本發明係有關對電子零件及電氣零件賦予優異之防濕性、撥水撥油性及防污性的水性塗覆劑。本發明中，所謂「電子零件」之用語係意指電子零件及電氣零件二者。The present invention relates to an aqueous coating agent which imparts excellent moisture resistance, water repellency and antifouling properties to electronic parts and electrical parts. In the present invention, the term "electronic component" means both an electronic component and an electrical component.
為了控制屋外之電子/電氣機器(例如電話、信號機、冷氣機之室外機、配電盤、柱上冷凝器、手機、可攜帶式中繼天線、汽車電子機器、船之電子機器、自動販賣機、行動電腦等)，而於其上裝設電子/電氣電路基板。此時，會有因雨、濕氣、灰塵、蟲等所產生之酸或鹽等而使金屬配線被腐蝕、電路被破壞之情形，故造成問題。於是，近年來，在裝設電子/電氣零件後，一般會在電路基板表面施行塗覆而提高防濕性。In order to control electronic/electrical machines outside the house (such as telephones, signal machines, outdoor units for air conditioners, switchboards, on-column condensers, mobile phones, portable relay antennas, automotive electronic machines, electronic machines for ships, vending machines, A mobile computer, etc., and an electronic/electrical circuit board is mounted thereon. At this time, there is a problem that the metal wiring is corroded and the circuit is broken due to acid, salt, or the like generated by rain, moisture, dust, insects, or the like, which causes a problem. Therefore, in recent years, after mounting electronic/electrical parts, coating is generally performed on the surface of the circuit board to improve moisture resistance.
若欲形成防濕塗覆，已知可採用塗佈撥水撥油劑之方法。If it is desired to form a moisture-proof coating, it is known to employ a method of applying a water-repellent oil-repellent agent.
塗佈撥水撥油劑之方法係將膜形成能力不良之低分子量之聚矽氧系或氟系之化合物(例如全氟聚醚寡聚物等)溶解於溶劑並噴塗於電路基板(參照專利文獻1(日本專利第3122443號說明書))，因此，在電路基板表面無法形成塗覆，且其效果會經時性地降低。The method of applying the water-repellent oil-repellent agent is to dissolve a low molecular weight polysulfonium-based or fluorine-based compound (for example, a perfluoropolyether oligomer, etc.) having a poor film forming ability in a solvent and spray it on a circuit substrate (refer to the patent) Document 1 (Japanese Patent No. 3122443)), therefore, coating cannot be formed on the surface of the circuit board, and the effect thereof is lowered with time.
在專利文獻2(日本特開昭61-189693號公報)中揭示將一種塗覆溶液塗佈於電子零件，該塗覆溶液係由含有聚氟烷基之聚合物溶解於不燃性之低沸點有機溶劑而成。然而，從塗佈作業及環境之觀點來看，有機溶劑係具有問題。It is disclosed in Patent Document 2 (JP-A-61-189693) that a coating solution is applied to an electronic component which is dissolved in a non-combustible low-boiling organic compound by a polymer containing a polyfluoroalkyl group. Made of solvent. However, organic solvents have problems from the viewpoints of coating work and environment.
其次，說明關於PFOA(Perfluorooctanoic acid，亦即全氟辛酸)之環境問題。由最近之研究結果[EPA報告“PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS”(http://www.epa.gov/opptintr/pfoa/pfoara.pdf)]等，已知屬於長鏈氟烷基化合物之一種PFOA(全氟辛酸)對於環境有造成負荷之虞，EPA(美國環保署)並於2003年4月14日發表要強化對於PFOA之科學性調查。Next, the environmental problem of PFOA (Perfluorooctanoic acid, that is, perfluorooctanoic acid) will be explained. From the recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)], etc., known A PFOA (perfluorooctanoic acid) belonging to a long-chain fluoroalkyl compound has a load on the environment, and the EPA (US EPA) published on April 14, 2003 to strengthen the scientific investigation of PFOA.
另一方面，Federal Register(FR Vol. 68,No. 73/April 16,2003[FRL-2303-8],http://www.epa.gov/opptintr/pfoa/pfoafr.pdf)或EPA Environmental News FOR RELEASE:MONDAY APRIL 14,2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID(http://www.epa.gov/opptintr/pfoa/pfoaras.pdf)或EPA OPPT FACT SHEET April 14,2003(http://www.epa.gov/opptintr/pfoa/pfoafaCts.pd f)則公開發表有因調聚物(telomer)之分解或代謝而生成PFOA之可能性(調聚物係指長鏈氟烷基)。另外，亦公開發表調聚物係使用於賦予撥水撥油性和防污性之泡沫滅火器、保養製品、洗淨製品、地毯、紡織品、紙、皮革等多種製品。On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) or EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaras.pdf) or EPA OPPT FACT SHEET April 14, 2003 (http:// Www.epa.gov/opptintr/pfoa/pfoafaCts.pd f) discloses the possibility of generating PFOA due to decomposition or metabolism of telomer (telomer refers to long chain fluoroalkyl). In addition, telomers have also been disclosed for use in foam fire extinguishers, maintenance products, cleaning products, carpets, textiles, paper, leather, and the like which impart water repellency and antifouling properties.
以往所提及之含氟共聚物之Rf基碳數為8以上時，即含有具活體蓄積性之PFOA及PFOA類似物質而造成問題，故現今已快速地轉成尋求含有碳數6以下之短鏈Rf基的氟丙烯酸酯聚合物、以及改善與其他素材及肌膚之親和性的含氟聚合物。When the Rf-based carbon number of the fluorinated copolymer mentioned in the related art is 8 or more, that is, it contains a PFOA and a PFOA-like substance having a living body accumulation, which causes problems, and has now rapidly turned into a short carbon number of 6 or less. A fluoroacrylate polymer having a chain Rf group and a fluoropolymer which improves affinity with other materials and skin.
