TWI832858B - Active energy ray curable composition - Google Patents
Active energy ray curable composition Download PDFInfo
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- TWI832858B TWI832858B TW108117511A TW108117511A TWI832858B TW I832858 B TWI832858 B TW I832858B TW 108117511 A TW108117511 A TW 108117511A TW 108117511 A TW108117511 A TW 108117511A TW I832858 B TWI832858 B TW I832858B
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- active energy
- energy ray
- curable composition
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Silicon Polymers (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Polyethers (AREA)
Abstract
本發明提供可賦予表面具有優異撥水撥油性、防污性及耐指紋性之硬化物的活性能量線硬化性組成物。 本發明之活性能量線硬化性組成物包含以下述式(1)表示之化合物(A)及光聚合起始劑(B), (式(1)中,Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之特定基,Q1 相互獨立為至少具有(a+b)個Si原子之(a+b)價之特定基,Q2 相互獨立為碳數1~20之二價烴基,X為下述式表示之基, (式中,R2 為氫原子或碳數1~20之一價烴基),且Rf為一價基時,a’為1,a為1~6之整數;Rf為二價基時,a’為2,a為1;b為1~20之整數,a+b為3~21之整數)。 The present invention provides an active energy ray-curable composition that can provide a cured product with excellent water- and oil-repellent properties, antifouling properties, and fingerprint resistance on its surface. The active energy ray curable composition of the present invention includes a compound (A) represented by the following formula (1) and a photopolymerization initiator (B), (In formula (1), Rf is independently a monovalent or divalent specific group with a number average molecular weight of 400 to 40,000 having a fluoropolyether structure, and Q 1 is independently a (a+b) Si atom having at least (a+b) Si atoms. a+b) is a specific group with valence, Q 2 is independently a bivalent hydrocarbon group having 1 to 20 carbon atoms, and X is a group represented by the following formula, (In the formula, R 2 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms), and when Rf is a monovalent group, a' is 1, and a is an integer from 1 to 6; when Rf is a divalent group, a ' is 2, a is 1; b is an integer from 1 to 20, a+b is an integer from 3 to 21).
Description
本發明有關活性能量線硬化性組成物。詳言之,有關含有光陽離子硬化性樹脂之活性能量線硬化性組成物,尤其有關亦可適用作為光陽離子型硬塗覆劑的用途、且作為紫外線硬化型防污表面賦予劑而有用之活性能量線硬化性組成物。The present invention relates to an active energy ray curable composition. Specifically, the active energy ray-curable composition containing a photocationic curable resin is particularly suitable for use as a photocationic hard coating agent and is useful as an ultraviolet curable antifouling surface-imparting agent. Energy ray hardening composition.
硬塗覆劑(或具有作為硬塗層之角色的塗料)藉由塗佈於塑膠樹脂為代表之各種物品表面而硬化,而作為可保護物品表面,對物品表面賦予新功能之材料於非常廣範圍用途中使用。Hard coating agents (or coatings that function as hard coatings) are hardened by being applied to the surfaces of various items including plastic resins. They are widely used as materials that can protect the surfaces of items and provide new functions to the surfaces of items. Used in range applications.
該等硬塗覆劑中,對應於其用途擴展,除了過去所要求之硬度、耐磨耗性、耐藥品性及耐久性等以外,亦要求撥水撥油性、防污性、耐指紋性、耐候性、摩擦性、抗靜電劑、防霧性、難焦性及抗反射性等之進一步高功能。尤其近幾年要求髒污防止性及髒污擦拭性之提高。Among these hard coating agents, in accordance with the expansion of their uses, in addition to the hardness, abrasion resistance, chemical resistance, durability, etc. required in the past, water and oil repellency, antifouling properties, fingerprint resistance, etc. are also required. Further advanced functions such as weather resistance, friction resistance, antistatic agent, anti-fog property, refractory properties and anti-reflective properties. In particular, in recent years, there has been a demand for improvements in stain prevention and stain wiping properties.
活性能量線硬化型之硬塗覆劑有紫外線・電子束硬化型硬塗覆劑與熱硬化型塗覆劑。作為紫外線・電子束硬化型硬塗覆劑舉例為例如含有藉由紫外線使自由基聚合而硬化之丙烯酸基之硬塗覆劑。近幾年來,已探討藉由對紫外線硬化型硬塗覆劑以非常少量添加而除了添加前塗覆劑具有之特性以外,又可對所得硬化表面賦予撥水撥油性及防污性、耐指紋性等之含氟化合物。Active energy ray-curing hard coating agents include ultraviolet and electron beam curing hard coating agents and thermosetting coating agents. An example of an ultraviolet/electron beam curable hard coating agent is a hard coating agent containing an acrylic group that is cured by radical polymerization with ultraviolet rays. In recent years, it has been studied that by adding a very small amount of ultraviolet curable hard coating agent, in addition to the characteristics of the pre-added coating agent, the resulting hardened surface can be given water and oil repellency, antifouling properties, and fingerprint resistance. Fluorine-containing compounds.
本發明人已於專利文獻1~4中提案可較好地使用作為紫外線或電子束硬化型硬塗覆劑用之添加劑,且可對所得硬化物賦予撥水撥油性及防污性、耐指紋性等之含氟化合物。 [先前技術文獻] [專利文獻]The present inventor has proposed in Patent Documents 1 to 4 an additive that can be preferably used as an ultraviolet or electron beam curing hard coating agent and can impart water and oil repellency, antifouling properties, and fingerprint resistance to the resulting cured product. Fluorine-containing compounds. [Prior technical literature] [Patent Document]
[專利文獻1] 日本特開2010-053114號公報 [專利文獻2] 日本特開2010-138112號公報 [專利文獻3] 日本特開2010-285501號公報 [專利文獻4] 日本特開2011-241190號公報[Patent Document 1] Japanese Patent Application Publication No. 2010-053114 [Patent Document 2] Japanese Patent Application Publication No. 2010-138112 [Patent Document 3] Japanese Patent Application Publication No. 2010-285501 [Patent Document 4] Japanese Patent Application Publication No. 2011-241190
如上述目的所用之藉自由基聚合而硬化之紫外線(UV)硬化型丙烯酸硬塗覆劑具有硬化快速,且可作為成分使用之丙烯酸化合物或起始劑種類豐富而容易調整與目的相符之組成之優點。另一方面,存在有因氧而受到硬化阻礙影響之硬化收縮較大等之起因於丙烯酸基之自由基聚合特定之本質問題點。 The ultraviolet (UV)-curing acrylic hard coating agent hardened by radical polymerization used for the above-mentioned purposes has rapid hardening and a wide variety of acrylic compounds or starters that can be used as ingredients, making it easy to adjust the composition to suit the purpose. advantage. On the other hand, there are fundamental problems specific to the radical polymerization of acrylic groups, such as large curing shrinkage due to the influence of curing inhibition due to oxygen.
尤其因氧所致之硬化阻礙於硬塗覆組成物所得之塗膜之空氣界面中越靠近最表面側越容易受影響,於對最表面賦予防污特性時成為較大障礙。且因丙烯酸聚合所致之硬化收縮,於為使硬度上升而多官能化時伴隨硬化收縮之捲曲、龜裂發生等之影響容易增大,對於近幾年之硬塗覆劑之高硬度化要求之進一步提高,以丙烯酸聚合型變得難以對應。 In particular, the air interface of the coating film obtained by the hard coating composition is hindered by oxygen-induced hardening, which is more likely to be affected closer to the outermost side, and becomes a greater obstacle in imparting antifouling properties to the outermost surface. In addition, the hardening shrinkage caused by the polymerization of acrylic acid easily increases the influence of curling and cracking caused by the hardening shrinkage when it is polyfunctionalized to increase the hardness. In recent years, there has been a demand for higher hardness of hard coating agents. As it increases further, it becomes difficult to cope with the acrylic polymer type.
另一方面,具有環氧基、氧雜環丁基、乙烯醚基等之化合物之紫外線硬化型之陽離子聚合系硬塗覆劑,由於並無氧所致之聚合阻礙故而具有表面硬化性優異,且即使硬化時體積收縮亦比丙烯酸型(自由基聚合型)小之較大特徵。 On the other hand, ultraviolet curable cationic polymer hard coating agents containing compounds such as epoxy group, oxetanyl group, vinyl ether group, etc. have excellent surface hardening properties because they do not have polymerization resistance caused by oxygen. And even when hardened, the volume shrinkage is smaller than that of acrylic type (radical polymerization type).
因此近幾年UV陽離子硬化型之硬塗覆劑之開發大量進行,對於陽離子系硬塗覆劑進行防污特性賦予之要求亦變高。 Therefore, in recent years, a large number of UV cationic hard coating agents have been developed, and the requirements for imparting antifouling properties to cationic hard coating agents have also become higher.
本發明係鑒於上述情況而完成者,其目的在於提供可賦予表面具有優異撥水撥油性、防污性及耐指紋性之硬化物的可適用作為光陽離子型塗覆劑之用途、作為紫外線硬化型防污表面賦予劑有用之活性能量線硬化性組成物。 The present invention was made in view of the above circumstances, and its object is to provide a cured product that can provide a surface with excellent water and oil repellency, antifouling properties, and fingerprint resistance, which can be used as a photocationic coating agent and as an ultraviolet curing agent. An active energy ray-hardening composition useful as an antifouling surface imparting agent.
本發明人為了解決上述課題而積極研究之結 果,發現包含以下述通式(1)表示之特定含氟環氧改質有機矽化合物(A)與光聚合起始劑(B)之活性能量線硬化性組成物(光陽離子聚合型組成物)之硬化物,於表面具有優異撥水撥油性、防污性及耐指紋性,因而完成本發明。 The inventors of the present invention have actively researched to solve the above-mentioned problems. As a result, an active energy ray curable composition (photocationic polymerization type composition) containing a specific fluorine-containing epoxy-modified organosilicon compound (A) represented by the following general formula (1) and a photopolymerization initiator (B) was discovered. ) has excellent water and oil repellency, antifouling properties and fingerprint resistance on the surface, thus completing the present invention.
(Rf、Q1、Q2、X、a、a’、b及a+b如下述)。 (Rf, Q1, Q2, X, a, a’, b and a+b are as follows).
亦即,本發明提供下述之活性能量線硬化性組成物。 That is, the present invention provides the following active energy ray curable composition.
[1]一種活性能量線硬化性組成物,其係包含以下述通式(1)表示之含氟環氧改質有機矽化合物(A)及選自重氮鎓鹽、錪鎓鹽及鋶鹽之光酸產生劑的光聚合起始劑(B)之活性能量線硬化性組成物,
(式(1)中,Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之基,Rf為一價基時,係以下述式表示:
(上述式中,j為1~3之整數,k為0~200之整數,k’為1~200之整數,l、m分別為1~100之整數),
Rf為二價基時,係以下述式表示:
(式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數),
(式中,j獨立為1~3之整數,h、i分別為0~200之整數,但h+i為2~300,各重複單位可以無規鍵結),
(式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數),或
(式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數),
Rf為一價基時,a’為1,a為1~6之整數,Rf為二價基時,a’為2,a為1,b為1~20之整數,a+b為3~21之整數,
Q1
相互獨立為至少具有(a+b)個Si原子之(a+b)價之基,且以下述式表示:
(式中,a及b如前述,虛線表示鍵結鍵,具有a個重複之括弧內所示之單位的各矽原子與前述式(1)中之Rf鍵結,具有b個重複之括弧內所示之單位的各矽原子與前述式(1)中之Q2
鍵結,括弧內所示之單位的排列可為無規),
Q2
相互獨立為可包含醚鍵或酯鍵,且可具有環狀構造之碳數1~20之二價烴基,
X相互獨立為下述式(I)或(II)表示之基,
(式(I)中,R1
相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基,可包含醚鍵或酯鍵,可具有環狀構造),
(式(II)中,R2
相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基)),
該活性能量線硬化性組成物係賦予表面之水接觸角為100°以上的硬化物者。
[2] 如[1]之活性能量線硬化性組成物,其中前述式(1)中,以-Q2
-X-表示之構造係自下述式(2)~(5)所示之基中選出者,
(上述式中,f為1~10之整數,e為0~5之整數,g為0~10之整數,f+2g+e於1~20之範圍內,n為1~20之整數,R2
相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基)。
[3] 如[1]或[2]之活性能量線硬化性組成物,其中前述式(1)中,Q2
相互獨立為自下述式所示之基中選出者,
[4] 如[2]或[3]之活性能量線硬化性組成物,其中前述式(1)中,以-Q2-X表示之構造係下述式,
[5]如[1]之活性能量線硬化性組成物,其中具有陽離子硬化性之化合物僅為(A)成分時,相對於(A)成分100質量份,(B)成分含有0.01~20質量份。 [5] The active energy ray curable composition of [1], in which the cationic curable compound is only component (A), component (B) contains 0.01 to 20 parts by mass relative to 100 parts by mass of component (A) share.
