-1-[4-(페닐티오)-2-(O-벤조일옥심)], 에탄온-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-1-(O-아세틸옥심), 2-히드록시-1-{4-[4-(2-히드록시-2-메틸-프로피오닐)-벤질]페닐}-2-메틸-프로판-1-온 등을 들 수 있고, 이것들은 1종 단독으로 사용해도 2종 이상을 병용해도 된다.Furthermore, the fluorine-containing active energy ray-curable composition of the present invention contains a photopolymerization initiator as component (D), so that the curable composition can be easily cured by ultraviolet rays among active energy rays. The photopolymerization initiator of component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, but is preferably used, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxy Toxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morph polynyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione -1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- 1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one These etc. can be mentioned, and these may be used individually or in combination of two or more types.
본 발명의 실시형태의 하나인 함불소 활성 에너지선 경화성 조성물은 (A) 성분을 포함하고, 경화 후의 표면에 발수발유성, 방오성, 내지문성, 마모내구성과 같은 특성을 부여하는 것이 그 본질이며, 각 성분의 배합량은 원하는 발수성, 발유성, 조성물의 용해성, 도공 조건, 경화 조건, 얻어지는 물품의 경도 등에 따라 적당히 결정하면 되고,The fluorine-containing active energy ray-curable composition, which is one of the embodiments of the present invention, contains component (A), and its essence is to impart properties such as water and oil repellency, antifouling properties, anti-fingerprinting properties, and abrasion durability to the surface after curing, The mixing amount of each component can be appropriately determined depending on the desired water repellency, oil repellency, solubility of the composition, coating conditions, curing conditions, hardness of the product to be obtained, etc.
(A) 성분 단독,(A) component alone;
(A) 성분과 (B) 성분,Component (A) and Component (B),
(A) 성분과 (C) 성분,Components (A) and (C),
(A) 성분과 (D) 성분,Components (A) and (D),
(A) 성분과 (B) 성분과 (C) 성분,(A) component and (B) component and (C) component,
(A) 성분과 (C) 성분과 (D) 성분,(A) component and (C) component and (D) component,
(A) 성분과 (B) 성분과 (C) 성분과 (D) 성분,(A) component and (B) component and (C) component and (D) component,
및 이것들 각각에, 필요에 따라 후술하는 그 밖의 첨가제를 가한 어느 조합으로도 사용할 수 있지만, 그중에서도 바람직한 것은 (A) 성분과 (B) 성분과 (C) 성분과 (D) 성분을 포함하는 조성물이다.and each of these can be used in any combination by adding other additives described later as necessary, but among them, a composition containing component (A), component (B), component (C), and component (D) is preferred. .
이때, (B) 성분을 배합하는 경우의 배합량은, 상기한 바와 같이, (A) 성분에 포함되는 수산기에 대한 (A) 성분과 (B) 성분에 포함되는 (메타)아크릴기의 합계의 몰비[(메타)아크릴기의 합계(몰)/수산기(몰)]가 0.2 이상 19 이하가 되는 양으로 배합하는 것이 바람직하다.At this time, the mixing amount when mixing component (B) is the molar ratio of the total of the (meth)acrylic group contained in component (A) and component (B) to the hydroxyl group contained in component (A), as described above. It is preferable to mix in an amount such that [total (mol) of (meth)acrylic groups/hydroxyl groups (mol)] is 0.2 or more and 19 or less.
(C) 성분을 배합하는 경우의 배합량은 특별히 제한되지 않지만, (A) 성분과 (B) 성분의 합계에 대한 비율로 생각하는 것이 바람직하고, 예를 들면, (A) 성분과 (B) 성분의 합계량을 1질량부로 했을 때, 0.1∼10,000질량부가 바람직하고, 보다 바람직하게는 1∼1,000질량부, 특히 바람직하게는 5∼800질량부이다. (C) 성분이 지나치게 적으면 (C) 성분의 배합에 의해 기대되는 도공 특성, 경화물 특성이 얻어지지 않는 경우가 있고, 지나치게 많으면, (A) 성분에 기대되는 방오 특성이 얻어지지 않는 경우가 있다.When mixing component (C), the mixing amount is not particularly limited, but it is preferable to think of it as a ratio to the total of component (A) and component (B), for example, component (A) and component (B). When the total amount is 1 part by mass, the amount is preferably 0.1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, and particularly preferably 5 to 800 parts by mass. If the component (C) is too small, the coating properties and cured product properties expected from the mixing of the component (C) may not be obtained, and if the component (C) is too large, the antifouling properties expected from the component (A) may not be obtained. there is.
또한, (D) 성분을 배합하는 경우의 배합량은, (A) 성분과 (B) 성분과 (C) 성분의 합계량을 100질량부로 했을 때, 0.1∼10질량부가 바람직하고, 특히 바람직하게는 0.5∼5질량부이다. (D) 성분이 지나치게 적으면 경화 불량이 발생하여, 기대되는 경화물 특성이 얻어지지 않는 경우가 있고, 지나치게 많으면, 경화물 표면에 결손이 발생하거나, 경화물에 탁함이 발생하거나, 착색이 강해지거나 하는 경우가 있다.In addition, the mixing amount when mixing component (D) is preferably 0.1 to 10 parts by mass, especially preferably 0.5 parts by mass, when the total amount of component (A), component (B), and component (C) is 100 parts by mass. ~5 parts by mass. (D) If the component is too small, curing failure may occur and the expected cured product characteristics may not be obtained. If it is too much, defects may occur on the surface of the cured product, cloudiness may occur in the cured product, or coloring may become stronger. There are cases where this happens.
또한, 상기 (C) 성분에 (D) 성분이 배합된 아크릴 조성물 및 하드 코트제는 각 회사에서 다양한 것이 시판되고 있다. 본 발명의 함불소 활성 에너지선 경화성 조성물은 이러한 시판품에 (A) 성분, 또는 (A) 성분과 (B) 성분을 첨가한 것이어도 된다. 시판품의 하드 코트제로서, 예를 들면, 아라카와카가쿠고교(주)「빔세트」, 오하시카가쿠고교(주)「유빅크」, 오리진덴키(주)「UV 코트」, 카슈(주)「카슈 UV」, JSR(주)「데솔라이트」, 다이이치세이카고교(주)「세이카빔」, 닛폰고세카가쿠(주)「시코」, 후지쿠라카세이(주)「후지하드」, 미츠비시레이온(주)「다이아빔」, 무사시토료(주)「울트라바인」, DIC(주)「유니딕」 등을 들 수 있다. 또 이들 시판의 조성물을 사용한 경우도, 필요에 따라 (C) 성분, (D) 성분을 추가해도 된다.In addition, a variety of acrylic compositions and hard coat agents containing the component (C) and component (D) are commercially available from each company. The fluorine-containing active energy ray-curable composition of the present invention may be obtained by adding component (A) or component (A) and component (B) to such a commercial product. Commercially available hard coat agents include, for example, “Beam Set” from Arakawa Chemical Industries, Ltd., “Ubik” from Ohashi Chemical Industries, Ltd., “UV Coat” from Origin Denki Co., Ltd., and “UV Coat” from Kashu Corporation. Kashu UV", JSR Co., Ltd. "Desolite", Daiichi Seika Kogyo Co., Ltd. "Seikabeam", Nippon Goseikagaku Co., Ltd. "Shico", Fujikura Kasei Co., Ltd. "Fujihard", Mitsubishi Rayon ( Examples include “Diabeam” (Co., Ltd.), “Ultra Vine” (Musashi Toryo Co., Ltd.), and “Unidic” (DIC Co., Ltd.). Moreover, even when these commercially available compositions are used, component (C) and component (D) may be added as needed.