[專利文獻1]日本專利第3122443號說明書[Patent Document 1] Japanese Patent No. 3122443
[專利文獻2]日本特開昭61-189693號公報[Patent Document 2] Japanese Laid-Open Patent Publication No. 61-189693
本發明之目的係提供一種塗覆作業性及環境性(不使用有機溶劑)優異之防濕塗覆劑(亦即，水性塗覆組成物)。An object of the present invention is to provide a moisture-proof coating agent (i.e., an aqueous coating composition) excellent in coating workability and environmental performance (without using an organic solvent).
本發明之另一目的係提供一種防濕塗覆劑，其係在電子零件表面容易形成塗覆，且可形成防濕性、耐藥品性、電絕緣性、耐侯性、耐久性優異之塗膜。Another object of the present invention is to provide a moisture-proof coating agent which is easy to form a coating on the surface of an electronic component and which can form a coating film excellent in moisture resistance, chemical resistance, electrical insulation, weather resistance, and durability. .
亦即，本發明係有關由含氟化合物(1)與水性液狀媒質(2)所組成之電子零件用防濕塗覆劑。That is, the present invention relates to a moisture-proof coating agent for an electronic component comprising a fluorine-containing compound (1) and an aqueous liquid medium (2).
含氟化合物(1)一般為含氟聚合物。含氟化合物(1)以具有從(A)含氟之丙烯酸酯單體所衍生之重複單元的聚合物為佳。含氟化合物(1)以具有從(A)含氟之丙烯酸酯單體所衍生之重複單元、以及從(B)含胺基之單體所衍生之重複單元的聚合物為特佳。The fluorine-containing compound (1) is generally a fluorine-containing polymer. The fluorine-containing compound (1) is preferably a polymer having a repeating unit derived from the (A) fluorine-containing acrylate monomer. The fluorine-containing compound (1) is particularly preferably a polymer having a repeating unit derived from the (A) fluorine-containing acrylate monomer and a repeating unit derived from the (B) amine group-containing monomer.
在本發明中，含氟聚合物係具有必須之對水之充分溶解性。當具有碳數7以下(尤其是碳數6以下)之短鏈氟烷基時，可獲得較高之溶解性。本發明之含氟聚合物具有充分高之水溶性，可賦予高防濕性於基材上。In the present invention, the fluoropolymer has the necessary sufficient solubility for water. When it has a short-chain fluoroalkyl group having a carbon number of 7 or less (especially, a carbon number of 6 or less), a high solubility can be obtained. The fluoropolymer of the present invention has sufficiently high water solubility and can impart high moisture resistance to a substrate.
本發明之塗覆劑可藉由低溫且短時間乾燥，即容易於電子零件表面上形成被膜。被膜係具有優異之防濕性、撥水撥油性及防污性，並且此等性質之持續性亦優異。由本發明之塗覆劑所形成之被膜之厚度即使薄，其防濕性、撥水撥油性及防污性亦高。更進一步，被膜之耐藥品性、電絕緣性、耐侯性、耐久性為優異。The coating agent of the present invention can be dried at a low temperature and for a short period of time, that is, it is easy to form a film on the surface of an electronic component. The film system has excellent moisture resistance, water repellency and antifouling properties, and the persistence of these properties is also excellent. The thickness of the film formed by the coating agent of the present invention is high, such as moisture resistance, water repellency, and antifouling property. Further, the film is excellent in chemical resistance, electrical insulation properties, weather resistance, and durability.
在本發明中，「丙烯酸酯單體」係不僅意指α位為氫原子之丙烯酸酯，亦包括α位之氫原子經甲基或鹵素原子等取代基所取代之丙烯酸酯。In the present invention, the "acrylate monomer" means not only an acrylate having a hydrogen atom at the α-position but also an acrylate having a hydrogen atom at the α-position substituted with a substituent such as a methyl group or a halogen atom.
在含氟聚合物中，含氟之丙烯酸酯單體(A)可列舉如具有下述基之單體：In the fluoropolymer, the fluorine-containing acrylate monomer (A) may, for example, be a monomer having the following groups:
選自氟烷基、氟烯基及氟醚基所成組群中之至少一種含氟之基(以下稱為「含氟基」)；以及At least one fluorine-containing group (hereinafter referred to as "fluorine-containing group") selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group, and a fluoroether group;
式：-O-CO-CX=CH2所示之不飽和基Formula: -O-CO-CX=Unsaturated group represented by CH2
[式中，X係氫原子、碳數1至6之直鏈狀或分支狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(惟X1及X2係氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或分支狀之氟烷基、取代或非取代之苯甲基、取代或非取代之苯基]。[In the formula, X-based hydrogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX1 X2 group (only X1 and X2 systems) a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted group Phenyl].
具有含氟基之丙烯酸酯單體係例示如下述式(I)所示者：The acrylate-based single system having a fluorine-containing group is exemplified as shown in the following formula (I):
CH2=C(-X)-C(=O)-O-Y-Rf (I)CH2 =C(-X)-C(=O)-OY-Rf (I)
[式中，X係氫原子、碳數1至6之直鏈狀或分支狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(惟X1及X2係氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或分支狀之氟烷基、取代或非取代之苯甲基、取代或非取代之苯基；[In the formula, X-based hydrogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX1 X2 group (only X1 and X2 systems) a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted group Phenyl group;
Y係直接鍵、可具有氧原子之碳數1至10之脂肪族基、可具有氧原子之碳數6至10之芳香族基、環狀脂肪族基或芳香脂肪族基、-CH2CH2N(R1)SO2-基(惟R1係碳數1至4之烷基)或-CH2CH(OY1)CH2-基(惟Y1係氫原子或乙醯基)；Y-type direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic aliphatic group, -CH2 CH2 N(R1 )SO2 -yl (only R1 is an alkyl group having 1 to 4 carbon atoms) or -CH2 CH(OY1 )CH2 - group (only a Y1 hydrogen atom or an ethylidene group);
Rf係碳數1至21之直鏈狀或分支狀之氟烷基、碳數2至7之氟烯基、或選自重複單元：-C3F6O-、-C2F4O-及-CF2O-所成組群中之至少一種重複單元之合計數為1至200之氟醚基]。Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: -C3 F6 O-, -C2 F4 O- And the total number of at least one repeating unit in the -CF2 O-group is 1 to 200 fluoroether groups].