[6]如[1]之活性能量線硬化性組成物,其中進而含有由(A)成分以外之1種以上之具有陽離子硬化性之化合物所成之(C)成分,相對於(A)成分與(C)成分之合計100質量份,(B)成分含有0.01~20質量份。 [6] The active energy ray curable composition of [1], which further contains component (C) consisting of one or more cationic curable compounds other than component (A). The total of 100 parts by mass of component (C) and component (B) contains 0.01 to 20 parts by mass.
[7]如[6]之活性能量線硬化性組成物,其中(C)成分係1分子中具有1個以上之環氧基、乙烯醚基、氧雜環丁基、羰基之任一者之化合物、脂肪族不飽和烴化合物、苯乙烯衍生物、雙環原酯、螺原碳酸酯、螺原酯或陽離子聚合性含氮化合物。 [7] The active energy ray curable composition of [6], wherein component (C) is one having at least one epoxy group, vinyl ether group, oxetanyl group, or carbonyl group per molecule. Compounds, aliphatic unsaturated hydrocarbon compounds, styrene derivatives, bicyclic protoesters, spiroprotocarbonate, spiroprotoesters or cationically polymerizable nitrogen-containing compounds.
[8]如[6]或[7]之活性能量線硬化性組成物,其中相 對於(C)成分100質量份,(A)成分含有0.01~10質量份,硬化後之硬化物表面的水接觸角為100°以上。 [8] The active energy ray hardening composition of [6] or [7], wherein the phase For 100 parts by mass of component (C), component (A) contains 0.01 to 10 parts by mass, and the water contact angle on the surface of the hardened product after hardening is 100° or more.
本發明之活性能量線硬化性組成物可賦予表面具有優異撥水撥油性、防污性及耐指紋性之硬化物。因此該活性能量線硬化性組成物可適用作為光陽離子型塗覆劑之用途、作為可藉由光陽離子聚合反應而硬化之紫外線硬化型防污表面賦予劑而有用。 The active energy ray curable composition of the present invention can provide a cured product with excellent water and oil repellency, antifouling properties and fingerprint resistance on the surface. Therefore, the active energy ray curable composition can be suitably used as a photocationic coating agent and is useful as an ultraviolet curable antifouling surface imparting agent that can be cured by photocationic polymerization reaction.
以下詳細說明本發明。 The present invention will be described in detail below.
本發明之活性能量線硬化性組成物之特徵為包含以下述所示之含氟環氧改質有機矽化合物(A)及光聚合起始劑(B)者。 The active energy ray curable composition of the present invention is characterized by containing a fluorine-containing epoxy modified organosilicon compound (A) and a photopolymerization initiator (B) shown below.
本發明第一成分之含氟環氧改質有機矽化合物(A)係以以下述通式(1)表示之陽離子硬化性化合物。 The fluorine-containing epoxy-modified organosilicon compound (A) as the first component of the present invention is a cationic curable compound represented by the following general formula (1).
(式(1)中,Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之基,Q1 相互獨立為至少具有(a+b)個Si原子之(a+b)價之後述特定基,Q2 相互獨立為可包含醚鍵或酯鍵且可具有環狀構造之碳數1~20之二價烴基,X為後述式(I)或(II)表示之基。且,Rf為一價基時,a’為1,a為1~6之整數。Rf為二價基時,a’為2,a為1,b為1~20之整數,a+b為3~21之整數)。(In formula (1), Rf is independently a monovalent or divalent group with a number average molecular weight of 400 to 40,000 having a fluoropolyether structure, and Q 1 is independently (a) having at least (a+b) Si atoms. + b) The specific group mentioned after the valence, Q 2 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms that may contain an ether bond or an ester bond and may have a cyclic structure, and X is represented by the formula (I) or (II) described below The base. And, when Rf is a monovalent base, a' is 1, a is an integer from 1 to 6. When Rf is a divalent base, a' is 2, a is 1, b is an integer from 1 to 20, a +b is an integer from 3 to 21).
式(1)中,X相互獨立為下述式(I)或(II)表示之基。 In formula (1), X is a group represented by the following formula (I) or (II) independently of each other.
式(I)中,R1 相互獨立為氫原子或碳數1~20,較好碳數1~10,更好碳數1~8之非取代或取代之一價烴基,可包含醚鍵或酯鍵,可具有環狀構造。作為上述一價烴基舉例為例如甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、己基、辛基、癸基等之烷基,乙烯基、烯丙基、丙烯基、丁烯基、己烯基等之烯基,環戊基、環己基等之環烷基等。又,亦可為該等烴基之氫原子之一部分或全部經氯、氟、溴等鹵原子取代之氟甲基、溴乙基、三氟丙基等之鹵素取代一價烴基。 較好,R1 為氫原子。In formula (I), R 1 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and may include an ether bond or The ester bond may have a cyclic structure. Examples of the above-mentioned monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, decyl, vinyl, and allyl. Alkenyl groups such as propenyl, butenyl, hexenyl, etc., cycloalkyl groups such as cyclopentyl, cyclohexyl, etc. Alternatively, it may be a halogen-substituted monovalent hydrocarbon group such as fluoromethyl, bromoethyl, trifluoropropyl, or the like, in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with halogen atoms such as chlorine, fluorine, or bromine. Preferably, R 1 is a hydrogen atom.
式(II)中,R2 相互獨立為氫原子或碳數1~20,較好碳數1~10,更好碳數1~8之非取代或取代之一價烴基。作為上述一價烴基舉例為例如甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、己基、辛基、癸基等之烷基,乙烯基、烯丙基、丙烯基、丁烯基、己烯基等之烯基等。又,亦可為該等烴基之氫原子之一部分或全部經氯、氟、溴等鹵原子取代之氟甲基、溴乙基、三氟丙基等之鹵素取代一價烴基。較好,R2 為氫原子。In formula (II), R 2 are independently hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Examples of the above-mentioned monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, decyl, vinyl, and allyl. Alkenyl, propenyl, butenyl, hexenyl, etc. Alternatively, it may be a halogen-substituted monovalent hydrocarbon group such as fluoromethyl, bromoethyl, trifluoropropyl, or the like, in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with halogen atoms such as chlorine, fluorine, or bromine. Preferably, R 2 is a hydrogen atom.
上述式(I)或(II)表示之構造舉例為例如下述者。 (式中,R2 如上述)。Examples of the structure represented by the above formula (I) or (II) are as follows. (In the formula, R 2 is as above).
上述式(1)中,Q2 相互獨立為碳數1~20,較好碳數2~15之二價烴基,可呈環狀構造,亦可於中途包含醚鍵(-O-)或酯鍵(-COO-)。In the above formula (1), Q 2 is independently a divalent hydrocarbon group with a carbon number of 1 to 20, preferably a carbon number of 2 to 15. It can have a cyclic structure, and can also contain an ether bond (-O-) or an ester in the middle. key(-COO-).
上述式(1)中,Q2 舉例為例如下述者。 (上述式中,f為1~10之整數,e為0~5之整數,g為0~10之整數,f+2g+e為1~20之範圍內。較好f為1~6之整數,e為1或2,g為0~4之整數,f+2g+e為3~10之範圍內。n為1~20之整數,較好為2~15之整數)。In the above formula (1), Q 2 is exemplified by the following. (In the above formula, f is an integer from 1 to 10, e is an integer from 0 to 5, g is an integer from 0 to 10, and f+2g+e is in the range of 1 to 20. Preferably, f is an integer from 1 to 6. Integer, e is 1 or 2, g is an integer from 0 to 4, f+2g+e is within the range of 3 to 10. n is an integer from 1 to 20, preferably an integer from 2 to 15).
作為該Q2 舉例為例如下述構造者。 An example of Q2 is the following constructor.
上述式(1)中,作為以-Q2 -X表示之構造,舉例為例如下述式(2)~(5)表示之構造。 In the above formula (1), examples of the structure represented by -Q 2 -X include structures represented by the following formulas (2) to (5).
上述式中,f、e、g、f+2g+e、n如上述。R2 如上述,較好為氫原子或甲基。In the above formula, f, e, g, f+2g+e, n are as above. R 2 is as mentioned above, preferably a hydrogen atom or a methyl group.
上述式(1)中,以-Q2 -X表示之構造特佳為下述式, Among the above formula (1), the structure represented by -Q 2 -X is particularly preferably the following formula:
上述式(1)中,Q1 相互獨立為至少具有(a+b)個Si原子之(a+b)價之基。 上述式(1)中Rf為一價基時,a’為1,a為1~6之整數,較好為1~4之整數,更好為1。Rf為二價基時,a’為2,a為1。b為1~20之整數,較好為1~6之整數,更好為2~4之整數。進而,a+b為3~21之整數,較好a+b=3~10之整數,更好a+b=3~6之整數,又更好a+b=4或5。In the above formula (1), Q 1 is independently a group having a valence of (a+b) of at least (a+b) Si atoms. When Rf is a monovalent base in the above formula (1), a' is 1, and a is an integer from 1 to 6, preferably an integer from 1 to 4, more preferably 1. When Rf is a divalent base, a' is 2 and a is 1. b is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 2 to 4. Furthermore, a+b is an integer from 3 to 21, preferably a+b=an integer from 3 to 10, more preferably a+b=an integer from 3 to 6, and more preferably a+b=4 or 5.
上述Q1 具有以下述式表示之(a+b)價環狀矽氧烷構造。 The above-mentioned Q 1 has a (a+b)-valent cyclic siloxane structure represented by the following formula.
上述式中,a及b如前述,虛線表示鍵結鍵,具有a個重複之括弧內所示之單位的各矽原子與前述式(1)中之Rf鍵結,具有b個重複之括弧內所示之單位的各矽原子與前述式(1)中之Q2 鍵結。括弧內所示之單位的排列可為無規。In the above formula, a and b are as mentioned above, and the dotted line represents the bonding bond. Each silicon atom with a repeated unit shown in the parentheses is bonded to Rf in the aforementioned formula (1), with b repeated units in the parentheses. Each silicon atom of the unit shown is bonded to Q 2 in the aforementioned formula (1). The arrangement of units shown in brackets may be random.
上述式(1)中,Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之基。Rf之數平均分子量較好為500~20,000之範圍。本發明中之數平均分子量係基於1 H-NMR及19 F-NMR由末端構造與主鏈構造之比例算出之值。In the above formula (1), Rf are independently monovalent or divalent groups having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. The number average molecular weight of Rf is preferably in the range of 500 to 20,000. The number average molecular weight in the present invention is a value calculated from the ratio of the terminal structure and the main chain structure based on 1 H-NMR and 19 F-NMR.
一價基的Rf係以下述式表示者。 (上述式中,j為1~3之整數,k為0~200之整數,較好為0~100之整數,k’為1~200之整數,較好為1~60之整數,l、m分別為1~100之整數)。Rf of the monovalent group is represented by the following formula. (In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, preferably an integer from 0 to 100, k' is an integer from 1 to 200, preferably an integer from 1 to 60, l, m is an integer from 1 to 100 respectively).
其中較好為以下之式表示者。 (上述式中,j為1~3之整數,k為0~200之整數,較好為0~100之整數,l、m分別為1~100之整數)。Among them, the preferred one is represented by the following formula. (In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, preferably an integer from 0 to 100, and l and m are respectively an integer from 1 to 100).