[그 밖의 첨가제][Other additives]
본 발명의 함불소 활성 에너지선 경화성 조성물에는, 또한 목적에 따라, 유기 용제, 중합금지제, 대전방지제, 소포제, 점도조정제, 내광안정제, 내열안정제, 산화방지제, 계면활성제, 착색제, 및 필러 등을 배합할 수도 있다. 또한, 상기한 바와 같이 시판품의 하드 코트제를 사용하는 경우이더라도, 목적에 따라, 유기 용제, 중합금지제, 대전방지제, 소포제, 점도조정제, 내광안정제, 내열안정제, 산화방지제, 계면활성제, 착색제, 및 필러 등을 배합할 수 있다.The fluorinated active energy ray-curable composition of the present invention may further contain an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, and a filler, depending on the purpose. It can also be combined. In addition, even if a commercially available hard coat agent is used as described above, depending on the purpose, organic solvents, polymerization inhibitors, antistatic agents, anti-foaming agents, viscosity modifiers, light-resistant stabilizers, heat-resistant stabilizers, antioxidants, surfactants, colorants, and fillers, etc. can be mixed.
또한, 피막 강도, 내찰상성, 투명성 등의 각종 특성 향상, 굴절률의 조정 등의 특성 향상을 위해, 반응성·비반응성 중공·중실 실리카 미립자 등의 각종 무기 미립자를 배합해도 된다.Additionally, in order to improve various properties such as film strength, scratch resistance, transparency, etc., and adjust the refractive index, various inorganic fine particles such as reactive and non-reactive hollow and solid silica fine particles may be mixed.
유기 용제로서는 1-프로판올, 2-프로판올, 이소프로필알코올, n-부탄올, 이소 부탄올, tert-부탄올, 디아세톤알코올 등의 알코올류; 메틸프로필케톤, 디에틸케톤, 메틸에틸케톤, 메틸이소부틸케톤(MIBK), 시클로헥산온 등의 케톤류; 디프로필에테르, 디부틸에테르, 아니솔, 디옥산, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르(PGME), 프로필렌글리콜모노메틸에테르아세테이트 등의 에테르류; 아세트산 에틸, 아세트산 프로필, 아세트산 부틸, 아세트산 시클로헥실 등의 에스테르류, m-크실렌헥사플루오라이드, 벤조트리플루오라이드 등의 불소 변성 방향족 탄화수소계 용제, 메틸퍼플루오로부틸에테르 등의 불소 변성 에테르계 용제 등을 들 수 있다. 상기 유기 용제는 1종을 단독으로 사용해도 되고, 2종 이상을 혼합하여 사용해도 된다.Organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, and diacetone alcohol; Ketones such as methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate; Ester such as ethyl acetate, propyl acetate, butyl acetate, and cyclohexyl acetate, fluorine-modified aromatic hydrocarbon solvents such as m-xylenehexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. etc. can be mentioned. The organic solvent may be used individually, or two or more types may be mixed.
유기 용제의 사용량은 특별히 제한되는 것은 아니지만, (A)∼(C) 성분의 합계100질량부에 대하여, 50∼10,000질량부가 바람직하고, 특히 80∼1,000질량부가 바람직하다.The amount of the organic solvent used is not particularly limited, but is preferably 50 to 10,000 parts by mass, and particularly preferably 80 to 1,000 parts by mass, relative to a total of 100 parts by mass of components (A) to (C).
또 그 밖에, 중합금지제, 대전방지제, 소포제, 점도조정제, 내광안정제, 내열안정제, 산화방지제, 계면활성제, 착색제, 및 필러로서 공지의 것을 본 발명의 목적을 손상시키지 않는 범위에서 특별히 제한되지 않고 사용할 수 있다.In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are known and are not particularly limited as long as they do not impair the purpose of the present invention. You can use it.
본 발명의 함불소 활성 에너지선 경화성 조성물의 경화 방법은 특별히 한정되지 않고, (A) 성분 단독, (A) 성분과 (B) 성분, (A) 성분과 (C) 성분, 또는 (A) 성분과 (B) 성분과 (C) 성분을 포함하는 조성물을, 적당히 용제로 희석, 도포한 것을 전자선 등의 활성 에너지선에 의해 경화시킬 수도 있지만, 또한 (D) 성분의 광중합 개시제를 함유하는 경우에는, 자외선에 의해 경화시킬 수 있다. 자외선에 의한 경화의 경우, 자외선 조사를 공기 중에서 행할 수도 있지만, 산소에 의한 경화 저해(저지)를 방지하기 위해 산소 농도를 5,000ppm 이하로 억제하는 것이 바람직하고, 질소, 이산화탄소, 아르곤 등의 불활성 가스 분위기하에서 경화시키는 것이 특히 바람직하다.The curing method of the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, and includes component (A) alone, component (A) and component (B), component (A) and component (C), or component (A). The composition containing component (B) and component (C) may be cured by appropriately diluting and applying a solvent with an active energy ray such as an electron beam. However, in the case where it also contains a photopolymerization initiator of component (D), , it can be hardened by ultraviolet rays. In the case of curing by ultraviolet rays, ultraviolet irradiation can be performed in the air, but it is preferable to suppress the oxygen concentration to 5,000 ppm or less to prevent curing inhibition by oxygen, and inert gas such as nitrogen, carbon dioxide, or argon It is particularly preferable to cure in an atmosphere.
또 필름 등의 기재의 코팅, 각종 물품의 도료 등으로서 사용하는 경우, 목적으로 하는 임의의 특성에 맞추어 (C) 성분이나 그 밖의 첨가제를 자유롭게 배합할 수 있다.In addition, when using it as a coating for a base material such as a film or as a paint for various articles, component (C) and other additives can be freely mixed according to the desired properties.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물의 일반적인 사용 형태로서는 본 발명의 함불소 활성 에너지선 경화성 조성물층이 경화 후에 밀착 또는 접착하는 것이면 어떠한 기재 위에 도포할 수도 있지만, 특히 수지 기재, 예를 들면, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리에틸렌, 폴리프로필렌, 셀로판, 디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부티레이트, 셀룰로오스아세테이트프로피오네이트, 시클로올레핀 폴리머, 시클로올레핀 코폴리머, 폴리염화비닐, 폴리염화비닐리덴, 폴리비닐알코올, 에틸렌-아세트산 비닐 공중합체, 폴리스티렌, 폴리카보네이트, 폴리메틸펜텐, 폴리술폰, 폴리에테르에테르케톤, 폴리에테르술폰, 폴리에테르이미드, 폴리이미드, 불소 수지, 나일론, 아크릴 수지 등의 수지를 들 수 있다. 이것들은 필름, 판 형상, 및 성형 부재 등 임의의 형태를 취하는 것에 대하여 그 표면에 사용할 수 있다.In addition, as a general use form of the fluorine-containing active energy ray-curable composition of the present invention, the fluorine-containing active energy ray-curable composition layer of the present invention can be applied on any substrate as long as it adheres or adheres to it after curing, but in particular, resin substrates, such as For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethyl pentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin. , nylon, and acrylic resin. These can be used on the surface of anything taking any form, such as films, plates, and molded members.
또 필름 기재에 도공한 경우, 함불소 활성 에너지선 경화성 조성물층을 도포·형성한 것과 반대의 면에 점착제를 도포한 구조를 취하고 있어도 되고, 또한 점착제를 보호하기 위한 이형 필름을 배치해도 된다.In addition, when coating on a film substrate, a structure may be adopted in which the adhesive is applied to the side opposite to that on which the fluorine-containing active energy ray-curable composition layer is applied and formed, and a release film may be disposed to protect the adhesive.