在式(I)中，當Rf基為氟烷基時，以全氟烷基為佳。Rf基之具體例可列舉如碳數1至7者，例如-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-(CF2)2H、-CF2CFHCF3、-(CF2)4H、-(CF2)6H等。當Rf基為氟烷基時，從前述之PFOA之觀點及機能之觀點來看，Rf基之碳數宜為1至7，例如以2至6為佳，以4至6為更佳，尤以6為特佳。In the formula (I), when the Rf group is a fluoroalkyl group, a perfluoroalkyl group is preferred. Specific examples of the Rf group include those having a carbon number of 1 to 7, such as -CF3 , -CF2 CF3 , -CF2 CF2 CF3 , -CF(CF3 )2 , -CF2 CF2 CF2 CF.3 , -CF2 CF(CF3 )2 , -C(CF3 )3 , -(CF2 )4 CF3 , -(CF2 )2 CF(CF3 )2 , -CF2 C(CF3 )3 , -CF(CF3 )CF2 CF2 CF3 , -(CF2 )5 CF3 , -(CF2 )3 CF(CF3 )2 , -(CF2 )4 CF(CF3 )2 , -(CF2 )2 H, -CF2 CFHCF3 , -(CF2 )4 H, -(CF2 )6 H, and the like. When the Rf group is a fluoroalkyl group, the carbon number of the Rf group is preferably from 1 to 7 from the viewpoint of the aforementioned PFOA and the function, for example, preferably from 2 to 6, more preferably from 4 to 6. It is especially good for 6.
當Rf基為氟烯基時，Rf基之例可列舉如-CF=CF(CF3)、-CF=C(CF3)2、-CF=C(CF3)(CF2CF2CF3)、-CF=C(CF3)(CF(CF3)2)、-C(CF3)=CF(CF(CF3)2)、-C(CF2CF3)=C(CF3)2等。當Rf基為氟烯基時，Rf基之碳數宜為2至7，以3至6為更佳，尤以6為特佳。When the Rf group is a fluoroalkenyl group, examples of the Rf group include, for example, -CF=CF(CF3 ), -CF=C(CF3 )2 , -CF=C(CF3 )(CF2 CF2 CF3 ). ), -CF=C(CF3 )(CF(CF3 )2 ), -C(CF3 )=CF(CF(CF3 )2 ), -C(CF2 CF3 )=C(CF3 )2 and so on. When the Rf group is a fluoroalkenyl group, the carbon number of the Rf group is preferably from 2 to 7, more preferably from 3 to 6, particularly preferably from 6.
當Rf基為氟醚基時，氟醚基具有選自-C3F6O-、-C2F4O-及-CF2O-所成組群中之至少一種重複單元(氧基全氟伸烷基)。-C3F6O-為-CF2CF2CF2O-或-CF2C(CF3)FO-。-C2F4O-通常為-CF2CF2O-。氧基全氟伸烷基重複單元之合計數為1至200，例如為1至100，尤其是5至50。氟醚基具有直接鍵結於氧基全氟伸烷基重複單元之末端基。末端基之例可列舉如氫原子、鹵素原子(例如氟原子)、醇基(例如HOCH2-)、環氧基(例如When the Rf group is a fluoroether group, the fluoroether group has at least one repeating unit selected from the group consisting of -C3 F6 O-, -C2 F4 O-, and -CF2 O- (oxygen group) Fluorine alkyl). -C3 F6 O- is -CF2 CF2 CF2 O- or -CF2 C(CF3 )FO-. -C2 F4 O- is usually -CF2 CF2 O-. The total number of oxyperfluoroalkylene repeating units is from 1 to 200, for example from 1 to 100, especially from 5 to 50. The fluoroether group has a terminal group directly bonded to the oxyperfluoroalkylene repeating unit. Examples of the terminal group include a hydrogen atom, a halogen atom (for example, a fluorine atom), an alcohol group (for example, HOCH2 -), and an epoxy group (for example,
胺基(例如H2N-)、羧酸基(例如HOOC-)、醯鹵基(例如F(O=)C-)、氯甲基(ClH2C-)。氟醚基中除了氧基全氟伸烷基重複單元及末端基以外，亦可具有碳數1至10之氟伸烷基(尤其是全氟伸烷基)。碳數1至10之氟伸烷基之例為-CF2-及-CF2CF2-。An amine group (e.g., H2 N-), a carboxylic acid group (e.g., HOOC-), a fluorenyl halide (e.g., F(O=)C-), chloromethyl (ClH2 C-). The fluoroether group may have a fluorine alkyl group having 1 to 10 carbon atoms (especially a perfluoroalkylene group) in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkyl group having 1 to 10 carbon atoms are -CF2 - and -CF2 CF2 -.