二價基的Rf係以下述式表示者。 (式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數)。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,但h+i為2~300,各重複單位可以無規鍵結)。 (式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數)。 (式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數)。Rf of the divalent group is represented by the following formula. (In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200 respectively, but k+t is an integer from 2 to 200, and s is an integer from 0 to 6). (In the formula, j is an independent integer from 1 to 3, h and i are integers from 0 to 200 respectively, but h+i is an integer from 2 to 300, and each repeating unit can be randomly bonded). (In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200 respectively, but k+t is an integer from 2 to 200, and s is an integer from 0 to 6). (In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200 respectively, but k+t is an integer from 2 to 200, and s is an integer from 0 to 6).
其中特別期望為以下之式表示者。 (式中,j為1~3之整數,h、i分別為0~200之整數,但h+i為2~300,各重複單位可以無規鍵結)。Among them, those expressed by the following formula are particularly desirable. (In the formula, j is an integer from 1 to 3, h and i are integers from 0 to 200 respectively, but h+i is 2 to 300, and each repeating unit can be bonded randomly).
上述通式(1)表示之化合物(含氟環氧改質有機矽化合物)可藉由例如如下方法製造。 首先起初,對末端具有烯烴基之含氟化合物(a)在SiH成為過量之條件下,加成反應分子中具有2個以上,較好3個以上SiH基之有機矽化合物(b)(矽氧烷或組合其2種以上而成之有機矽化合物)。藉由該反應,合成具有複數SiH基之含氟化合物(c)。The compound represented by the general formula (1) (fluorine-containing epoxy modified organosilicon compound) can be produced, for example, by the following method. Firstly, to the fluorine-containing compound (a) having an olefin group at the terminal, under conditions where SiH becomes excessive, the organic silicon compound (b) (silicone) having two or more, preferably three or more SiH groups in the molecule is added. alkane or an organosilicon compound formed by combining two or more thereof). Through this reaction, the fluorine-containing compound (c) having a plurality of SiH groups is synthesized.
化合物(a)尤其可以下述式(6)表示。 (上述式(6)中,於Rf0 為一價時x為1,於Rf0 為二價時x為2)。In particular, compound (a) can be represented by the following formula (6). (In the above formula (6), x is 1 when Rf 0 is monovalent, and x is 2 when Rf 0 is divalent).
Rf0 為下述式(7)表示之一價基或下述式(8)表示之二價基。 Rf 0 is a monovalent group represented by the following formula (7) or a divalent group represented by the following formula (8).
上述式(7)中,Rf2 係以下述式表示: (上述式中,j為1~3之整數,k為0~200之整數,較好為0~100之整數,k’為1~200之整數,較好為1~60之整數,l、m分別為1~100之整數)。In the above formula (7), Rf 2 is represented by the following formula: (In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, preferably an integer from 0 to 100, k' is an integer from 1 to 200, preferably an integer from 1 to 60, l, m is an integer from 1 to 100 respectively).
又,上述式(8)中,Rf1 係以下述式表示: (式中,r為2~6之整數,k、t分別為0~200之整數,但k+t為2~200,s為0~6之整數)。 (式中,j為1~3之整數,h、i分別為0~200之整數,但h+i為2~300)。In addition, in the above formula (8), Rf 1 is represented by the following formula: (In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200 respectively, but k+t is an integer from 2 to 200, and s is an integer from 0 to 6). (In the formula, j is an integer from 1 to 3, h and i are integers from 0 to 200 respectively, but h+i is an integer from 2 to 300).
又,上述式(7)及(8)中,Q6 互相獨立為可含有氧原子、氮原子或矽原子之碳數2~10,較好碳數2之二價有機基。Moreover, in the above formulas (7) and (8), Q 6 are independently a divalent organic group having 2 to 10 carbon atoms, preferably 2 carbon atoms, which may contain an oxygen atom, a nitrogen atom or a silicon atom.
作為上述Q6 舉例為以下述式表示者。 An example of Q 6 is represented by the following formula.
作為一價之Rf0 的化合物(a),舉例為例如下述者。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,j為1~3之整數,k’為1~200之整數,較好為1~60之整數)。 (上述式中,j為1~3之整數,l、m分別為1~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。Examples of the monovalent Rf 0 compound (a) include the following. (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, j is an integer from 1 to 3, and k' is an integer from 1 to 200, preferably an integer from 1 to 60). (In the above formula, j is an integer from 1 to 3, and l and m are respectively integers from 1 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100).
作為二價之Rf0 的化合物(a),舉例為例如下述者。 (式中,r為2~6之整數,k、t分別為0~200之整數,較好為0~100之整數,但k+t為2~200,較好為3~150,s為0~6之整數)。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,較好為2~100之整數,但h+i為2~300,較好為4~200,各重複單位可以無規鍵結)。 (式中,r為2~6之整數,k、t分別為0~200之整數,較好為0~100之整數,但k+t為2~200,較好為3~150,s為0~6之整數)。 (式中,r為2~6之整數,k、t分別為0~200之整數,較好為0~100之整數,但k+t為2~200,較好為3~150,s為0~6之整數)。Examples of the divalent Rf 0 compound (a) include the following. (In the formula, r is an integer from 2 to 6, k and t are respectively an integer from 0 to 200, preferably an integer from 0 to 100, but k+t is 2 to 200, preferably 3 to 150, and s is an integer from 0 to 6). (In the formula, j is independently an integer from 1 to 3, h and i are respectively an integer from 0 to 200, preferably an integer from 2 to 100, but h+i is an integer from 2 to 300, preferably 4 to 200, each Repeating units can be bonded randomly). (In the formula, r is an integer from 2 to 6, k and t are respectively an integer from 0 to 200, preferably an integer from 0 to 100, but k+t is 2 to 200, preferably 3 to 150, and s is an integer from 0 to 6). (In the formula, r is an integer from 2 to 6, k and t are respectively an integer from 0 to 200, preferably an integer from 0 to 100, but k+t is 2 to 200, preferably 3 to 150, and s is an integer from 0 to 6).
化合物(b)特別可由下述式(9)表示。 (式(9)中,Q1 、a及b如上述。括弧內所示之H係與Q1 構造中之Si原子直接鍵結之氫原子)。Compound (b) is particularly represented by the following formula (9). (In formula (9), Q 1 , a and b are as described above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the structure of Q 1 ).
作為該化合物(b),舉例為例如下述者。 (上述式中,a、b如上述)。Examples of the compound (b) include the following. (In the above formula, a and b are as above).
特別較好為以下者。 Particularly preferred are the following.
化合物(a)中Rf0 為一價基時,宜使相對於化合物(b)於1分子中具有之SiH基個數(a+b)個,化合物(a)具有之烯烴基個數成為未達(a+b)個,較好成為a個之量反應。所得化合物(c)之構造可以下述式(10)表示。 (上述式中,Rf0 、Q1 、a及b如上述)。When Rf 0 in compound (a) is a monovalent group, it is preferable that the number of alkene groups in compound (a) is equal to the number (a + b) of SiH groups in one molecule of compound (b). If it reaches (a+b), it is better to become a quantitative response. The structure of the obtained compound (c) can be represented by the following formula (10). (In the above formula, Rf 0 , Q 1 , a and b are as above).
作為以式(10)表示之化合物(c),舉例為例如下述者。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。Examples of the compound (c) represented by formula (10) include the following. (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100).
化合物(a)中Rf0 為二價基時,期望以化合物(a):化合物(b)=1:2之莫耳比反應,所得化合物(c)之構造例如可以下述式(11)表示。亦即,成為於化合物(a)之兩末端各導入1分子化合物(b)之構造。 (上述式中,Q1 、Rf0 及b如上述。括弧內所示之H係與Q1 構造中之Si原子直接鍵結之氫原子)。When Rf 0 in compound (a) is a divalent group, it is desired to react in a molar ratio of compound (a): compound (b) = 1:2. The structure of the obtained compound (c) can be represented by the following formula (11), for example. . That is, it is a structure in which one molecule of compound (b) is introduced at each end of compound (a). (In the above formula, Q 1 , Rf 0 and b are as above. The H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q 1 structure).
作為以式(11)表示之化合物(c),舉例為例如下述者。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,較好為2~100之整數,但h+i為2~300,較好為4~200,各重複單位可以無規鍵結)。Examples of the compound (c) represented by formula (11) include the following. (In the formula, j is independently an integer from 1 to 3, h and i are respectively an integer from 0 to 200, preferably an integer from 2 to 100, but h+i is an integer from 2 to 300, preferably 4 to 200, each Repeating units can be bonded randomly).
上述加成反應可在無溶劑下進行,但亦可根據需要於溶劑存在下進行。該溶劑只要使用甲苯、二甲苯、異辛烷等之一般廣泛使用之有機溶劑即可。但,較好為沸點係目的的反應溫度以上,且不阻礙反應,反應後生成之含氟化合物(c)於反應溫度下可溶。例如,期望為六氟化間-二甲苯、三氟甲苯(benzotrifluoride)等之氟改質芳香族烴系溶劑、甲基全氟丁基醚等之氟改質醚系溶劑等之部分經氟改質之溶劑,尤其佳為六氟化間-二甲苯。The above-mentioned addition reaction can be carried out without a solvent, but can also be carried out in the presence of a solvent if necessary. As the solvent, generally widely used organic solvents such as toluene, xylene, and isooctane can be used. However, it is preferable that the reaction temperature is higher than the boiling point and does not hinder the reaction, and that the fluorine-containing compound (c) generated after the reaction is soluble at the reaction temperature. For example, it is desirable that parts of fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, fluorine-modified ether solvents such as methyl perfluorobutyl ether, etc., are fluorine-modified. The preferred solvent is meta-xylene hexafluoride.
加成反應觸媒只要使用以往習知者即可。例如可使用包含鉑、銠或鈀之化合物。其中較好為包含鉑之化合物,可使用六氯鉑(IV)酸六水合物、鉑羰基乙烯基甲基錯合物、鉑-二乙烯基四甲基二矽氧烷錯合物、鉑-環乙烯基甲基矽氧烷錯合物、鉑-辛醛/辛醇錯合物或擔持於活性碳之鉑。觸媒之調配量若為有效量即可。尤其,對於化合物(a),所含之金屬量成為0.1~5,000質量ppm,更好為1~1,000質量ppm之量即可。As the additive reaction catalyst, only those familiar with it can be used. For example compounds containing platinum, rhodium or palladium may be used. Among them, compounds containing platinum are preferred, and hexachloroplatinum(IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, and platinum- cyclovinylmethylsiloxane complex, platinum-octanal/octanol complex or platinum supported on activated carbon. The amount of catalyst prepared can be an effective amount. In particular, the amount of metal contained in the compound (a) should be 0.1 to 5,000 ppm by mass, and more preferably 1 to 1,000 ppm by mass.
加成反應中,各成分之饋入順序並未特別限制。舉例為例如如下方法:將化合物(a)、化合物(b)及觸媒之混合物自室溫緩緩加熱至加成反應溫度之方法,將化合物(a)、化合物(b)及稀釋溶劑之混合物加熱至目的之反應溫度後添加觸媒之方法,將加熱至目的之反應溫度的化合物(b)與觸媒之混合物中滴加化合物(a)之方法,於加熱至目的之反應溫度的化合物(b)中滴加化合物(a)與觸媒之混合物之方法。其中,特佳為將化合物(a)、化合物(b)及稀釋溶劑之混合物加熱至目的之反應溫度後添加觸媒之方法,或者,於加熱至目的之反應溫度的化合物(b)中滴加化合物(a)與觸媒之混合物之方法。上述加成反應條件只要依據以往習知方法即可。尤其期望於乾燥環境下,於空氣或惰性氣體(N2 、Ar等)中,於反應溫度50~150℃,較好70~120℃,進行0.5~96小時,較好進行1~48小時。In the addition reaction, the order in which the components are fed is not particularly limited. An example is the following method: a method of slowly heating a mixture of compound (a), compound (b) and a catalyst from room temperature to the addition reaction temperature; heating a mixture of compound (a), compound (b) and a diluting solvent. The method of adding the catalyst after reaching the target reaction temperature, the method of adding dropwise the compound (a) to the mixture of the compound (b) and the catalyst heated to the target reaction temperature, and the method of adding the compound (b) dropwise to the mixture of the compound (b) heated to the target reaction temperature. ) is a method of adding dropwise the mixture of compound (a) and catalyst. Among them, a particularly preferred method is to add a catalyst after heating a mixture of compound (a), compound (b) and diluting solvent to a target reaction temperature, or to add dropwise to compound (b) heated to a target reaction temperature. Method for mixture of compound (a) and catalyst. The above-mentioned addition reaction conditions may be based on conventionally known methods. It is especially desirable to carry out the reaction in a dry environment, in air or inert gas (N 2 , Ar, etc.), at a reaction temperature of 50 to 150°C, preferably 70 to 120°C, for 0.5 to 96 hours, preferably 1 to 48 hours.