또한, 상기 필름 기재는 상기에서 든 수지 필름만으로 이루어지는 기재이어도 되지만, 본 발명의 함불소 활성 에너지선 경화성 조성물과의 밀착성을 향상시키기 위해, 상기 수지 필름에 프라이머층을 마련한 필름 기재이어도 된다. 상기 프라이머층으로서는, 예를 들면, 폴리에스테르계 수지, 우레탄계 수지, 아크릴계 수지 등으로 이루어지는 것을 들 수 있다.In addition, the film substrate may be a substrate consisting of only the resin film mentioned above, but may be a film substrate in which a primer layer is provided on the resin film in order to improve adhesion to the fluorine-containing active energy ray-curable composition of the present invention. Examples of the primer layer include those made of polyester resin, urethane resin, and acrylic resin.
또 본 발명의 함불소 활성 에너지선 경화성 조성물은 경화·미경화의 본 발명에 해당하지 않는 경화성 조성물층 위에 도공 경화해도 된다. 예를 들면, 경도, 내구성, 대전방지성, 컬 등의 변형 방지성이 더 높은 경화물층의 위에 본 발명의 함불소 활성 에너지선 경화성 조성물을 겹쳐서 도포할 수 있다.Additionally, the fluorine-containing active energy ray-curable composition of the present invention may be applied and cured on a cured or uncured layer of the curable composition that does not correspond to the present invention. For example, the fluorine-containing active energy ray curable composition of the present invention can be applied in an overlapping manner on a cured layer having higher hardness, durability, antistatic properties, and higher deformation resistance such as curl.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물과의 밀착성을 향상시킬 목적으로, 수지 필름 표면을 샌드 블라스팅법, 용제 처리법 등에 의한 표면의 요철화 처리, 코로나 방전 처리, 크롬산 처리, 화염 처리, 열풍 처리, 오존·자외선 조사 처리, 산화 처리 등에 의해 처리를 할 수도 있다.In addition, for the purpose of improving adhesion with the fluorine-containing active energy ray curable composition of the present invention, the surface of the resin film is subjected to roughening treatment by sand blasting, solvent treatment, etc., corona discharge treatment, chromic acid treatment, flame treatment, and hot air treatment. Treatment can also be carried out by treatment, ozone/ultraviolet irradiation treatment, oxidation treatment, etc.
본 발명의 함불소 활성 에너지선 경화성 조성물을 상기 기재나 물품에 도포하는 방법으로서는, 특별히 제한은 되지 않지만, 예를 들면, 롤 코팅, 그라비아 코팅, 플로우 코팅, 커튼 코팅, 딥 코팅, 스프레이 코팅, 스핀 코팅, 바 코팅, 스크린 인쇄 등의 공지의 도공 방법을 사용할 수 있다.The method for applying the fluorine-containing active energy ray-curable composition of the present invention to the substrate or article is not particularly limited, and includes, for example, roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, and spin. Known coating methods such as coating, bar coating, and screen printing can be used.
도공 후, 도포막에 활성 에너지선을 조사하여 이것을 경화시킨다. 여기에서, 활성 에너지선으로서는 전자선, 자외선 등 임의의 것을 사용할 수 있지만, 특히 자외선이 바람직하다. 자외선원으로서는 수은 램프, 메탈 할라이드 램프, LED 램프가 적합하다. 자외선 조사량으로서는 지나치게 적으면 미경화 성분이 잔존하고, 지나치게 많으면 도포막 및 기재가 열화될 가능성이 있기 때문에, 10∼10,000mJ/cm2, 특히 100∼4,000mJ/cm2의 범위에 있는 것이 바람직하다.After coating, the coating film is irradiated with active energy rays to harden it. Here, any active energy ray, such as an electron beam or an ultraviolet ray, can be used, but ultraviolet rays are particularly preferable. Mercury lamps, metal halide lamps, and LED lamps are suitable as ultraviolet ray sources. The amount of ultraviolet irradiation is preferably in the range of 10 to 10,000 mJ/cm 2 , especially 100 to 4,000 mJ/cm 2 , because if it is too small, uncured components may remain, and if it is too much, the coating film and base material may deteriorate. .
또 산소에 의한 경화 저해를 방지하기 위해, 자외선 조사 시에 조사 분위기를 질소, 이산화탄소, 아르곤 등의 산소 분자를 포함하지 않는 불활성 가스로 치환하거나, 도포막 표면을 이형성을 가지는 자외선 투과성이 있는 보호층으로 덮고, 그 위에서 자외선을 조사하거나, 기재가 자외선 투과성을 가지는 경우에는 도포막 표면을 이형성이 있는 보호층으로 덮은 다음에 기재의 도공면과는 반대측에서 자외선을 조사해도 된다. 또 도포막의 레벨링 혹은 도포막 중의 (메타)아크릴기의 중합을 효과적으로 행하기 위해, 자외선 조사 전 및 조사 중에 도포막 및 기재를 적외선이나 열풍 건조로 등 임의의 수법으로 가열해도 된다.In addition, in order to prevent curing inhibition by oxygen, when irradiating ultraviolet rays, the irradiation atmosphere must be replaced with an inert gas that does not contain oxygen molecules, such as nitrogen, carbon dioxide, or argon, or the surface of the coating film must be covered with a UV-transmitting protective layer with release properties. and irradiating ultraviolet rays on it, or if the substrate has ultraviolet ray transparency, the surface of the coating film may be covered with a protective layer with release properties and then irradiated with ultraviolet rays from the side opposite to the coated surface of the substrate. In addition, in order to effectively level the coating film or polymerize the (meth)acrylic groups in the coating film, the coating film and the base material may be heated by any method such as infrared rays or a hot air dryer before and during irradiation with ultraviolet rays.
이렇게 하여 얻어지는 함불소 활성 에너지선 경화성 조성물의 경화물층의 두께로서는 특별히 제한되지 않지만, 0.01∼5,000㎛, 특히 0.05∼200㎛인 것이 바람직하다.The thickness of the cured layer of the fluorine-containing active energy ray-curable composition obtained in this way is not particularly limited, but is preferably 0.01 to 5,000 μm, especially 0.05 to 200 μm.
또한, 이렇게 하여 얻어지는 본 발명의 함불소 활성 에너지선 경화성 조성물의 경화물층은 이온교환수의 2μL의 액적이 액 접촉으로부터 1초 후에 액체 표면과 고체면과 이루는 각에 의해 측정한 정적 수접촉각이 100° 이상, 특히 105° 이상, 올레산의 4μL의 액적이 액 접촉으로부터 1초 후에 액체 표면과 고체면이 이루는 각에 의해 측정한 정적 올레산 접촉각이 60° 이상, 특히 65° 이상인 발수발유성 표면이 될 수 있는 것이 바람직하다. 또한, 상기 접촉각으로 하기 위해서는, 본 발명의 함불소 활성 에너지선 경화성 조성물의 경화물층이 이 경화물층의 전체 표면적에 대하여 평균하여 두께 10nm 이상의 층을 이룰 수 있는 양인 것이 바람직하다. 또한, 경화물층 표면에는 미반응의 (메타)아크릴기가 잔존하지 않을수록 바람직하고, 이 때문에 질소, 이산화탄소 등의 불활성 가스 분위기하에서 경화시킨 경화물층인 것이 바람직하다.In addition, the cured layer of the fluorine-containing active energy ray-curable composition of the present invention obtained in this way has a static water contact angle measured by the angle formed by a 2 μL droplet of ion-exchanged water between the liquid surface and the solid surface 1 second after liquid contact. A water- and oil-repellent surface having a static oleic acid contact angle of 100° or more, especially 105° or more, and a static oleic acid contact angle of 60° or more, especially 65° or more, as measured by the angle formed by the liquid surface and the solid surface 1 second after a 4 μL droplet of oleic acid comes into contact with the liquid. It is desirable to be able to do so. In addition, in order to achieve the above contact angle, it is preferable that the cured layer of the fluorine-containing active energy ray-curable composition of the present invention is in an amount that can form a layer with a thickness of 10 nm or more on average with respect to the total surface area of the cured layer. In addition, the less unreacted (meth)acrylic groups remaining on the surface of the cured layer, the more desirable it is. For this reason, it is preferable that the cured layer is cured in an inert gas atmosphere such as nitrogen or carbon dioxide.