作為Rf基之例之氟醚基(特別是全氟醚基)，係例示如下：The fluoroether group (particularly a perfluoroether group) as an example of the Rf group is exemplified as follows:
F-(CF2CF2CF2O)n-CF2CF2- (n為1至200)F-(CF2 CF2 CF2 O)n -CF2 CF2 - (n is 1 to 200)
F-(CF2C(CF3)FO)n-CF2CF2- (n為1至200)F-(CF2 C(CF3 )FO)n -CF2 CF2 - (n is 1 to 200)
F-(CF2C(CF3)FO)n-(CF2O)m-CF2CF2- (n與m之合計為1至200)F-(CF2 C(CF3 )FO)n -(CF2 O)m -CF2 CF2 - (the total of n and m is 1 to 200)
F-(CF2CF2O)n-(CF2O)m-CF2CF2- (n與m之合計為1至200)F-(CF2 CF2 O)n -(CF2 O)m -CF2 CF2 - (the total of n and m is 1 to 200)
Y係直接鍵、可具有氧原子之碳數1至10之脂肪族基、可具有氧原子之碳數6至10之芳香族基、環狀脂肪族基或芳香脂肪族基、-CH2CH2N(R1)SO2-基(惟R1係碳數1至4之烷基)或-CH2CH(OY1)CH2-基(惟Y1係氫原子或乙醯基)。脂肪族基係以伸烷基(尤其是碳數1至4，例如1或2者)為較佳。芳香族基及環狀脂肪族基可經取代，亦可不經取代。Y-type direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic aliphatic group, -CH2 CH2 N(R1 )SO2 - group (only R1 is an alkyl group having 1 to 4 carbon atoms) or -CH2 CH(OY1 )CH2 - group (only a Y1 hydrogen atom or an ethylidene group). The aliphatic group is preferably an alkylene group (especially a carbon number of 1 to 4, such as 1 or 2). The aromatic group and the cyclic aliphatic group may be substituted or unsubstituted.
上述含氟之丙烯酸酯單體可例示如下：The above fluorine-containing acrylate monomer can be exemplified as follows:
Rf-(CH2)10OCOCH=CH2Rf-(CH2 )10 OCOCH=CH2
Rf-(CH2)10OCOC(CH3)=CH2Rf-(CH2 )10 OCOC(CH3 )=CH2
Rf-CH2OCOCH=CH2Rf-CH2 OCOCH=CH2
Rf-CH2OCOC(CH3)=CH2Rf-CH2 OCOC(CH3 )=CH2
Rf-(CH2)2OCOCH=CH2Rf-(CH2 )2 OCOCH=CH2
Rf-(CH2)2OCOC(CH3)=CH2Rf-(CH2 )2 OCOC(CH3 )=CH2
Rf-SO2N(CH3)(CH2)2OCOCH=CH2Rf-SO2 N(CH3 )(CH2 )2 OCOCH=CH2
Rf-SO2N(C2H5)(CH2)2OCOCH=CH2Rf-SO2 N(C2 H5 )(CH2 )2 OCOCH=CH2
Rf-CH2CH(OCOCH3)CH2OCOC(CH3)=CH2Rf-CH2 CH(OCOCH3 )CH2 OCOC(CH3 )=CH2
Rf-CH2CH(OH)CH2OCOCH=CH2Rf-CH2 CH(OH)CH2 OCOCH=CH2
[式中，Rf基較佳係碳數1至7之直鏈狀或分支狀之氟烷基、碳數2至7之氟烯基、或選自重複單元：-C3F6O-、-C2F4O-及-CF2O-所成組群中之至少一種重複單元之合計數為1至200之氟醚基]。[wherein, the Rf group is preferably a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: -C3 F6 O-, The total number of at least one repeating unit in the group of -C2 F4 O- and -CF2 O- is 1 to 200 fluoroether groups].
含胺基之單體(B)係具有胺基與碳-碳雙鍵之化合物。含胺基之單體(B)係以不含有氟原子為佳。The amine group-containing monomer (B) is a compound having an amine group and a carbon-carbon double bond. The amine group-containing monomer (B) is preferably one which does not contain a fluorine atom.
含胺基之單體(B)係例示如下述式(II)所示者：The amine group-containing monomer (B) is exemplified as shown in the following formula (II):
[式中，R11、R12、R21係相同或不同，表示氫原子或碳數1至4之烷基；Y11係氧原子或NH；Z係碳數1至10之分支狀或直鏈狀之伸烷基；R11與R12可互相結合而與鄰接之氮原子一起形成環]。Wherein R11 , R12 and R21 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a Y11 -based oxygen atom or NH; a Z-based branched or straight carbon number of 1 to 10; a chain extending alkyl group; R11 and R12 may be bonded to each other to form a ring together with an adjacent nitrogen atom].
由於共聚物含有胺基，故例如以質子酸形成鹽時，則當溶解於水時會解離而呈現陽離子性。Since the copolymer contains an amine group, for example, when a salt is formed with a protonic acid, it dissociates when it is dissolved in water to exhibit cationicity.
R11、R12、R21分別表示氫原子或碳數1至4之烷基(例如甲基、乙基、丙基、丁基等)。R21係以氫原子或甲基為較佳。當R11與R12互相結合並與鄰接之氮原子一起形成環時，R11與R12亦可隔介氮原子、氧原子、硫原子等雜原子而結合。由R11與R12互相結合並與鄰接之氮原子所一起形成之環，可列舉如氮丙啶(aziridine)環、吡咯啶環、哌啶環、哌環、嗎啉環等。R11 , R12 and R21 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, etc.). R21 is preferably a hydrogen atom or a methyl group. When R11 and R12 are bonded to each other and form a ring together with an adjacent nitrogen atom, R11 and R12 may be bonded via a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. The ring formed by R11 and R12 bonded to each other and to the adjacent nitrogen atom may, for example, be an aziridine ring, a pyrrolidine ring, a piperidine ring or a piperidine. Ring, morpholine ring, etc.