化合物(a)之調配量,相對於具有(a+b)個SiH基之化合物(b) 1分子,宜為化合物(a)具有之烯烴基的個數成為未達(a+b)個,較好成為a個之量。尤其,化合物(a)之Rf0 為二價基時,期望以化合物(a):化合物(b)=1:2之莫耳比反應。尤其,為了防止三維交聯,期望對於化合物(a)之烯烴基,化合物(b)使用過量進行加成反應後,藉由減壓蒸餾去除未反應之化合物(b)。The compounding amount of compound (a) is preferably such that the number of olefin groups of compound (a) does not reach (a+b) per 1 molecule of compound (b) having (a+b) SiH groups. It is better to become a quantity. In particular, when Rf 0 of compound (a) is a divalent group, it is desired to react at a molar ratio of compound (a): compound (b) = 1:2. In particular, in order to prevent three-dimensional crosslinking, it is desirable to perform an addition reaction using an excess amount of compound (b) to the olefin group of compound (a), and then remove the unreacted compound (b) by distillation under reduced pressure.
其次,進行上述所得之含氟化合物(c)之SiH基與一分子中具有末端烯烴基與環氧基之化合物(d)之加成反應,可獲得上述式(1)表示之含氟環氧改質有機矽化合物。Next, the addition reaction of the SiH group of the fluorine-containing compound (c) obtained above and the compound (d) having a terminal olefin group and an epoxy group in one molecule is carried out to obtain the fluorine-containing epoxy represented by the above formula (1). Modified organosilicon compounds.
化合物(d)舉例為例如下述式(2a)~(5a)表示之化合物。 Examples of the compound (d) include compounds represented by the following formulas (2a) to (5a).
上述式中,f’為0~8之整數,e為0~5之整數,g為0~10之整數,f’+2g+e為2~18之範圍內。較好f為0~6之整數,e為1或2,g為0~4之整數,f’+2g+e為2~8之範圍內。n’為0~18之整數,較好為0~13之整數。R2 如上述,較好為氫原子或甲基。In the above formula, f' is an integer from 0 to 8, e is an integer from 0 to 5, g is an integer from 0 to 10, and f'+2g+e is in the range of 2~18. Preferably, f is an integer from 0 to 6, e is 1 or 2, g is an integer from 0 to 4, and f'+2g+e is within the range of 2 to 8. n' is an integer from 0 to 18, preferably an integer from 0 to 13. R 2 is as mentioned above, preferably a hydrogen atom or a methyl group.
作為化合物(d)例示以下者。該化合物可單獨使用1種或組合2種以上使用。 Examples of the compound (d) include the following. This compound can be used individually by 1 type or in combination of 2 or more types.
化合物(c)與化合物(d)之加成反應條件只要依據以往習知方法即可。較好於上述加成反應觸媒存在下,於乾燥環境下,於空氣或惰性氣體(N2 、Ar等)中,於反應溫度50~150℃,較好50~120℃,進行0.5~96小時,較好進行1~48小時即可。該反應亦可根據需要使用溶劑。The conditions for the addition reaction of compound (c) and compound (d) may be based on conventionally known methods. Preferably, in the presence of the above addition reaction catalyst, in a dry environment, in air or inert gas (N 2 , Ar, etc.), at a reaction temperature of 50 to 150°C, preferably 50 to 120°C, for 0.5 to 96 hours, preferably 1 to 48 hours. This reaction can also use a solvent as needed.
化合物(d)對於化合物(c)之調配量可使用任意值,但期望使用相對於化合物(c)具有之SiH基個數,化合物(d)具有之末端烯烴基的個數成為相等,或末端烯烴基之個數成為過剩之量而進行,進行加成反應後,藉由減壓蒸餾等去除未反應之化合物(d)。尤其期望相對於化合物(c)具有之1個SiH基之化合物(d)具有的末端烯烴基個數之比成為1.0~5.0,較好1.0~2.0之量進行反應。Any value can be used for the compounding amount of compound (d) with respect to compound (c), but it is preferable to use the number of terminal olefin groups that compound (d) has relative to the number of SiH groups that compound (c) has, or the number of terminal olefin groups that compound (d) has. The addition reaction proceeds until the number of olefin groups becomes excessive, and then the unreacted compound (d) is removed by vacuum distillation or the like. In particular, it is desired that the ratio of the number of terminal alkenyl groups of compound (d) to one SiH group of compound (c) is 1.0 to 5.0, preferably 1.0 to 2.0, to carry out the reaction.
作為上述通式(1)所示之化合物(A)特佳可舉例下述所示化合物。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,k為0~200之整數,較好為0~100之整數)。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,較好為2~100之整數,但h+i為2~300,較好為4~200,各重複單位可以無規鍵結)。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,較好為2~100之整數,但h+i為2~300,較好為4~200,各重複單位可以無規鍵結)。 (式中,j獨立為1~3之整數,h、i分別為0~200之整數,較好為2~100之整數,但h+i為2~300,較好為4~200,各重複單位可以無規鍵結)。Particularly preferred examples of the compound (A) represented by the general formula (1) include the following compounds. (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, k is an integer from 0 to 200, preferably an integer from 0 to 100). (In the formula, j is independently an integer from 1 to 3, h and i are respectively an integer from 0 to 200, preferably an integer from 2 to 100, but h+i is an integer from 2 to 300, preferably 4 to 200, each Repeating units can be bonded randomly). (In the formula, j is independently an integer from 1 to 3, h and i are respectively an integer from 0 to 200, preferably an integer from 2 to 100, but h+i is an integer from 2 to 300, preferably 4 to 200, each Repeating units can be bonded randomly). (In the formula, j is independently an integer from 1 to 3, h and i are respectively an integer from 0 to 200, preferably an integer from 2 to 100, but h+i is an integer from 2 to 300, preferably 4 to 200, each Repeating units can be bonded randomly).
該等化合物(A)可為單獨種類,亦可混合複數種不同化合物(A)而使用。These compounds (A) may be of a single type or may be used in mixture of a plurality of different compounds (A).
本發明係含有上述化合物(A)及至少一種光聚合起始劑(B)之活性能量線硬化性組成物。光聚合起始劑(B)若為可藉由光(尤其是紫外線)照射而可使化合物(A)之環氧基開始聚合之化合物,則未特別限定,但尤其是光酸產生劑,作為一般廣泛使用者可舉例光分解之各種鎓鹽。The present invention is an active energy ray curable composition containing the above compound (A) and at least one photopolymerization initiator (B). The photopolymerization initiator (B) is not particularly limited as long as it is a compound that can initiate polymerization of the epoxy group of the compound (A) by irradiation with light (especially ultraviolet rays). However, in particular, it is a photoacid generator. Commonly used examples include various onium salts that are photodecomposable.
作為此等之例,可舉例為具有作為抗衡陰離子之SbF6 - 、AsF6 - 、BF4 - 、B(C6 F5 )4 - 、PF6 - 、(Rf””)x PF6-x - (式中(Rf””相互獨立為碳數1~8之烷基、碳數2~8之烯基、碳數6~10之芳基,且與各基之碳原子鍵結之氫原子經氟原子取代80mol%以上之基,x為1~5之整數)等之烯丙基重氮鎓鹽(重氮鎓鹽)、二烯丙基錪鎓鹽(錪鎓鹽)、三烯丙基鋶鹽(鋶鹽)等,但基於毒性之觀點,特別期望為具有硼、磷系之抗衡陰離子之鎓鹽。Examples of these include SbF 6 - , AsF 6 - , BF 4 - , B(C 6 F 5 ) 4 - , PF 6 - and (Rf””) x PF 6-x having counter anions. - (In the formula (Rf"" are independently an alkyl group with 1 to 8 carbon atoms, an alkenyl group with 2 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms, and a hydrogen atom bonded to the carbon atom of each group Allyl diazonium salts (diazonium salts), diallyl quinium salts (diallyl quinium salts), triallyl quinium salts, etc., with more than 80 mol% of groups substituted by fluorine atoms, x is an integer from 1 to 5), etc. sulfonium salts (sulfonium salts), etc., but from the viewpoint of toxicity, onium salts having boron or phosphorus-based counter anions are particularly desirable.
作為光聚合起始劑(B)包含上述所示之例,各種化合物及該等之混合物多有市售。作為具體之商品名為SAN APRO股份有限公司「CPI系列」(例如CPI-100P、CPI-101A8、CPI-200K、CPI-210S、CPI-310B、CPI-400PG)、ADEKA股份有限公司「ADEKA OPTOMER SP系列」(例如SP150、SP152、SP170、ADEKAO SP172)、三新化學製「SANAID SI系列」(例如SI-60L、SI-80L、SI-100L)、富士軟片和光純藥工業股份有限公司「光WPI系列」(例如PI-169、WPI-170、WPI-124、WPI-116、WPI-113)、BASF公司「IGRACURE 250、IGRACURE 270、IGRACURE 290」等,該等可以單體及複數種混合使用。且近幾年,亦市售有同時具有光陽離子產生及熱陽離子產生功能之聚合起始劑,亦可使用此等。可舉例為例如SAN APRO股份有限公司之TA-100。Examples of the photopolymerization initiator (B) include those shown above, and various compounds and mixtures thereof are commercially available. Specific product names are SAN APRO Co., Ltd. "CPI series" (such as CPI-100P, CPI-101A8, CPI-200K, CPI-210S, CPI-310B, CPI-400PG), ADEKA Co., Ltd. "ADEKA OPTOMER SP" Series" (such as SP150, SP152, SP170, ADEKAO SP172), Sanshin Chemical Co., Ltd. "SANAID SI Series" (such as SI-60L, SI-80L, SI-100L), Fujifilm Wako Pure Chemical Industries, Ltd. "Hikari WPI Series" (such as PI-169, WPI-170, WPI-124, WPI-116, WPI-113), BASF's "IGRACURE 250, IGRACURE 270, IGRACURE 290", etc., which can be used singly or in combination. In recent years, polymerization initiators that have both photocation generation and thermal cation generation functions are also commercially available, and these can also be used. An example is TA-100 of SAN APRO Co., Ltd.
本發明中,除了(A)成分與(B)成分以外,亦可進而包含由(A)成分以外之1種以上的具有陽離子硬化性之化合物所成之(C)成分。 作為具有陽離子硬化性之化合物可舉例為1分子中具有1個以上環氧基、氧雜環丁基等之環狀醚之化合物、具有乙烯醚基之化合物、異丁烯(IB)等之脂肪族不飽和烴化合物、苯乙烯衍生物、內酯或環狀碳酸酯等之具有羰基之化合物、雙環原酯、螺原碳酸酯、螺原酯、N-乙烯基咔唑等之陽離子聚合性含氮化合物(單體)等。In the present invention, in addition to the component (A) and the component (B), the component (C) composed of one or more compounds having cationic curability other than the component (A) may be further included. Examples of the compound having cationic curability include cyclic ether compounds having one or more epoxy groups, oxetanyl groups, etc. per molecule, compounds having vinyl ether groups, and aliphatic non-alphatic compounds such as isobutylene (IB). Saturated hydrocarbon compounds, styrene derivatives, compounds with carbonyl groups such as lactones or cyclic carbonates, cationic polymerizable nitrogen-containing compounds such as bicyclic protoesters, spiroprotocarbonate, spiroprotoester, N-vinylcarbazole, etc. (monomer) etc.
該等之中,作為含環氧基之化合物包含芳香族環氧化物、脂環式環氧化物及脂肪族環氧化物。Among these, the epoxy group-containing compound includes aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
作為芳香族環氧化物舉例為具有至少1個芳香環之一價或多價酚衍生物例如酚、雙酚A、雙酚F、雙酚AF、酚酚醛清漆之縮水甘油醚等。且亦可使用於該等縮水甘油醚構造之一部分導入烷基醚、酯構造之化合物。Examples of aromatic epoxides include monovalent or polyvalent phenol derivatives having at least one aromatic ring, such as phenol, bisphenol A, bisphenol F, bisphenol AF, glycidyl ether of phenol novolac, and the like. In addition, compounds in which an alkyl ether or ester structure is introduced into a part of the glycidyl ether structure can also be used.