이상과 같이, 본 발명의 함불소 활성 에너지선 경화성 조성물은 자외선 등의 활성 에너지선에 의해 경화 가능하며, 물품의 표면에, 발수발유성, 방오성, 미끄럼성, 내마모성이 우수한 경화 수지층을 형성할 수 있다.As described above, the fluorine-containing active energy ray-curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and can form a cured resin layer excellent in water and oil repellency, anti-fouling properties, slipperiness, and abrasion resistance on the surface of the article. You can.
또한, 본 발명에서는, 상기한 본 발명의 함불소 활성 에너지선 경화성 조성물을 표면에 도포하고 경화시킨 경화 피막을 갖는 물품을 제공한다. 상기한 바와 같이, 본 발명의 함불소 활성 에너지선 경화성 조성물을 사용하면, 기재(물품)의 표면 이 우수한 표면 특성을 가지는 경화 피막(경화 수지층)을 형성하는 것이 가능하게 된다. 특히, 아크릴 하드 코트의 표면에 발수성, 발유성, 방오성을 부여하는데 유용하다. 이것에 의해, 지문, 피지, 땀 등의 인지(人脂), 화장품 등에 의한 오염, 기계유 등이 부착되기 어려워지고, 또한 닦아냄성도 우수한 하드 코트 표면을 기재에 공급할 수 있다. 이 때문에, 본 발명의 함불소 활성 에너지선 경화성 조성물은 사람이 접촉하여 인지, 화장품 등에 의해 더럽혀질 가능성이 있는 기재(물품), 또 작업자의 인지나 기계유 등으로 오염될 가능성이 있는 기계 내부에 사용되는 공정 재료 필름 등의 표면에 대한 방오도장막 혹은 보호막을 제공할 수 있다.Additionally, the present invention provides an article having a cured film obtained by applying the fluorine-containing active energy ray-curable composition of the present invention described above and curing the surface. As described above, by using the fluorine-containing active energy ray-curable composition of the present invention, it becomes possible to form a cured film (cured resin layer) having excellent surface properties on the surface of a substrate (article). In particular, it is useful for providing water repellency, oil repellency, and stain resistance to the surface of an acrylic hard coat. As a result, it becomes difficult for fingerprints, sebum, sweat, etc., contamination from cosmetics, etc., and machine oil to adhere, and a hard coat surface with excellent wiping properties can be provided to the substrate. For this reason, the fluorine-containing active energy ray-curable composition of the present invention is used on substrates (articles) that may be contaminated by human contact, such as fingerprints or cosmetics, and on the inside of machines that may be contaminated by workers' fingerprints or machine oil, etc. It is possible to provide an anti-fouling coating or protective film on the surface of the process material film, etc.
본 발명의 함불소 활성 에너지선 경화성 조성물을 사용하여 형성되는 경화 피막(경화 수지층)은 태블릿형 컴퓨터, 노트 PC, 휴대전화·스마트폰 등의 휴대(통신) 정보 단말, 디지털 미디어 플레이어, 전자북 리더 등 각종 기기의 케이싱, 시계형·안경형 웨어러블 컴퓨터; 액정 디스플레이, 플라즈마 디스플레이, 유기 EL(일렉트로루미네슨스) 디스플레이, 배면 투사형 디스플레이, 형광 표시관(VFD), 필드 에미션 프로젝션 디스플레이, CRT, 토너계 디스플레이 등의 각종 플랫 패널 디스플레이 및 TV의 화면 등의 표시 조작 기기 표면 및 이것들의 내부에 사용되는 각종 광학 필름류, 자동차의 외장, 피아노나 가구의 광택 표면, 대리석 등의 건축용 석재 표면, 화장실, 목욕, 세면소 등의 물 주변의 장식 건재, 미술품 전시용 보호 글라스, 쇼윈도우, 진열장, 포토 프레임용 커버, 손목시계, 자동차 창유리, 열차, 항공기 등의 창유리, 자동차 헤드라이트, 테일 램프 등의 투명한 글라스제 또는 투명한 플라스틱제(아크릴, 폴리카보네이트 등) 부재, 각종 미러 부재 등의 도장막 및 표면보호막으로서 유용하다.The cured film (cured resin layer) formed using the fluorine-containing active energy ray curable composition of the present invention can be used in portable (communication) information terminals such as tablet computers, notebook PCs, mobile phones and smartphones, digital media players, and e-books. Casings for various devices such as readers, watch-type and glasses-type wearable computers; Various flat panel displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent displays (VFDs), field emission projection displays, CRTs, toner displays, and TV screens. Various optical films used on the surfaces of display and operation devices and their interiors, automobile exteriors, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, decorative building materials around water in toilets, baths, washrooms, etc., and protection for art exhibitions. Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) materials such as glass, show windows, showcases, covers for photo frames, watches, automobile window glass, train and aircraft window glass, automobile headlights, tail lamps, etc., various materials. It is useful as a coating film and surface protection film for mirror members, etc.
그중에서도 특히, 터치패널 디스플레이 등 사람의 손가락 혹은 손바닥으로 화면상의 조작을 행하는 표시 입력 장치를 갖는 각종 기기, 예를 들면, 태블릿형 컴퓨터, 노트 PC, 스마트폰, 휴대전화, 기타 휴대(통신) 정보 단말, 스마트 워치, 디지털 미디어 플레이어, 전자북 리더, 디지털 포토 프레임, 게임기, 디지털 카메라, 디지털 비디오카메라, GPS 표시 기록 기기, 자동차용 등의 네비게이션 장치, 자동차용 등의 제어 패널, 자동 현금 인출예입 장치, 현금 자동 지불기, 자동판매기, 디지털 사이니지(전자 간판), 시큐러티 시스템 단말, POS 단말, 리모트 콘트롤러 등 각종 콘트롤러, 차량 탑재 장치용 패널 스위치 등의 표시 입력 장치 등의 표면보호막으로서 유용하다.Among them, in particular, various devices having display input devices for performing on-screen operations with a person's fingers or palm, such as a touch panel display, such as tablet computers, note PCs, smartphones, mobile phones, and other portable (communication) information terminals. , smart watches, digital media players, e-book readers, digital photo frames, game consoles, digital cameras, digital video cameras, GPS display and recording devices, navigation devices for automobiles, etc., control panels for automobiles, etc., automatic cash withdrawal and deposit devices, It is useful as a surface protection film for various controllers such as automatic teller machines, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for vehicle-mounted devices.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물에 의해 형성되는 경화 피막은 광자기디스크, 광디스크 등의 광기록 매체; 안경 렌즈, 프리즘, 렌즈 시트, 펠리클막, 편광판, 광학 필터, 렌티큘러 렌즈, 프레넬 렌즈, 반사방지막, 각종 카메라용 렌즈, 각종 렌즈용 보호 필터, 광파이버나 광커플러 등의 광학 부품·광디바이스의 표면 보호 피막으로서도 유용하다.In addition, the cured film formed by the fluorine-containing active energy ray curable composition of the present invention can be used in optical recording media such as magneto-optical disks and optical disks; Surfaces of optical components and optical devices such as spectacle lenses, prisms, lens sheets, pellicle films, polarizers, optical filters, lenticular lenses, Fresnel lenses, anti-reflective films, various camera lenses, protective filters for various lenses, optical fibers and optical couplers It is also useful as a protective film.