就Z之伸烷基而言，可列舉如亞甲基(methylene)、伸乙基、伸丙基、三亞甲基、四亞甲基、六亞甲基等分支狀或直鏈狀之碳數1至6(較佳為碳數1至4)之伸烷基。Examples of the alkyl group of Z may include a branched or linear carbon number such as a methylene group, an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, or a hexamethylene group. An alkylene group of 1 to 6 (preferably having 1 to 4 carbon atoms).
含胺基之單體(B)之具體例可列舉如：(甲基)丙烯酸二甲基胺基甲酯、(甲基)丙烯酸二乙基胺基甲酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯、(甲基)丙烯酸二乙基胺基丙酯等在化學式(II)中Y11為氧原子之化合物；二甲基胺基乙基(甲基)丙烯醯胺、二甲基胺基丙基(甲基)丙烯醯胺等在化學式(II)中Y11為NH之化合物等。含胺基之單體(B)可單獨使用，亦可組合2種以上使用。Specific examples of the amino group-containing monomer (B) include dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, and dimethyl (meth)acrylate. Aminoethyl ester, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, etc. in the chemical formula (II) a compound in which Y11 is an oxygen atom; a compound in which Y11 is NH in the chemical formula (II), such as dimethylaminoethyl (meth) acrylamide or dimethylaminopropyl (meth) acrylamide Wait. The amine group-containing monomer (B) may be used singly or in combination of two or more.
構成含氟聚合物之單體，除了單體(A)及單體(B)以外，亦可含有親水性非氟單體(C)。親水性非氟單體(C)具有親水性，不含有氟原子。The monomer constituting the fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to the monomer (A) and the monomer (B). The hydrophilic non-fluorine monomer (C) is hydrophilic and does not contain a fluorine atom.
親水性基之例為氧基伸烷基。An example of a hydrophilic group is an alkyloxy group.
親水性非氟單體(C)亦可為具有屬於氧基伸烷基(伸烷基之碳數為2至6)之親水性基及碳-碳雙鍵的單體。The hydrophilic non-fluorine monomer (C) may also be a monomer having a hydrophilic group and a carbon-carbon double bond which are an alkylene group (the alkyl group has a carbon number of 2 to 6).
屬於氧基伸烷基之親水性基係非離子性。親水性非氟單體(C)中之氧基伸烷基之數為2至200，例如可為3至50。The hydrophilic group belonging to the oxyalkylene group is nonionic. The number of alkyloxy groups in the hydrophilic non-fluorine monomer (C) is from 2 to 200, for example, from 3 to 50.
親水性非氟單體(C)亦可為聚烷二醇單(甲基)丙烯酸酯及/或聚烷二醇二(甲基)丙烯酸酯。The hydrophilic non-fluorine monomer (C) may also be a polyalkylene glycol mono(meth)acrylate and/or a polyalkylene glycol di(meth)acrylate.
親水性非氟單體(C)之分子量為100以上，例如可為150以上，尤其可為200以上，特別是可為250至3000。The hydrophilic non-fluorine monomer (C) has a molecular weight of 100 or more, and may be, for example, 150 or more, particularly 200 or more, and particularly preferably 250 to 3,000.
聚烷二醇單(甲基)丙烯酸酯宜為下述通式(III)所示者：The polyalkylene glycol mono(meth)acrylate is preferably one represented by the following formula (III):
CH2=CX1C(=O)-O-(RO)n-X2 (III)CH2 =CX1 C(=O)-O-(RO)n -X2 (III)
[式中，X1為氫原子或甲基，X2為氫原子或碳數1至22之不飽和或飽和之烴基，R為碳數2至6之伸烷基，n為2至90之整數]。n特別可為3至30，尤其可為例如4至20。Wherein X1 is a hydrogen atom or a methyl group, X2 is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is a C 2 to 6 alkylene group, and n is 2 to 90 Integer]. n may in particular be from 3 to 30, in particular for example from 4 to 20.
通式(III)中之R係以伸乙基、伸丙基及伸丁基為佳，尤以伸乙基為特佳。The R in the formula (III) is preferably an ethyl group, a propyl group and a butyl group, and particularly preferably an ethyl group.
通式(III)中之R亦可為2種以上伸烷基之組合。此時，以R之至少一者為伸乙基較佳。R之組合可列舉如伸乙基/伸丙基之組合、伸乙基/伸丁基之組合。R in the formula (III) may also be a combination of two or more kinds of alkylene groups. In this case, it is preferred that at least one of R is an ethylidene group. The combination of R may, for example, be a combination of an exoethyl/extended propyl group and a combination of an exoethyl/t-butyl group.
親水性非氟單體(C)可為2種以上之混合物。此時，以親水性非氟單體(C)之至少一者係通式(III)中之R為伸乙基者較佳。The hydrophilic non-fluorinated monomer (C) may be a mixture of two or more kinds. In this case, it is preferred that at least one of the hydrophilic non-fluorine monomers (C) is R in the formula (III).