作為脂環式環氧化物亦可使用將具有至少一個環己烯環、環戊烯環之化合物環氧化所得之化合物,且係其構造之一部分於構造中導入有烷基醚或烷基醚寡聚物、酯構造、ε-己內酯寡聚物之化合物。具體可舉例為乙烯基環己烯二氧化物、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、檸烯二氧化物、雙(3,4-環氧基環己基甲基)己二酸酯、二環戊二烯二氧化物1,4-環己烷二甲醇雙(3,4-環氧基環碳酸酯)等。As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene ring or cyclopentene ring and in which an alkyl ether or alkyl ether oligo is introduced into the structure as part of the structure can also be used. Polymer, ester structure, ε-caprolactone oligomer compound. Specific examples include vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, limonene dioxide, bis(3,4 -Epoxycyclohexylmethyl)adipate, dicyclopentadiene dioxide 1,4-cyclohexanedimethanol bis(3,4-epoxycyclocarbonate), etc.
作為脂防族環氧化物舉例為脂肪族多元醇或該等之環氧烷加成體之聚縮水甘油醚(1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚等)、脂肪族多元酸之聚縮水甘油酯(二縮水甘油基四氫苯二甲酸酯等)、長鏈不飽和化合物之環氧化物(環氧化聚丁二烯、源自植物之不飽和烴化合物之環氧化物)。Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Glyceryl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), epoxides of long-chain unsaturated compounds (epoxidized polybutadiene, plant-derived Epoxides of unsaturated hydrocarbon compounds).
作為具有氧雜環丁基之化合物可使用習知者,舉例為例如3-乙基-3-羥基甲基氧雜環丁烷、2-乙基己基(3-乙基-3-氧雜環丁基甲基)醚、2-羥基乙基(3-乙基-3-氧雜環丁基甲基)醚、2-羥基丙基(3-乙基-3-氧雜環丁基甲基)醚、1,4-雙[(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、氧雜環丁基倍半矽氧烷及酚酚醛清漆氧雜環丁烷等。作為具體之商品名可舉例東亞合成股份有限公司製「ARONE OXETANE系列」等。As the compound having an oxetanyl group, those known in the art can be used, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetane) Butylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4 -Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanyl sesquioxane and phenolic novolak oxetane, etc. As a specific product name, "ARONE OXETANE series" manufactured by Toa Gosei Co., Ltd. can be exemplified.
作為具有乙烯醚基之化合物可舉例為甲基乙烯醚、乙基乙烯醚、丁基乙烯醚、環己基乙烯醚等之脂肪族乙烯醚,2-苯氧基乙基乙烯醚、苯基乙烯醚、對-甲氧基苯基乙烯醚等之芳香族乙烯醚。進而可舉例丁二醇-1,4-二乙烯醚、三乙二醇二乙烯醚、二丙二醇二乙烯醚等之2官能乙烯醚。Examples of the compound having a vinyl ether group include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether, 2-phenoxyethyl vinyl ether, and phenyl vinyl ether. , aromatic vinyl ethers such as p-methoxyphenyl vinyl ether. Further examples include bifunctional vinyl ethers such as butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol divinyl ether.
作為苯乙烯衍生物除了苯乙烯以外,可舉例α-甲基苯乙烯、對-甲氧基苯乙烯及對-第三丁氧基苯乙烯等之衍生物。Examples of the styrene derivatives other than styrene include derivatives of α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and the like.
作為脂肪族不飽和烴化合物可舉例異丁烯、環戊二烯、降冰片二烯、茚、四氫茚等。Examples of the aliphatic unsaturated hydrocarbon compound include isobutylene, cyclopentadiene, norbornadiene, indene, tetrahydroindene, and the like.
作為陽離子聚合性含氮單體舉例為伸乙基亞胺等之環狀胺、噁唑啉、N-乙烯基咔唑及N-乙烯基吡咯啶酮等。Examples of the cationically polymerizable nitrogen-containing monomer include cyclic amines such as ethyleneimine, oxazoline, N-vinylcarbazole, and N-vinylpyrrolidone.
作為雙環原酯舉例為1-苯基-4-乙基-2,6,7-三氧雜雙環[2.2.2]辛烷及1-乙基-4-羥基甲基-2,6,7-三氧雜雙環-[2.2.2]辛烷等。Examples of bicyclic protoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7 -Trioxabicyclo-[2.2.2]octane, etc.
作為螺原碳酸酯舉例為1,5,7,11-四氧雜螺[5.5]十一烷及3,9-二苄基-1,5,7,11-四氧雜螺[5.5]十一烷等。Examples of spiroorthocarbonate include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]decane. Yikan et al.
其中尤其較好為具有環氧基、氧雜環丁基、乙烯醚基者,進而該等聚合性反應基除了上述形態之單體以外,亦可使用導入於矽氧烷聚合物(寡聚物)之末端及側鏈之形態者。Among them, those having an epoxy group, an oxetanyl group, or a vinyl ether group are particularly preferred. In addition to the monomers in the above-mentioned forms, these polymerizable reactive groups can also be used to be introduced into siloxane polymers (oligomers). ) terminal and side chain shape.
本發明之活性能量線硬化性組成物之各成分比率,係考慮陽離子聚合性化合物之性質或能量線之種類與照射量、溫度、硬化時間、濕度、塗膜厚度等之各種要因而決定並未特別限定,但僅具有陽離子硬化性之化合物為(A)成分時,相對於(A)成分100質量分,(B)成分較好包含0.01~20質量份,特佳包含0.05~10質量份。(B)成分之量過少時,由於起始劑成分之濃度較稀故容易發生硬化不良,且反應速度降低。過多時硬化後之硬化物中所含之未參與交聯構造之起始劑斷片量變得過多而有對硬化物物性造成意外影響之情況。The ratio of each component of the active energy ray curable composition of the present invention is determined by taking into account various factors such as the nature of the cationic polymerizable compound or the type of energy ray and the amount of irradiation, temperature, curing time, humidity, coating film thickness, etc. It is particularly limited, but when the compound having only cationic hardening properties is the component (A), the component (B) preferably contains 0.01 to 20 parts by mass, particularly preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the component (A). When the amount of component (B) is too small, hardening failure is likely to occur due to the dilute concentration of the starter component, and the reaction speed is reduced. When too much, the amount of starter fragments that are not involved in the cross-linked structure contained in the cured product after curing becomes excessive and may cause unexpected effects on the physical properties of the cured product.
又,作為本發明之活性能量線硬化性組成物進而包含前述(C)成分時,相對於(A)成分與(C)成分之合計100質量份,(B)成分較好包含0.01~20質量份,特佳包含0.05~10質量份。該情況亦(B)成分之量過少時,由於起始劑成分之濃度較稀故容易發生硬化不良,且反應速度降低。過多時硬化後之硬化物中所含之未參與交聯構造之起始劑斷片量變得過多而有對硬化物物性造成意外影響之情況。Moreover, when the active energy ray curable composition of the present invention further contains the aforementioned component (C), component (B) preferably contains 0.01 to 20 parts by mass relative to 100 parts by mass of the total of components (A) and (C). parts, preferably including 0.05~10 parts by mass. In this case, if the amount of component (B) is too small, hardening failure is likely to occur due to the dilute concentration of the starter component, and the reaction speed is reduced. When too much, the amount of starter fragments that are not involved in the cross-linked structure contained in the cured product after curing becomes excessive and may cause unexpected effects on the physical properties of the cured product.
又,本發明之活性能量線硬化性組成物中,包含(C)成分時,相對於(C)成分100質量份,(A)成分較好包含0.01~10質量份,特別更好包含0.05~5質量份。Moreover, when the active energy ray curable composition of the present invention contains component (C), component (A) preferably contains 0.01 to 10 parts by mass, and particularly preferably contains 0.05 to 100 parts by mass of component (C). 5 parts by mass.
本發明之活性能量線硬化性組成物中,作為補足硬化性者,亦可根據需要含有增感劑。作為此等增感劑,可使用例如日本特開平11-279212號及日本特開平09-183960號等揭示之增感劑等,具體可舉例為蒽{蒽、9,10-二丁氧基蒽、9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二丙氧基蒽等};芘;1,2-苯并蒽;苝;四并苯;蒄(Coronene);噻噸酮{噻噸酮、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2-異丙基噻噸酮及2,4-二乙基噻噸酮等};吩噻嗪{吩噻嗪、N-甲基吩噻嗪、N-乙基吩噻嗪、N-苯基吩噻嗪等};呫噸酮;萘{1-萘酚、2-萘酚、1-甲氧基萘、2-甲氧基萘、1,4-二羥基萘及4-甲氧基-1-萘酚等};酮{二甲氧基苯乙酮、二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、4’-異丙基-2-羥基-2-甲基苯丙酮及4-苯甲醯基-4’-甲基二苯基硫醚等};咔唑{N-苯基咔唑、N-乙基咔唑、聚-N-乙烯基咔唑及N-縮水甘油基咔唑等};䓛(chrysene){1,4-二甲氧基䓛及1,4-二-α-甲基苄氧基䓛等};菲{9-羥基菲、9-甲氧基菲、9-羥基-10-甲氧基菲及9-羥基-10-乙氧基菲等}等。含有增感劑時,增感劑含量相對於(B)成分100質量份,較好為1~300質量份,更好為5~200質量份。The active energy ray curable composition of the present invention may also contain a sensitizer as necessary to supplement the curability. As such sensitizers, for example, sensitizers disclosed in Japanese Patent Application Laid-Open No. 11-279212 and Japanese Patent Application Laid-Open No. 09-183960 can be used. Specific examples include anthracene and 9,10-dibutoxyanthracene. , 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; Pyrene; 1,2-benzanthracene; perylene; tetraacecene; coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-Isopropylthioxanthone and 2,4-diethylthioxanthone, etc.}; Phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenyl Phenothiazine, etc.}; 1-naphthol, etc.}; ketones {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl -2-Hydroxy-2-methylpropiophenone and 4-benzoyl-4'-methyldiphenyl sulfide, etc.}; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly -N-vinylcarbazole and N-glycidylcarbazole, etc.}; 䓛 (chrysene) {1,4-dimethoxy 䓛 and 1,4-di-α-methylbenzyloxy 䓛, etc.}; Phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene and 9-hydroxy-10-ethoxyphenanthrene, etc.} etc. When a sensitizer is contained, the sensitizer content is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass based on 100 parts by mass of component (B).
本發明之硬化性組成物中,另可根據需要含有習知添加劑(顏料、填充劑、抗靜電劑、難燃劑、消泡劑、流動調整劑、光安定劑、抗氧化劑、密著性賦予劑、離子補充劑、著色防止劑、溶劑、非反應性樹脂及油、寡聚物等)。The curable composition of the present invention may also contain conventional additives (pigments, fillers, antistatic agents, flame retardants, defoaming agents, flow regulators, light stabilizers, antioxidants, adhesion-imparting agents) as needed. agents, ion supplements, coloration inhibitors, solvents, non-reactive resins and oils, oligomers, etc.).