이상과 같은, 본 발명의 함불소 활성 에너지선 경화성 조성물은 목적으로 하는 물품의 표면에 본 발명에 따른 함불소 화합물 (A)의 퍼플루오로폴리에테르 구조를 배치시킴으로써, 발수성, 발유성, 미끄럼성, 방오성, 지문의 시인 곤란성, 지문 닦아냄성, 내마모성, 저굴절률 특성, 내용제성, 내약품성 등이 우수한 성질을 제공하는 것을 그 본질로 하고 있다.As described above, the fluorinated active energy ray-curable composition of the present invention has water-repellent, oil-repellent and slippery properties by disposing the perfluoropolyether structure of the fluorinated compound (A) according to the present invention on the surface of the target article. Its essence is to provide excellent properties such as stain resistance, difficulty in recognizing fingerprints, fingerprint wipeability, abrasion resistance, low refractive index characteristics, solvent resistance, and chemical resistance.
이러한 본 발명의 함불소 활성 에너지선 경화성 조성물을 사용할 때는, 배합물의 조합, 조성비, 어떤 특성을 중시할지에 따라, 적절한 사용 방법을 각각의 용도에 따른 공지의 기술을 바탕으로 선정하면 된다. 이러한 공지의 기술은 불소를 포함하는 조성물에 대한 것뿐만 아니라 기존의 활성 에너지선 경화성 조성물에 사용되고 있는 수법을 포함하여 검토의 범위에 포함시킬 수 있다.When using the fluorine-containing active energy ray-curable composition of the present invention, an appropriate method of use may be selected based on known techniques for each application, depending on the combination, composition ratio, and characteristics to be emphasized. These known techniques can be included in the scope of examination, including methods used not only for compositions containing fluorine but also for existing active energy ray-curable compositions.
예를 들면, 본 발명의 함불소 활성 에너지선 경화성 조성물을 배합 조제함에 있어서, 본 발명에 따른 함불소 화합물 (A)에 더하여, 상기한 본 경화성 조성물에 있어서의 각종 배합물을 조합시킬 때, 저굴절률 특성이나 이것을 이용한 저반사 특성을 중시하는 경우에는, 반응성 중공 실리카나 반응성 기를 가지지 않는 중공 실리카, 다작용 아크릴 화합물을 사용하는 것, 또 피막 강도나 내찰상성을 향상시키는 경우에는, 다작용 아크릴 화합물을 적합한 양으로 배합하는 것, 혹은 경도와 굴곡성의 균형을 취하기 위해서는, 6작용 이상의 다작용 아크릴 화합물과 3작용 이하의 아크릴 화합물의 조합을 행하는 것 등은 공지의 아크릴 경화성 조성물 배합의 지견으로부터 용이하게 유추할 수 있다.For example, when mixing and preparing the fluorine-containing active energy ray-curable composition of the present invention, in addition to the fluorine-containing compound (A) according to the present invention, various formulations in the present curable composition are combined, and the low refractive index When focusing on properties or low-reflection characteristics, use reactive hollow silica, hollow silica without a reactive group, or multifunctional acrylic compounds. Also, when improving film strength or scratch resistance, use multifunctional acrylic compounds. It can be easily inferred from the knowledge of known acrylic curable composition formulations to mix in an appropriate amount, or to combine a polyfunctional acrylic compound with 6 or more functions and an acrylic compound with 3 or less functions in order to achieve a balance between hardness and flexibility. can do.
또한, 본 발명의 함불소 활성 에너지선 경화성 조성물을 도포함으로써 물품을 얻는 경우, 예를 들면, 필름 기재에의 도공을 행할 때, 간섭 줄무늬를 막기 위해 적절한 도공막 두께가 되도록 조정을 행하는 것, 필름 기재의 두께를 조정하여 컬을 억제하기 쉽게 하거나, 기재 필름의 탄성률을 조정함으로써 함불소 활성 에너지선 경화성 조성물의 도포막 경화 후의 변형이나 도포막의 균열을 억제하는 것 등은 각각의 특성에 따른 기존의 조건의 조합을 바탕으로 스크리닝 작업을 행하여 선정시키는 것이며, 기존 기술의 조합에 의해 용이하게 달성 가능하다.In addition, when obtaining an article by applying the fluorine-containing active energy ray-curable composition of the present invention, for example, when applying to a film substrate, adjustments are made to obtain an appropriate coating film thickness to prevent interference fringes, and the film Easily suppressing curl by adjusting the thickness of the base material, or suppressing deformation or cracking of the coating film after curing of the fluorine-containing active energy ray curable composition by adjusting the elastic modulus of the base film, can be achieved by using existing methods according to each characteristic. Selection is carried out through screening based on a combination of conditions, and can be easily achieved by combining existing technologies.
실시예Example
이하에, 합성예, 실시예, 참고예 및 비교예를 들어, 본 발명을 구체적으로 설명하지만, 본 발명은 하기의 실시예에 제한되는 것은 아니다.Below, the present invention will be described in detail using synthesis examples, examples, reference examples and comparative examples, but the present invention is not limited to the following examples.
[합성예 1] 함불소 아크릴 화합물 (A-1)의 합성[Synthesis Example 1] Synthesis of fluorinated acrylic compound (A-1)
건조 공기 분위기하에서, 하기 식Under dry air atmosphere, the following formula
Rf1: -CF2O(CF2O)p1(CF2CF2O)q1CF2-Rf 1 : -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2 -
(q1/p1=0.9, p1+q1≒45)(q1/p1=0.9, p1+q1≒45)
으로 표시되는 함불소 알코올 화합물 (E-1) 50.0g(수산기량 0.056몰)에, 메틸에틸케톤 50.0g, 및 아크릴로일옥시에틸이소시아네이트 1.34g(0.00950몰)을 혼합하고, 50℃로 가열하여 1시간 교반했다. 거기에 디옥틸주석디라우레이트 0.05g을 첨가하고, 50℃하 8시간 교반했다. 1H-NMR의 결과로부터, 미반응의 아크릴로일옥시에틸이소시아네이트의 4.2ppm의 메틸렌 피크가 우레탄 결합 형성 후의 4.1ppm의 메틸렌 피크로 모두 변화된 것을 확인하고, 또 IR 스펙트럼에서 2,260cm-1의 이소시아네이트기의 피크의 소실을 확인했다. 가열 종료 후, 얻어진 반응액에 활성탄 처리를 행하고, 얻어진 담황색 액체를 이배포레이터에서 80℃/133Pa로 2시간 처리하고, 하기 식으로 표시되는 아크릴기/수산기량=0.20의 담황색 고점조 물질인 함불소 아크릴 화합물 (A-1) 47.2g을 얻었다.Mix 50.0 g (hydroxyl group amount: 0.056 mol) of fluorinated alcohol compound (E-1), 50.0 g of methyl ethyl ketone, and 1.34 g (0.00950 mol) of acryloyloxyethyl isocyanate, and heat to 50°C. Stirred for 1 hour. 0.05 g of dioctyltin dilaurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate changed to a 4.1 ppm methylene peak after urethane bond formation, and in the IR spectrum, the isocyanate at 2,260 cm -1 The disappearance of the group peak was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, and the obtained light yellow liquid is treated in an evaporator at 80°C/133Pa for 2 hours to obtain a light yellow, highly viscous substance with an acrylic group/hydroxyl group amount = 0.20 expressed by the following formula. 47.2 g of fluorine acrylic compound (A-1) was obtained.