親水性非氟單體(C)之具體例可例示如下述者，惟不限定於此等：Specific examples of the hydrophilic non-fluorinated monomer (C) are exemplified as follows, but are not limited thereto:
CH2=CX1COO-(CH2CH2O)n-HCH2 =CX1 COO-(CH2 CH2 O)n -H
CH2=CX1-(CH2CH2O)n-CH3CH2 =CX1 -(CH2 CH2 O)n -CH3
CH2=CX1COO-(CH2CH(CH3)O)n-HCH2 =CX1 COO-(CH2 CH(CH3 )O)n -H
CH2=CX1COO-(CH2CH(CH3)O)n-CH3CH2 =CX1 COO-(CH2 CH(CH3 )O)n -CH3
CH2=CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)2-HCH2 =CX1 COO-(CH2 CH2 O)5 -(CH2 CH(CH3 )O)2 -H
CH2=CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3CH2 =CX1 COO-(CH2 CH2 O)5 -(CH2 CH(CH3 )O)3 -CH3
CH2=CX1COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9CH2 =CX1 COO-(CH2 CH2 O)8 -(CH2 CH(CH3 )O)6 -CH2 CH(C2 H5 )C4 H9
CH2=CX1COO-(CH2CH2O)23-OOC(CH3)C=CH2CH2 =CX1 COO-(CH2 CH2 O)23 -OOC(CH3 )C=CH2
CH2=CX1COO-(CH2CH2O)20-(CH2CH(CH3)O)5-CH2-CH=CH2CH2 =CX1 COO-(CH2 CH2 O)20 -(CH2 CH(CH3 )O)5 -CH2 -CH=CH2
構成含氟聚合物之單體，除了單體(A)、單體(B)、單體(C)以外，亦可因應需要而含有其他單體(D)。其他單體(D)係以非氟單體為佳。其他單體(D)之例可例示如含有烴基之單體、乙烯、乙酸乙烯酯、鹵化乙烯(vinyl halide)(例如氯化乙烯)、偏二鹵乙烯(vinylidene halide)(例如偏二氯乙烯)、丙烯腈、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸3-氯-2-羥基丙酯、乙烯基烷基酮、乙烯基烷基醚、異戊二烯(isoprene)、氯丁二烯(chloroprene)、丁二烯等，惟不限定於此等。The monomer constituting the fluoropolymer may contain other monomers (D) as needed in addition to the monomer (A), the monomer (B), and the monomer (C). The other monomer (D) is preferably a non-fluorinated monomer. Examples of the other monomer (D) may, for example, be a monomer having a hydrocarbon group, ethylene, vinyl acetate, vinyl halide (e.g., chlorinated ethylene), vinylidene halide (e.g., vinylidene chloride). ), acrylonitrile, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, mono (meth) acrylate, tetrahydrofuran (meth) acrylate, (meth) acrylate 3 -chloro-2-hydroxypropyl ester, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, butadiene, etc., but is not limited thereto.
其他單體(D)之其他例可列舉如具有矽烷基之單體。具有矽烷基之單體係以具有矽烷基(尤其是末端矽烷基)及碳-碳雙鍵之化合物為較佳。具有矽烷基之單體可為具有末端矽烷偶合劑、或在側鏈具有矽烷偶合劑之單體。Other examples of the other monomer (D) include a monomer having a decyl group. A single system having a decyl group is preferably a compound having a decyl group (especially a terminal decyl group) and a carbon-carbon double bond. The monomer having a decyl group may be a monomer having a terminal decane coupling agent or a decane coupling agent in a side chain.
具有矽烷基之單體之具體例係如下述：Specific examples of the monomer having a decyl group are as follows:
CH2=CHCO2(CH2)3Si(OCH3)3、CH2 =CHCO2 (CH2 )3 Si(OCH3 )3 ,
CH2=CHCO2(CH2)3Si(OC2H5)3、CH2 =CHCO2 (CH2 )3 Si(OC2 H5 )3 ,
CH2=C(CH3)CO2(CH2)3Si(OCH3)3CH2 =C(CH3 )CO2 (CH2 )3 Si(OCH3 )3
(γ-甲基丙烯醯氧基丙基三甲氧基矽烷)、(γ-methacryloxypropyltrimethoxydecane),
CH2=C(CH3)CO2(CH2)3Si(OC2H5)3、CH2 =C(CH3 )CO2 (CH2 )3 Si(OC2 H5 )3 ,
CH2=CHCO2(CH2)3SiCH3(OC2H5)2、CH2 =CHCO2 (CH2 )3 SiCH3 (OC2 H5 )2 ,
CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2、CH2 =C(CH3 )CO2 (CH2 )3 SiC2 H5 (OCH3 )2 ,
CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5)、CH2 =C(CH3 )CO2 (CH2 )3 Si(CH3 )2 (OC2 H5 ),
CH2=C(CH3)CO2(CH2)3Si(CH3)2OH、CH2 =C(CH3 )CO2 (CH2 )3 Si(CH3 )2 OH,
CH2=CHCO2(CH2)3SiCH3[ON(CH3)C2H5]2、CH2 =CHCO2 (CH2 )3 SiCH3 [ON(CH3 )C2 H5 ]2 ,
CH2=C(CH3)CO2(CH2)3SiC6H5[ON(CH3)C2H5]2、CH2 =C(CH3 )CO2 (CH2 )3 SiC6 H5 [ON(CH3 )C2 H5 ]2 ,
CH2=CHSi(OCH3)3、CH2 =CHSi(OCH3 )3 ,
CH2=CHSi(OC2H5)3、CH2 =CHSi(OC2 H5 )3 ,
CH2=CHSiCH8(OCH3)2、CH2 =CHSiCH8 (OCH3 )2 ,
CH2=CHSi(CH3)2(OC2H5)、CH2 =CHSi(CH3 )2 (OC2 H5 ),
CH2=CHSi(CH3)2SiCH3(OCH3)2、CH2 =CHSi(CH3 )2 SiCH3 (OCH3 )2 ,
CH2=CHsiCH3[ON(CH3)C2H5]2、CH2 =CHsiCH3 [ON(CH3 )C2 H5 ]2 ,
乙烯基三氯矽烷、乙烯基參(2-甲氧基乙氧基)矽烷。Vinyl trichloromethane, vinyl ginseng (2-methoxyethoxy) decane.
含氟聚合物之重量平均分子量為例如1000至1000000，特別為2000至100000，尤其可為4000至20000。含氟聚合物之重量平均分子量係依GPC(凝膠滲透層析法)所求得者(換算成聚苯乙烯)。The weight average molecular weight of the fluoropolymer is, for example, from 1,000 to 1,000,000, particularly from 2,000 to 100,000, particularly from 4,000 to 20,000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (in terms of polystyrene).