關於如以上之(B)成分、(C)成分及其他可任意調配之添加劑,於例如TECHNONET公司編「光硬化技術資料手冊 材料篇」(2000年,TECHNONET公司)、日本光聚合物技術協會編「光聚合物手冊」(1989年,工業調查會)、綜合技術中心編「UV・EB硬化技術」(1982年,綜合技術中心)、RADTECH研究會編「UV・EB硬化劑」(1992年,CMC)、技術情報協會編「UV硬化下之硬化不良、阻礙原因與其對策」(2003年,技術情報協會)、色材,68,(5),286-293(1995)、FINE CHEMICAL, 29, (19), 5-14(2000)、「Network Polymer」 Vol.30, No.5(2009)、「Network Polymer」Vol.30, No.5(2009)、「Network Polymer」Vol.31, No.4(2010)、技術情報協會編「UV硬化樹脂之調配設計、特性評價與新的應用」(2017年,技術情報協會)、CMC出版社編「UV・EB硬化材料、製品之市場實際狀態與展望」(2007年,CMC出版)、Science & Technology編「UV硬化製程之最適化」(2008年,Science & Technology)等中已揭示眾多習知者,該等可任意組合使用。Regarding the above components (B), (C) and other optional additives, see "Photohardening Technical Information Manual Materials" compiled by TECHNONET (2000, TECHNONET) and Japan Photopolymer Technology Association. "Photopolymer Handbook" (Industrial Research Council, 1989), Comprehensive Technology Center "UV・EB Hardening Technology" (Comprehensive Technology Center, 1982), RADTECH Research Institute "UV・EB Hardener" (1992, CMC), Technical Information Association, "Harding defects under UV curing, causes of obstacles and countermeasures" (2003, Technical Information Association), Color Materials, 68, (5), 286-293 (1995), FINE CHEMICAL, 29, (19), 5-14(2000), "Network Polymer" Vol.30, No.5(2009), "Network Polymer" Vol.30, No.5(2009), "Network Polymer" Vol.31, No .4 (2010), "Preparation design, characteristic evaluation and new applications of UV curable resin" compiled by the Technical Information Association (2017, Technical Information Association), "The actual market status of UV・EB hardening materials and products" compiled by CMC Publishing House and Prospects" (2007, CMC Publishing), "Optimization of UV Curing Processes" edited by Science & Technology (2008, Science & Technology), etc. have been disclosed by many experts, and these can be used in any combination.
進而本發明之活性能量線硬化性組成物亦可根據需要含有溶劑。作為較佳溶劑舉例為異丙醇、丁醇等之醇類,四氫呋喃、二乙二醇二甲醚等之醚類,甲基乙基酮、甲基異丁基酮等之酮類,及乙酸乙酯、乳酸乙酯等之酯類,丙二醇單甲醚乙酸酯等之二醇醚之酯化物等。溶劑之調配量並未特別限制,但較好相對於上述(A)成分與(B)成分之合計100質量份(包含(C)成分時,為(A)、(B)、(C)成分之合計100質量份),宜為20~900質量份,尤其宜為50~400質量份。Furthermore, the active energy ray curable composition of the present invention may also contain a solvent if necessary. Examples of preferred solvents include alcohols such as isopropyl alcohol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and acetic acid. Esters such as ethyl ester and ethyl lactate, esterification products of glycol ethers such as propylene glycol monomethyl ether acetate, etc. The amount of the solvent to be prepared is not particularly limited, but it is preferably the components (A), (B), and (C) based on 100 parts by mass of the total of the above-mentioned (A) component and (B) component (including the (C) component). The total amount is 100 parts by mass), preferably 20 to 900 parts by mass, especially 50 to 400 parts by mass.
本發明之活性能量線硬化性組成物之調製方法並未特別限制。本發明之硬化性組成物可依據以往習知方法,將上述(A)成分與(B)成分、根據需要之(C)成分、其他任意添加劑及溶劑混合而獲得。The preparation method of the active energy ray curable composition of the present invention is not particularly limited. The curable composition of the present invention can be obtained by mixing the above-mentioned component (A) and component (B), component (C) if necessary, other optional additives, and a solvent according to conventional methods.
又,作為本發明之活性能量線硬化性組成物之一般使用形態,若為使本發明之活性能量線硬化性組成物層硬化後而密著或接著者則可塗佈於任何基材上,但特別可舉例為樹脂基材例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚乙烯、聚丙烯、賽路吩、二乙醯基纖維素、三乙醯基纖維素、乙醯基纖維素丁酸酯、纖維素乙酸酯丙酸酯、環烯烴聚合物、環烯烴共聚物、聚氯乙烯、聚偏氯乙烯、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、聚苯乙烯、聚碳酸酯、聚甲基戊烯、聚碸、聚醚醚酮、聚醚碸、聚醚醯亞胺、聚醯亞胺、氟樹脂、尼龍、丙烯酸樹脂等之樹脂。可對於將該等採取為薄膜、板狀及成形構件等任意形態者於其表面使用。In addition, as a general usage form of the active energy ray curable composition of the present invention, if the active energy ray curable composition layer of the present invention is hardened and then closely adhered or adhered, it can be coated on any base material. However, resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cylindrone, and diethyl fiber can be particularly exemplified. Cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cyclic olefin polymer, cyclic olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, Ethylene vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polystyrene, polyether ether ketone, polyether styrene, polyether imide, polyimide, fluororesin, nylon, Resins such as acrylic resin. It can be used on the surface of any form such as film, plate, or shaped member.
且塗佈於薄膜基材時,亦可為於與塗佈・形成含氟活性能量線硬化性組成物層之相反面塗佈黏著劑之構造,進而亦可配置為了保護黏著劑之脫模薄膜。When coating on a film base material, the adhesive may be coated on the opposite side to which the fluorine-containing active energy ray curable composition layer is applied and formed, and a release film may be provided to protect the adhesive. .
又前述薄膜基材可為僅由上述舉例之樹脂薄膜所成之基材,但為了提高與使本發明之活性能量線硬化性組成物之密著性,亦可為於前述樹脂薄膜設置底塗層之薄膜基材。作為前述底塗層舉例為例如由聚酯系樹脂、胺基甲酸酯系樹脂、丙烯酸系樹脂等所成者。The film base material may be a base material made only of the resin films exemplified above. However, in order to improve the adhesion with the active energy ray curable composition of the present invention, a primer may be provided on the resin film. layer of film substrate. Examples of the undercoat layer include those made of polyester resin, urethane resin, acrylic resin, and the like.
又本發明之活性能量線硬化性組成物亦可塗佈於硬化・未硬化之不相當於本發明之硬化性組成物層上。例如可於硬度、耐久性、抗靜電性、捲曲等之變形防止性更高的硬化物層上重複塗佈本發明之活性能量線硬化性組成物。In addition, the active energy ray curable composition of the present invention can also be coated on a hardened or unhardened layer that is not equivalent to the curable composition of the present invention. For example, the active energy ray curable composition of the present invention can be repeatedly coated on a cured material layer that has higher hardness, durability, antistatic properties, and higher resistance to deformation such as curling.
又基於提高與本發明之活性能量線硬化性組成物之密著性之目的,樹脂薄膜表面亦可實施利用噴砂法、溶劑處理法等之表面凹凸化處理、電暈放電處理、鉻酸處理、火焰處理、熱風處理、臭氧・紫外線照射處理、氧化處理等之處理。In addition, for the purpose of improving the adhesion with the active energy ray curable composition of the present invention, the surface of the resin film can also be subjected to surface roughening treatment using sand blasting, solvent treatment, etc., corona discharge treatment, chromic acid treatment, Flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment, oxidation treatment, etc.
作為將本發明之活性能量線硬化性組成物塗佈於上述基材或物品之方法,並未特別限制,但可使用例如輥塗佈、凹版塗佈、流塗、簾塗、浸漬塗佈、噴霧塗佈、旋轉塗佈、棒塗佈、噴墨印刷、網版印刷等之習知塗佈方法。The method of coating the active energy ray curable composition of the present invention on the above-mentioned base material or article is not particularly limited, but for example, roll coating, gravure coating, flow coating, curtain coating, dip coating, Common coating methods include spray coating, spin coating, rod coating, inkjet printing, screen printing, etc.
塗佈後,對塗膜照射活性能量線使之硬化。此處,作為活性能量線可使用電子束、紫外線等任意者,但特佳為紫外線。作為紫外線源,較好為水銀燈、金屬鹵素燈、LED燈。作為紫外線照射量,若過少則殘存未硬化成分,若過多則塗膜及基材有劣化之可能性,故期望為10~10,000mJ/cm2 ,尤其期望為100~4,000mJ/cm2 之範圍。After coating, the coating film is irradiated with active energy rays to harden it. Here, as the active energy rays, any of electron beams, ultraviolet rays, etc. can be used, but ultraviolet rays are particularly preferred. As the ultraviolet source, a mercury lamp, a metal halide lamp, or an LED lamp is preferred. As the amount of ultraviolet irradiation, if it is too small, unhardened components will remain, and if it is too much, the coating film and the base material may be deteriorated, so it is preferably 10 to 10,000mJ/cm 2 , and particularly preferably within the range of 100 to 4,000mJ/cm 2 .
又,為了防止水分所致之硬化阻礙,於紫外線照射時將照射環境以氣體中之水份量經管理之空氣、氮氣、二氧化碳、氬等之氣體置換,或塗膜表面以具有脫模性之有紫外線透過性之保護層覆蓋,自其上照射紫外線,或於基材具有紫外線透過性時,塗膜表面以具有脫模性之保護層覆蓋後自與基材之塗佈面相反側照射紫外線。且為了有效進行塗膜之調平或塗膜中之陽離子聚合性基之反應,亦可於紫外線照射前及照射中以紫外線或熱風乾燥爐等之任意方法加熱塗膜及基材。In addition, in order to prevent the hardening obstruction caused by moisture, during ultraviolet irradiation, the irradiation environment is replaced with a gas such as air, nitrogen, carbon dioxide, argon, etc. that has a controlled amount of moisture in the gas, or the surface of the coating film is replaced with a gas having release properties. Cover it with a UV-transmissive protective layer and irradiate UV rays from the top, or when the base material is UV-transparent, cover the surface of the coating film with a releasable protective layer and then irradiate UV rays from the side opposite to the coating surface of the base material. In order to effectively level the coating film or react with the cationic polymerizable groups in the coating film, the coating film and the substrate can be heated by any method such as ultraviolet rays or a hot air drying oven before and during ultraviolet irradiation.
作為如此所得之活性能量線硬化性組成物之硬化物層的厚度並未特別限制,但較好為0.01~5,000μm,特佳為0.05~200μm。The thickness of the hardened material layer of the active energy ray curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 μm, particularly preferably 0.05 to 200 μm.
又,如此所得之本發明之活性能量線硬化性組成物之硬化物層,成為在從離子交換水之2μL液滴著液起1秒後根據液面與固體面所成之角所測定之靜水接觸角(亦簡稱為水接觸角)為100°以上,尤其是105°以上之表面。又,較好可成為將油酸之4μL液滴著液起1秒後根據液面與固體面所成之角所測定之靜油酸接觸角(亦簡稱為油酸接觸角)為60°以上,尤其是65°以上之撥水撥油性表面。又,為了成為上述接觸角,本發明之含氟活性能量線硬化性組成物之硬化物層較好成為對該硬化物層之全部表面積載置平均厚度10nm以上之層的量。且,於硬化物層表面越未殘存未反應之陽離子聚合性基越佳,因此可任意進行於水分經管理之環境或加熱條件下之活性能量線硬化處理、光聚合起始劑(B)之調配量調整、活性能量線照射後為了於乾淨環境下進行暗反應所作之保持等。Moreover, the hardened material layer of the active energy ray curable composition of the present invention thus obtained has a static value measured based on the angle formed by the liquid surface and the solid surface 1 second after the drop of 2 μL of ion-exchange water. The water contact angle (also referred to as water contact angle) is above 100°, especially for surfaces above 105°. Furthermore, it is preferable that the static oleic acid contact angle (also referred to as oleic acid contact angle) measured from the angle between the liquid surface and the solid surface 1 second after dropping 4 μL of oleic acid is 60° or more. , especially for water- and oil-repellent surfaces above 65°. Furthermore, in order to achieve the above-mentioned contact angle, the cured material layer of the fluorine-containing active energy ray curable composition of the present invention is preferably in an amount such that a layer with an average thickness of 10 nm or more is placed on the entire surface area of the cured material layer. In addition, the less unreacted cationic polymerizable groups remain on the surface of the hardened material layer, the better. Therefore, active energy ray hardening treatment and photopolymerization initiator (B) can be carried out in an environment with controlled moisture or under heating conditions. Adjustment of the amount of preparation, maintenance of the dark reaction in a clean environment after irradiation with active energy rays, etc.
如以上,本發明之活性能量線硬化性組成物可藉由紫外線等之活性能量線而硬化,可於物品表面形成撥水波油性、防污性、耐指紋性、摩擦性、耐磨耗性優異之硬化樹脂層。As mentioned above, the active energy ray curable composition of the present invention can be hardened by active energy rays such as ultraviolet rays, and can form water-repellent waves on the surface of articles. It has excellent oil properties, antifouling properties, fingerprint resistance, friction properties, and abrasion resistance. The hardened resin layer.