Rf1: -CF2O(CF2O)p1(CF2CF2O)q1CF2-Rf 1 : -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2 -
(q1/p1=0.9, p1+q1≒45)(q1/p1=0.9, p1+q1≒45)
[합성예 2] 함불소 아크릴 화합물 (A-2)의 합성[Synthesis Example 2] Synthesis of fluorinated acrylic compound (A-2)
합성예 1의 아크릴로일옥시에틸이소시아네이트의 사용량을 2.64g(0.0187몰)으로 한 이외는 동일한 조작을 행하여, 아크릴기/수산기량=0.5의 담황색 고점조 물질인 함불소 아크릴 화합물 (A-2) 48.0g을 얻었다.The same operation as in Synthesis Example 1 was performed except that the amount of acryloyloxyethyl isocyanate used was 2.64 g (0.0187 mol), and a fluorinated acrylic compound (A-2), which is a pale yellow, highly viscous material with acrylic group/hydroxyl group amount = 0.5, was obtained. 48.0g was obtained.
[합성예 3] 함불소 아크릴 화합물 (A-3)의 합성[Synthesis Example 3] Synthesis of fluorinated acrylic compound (A-3)
합성예 1의 아크릴로일옥시에틸이소시아네이트의 사용량을 7.50g(0.0532몰)으로 한 이외는 동일한 조작을 행하여, 아크릴기/수산기량=19의 담황색 고점조 물질인 함불소 아크릴 화합물 (A-3) 52.8g을 얻었다.The same operation as in Synthesis Example 1 was performed except that the amount of acryloyloxyethyl isocyanate used was 7.50 g (0.0532 mol), and a fluorinated acrylic compound (A-3) was obtained, which is a pale yellow, highly viscous substance with acrylic group/hydroxyl group amount = 19. 52.8g was obtained.
[합성예 4] 함불소 아크릴 화합물 (A-4)의 합성[Synthesis Example 4] Synthesis of fluorinated acrylic compound (A-4)
건조 공기 분위기하에서, 하기 식Under dry air atmosphere, the following formula
Rf2: -CF2O(CF2O)p2(CF2CF2O)q2CF2-Rf 2 : -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2 -
(q2/p2=1.2, p2+q2≒18.5)(q2/p2=1.2, p2+q2≒18.5)
으로 표시되는 함불소 알코올 화합물 (E-2) 50.0g(수산기량 0.098몰)에, 메틸에틸케톤 50.0g, 및 아크릴로일옥시에틸이소시아네이트 4.61g(0.0327몰)을 혼합하고, 50℃로 가열하여 1시간 교반했다. 거기에 디옥틸주석디라우레이트 0.10g을 첨가하고, 50℃하에 8시간 교반했다. 1H-NMR의 결과로부터, 미반응의 아크릴로일옥시에틸이소시아네이트의 4.2ppm의 메틸렌 피크가 우레탄 결합 형성 후의 4.1ppm의 메틸렌 피크로 모두 변화된 것을 확인하고, 또 IR 스펙트럼에서 2,260cm-1의 이소시아네이트기의 피크의 소실을 확인했다. 가열 종료 후, 얻어진 반응액에 활성탄 처리를 행하고, 얻어진 담황색 액체를 이배포레이터에서 60℃/133Pa로 2시간 처리하여, 하기 식으로 표시되는 아크릴기/수산기량=0.5의 담황색 고점조 물질인 함불소 아크릴 화합물 (A-4) 50.8g을 얻었다.50.0 g (hydroxyl group amount: 0.098 mol) of the fluorinated alcohol compound (E-2), 50.0 g of methyl ethyl ketone, and 4.61 g (0.0327 mol) of acryloyloxyethyl isocyanate were mixed and heated to 50°C. Stirred for 1 hour. 0.10 g of dioctyltin dilaurate was added thereto, and stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate changed to a 4.1 ppm methylene peak after urethane bond formation, and in the IR spectrum, the isocyanate at 2,260 cm -1 The disappearance of the group peak was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, and the obtained light yellow liquid is treated in an evaporator at 60°C/133Pa for 2 hours to obtain a light yellow, highly viscous substance with acrylic group/hydroxyl group amount = 0.5 as expressed by the following formula. 50.8 g of fluorine acrylic compound (A-4) was obtained.
Rf2: -CF2O(CF2O)p2(CF2CF2O)q2CF2-Rf 2 : -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2 -
(q2/p2=1.2, p2+q2≒18.5)(q2/p2=1.2, p2+q2≒18.5)
[합성예 5] 함불소 아크릴 화합물 (B-1)의 합성[Synthesis Example 5] Synthesis of fluorinated acrylic compound (B-1)
합성예 1의 아크릴로일옥시에틸이소시아네이트의 사용량을 8.59g(0.0609몰)으로 한 이외는 동일한 조작을 행하고, 13C-NMR 스펙트럼에서 62ppm의 수산기에 인접한 탄소 원자 유래의 피크의 소실을 확인하여, 하기 식으로 표시되는 수산기가 잔존하지 않는 담황색 고점조 물질인 함불소 아크릴 화합물 (B-1) 53.0g을 얻었다.The same operation was performed except that the amount of acryloyloxyethyl isocyanate used in Synthesis Example 1 was 8.59 g (0.0609 mol), and the disappearance of the peak derived from the carbon atom adjacent to the hydroxyl group at 62 ppm was confirmed in the 13 C-NMR spectrum. 53.0 g of fluorinated acrylic compound (B-1), a pale yellow, highly viscous material with no remaining hydroxyl group represented by the following formula, was obtained.
Rf1: -CF2O(CF2O)p1(CF2CF2O)q1CF2-Rf 1 : -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2 -
(q1/p1=0.9, p1+q1≒45)(q1/p1=0.9, p1+q1≒45)
[합성예 6] 함불소 아크릴 화합물 (B-2)의 합성[Synthesis Example 6] Synthesis of fluorinated acrylic compound (B-2)
합성예 4의 아크릴로일옥시에틸이소시아네이트의 사용량을 15.1g(0.107몰)으로 한 이외는 동일한 조작을 행하고, 13C-NMR 스펙트럼에서 62ppm의 수산기에 인접한 탄소 원자 유래의 피크의 소실을 확인하여, 하기 식으로 표시되는 수산기가 잔존하지 않는 담황색 고점조 물질인 함불소 아크릴 화합물 (B-2) 58.9g을 얻었다.The same operation as in Synthesis Example 4 was performed except that the amount of acryloyloxyethyl isocyanate used was 15.1 g (0.107 mol), and the disappearance of the peak derived from the carbon atom adjacent to the hydroxyl group at 62 ppm was confirmed in the 13 C-NMR spectrum. 58.9 g of fluorinated acrylic compound (B-2), a pale yellow, highly viscous material with no remaining hydroxyl groups represented by the following formula, was obtained.