含氟聚合物係溶解於水。含氟聚合物之溶解度(於25℃中，可能溶解於100g水之含氟聚合物之量)係5g以上，可為10g以上，尤其可為20g以上。溶解度之上限為500g，例如可為200g。The fluoropolymer is dissolved in water. The solubility of the fluoropolymer (the amount of the fluoropolymer which may be dissolved in 100 g of water at 25 ° C) is 5 g or more, and may be 10 g or more, and particularly 20 g or more. The upper limit of the solubility is 500 g, for example, 200 g.
含氟聚合物可由衍生自下述單體之重複單元之組合所構成：The fluoropolymer may consist of a combination of repeating units derived from the following monomers:
(1)單體(A)＋單體(B)(1) Monomer (A) + Monomer (B)
(2)單體(A)＋單體(B)＋單體(C)(2) Monomer (A) + Monomer (B) + Monomer (C)
(3)單體(A)＋單體(B)＋單體(D)(3) Monomer (A) + Monomer (B) + Monomer (D)
(4)單體(A)＋單體(B)＋單體(C)＋單體(D)(4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)
在含氟聚合物中，相對於單體(A)100重量份，單體(B)之量為1至500重量份，例如可為2至100重量份，特別為3至80重量份，尤其可為5至70重量份；單體(C)之量為0至10重量份，例如可為1至5重量份；單體(D)之量為0至10重量份，例如可為1至5重量份。In the fluoropolymer, the amount of the monomer (B) is from 1 to 500 parts by weight, based on 100 parts by weight of the monomer (A), for example, may be from 2 to 100 parts by weight, particularly from 3 to 80 parts by weight, particularly It may be 5 to 70 parts by weight; the amount of the monomer (C) is 0 to 10 parts by weight, for example, may be 1 to 5 parts by weight; the amount of the monomer (D) is 0 to 10 parts by weight, for example, may be 1 to 5 parts by weight.
本發明之含氟聚合物可藉由任一種通常之聚合方法而製造，另外，亦可任意選擇聚合反應之條件。此等聚合方法可列舉如溶液聚合、懸濁聚合、乳化聚合。尤以溶液聚合為特佳。The fluoropolymer of the present invention can be produced by any usual polymerization method, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Especially solution polymerization is particularly preferred.
就溶液聚合而言，係採用在聚合起始劑之存在下，使單體溶解於有機溶劑，並予以氮氣取代後，例如在50至120℃之範圍中加熱攪拌1至10小時的方法。聚合起始劑可列舉如偶氮雙異丁腈、偶氮雙異戊腈、過氧化苯甲醯、過氧化二(第三丁基)、過氧化月桂醯、氫過氧化異丙苯、過氧化三甲基乙酸第三丁酯(t-butyl peroxypivalate)、過氧化二碳酸二異丙酯等。相對於單體100重量份，聚合起始劑可以0.01至5重量份之範圍使用。In the case of solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator and substituted with nitrogen, for example, heating and stirring in the range of 50 to 120 ° C for 1 to 10 hours is employed. The polymerization initiator may, for example, be azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, bis(tert-butyl peroxide), laurel peroxide, cumene hydroperoxide or the like. Oxidized t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator may be used in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.
有機溶劑係對單體為惰性且可溶解該等單體者，可列舉如戊烷、己烷、庚烷、辛烷、異辛烷、環己烷、苯、甲苯、二甲苯、石油醚、市售石油系溶劑(例如Exxon Mobil公司製EXXSOL D40、ISOPER E等)、四氫呋喃、1,4-二烷、丙酮、甲基乙基酮、甲基異丁基酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸第三丁酯、異丙醇、丙二醇甲基醚乙酸酯、對氯三氟甲苯(p-chlorobenzotrifluoride)、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、全氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。相對於單體之合計100重量份，有機溶劑可以50至1000重量份之範圍使用。The organic solvent is inert to the monomer and can dissolve the monomers, and examples thereof include pentane, hexane, heptane, octane, isooctane, cyclohexane, benzene, toluene, xylene, petroleum ether, and the like. Commercially available petroleum solvents (such as EXXSOL D40, ISOPER E, etc. by Exxon Mobil Co., Ltd.), tetrahydrofuran, 1,4-two Alkane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, tert-butyl acetate, isopropanol, propylene glycol methyl ether acetate, p-chlorotrim P-chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloros Fluoroethane and the like. The organic solvent may be used in the range of 50 to 1000 parts by weight based on 100 parts by weight of the total of the monomers.
聚合反應後，藉由將水加入反應混合物中並去除(以蒸餾等)有機溶劑，即可獲得聚合物之水溶液。After the polymerization, an aqueous solution of the polymer can be obtained by adding water to the reaction mixture and removing (by distillation, etc.) the organic solvent.
在本發明中，塗覆劑(例如撥水撥油劑或防污劑)係含有(1)含氟聚合物及(2)水性液狀媒質(亦即水、或水與水溶性有機溶劑之混合物)。水溶性有機溶劑可列舉如：醇類，例如甲醇、乙醇、正丙醇、異丙醇；酮類，例如丙酮等。相對於混合物(水與水溶性有機溶劑之合計)，水溶性有機溶劑之量係50重量%以下，例如可為1至30重量%。In the present invention, a coating agent (for example, a water-repellent oil-repellent agent or an antifouling agent) contains (1) a fluoropolymer and (2) an aqueous liquid medium (that is, water, or water and a water-soluble organic solvent). mixture). The water-soluble organic solvent may, for example, be an alcohol such as methanol, ethanol, n-propanol or isopropanol; or a ketone such as acetone. The amount of the water-soluble organic solvent is 50% by weight or less, for example, 1 to 30% by weight based on the mixture (the total of water and the water-soluble organic solvent).