進而,本發明中,提供具有將上述本發明之活性能量線硬化性組成物塗佈於表面並硬化之硬化被膜之物品。如上述,若使用本發明之活性能量線硬化性組成物,則可於基材(物品)表面形成具有優異表面特性之硬化被膜(硬化樹脂層)。尤其,可用於對陽離子硬化型硬塗層表面賦予撥水性、撥油性、防污性。藉此,可對基材賦予因指紋、皮脂、汗等之人類油脂、化妝品等所致之髒污、機械油等難以附著,且擦拭性亦優異之硬塗覆表面。因此,本發明之活性能量線硬化性組成物可提供對於有因人接觸而因人類油脂、化妝品等所致之髒污的可能性之基材(物品)或有作業者之人類油脂或機械油等污染之可能性的機械內部所用之工程材料薄膜等之表面之防污塗裝膜或保護膜。Furthermore, the present invention provides an article having a cured film in which the active energy ray curable composition of the present invention is applied to the surface and cured. As described above, if the active energy ray curable composition of the present invention is used, a cured film (hardened resin layer) having excellent surface properties can be formed on the surface of the base material (article). In particular, it can be used to impart water-repellent properties, oil-repellent properties, and antifouling properties to the surface of a cationic hardening hard coat layer. This makes it possible to provide a base material with a hard coating surface that is difficult to adhere to dirt caused by fingerprints, sebum, sweat and other human oils, cosmetics, etc., and machine oil, and has excellent wipeability. Therefore, the active energy ray curable composition of the present invention can provide human grease or machine oil for base materials (articles) that may be contaminated by human grease, cosmetics, etc. due to human contact or for workers. Anti-fouling coating film or protective film on the surface of engineering material films used inside machinery that have the possibility of contamination.
使用本發明之活性能量線硬化性組成物形成之硬化被膜(硬化樹脂層)作為平板型個人電腦、筆記型電腦、行動電話、智慧型手機等之攜帶(通訊)資訊終端、數位媒體播放器、電子書讀取機等各種機器之框體、手錶型・眼鏡型穿戴式電腦;液晶顯示器、電漿顯示器、有機EL(電致發光)顯示器、背面投影型顯示器、螢光顯示管(VFD)、場發射投影顯示器、CRT、碳粉系顯示器等之各種黑色面板顯示器及TV之畫面等之顯示操作機器表面及該等之內部所使用之各種光學薄膜類、汽車外裝、鋼琴或傢俱之光澤表面、大理石等之建築用石材表面、廁所、浴室、洗臉台等之水流繞之裝飾建材、美術品展示用保護玻璃、展示窗、展示櫃、相框用蓋體、手錶、汽車窗用玻璃、火車、飛機等之窗玻璃、汽車頭燈、尾燈等之透明玻璃製或透明塑膠製(丙烯酸、聚碳酸酯等)構件、各種鏡面構件等之塗裝膜及表面飽護膜而有用。The cured film (hardened resin layer) formed by using the active energy ray curable composition of the present invention is used as a portable (communication) information terminal, digital media player, etc. for tablet personal computers, notebook computers, mobile phones, smart phones, etc. Frames for various devices such as e-book readers, watch-type and glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), Field emission projection monitors, CRT, toner-based monitors, various black panel monitors and TV screens, etc., surfaces of display operating machines and various optical films used in their interiors, automotive exteriors, glossy surfaces of pianos or furniture , marble and other building stone surfaces, decorative building materials for water flow around toilets, bathrooms, washstands, etc., protective glass for art display, display windows, display cabinets, photo frame covers, watches, car window glass, trains, It is useful as a coating film and surface protective film on transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as aircraft window glass, automobile headlights, and taillights, and various mirror components.
其中尤其作為具有觸控顯示器等之以人類手指或手掌進行畫面上之操作的顯示輸入裝置之各種機器例如平板型個人電腦、筆記型電腦、智慧型手機、行動電話、其他攜帶(通訊)資訊終端、智慧型手錶、數位媒體播放器、電子書讀取機、數位相框、遊戲機、數位相機、數位攝影機、GPS顯示記錄機器、汽車用等之導航裝置、汽車用等之控制面板、自動現金領錢存錢裝置、現金自動櫃員機、自動販賣機、數位標牌(電子看板)、保全系統終端、POS終端、遙控器等各種控制器、車載裝置用面板開關等之顯示輸入裝置等之表面保護膜而有用。In particular, various devices such as tablet personal computers, notebook computers, smartphones, mobile phones, and other portable (communication) information terminals are provided with display input devices such as touch monitors that allow on-screen operations to be performed using human fingers or palms. , smart watches, digital media players, e-book readers, digital photo frames, game consoles, digital cameras, digital video cameras, GPS display recording machines, navigation devices for automobiles, etc., control panels for automobiles, etc., automatic cash withdrawals It is used as a surface protective film for money deposit devices, cash ATMs, vending machines, digital signage (electronic signage), security system terminals, POS terminals, various controllers such as remote controls, and display input devices such as panel switches for vehicle-mounted devices. it works.
再者藉由本發明之活性能量線硬化性組成物形成之硬化被膜作為光磁碟、光碟等之光記錄媒體;眼鏡鏡片、稜鏡、透鏡片、防護膜、偏光板、光學濾光器、雙凸透鏡、菲涅爾透鏡、抗反射膜、各種相機用透鏡、各種透鏡用保護濾光器、光纖或光耦合器等之光學零件・光裝置之表面保護被膜亦有用。Furthermore, the cured film formed by the active energy ray curable composition of the present invention can be used as optical recording media for optical disks, optical discs, etc.; spectacle lenses, glasses, lens sheets, protective films, polarizing plates, optical filters, double It is also useful for surface protective coatings on optical components and optical devices such as convex lenses, Fresnel lenses, anti-reflection films, various camera lenses, protective filters for various lenses, optical fibers, optical couplers, etc.
如以上,本發明之活性能量線硬化性組成物其本質係藉由對目的的物品表面配置本發明之含氟環氧改質有機矽化合物(A)之全氟聚醚構造,而賦予撥水性、撥油性、摩擦性、防污性、指紋不易顯眼、指紋擦拭性佳、耐磨耗性、低折射率特性、耐溶劑性、耐藥品性等優異性質。As mentioned above, the active energy ray curable composition of the present invention essentially imparts water repellency by arranging the perfluoropolyether structure of the fluorine-containing epoxy modified organosilicon compound (A) of the present invention on the surface of the target object. , oil repellency, friction resistance, anti-fouling properties, fingerprint inconspicuousness, good fingerprint wipeability, abrasion resistance, low refractive index properties, solvent resistance, chemical resistance and other excellent properties.
如此使用本發明之含氟活性能量線硬化性組成物時,對應於重視調配物之組合、組成比等之特性,而基於對應於個別用途之習知技術選定適切的使用方法即可。此等習知技術不僅對於含氟之組成物者,亦可包含既有之活性能量線硬化性組成物所用之方法在內而包含於檢討範圍內。When using the fluorine-containing active energy ray curable composition of the present invention in this way, it is sufficient to select an appropriate method of use based on the conventional technology corresponding to the individual application by paying attention to the characteristics of the combination and composition ratio of the formulation. These conventional techniques are not only for fluorine-containing compositions, but also include methods used in existing active energy ray curable compositions, and are included in the scope of review.
例如調配調製本發明之活性能量線硬化性組成物時,除了本發明之含氟環氧改質有機矽化合物(A)以外,組合前述之本硬化性組成物中之各種調配物時,於重視低折射率特性或利用其之低反射特性時,若使用反應性中空氧化矽或不具有反應性基之中空氧化矽、作為化合物(C)之各種多官能化合物,且提高被膜強度或耐擦傷性之情況下,調配適當量之作為化合物(C)之各種多官能化合物,於使用作為化合物(C)之硬化速度較慢之含環氧基化合物時,藉由調配含氧雜環丁基化合物或含乙烯醚化合物而提高硬化速度等,係基於習知陽離子硬化性組成物調配之見解可容易類推之方法。 [實施例]For example, when formulating the active energy ray curable composition of the present invention, in addition to the fluorine-containing epoxy modified organosilicon compound (A) of the present invention, when combining various formulations in the curable composition mentioned above, attention should be paid to When utilizing low refractive index characteristics or low reflection characteristics, reactive hollow silicon oxide or hollow silicon oxide without a reactive group, or various polyfunctional compounds as compound (C) can be used to improve film strength or scratch resistance. In this case, an appropriate amount of various polyfunctional compounds as the compound (C) is prepared. When using an epoxy group-containing compound with a slow hardening speed as the compound (C), by preparing an oxetanyl-containing compound or Containing a vinyl ether compound to increase the curing speed is a method that can be easily deduced based on the conventional knowledge of formulating cationic curable compositions. [Example]
以下顯示實施例及比較例,更詳細說明本發明,但本發明並非限定於下述實施例。Examples and comparative examples are shown below to explain the present invention in more detail. However, the present invention is not limited to the following examples.
[合成例1] ・化合物(A-1)之製造 於乾燥氮環境下,於具備回流裝置與攪拌裝置之100ml三頸燒瓶中,饋入以下述式表示之含氟環狀矽氧烷30.0g: (式中,Rf”為下述基,重複單位數具有分佈,5.2係平均值,) 與六氟化間-二甲苯30.0g,邊攪拌邊加熱至90℃。於其中以30分鐘滴加烯丙基縮水甘油醚8.0g與鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.010g(以鉑換算2.49×10-8 mol)之混合溶液,於90℃攪拌8小時。該情況下,烯丙基縮水甘油醚所具有之末端烯烴基之個數相對於上述含氟環狀矽氧烷具有之SiH基1個之比為1.02。以1 H-NMR確認原料的Si-H消失後,進行活性碳處理。隨後減壓餾除溶劑或過量烯丙基縮水甘油醚,獲得以下述式表示之化合物(A-1) 34.2g。 [Synthesis Example 1] ・Production of compound (A-1) In a dry nitrogen environment, 30.0 g of fluorine-containing cyclic siloxane represented by the following formula was fed into a 100 ml three-neck flask equipped with a reflux device and a stirring device. : (In the formula, Rf” is the following base, the number of repeating units has a distribution, and 5.2 is the average value, ) and 30.0g of m-xylene hexafluoride, and heat to 90°C while stirring. 8.0 g of allyl glycidyl ether and 0.010 g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (2.49×10 -8 in terms of platinum) were added dropwise over 30 minutes. mol), stirred at 90°C for 8 hours. In this case, the ratio of the number of terminal olefin groups of allyl glycidyl ether to one SiH group of the fluorine-containing cyclic siloxane is 1.02. After confirming the disappearance of Si-H in the raw material by 1 H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 34.2 g of compound (A-1) represented by the following formula.
[合成例2] ・化合物(A-2)之製造 於乾燥氮環境下,於具備回流裝置與攪拌裝置之2000ml三頸燒瓶中,投入以下述式表示之兩末端具有α-不飽和鍵之全氟聚醚500g: 與六氟化間-二甲苯700g及四甲基環四矽氧烷361g,邊攪拌邊加熱至90℃。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.442g(以Pt單體計為1.1×10-6 mol),使內溫維持於90℃以上之狀態持續攪拌4小時。以1 H-NMR確認原料的烯丙基消失後,減壓餾除溶劑或過量之四甲基環四矽氧烷,隨後進行活性碳處理。獲得以下述式表示之無色透明之液狀化合物(P-1) 498g。 [Synthesis Example 2] ・Compound (A-2) was produced in a dry nitrogen environment. In a 2000 ml three-neck flask equipped with a reflux device and a stirring device, a compound having α-unsaturated bonds at both ends represented by the following formula was put into it. Fluoropolyether 500g: Add 700g of m-xylene hexafluoride and 361g of tetramethylcyclotetrasiloxane, and heat to 90°C while stirring. Add 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (1.1×10 -6 mol based on Pt monomer) to maintain the internal temperature at 90°C. Continue stirring in the above state for 4 hours. After confirming the disappearance of the allyl group of the raw material by 1 H-NMR, the solvent or excess tetramethylcyclotetrasiloxane was distilled off under reduced pressure, and then treated with activated carbon. 498 g of a colorless and transparent liquid compound (P-1) represented by the following formula was obtained.