Rf2: -CF2O(CF2O)p2(CF2CF2O)q2CF2-Rf 2 : -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2 -
(q2/p2=1.2, p2+q2≒18.5)(q2/p2=1.2, p2+q2≒18.5)
[실시예 1∼6, 참고예 1, 비교예 1∼5][Examples 1 to 6, Reference Example 1, Comparative Examples 1 to 5]
함불소fluoride 활성 activation 에너지선energy line 경화성 조성물의 조제 Preparation of curable composition
하기 표 1, 2에 나타내는 배합 비율로, 상기 합성예에서 얻어진 화합물 (A-1)∼(A-4), (B-1), (B-2), 및 하기에 나타내는 아크릴 화합물 (C-1)∼(C-4), 광중합 개시제 (D-1), (D-2), 유기 용제 (S-1)∼(S-4)를 혼합하고, 함불소 및 비불소의 활성 에너지선 경화성 조성물을 조제했다. 또한, 각 조성물의 (A) 성분과 (B) 성분에 포함되는 아크릴기 합계 몰량의 이론값을 NA, 수산기 몰량의 이론값을 NH로 하여 각 조성물에 있어서의 NA/NH의 값을 하기 표 1, 2에 나타냈다.Compounds (A-1) to (A-4), (B-1), (B-2) obtained in the above synthesis examples, and the acrylic compound (C-) shown below in the mixing ratios shown in Tables 1 and 2 below. 1) - (C-4), photopolymerization initiator (D-1), (D-2), organic solvent (S-1) - (S-4) are mixed, and fluorine-containing and non-fluorine active energy ray curing properties are obtained. A composition was prepared. In addition, the theoretical value of the total molar amount of acrylic groups contained in component (A) and component (B) of each composition is N A , and the theoretical value of the molar amount of hydroxyl group is NH , and the value of N A /N H in each composition is are shown in Tables 1 and 2 below.
(C-1): 펜타에리트리톨트리아크릴레이트(분자 중의 아크릴기 수: 3개, 수산기 수: 1개)(C-1): Pentaerythritol triacrylate (number of acrylic groups in molecule: 3, number of hydroxyl groups: 1)
(C-2): 디펜타에리트리톨펜타아크릴레이트(분자 중의 아크릴기 수: 5개, 수산기 수: 1개)/디펜타에리트리톨헥사아크릴레이트(분자 중의 아크릴기 수: 6개, 수산기 수: 0개)의 혼합물(C-2): Dipentaerythritol pentaacrylate (Number of acrylic groups in molecule: 5, Number of hydroxyl groups: 1) / Dipentaerythritol hexaacrylate (Number of acrylic groups in molecule: 6, Number of hydroxyl groups: 1) 0) mixture
(C-3): 신나카무라카가쿠 가부시키가이샤제 다작용 우레탄 아크릴레이트 「U-6LPA」(분자 중의 아크릴기 수: 6개 이상)(C-3): Multifunctional urethane acrylate “U-6LPA” manufactured by Shinnakamura Kagaku Co., Ltd. (Number of acrylic groups in molecule: 6 or more)
(C-4): 네가미고교 가부시키가이샤제 다작용 우레탄아크릴레이트 「UN-3320HS」(분자 중의 아크릴기 수: 6개 이상)(C-4): Multifunctional urethane acrylate “UN-3320HS” manufactured by Negami Kogyo Co., Ltd. (Number of acrylic groups in molecule: 6 or more)
(D-1): 1-히드록시-시클로헥실-페닐-케톤(D-1): 1-Hydroxy-cyclohexyl-phenyl-ketone
(D-2): 2-히드록시-1-{4-[4-(2-히드록시-2-메틸-프로피오닐)-벤질]페닐}-2-메틸-프로판-1-온 (D-2): 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one
(S-1): 메틸에틸케톤(S-1): Methyl ethyl ketone
(S-2): 아세트산 에틸(S-2): Ethyl acetate
(S-3): 프로필렌글리콜모노메틸에테르(S-3): Propylene glycol monomethyl ether
(S-4): 2-프로판올(S-4): 2-propanol
도공과 Pottery Department 경화막의of cured film 제작 produce
실시예, 참고예 및 비교예의 각 활성 에너지선 경화성 조성물을 폴리카보네이트 기판 위에 스핀 코팅으로 도공했다. 컨베이어식 메탈 할라이드 UV 조사 장치(파나소닉덴코 가부시키가이샤제)를 사용하고, 질소 분위기 중에서, 적산 조사량 1,600mJ/cm2의 자외선을 도공면에 조사하여 조성물을 경화시켜, 두께 약 5㎛, 실시예 4에 대해서는 약 3㎛의 경화막을 얻었다.Each active energy ray-curable composition of Examples, Reference Examples, and Comparative Examples was coated on a polycarbonate substrate by spin coating. Using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko Co., Ltd.), in a nitrogen atmosphere, ultraviolet rays with an integrated irradiation amount of 1,600 mJ/cm 2 were irradiated on the coated surface to cure the composition to a thickness of about 5 μm, Example. For case 4, a cured film of approximately 3 μm was obtained.
경화막의of cured film 평가 evaluation
상기에서 얻어진 경화막에 대하여, 하기에 나타내는 방법에 의해 수접촉각과 올레산 접촉각의 측정, 내마모성, 내지문성 및 내매직성의 평가를 행했다. 이것들의 결과를 표 3, 4에 나타낸다.For the cured film obtained above, water contact angle and oleic acid contact angle were measured, and abrasion resistance, fingerprint resistance, and magic resistance were evaluated by the methods shown below. These results are shown in Tables 3 and 4.
[수접촉각 측정][Water contact angle measurement]
접촉각계(쿄와카이멘카가쿠 가부시키가이샤제 DropMaster)를 사용하여, 2μL의 액적을 경화막 위에 적하하고 1초 후의 접촉각을 측정했다. N=5의 평균값을 측정값으로 했다.Using a contact angle meter (DropMaster manufactured by Kyowa Kaimen Chemical Co., Ltd.), a 2-μL droplet was dropped onto the cured film, and the contact angle 1 second later was measured. The average value of N=5 was taken as the measured value.
[올레산 접촉각 측정][Oleic acid contact angle measurement]
접촉각계(쿄와카이멘카가쿠 가부시키가이샤제 DropMaster)를 사용하여, 4μL의 액적을 경화막 위에 적하하고 1초 후의 접촉각을 측정했다. N=5의 평균값을 측정값으로 했다.Using a contact angle meter (DropMaster manufactured by Kyowa Kaimen Chemical Co., Ltd.), a 4-μL droplet was dropped onto the cured film, and the contact angle 1 second later was measured. The average value of N=5 was taken as the measured value.
[내마모성][Abrasion resistance]
이하의 조건으로 왕복 마모 시험을 행하고, 2,000회마다 수접촉각을 측정하여, 수접촉각이 100° 이하가 된 횟수를 기록했다.A reciprocating abrasion test was performed under the following conditions, the water contact angle was measured every 2,000 times, and the number of times the water contact angle became 100° or less was recorded.
마찰재: 부직포(아사히카세이 가부시키가이샤제 BEMCOT M-3II)Friction material: Non-woven fabric (BEMCOT M-3II manufactured by Asahi Kasei Corporation)
하중: 1kgLoad: 1kg
접촉 면적: 3cm2 Contact area: 3 cm 2
마찰 속도: 90mm/sFriction speed: 90mm/s
마찰 거리: 20mmFriction distance: 20mm
[지문의 시인 용이성의 평가][Evaluation of fingerprint recognition ease]
지문을 묻혔을 때의 시인 용이성을 이하의 기준으로 육안 평가했다.The ease of recognition when a fingerprint was applied was visually evaluated based on the following criteria.
1: 눈에 띄기 어려움1: Hard to stand out
2: 다소 눈에 띄기 어려움2: Somewhat difficult to notice
3: 비교예 1과 동등3: Equivalent to Comparative Example 1
[지문의 닦아냄 용이성의 평가][Evaluation of the ease of wiping off fingerprints]
지문을 티슈로 닦아낼 때의 닦아냄 용이성을 이하의 기준으로 육안 평가했다.Ease of wiping off fingerprints with a tissue was visually evaluated based on the following criteria.
○: 용이하게 닦아낼 수 있음○: Easy to wipe off
×: 닦아낼 수 없음×: Cannot be wiped off
[매직 튀겨냄성의 평가][Evaluation of magic frying properties]
경화막 표면에 매직펜(지브라 가부시키가이샤제 하이막키 굵은 글씨)으로 직선을 그리고, 잉크를 튀겨내는 것을 ○, 튀겨내지 않는 것을 ×로 했다.A straight line was drawn on the surface of the cured film with a marker pen (Himacki Bold, manufactured by Zebra Co., Ltd.), and the ink that splashed out was marked as ○, and the one that did not splash ink was marked as ×.
[매직 닦아냄성의 평가][Evaluation of magic wipeability]
매직 튀김성의 평가에 사용한 각 샘플에 대하여, 10분 후에 티슈로 닦아내기를 행하고, 자국을 남기지 않고 닦아낼 수 있는 것을 ○, 자국이 남는 것을 ×로 했다.Each sample used to evaluate the magic splash property was wiped off with a tissue after 10 minutes, and those that could be wiped off without leaving marks were rated as ○, and those that left marks were rated as ×.
*： 시험 이전에 수접촉각이 100° 이하이기 때문에 시험하지 않음*: Not tested because the water contact angle before testing is less than 100°
상기의 결과로부터 명확한 바와 같이, 함불소 아크릴 화합물 (A-1)∼(A-4)를 배합하여 이루어지는 본 발명의 함불소 활성 에너지선 경화성 조성물을 사용한 실시예 1∼6, 및 참고예 1은 발수성, 발유성, 내마모성, 지문의 시인 곤란성, 지문의 닦아냄 용이성, 매직 튀김성, 매직 닦아냄성이 우수한 것이다. 또한, 함불소 아크릴 화합물 (A)를 배합하지 않고, 함불소 아크릴 화합물 (B-1), (B-2)를 배합하여 이루어지는 함불소 활성 에너지선 경화성 조성물을 사용한 비교예 1∼4는 이것들에 상당하는 실시예, 참고예보다도 내마모성이 뒤떨어지고, 지문이 눈에 띄는 것이다. 또한, 함불소 아크릴 화합물 (A-1)∼(A-4)도 함불소 아크릴 화합물 (B-1), (B-2)도 배합하지 않는 비불소의 활성 에너지선 경화성 조성물을 사용한 비교예 5는 상기 실시예, 참고예보다도 발수성, 발유성, 내마모성, 지문의 닦아냄 용이성, 매직 튀김성, 매직 닦아냄성이 뒤떨어지는 것이다.As is clear from the above results, Examples 1 to 6 and Reference Example 1 using the fluorinated active energy ray-curable composition of the present invention comprising fluorinated acrylic compounds (A-1) to (A-4) It is excellent in water repellency, oil repellency, abrasion resistance, difficulty in recognizing fingerprints, ease of wiping off fingerprints, magic splash resistance, and magic wipe-off property. In addition, Comparative Examples 1 to 4 using fluorinated active energy ray-curable compositions obtained by blending fluorinated acrylic compounds (B-1) and (B-2) without blending fluorinated acrylic compound (A). The wear resistance was inferior to that of the corresponding examples and reference examples, and fingerprints were noticeable. In addition, Comparative Example 5 using a non-fluorinated active energy ray curable composition containing neither the fluorinated acrylic compounds (A-1) to (A-4) nor the fluorinated acrylic compounds (B-1) and (B-2). is inferior to the above-mentioned examples and reference examples in terms of water repellency, oil repellency, abrasion resistance, ease of wiping off fingerprints, magic spattering properties, and magic wiping properties.
Claims (11)
X1-Z-Rf-Z-X1 (1)
[식 중, Rf는 하기 식 (2)∼(5)
(식 중, Y는 서로 독립적으로 F 또는 CF3이고, r은 2∼6의 정수이고, m, n은 각각 0∼200의 정수이며, 단, m+n은 2∼200이고, s는 0∼6의 정수이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)
(식 중, j는 독립적으로 1∼3의 정수이며, k는 1∼200의 정수이다.)
(식 중, Y, j는 상기와 같고, p, q는 각각 0∼200의 정수이며, 단, p+q는 2∼200이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.)
(식 중, t는 1∼100의 정수이다.)
로 표시되는 기로부터 선택되는 분자량 500∼30,000의 2가의 퍼플루오로폴리에테르기이며, X1은 서로 독립적으로, 하기 식 (6)
[식 중, Q1은 탄소수 3∼20의 에테르 결합, 에스테르 결합, 아미드 결합 및 우레탄 결합으로부터 선택되는 결합을 포함하고 있어도 되는 2가의 연결기이며, 도중 환상 구조나 분기 구조를 포함하고 있어도 되고, 각각 동일하여도 상이하여도 된다. R1은 하기 식 (7)
(식 중, R2는 독립적으로, 수소 원자 또는 메틸기이고, R3은 탄소수 1∼18의 에테르 결합 및/또는 에스테르 결합을 포함하고 있어도 되는 2가 혹은 3가의 연결기이며, c는 1 또는 2이다.)
로 표시되는 (메타)아크릴기 함유 기이고, a 및 b는 각각 0∼6의 정수이며, 단, a+b는 2∼11이다. 각 반복단위는 랜덤으로 결합되어 있어도 된다.]
으로 표시되는 기이며, 분자 중에 존재하는 X1 중의 a, b의 합계는 각각 2 이상이다. Z는 하기 식
중 어느 하나로 표시되는 2가의 유기기이다.]
로 표시되고, 상기 화합물 중에 포함되는 포함되는 수산기에 대한 (메타)아크릴기의 몰비[(메타)아크릴기(몰)/수산기(몰)]가 평균값으로서 0.1 이상 19 미만인 함불소 화합물 (A)를 함유하는 것을 특징으로 하는 함불소 활성 에너지선 경화성 조성물.A cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group through a divalent linking group, a hydroxyl group is bonded to the cyclopolysiloxane structure through a divalent linking group, and ( In the fluorine-containing compound (A) having a meth)acrylic group on one or both sides of the cyclopolysiloxane structure at both ends, the general formula (1)
X 1 -Z-Rf-ZX 1 (1)
[Wherein, Rf is represented by the following formulas (2) to (5)
(In the formula, Y is independently F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, provided that m+n is 2 to 200, and s is 0 It is an integer of ~6. Each repeating unit may be randomly combined.)
(In the formula, j is independently an integer from 1 to 3, and k is an integer from 1 to 200.)
(In the formula, Y and j are the same as above, p and q are each integers from 0 to 200, but p+q is from 2 to 200. Each repeating unit may be randomly combined.)
(In the formula, t is an integer from 1 to 100.)
is a divalent perfluoropolyether group with a molecular weight of 500 to 30,000 selected from groups represented by, and
[In the formula, Q 1 is a divalent linking group that may contain a bond selected from an ether bond, an ester bond, an amide bond, and a urethane bond having 3 to 20 carbon atoms, and may contain a cyclic structure or a branched structure, respectively. They may be the same or different. R 1 is given by the following formula (7)
(In the formula, R 2 is independently a hydrogen atom or a methyl group, R 3 is a divalent or trivalent linking group that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms, and c is 1 or 2. .)
It is a (meth)acrylic group-containing group represented by , and a and b are each integers of 0 to 6, provided that a+b is 2 to 11. Each repeating unit may be randomly combined.]
It is a group represented by , and the total of a and b among X 1 present in the molecule is each 2 or more. Z is the following expression
It is a divalent organic group represented by one of the following.]
A fluorine-containing compound (A), which is represented by and the molar ratio of the (meth)acrylic group to the hydroxyl group contained in the compound [(meth)acrylic group (mol)/hydroxyl group (mol)] is 0.1 or more and less than 19 as an average value. A fluorine-containing active energy ray-curable composition comprising:
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