將上述化合物(P-1) 60.0g與烯丙烯縮水甘油醚10.0g、六氟化間-二甲苯60.0g混合,邊攪拌邊於氮氣環境下加熱至80℃。該情況,烯丙基縮水甘油醚所具有之末端烯烴基之個數相對於上述化合物(P-1)具有之SiH基1個之比為1.15。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.0221g(以Pt單體計為5.6×10-8 mol),使內溫維持於90~120℃之狀態持續攪拌6小時。以1 H-NMR確認原料的Si-H基消失後,進行活性碳處理。隨後減壓餾除溶劑或過量烯丙基縮水甘油醚,獲得半透明狀之以下述式表示之化合物(A-2) 66.2g。 60.0 g of the above compound (P-1), 10.0 g of allyl glycidyl ether, and 60.0 g of m-xylene hexafluoride were mixed, and heated to 80°C in a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups of allyl glycidyl ether to one SiH group of the compound (P-1) is 1.15. Add 0.0221g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (5.6×10 -8 mol based on Pt monomer) to maintain the internal temperature at 90~ Continue stirring at 120°C for 6 hours. After confirming the disappearance of the Si-H group of the raw material by 1 H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 66.2 g of a translucent compound (A-2) represented by the following formula.
[合成例3] ・化合物(A-3)之製造 將上述化合物(P-1) 60.0g與3-乙烯基環己烯氧化物10.9g、六氟化間-二甲苯60.0g混合,邊攪拌邊於氮氣環境下加熱至80℃。該情況,3-乙烯基環己烯氧化物所具有之末端烯烴基之個數相對於上述化合物(P-1)具有之SiH基1個之比為1.14。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.0221g(以Pt單體計為5.6×10-8 mol),使內溫維持於90~120℃之狀態持續攪拌6小時。以1 H-NMR確認原料的Si-H基消失後,進行活性碳處理。隨後減壓餾除溶劑或過量3-乙烯基環己烯氧化物,獲得半透明狀之以下述式表示之化合物(A-3) 66.1g。 [Synthesis Example 3] ・Preparation of compound (A-3) 60.0 g of the above compound (P-1), 10.9 g of 3-vinylcyclohexene oxide, and 60.0 g of m-xylene hexafluoride were mixed with stirring. While heating to 80°C under nitrogen atmosphere. In this case, the ratio of the number of terminal olefin groups of 3-vinylcyclohexene oxide to one SiH group of the compound (P-1) is 1.14. Add 0.0221g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (5.6×10 -8 mol based on Pt monomer) to maintain the internal temperature at 90~ Continue stirring at 120°C for 6 hours. After confirming the disappearance of the Si-H group of the raw material by 1 H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess 3-vinylcyclohexene oxide was distilled off under reduced pressure to obtain 66.1 g of a translucent compound (A-3) represented by the following formula.
[合成例4] ・化合物(A-4)之製造 於乾燥氮環境下,於具備回流裝置與攪拌裝置之2000ml三頸燒瓶中,投入以下述式表示之兩末端具有α-不飽和鍵之全氟聚醚500g: (h’=6.8、i’=5.7、h’及i’分別為平均值) 與六氟化間-二甲苯700g及五甲基環五矽氧烷865g,邊攪拌邊加熱至90℃。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.442g(以Pt單體計為1.1×10-6 mol),使內溫維持於90℃以上之狀態持續攪拌4小時。以1 H-NMR確認原料的烯丙基消失後,減壓餾除溶劑或過量之五甲基環五矽氧烷,隨後進行活性碳處理。獲得以下述式表示之無色透明之液狀化合物(P-2) 538g。 (h’=6.8、i’=5.7、h’及i’分別為平均值)[Synthesis Example 4] ・Compound (A-4) was produced in a dry nitrogen environment. In a 2000 ml three-neck flask equipped with a reflux device and a stirring device, a compound having α-unsaturated bonds at both ends represented by the following formula was put into it. Fluoropolyether 500g: (h'=6.8, i'=5.7, h' and i' are average values respectively) Add 700g of m-xylene hexafluoride and 865g of pentamethylcyclopentasiloxane, and heat to 90°C while stirring. Add 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (1.1×10 -6 mol based on Pt monomer) to maintain the internal temperature at 90°C. Continue stirring in the above state for 4 hours. After confirming the disappearance of the allyl group of the raw material by 1 H-NMR, the solvent or excess pentamethylcyclopentasiloxane was distilled off under reduced pressure, and then treated with activated carbon. 538 g of a colorless and transparent liquid compound (P-2) represented by the following formula was obtained. (h'=6.8, i'=5.7, h' and i' are average values respectively)
將上述化合物(P-2) 100.0g與烯丙烯縮水甘油醚41.0g、六氟化間-二甲苯100.0g混合,邊攪拌邊於氮氣環境下加熱至80℃。該情況,烯丙基縮水甘油醚所具有之末端烯烴基之個數相對於上述化合物(P-2)具有之Si-H基1個之比為1.2。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.0221g(以Pt單體計為5.6×10-8 mol),使內溫維持於90~120℃之狀態持續攪拌6小時。以1 H-NMR確認原料的Si-H基消失後,進行活性碳處理。隨後減壓餾除溶劑或過量烯丙基縮水甘油醚,獲得無色透明狀之以下述式表示之化合物(A-4) 134g。 (h’=6.8、i’=5.7、h’及i’分別為平均值)100.0 g of the above compound (P-2), 41.0 g of allyl glycidyl ether, and 100.0 g of m-xylene hexafluoride were mixed, and heated to 80°C in a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups of allyl glycidyl ether to one Si-H group of the compound (P-2) is 1.2. Add 0.0221g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (5.6×10 -8 mol based on Pt monomer) to maintain the internal temperature at 90~ Continue stirring at 120°C for 6 hours. After confirming the disappearance of the Si-H group of the raw material by 1 H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 134 g of a colorless and transparent compound (A-4) represented by the following formula. (h'=6.8, i'=5.7, h' and i' are average values respectively)
[實施例及比較例] (活性能量線硬化性組成物之調製) 以下述表1中記載之組成混合各成分,調製活性能量線硬化性組成物。[Examples and Comparative Examples] (Preparation of active energy ray curable composition) Each component was mixed in the composition shown in Table 1 below to prepare an active energy ray curable composition.
B-1:光陽離子聚合起始劑CPI-200K(磷系陰離子型三芳基鏻鹽,溶劑稀釋品,SAN APRO股份有限公司製) B-2:光陽離子聚合起始劑CPI-210S(磷系陰離子型三芳基鏻鹽,粉體,SAN APRO股份有限公司製) B-3:光・熱陽離子聚合起始劑TA-100(鋶鹽,粉體,SAN APRO股份有限公司製) C-1:液狀環氧樹脂EPOTOTE ZX-1059(下述式之雙酚A、雙酚F單體混合物,新日鐵住金化學股份有限公司) C-2:下述式之4官能環氧化合物 D-1:甲基乙基酮 D-2:乙酸丁酯 B-1: Photocationic polymerization initiator CPI-200K (phosphorus-based anionic triaryl phosphonium salt, solvent diluent, manufactured by SAN APRO Co., Ltd.) B-2: Photocationic polymerization initiator CPI-210S (phosphorus-based Anionic triaryl phosphonium salt, powder, manufactured by SAN APRO Co., Ltd.) B-3: Photo-thermal cationic polymerization initiator TA-100 (sulfonium salt, powder, manufactured by SAN APRO Co., Ltd.) C-1: Liquid epoxy resin EPOTOTE ZX-1059 (bisphenol A and bisphenol F monomer mixture of the following formula, Nippon Steel and Sumitomo Metal Chemical Co., Ltd.) C-2: tetrafunctional epoxy compound of the following formula D-1: Methyl ethyl ketone D-2: Butyl acetate
(硬化膜之形成) 以旋轉塗佈器將調配例1~14之各組成物以厚約12μm (濕膜厚)塗佈於厚2mm之聚碳酸酯板上,以熱風乾燥器實施乾燥。乾燥後之乾膜厚約為5μm。隨後使用輸送式金屬鹵素UV照射裝置(Panasonic電工(股)製,80w/cm),以表2所示條件於氮氣環境下照射特定累積光量之紫外線,獲得硬化之硬化膜。 且,以旋轉塗佈器將調配例6~8、12~14之各組成物以厚約12μm(濕膜厚)塗佈於厚2mm之聚碳酸酯板上,以熱風乾燥器實施乾燥。乾燥後之乾膜厚約為5μm。隨後使用輸送式金屬鹵素UV照射裝置(Panasonic電工(股)製,80w/cm),以表3所示條件於氮氣環境下照射特定累積光量之紫外線,獲得硬化之硬化膜。(Formation of hardened film) Each composition of Preparation Examples 1 to 14 was applied to a polycarbonate plate with a thickness of about 12 μm (wet film thickness) using a spin coater and dried using a hot air dryer. The dry film thickness after drying is approximately 5μm. Then, a conveyor-type metal halogen UV irradiation device (manufactured by Panasonic Electric Co., Ltd., 80w/cm) was used to irradiate ultraviolet rays with a specific cumulative light amount under the conditions shown in Table 2 in a nitrogen environment to obtain a hardened cured film. Furthermore, each composition of Preparation Examples 6 to 8 and 12 to 14 was applied to a polycarbonate plate with a thickness of about 12 μm (wet film thickness) with a spin coater and dried with a hot air dryer. The dry film thickness after drying is approximately 5μm. Then, a conveyor-type metal halogen UV irradiation device (manufactured by Panasonic Electric Co., Ltd., 80w/cm) was used to irradiate ultraviolet rays with a specific cumulative light amount under the conditions shown in Table 3 in a nitrogen environment to obtain a hardened cured film.
(評價方法) [撥水撥油性之評價] 使用接觸角計DropMaster(協和界面科學公司製),測定上述所得之硬化膜表面對於水之接觸角(水接觸角)及對於油酸之25℃下之接觸角(油酸接觸角)。測定係於UV照射起30分鐘後實施。 又,水接觸角係於離子交換水之2μL液滴著液起1秒後根據液面與固體面所成之角而測定。又,油酸接觸角係於油酸之4μL液滴著液起1秒後根據液面與固體面所成之角而測定。(evaluation method) [Evaluation on water and oil repellency] The contact angle of the cured film surface obtained above with respect to water (water contact angle) and the contact angle with oleic acid at 25° C. (oleic acid contact angle) were measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The measurement was performed 30 minutes after UV irradiation. In addition, the water contact angle is measured based on the angle formed by the liquid surface and the solid surface 1 second after 2 μL of ion-exchange water is dropped. In addition, the oleic acid contact angle is measured based on the angle formed by the liquid surface and the solid surface 1 second after 4 μL of oleic acid is dropped.
[油性墨水(magic ink)不沾著性] 於硬化物表面塗佈油性墨水(ZEBRA股份有限公司製,Hi-Mckee粗字),使用下述指標,藉由目視評價墨水之不沾著性。測定係於UV照射起45分鐘後實施。 A:快速不沾著 B:不沾著 C:完全無不沾著[Non-stick properties of oil-based ink (magic ink)] Oil-based ink (made by ZEBRA Co., Ltd., Hi-Mcckee bold letters) was applied to the surface of the cured product, and the non-stick properties of the ink were visually evaluated using the following indexes. The measurement was performed 45 minutes after UV irradiation. A: Quick and non-sticky B: Not sticky C: Completely attached to everything
[指紋擦拭性] 由5位試驗員,以手指將額頭皮脂轉印至硬化物表面,藉由下述評價基準評價以BEMCOT(旭化成公司製)擦拭時之擦拭性。測定係於UV照射起1小時~2小時後實施。 A:指紋容易擦拭掉 B:指紋擦拭掉 C:指紋無法擦拭掉 以上評價結果分別示於表2、表3。[Fingerprint wipeability] Five testers used their fingers to transfer forehead sebum to the surface of the hardened material, and evaluated the wipeability when wiping with BEMCOT (manufactured by Asahi Kasei Co., Ltd.) based on the following evaluation criteria. The measurement is performed 1 to 2 hours after UV irradiation. A: Fingerprints are easy to wipe off B: Wipe off fingerprints C: Fingerprints cannot be wiped off The above evaluation results are shown in Table 2 and Table 3 respectively.
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