塗覆劑之型態為含氟聚合物之溶液(水溶液)。The type of coating agent is a solution (aqueous solution) of a fluoropolymer.
在塗覆劑中，含氟聚合物之量並無特別限定，只要從可均一溶解之範圍中適當選擇即可。例如相對於塗覆劑，含氟聚合物之量為0.1至50重量%，例如可為0.2至20重量%，尤其可為0.5至10重量%。The amount of the fluoropolymer in the coating agent is not particularly limited as long as it is appropriately selected from the range in which the coating can be uniformly dissolved. For example, the amount of the fluoropolymer is from 0.1 to 50% by weight, for example from 0.2 to 20% by weight, especially from 0.5 to 10% by weight, relative to the coating agent.
本發明之塗覆劑中除了(1)含氟聚合物及(2)水性液狀媒質以外，亦可含有(3)添加劑。The coating agent of the present invention may contain (3) an additive in addition to the (1) fluoropolymer and (2) aqueous liquid medium.
(3)添加劑例如為含矽化合物等。(3) The additive is, for example, a ruthenium containing compound or the like.
含矽化合物係以具有至少一個矽氧烷鍵之化合物為佳。含矽化合物一般係指具有矽烷基之單體以外的化合物。The ruthenium containing compound is preferably a compound having at least one decane bond. The ruthenium-containing compound generally means a compound other than the monomer having a decyl group.
含矽化合物例如為矽酸烷基酯(alkyl silicate)、矽酸鹽(siliconate)等。The cerium-containing compound is, for example, an alkyl silicate, a siliconate or the like.
矽酸烷基酯之例，可例示如下述通式(I)所示者：Examples of the alkyl phthalate are exemplified by the following formula (I):
[式中，R1n表示碳數1至18之烷基，當nn為2以上時，該等可為相同或不同；R2n表示氫原子或碳數1至5之烷基，當nn為2以上時，該等可為相同或不同；nn表示1至20之整數]。[wherein, R1n represents an alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, the same may be the same or different; and R2n represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, when nn is 2 In the above, the terms may be the same or different; nn represents an integer from 1 to 20].
關於上述R1n，就碳數l至18之烷基(亦即飽和鏈狀脂肪族烴基)而言並無特別限定，可列舉如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等，此等可為直鏈狀或分支狀。The above R1n is not particularly limited in terms of an alkyl group having 1 to 18 carbon atoms (that is, a saturated chain aliphatic hydrocarbon group), and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. , heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl An alkyl group or the like, which may be linear or branched.
關於上述R2n，就碳數1至5之烷基而言並無特別限定，可列舉如甲基、乙基、丙基、丁基、戊基等，此等可為直鏈狀或分支狀。The above R2n is not particularly limited in terms of the alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and these may be linear or branched. .
上述nn為1至20之整數，例如為1至10之整數。The above nn is an integer of 1 to 20, for example, an integer of 1 to 10.
就矽酸烷基酯而言，更具體之例可列舉如甲基三甲氧基矽烷、乙基三甲氧基矽烷、丙基三甲氧基矽烷、丁基三甲氧基矽烷、戊基三甲氧基矽烷、己基三甲氧基矽烷、庚基三甲氧基矽烷、辛基三甲氧基矽烷、壬基三甲氧基矽烷、癸基三甲氧基矽烷、十一烷基三甲氧基矽烷、十二烷基三甲氧基矽烷、十三烷基三甲氧基矽烷、十四烷基三甲氧基矽烷、十五烷基三甲氧基矽烷、十六烷基三甲氧基矽烷、十七烷基三甲氧基矽烷、十八烷基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三乙氧基矽烷、丙基三乙氧基矽烷、丁基三乙氧基矽烷、戊基三乙氧基矽烷、己基三乙氧基矽烷、庚基三乙氧基矽烷、辛基三乙氧基矽烷、壬基三乙氧基矽烷、癸基三乙氧基矽烷、十一烷基三乙氧基矽烷、十二烷基三乙氧基矽烷、十三烷基三乙氧基矽烷、十四烷基三乙氧基矽烷、十五烷基三乙氧基矽烷、十六烷基三乙氧基矽烷、十七烷基三乙氧基矽烷、十八烷基三乙氧基矽烷等，其中以甲基三甲氧基矽烷、甲基三乙氧基矽烷、己基三乙氧基矽烷、辛基三乙氧基矽烷為較佳。As the alkyl phthalate, a more specific example may, for example, be methyltrimethoxydecane, ethyltrimethoxydecane, propyltrimethoxydecane, butyltrimethoxydecane or pentyltrimethoxydecane. , hexyltrimethoxydecane, heptyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane,decyltrimethoxydecane,undecyltrimethoxydecane,dodecyltrimethoxy Baseline, tridecyltrimethoxydecane, tetradecyltrimethoxydecane, pentadecyltrimethoxydecane,hexadecyltrimethoxydecane,heptadecyltrimethoxydecane,eighteen Alkyl trimethoxy decane, methyl triethoxy decane, ethyl triethoxy decane, propyl triethoxy decane, butyl triethoxy decane, pentyl triethoxy decane, hexyl triethyl Oxydecane, heptyltriethoxydecane, octyltriethoxydecane, decyltriethoxydecane,decyltriethoxydecane,undecyltriethoxydecane,dodecyl Triethoxy decane, tridecyl triethoxy decane, tetradecyl triethoxy decane, pentadecane Triethoxy decane, cetyl triethoxy decane, heptadecyl triethoxy decane, octadecyl triethoxy decane, etc., among which methyl trimethoxy decane, methyl triethyl Oxydecane, hexyltriethoxydecane, and octyltriethoxydecane are preferred.
另外，含矽化合物之二聚物等亦可作為含矽化合物使用，此等可列舉如上述通式(I)中之nn為2或3者等。另外，亦可為nn係至20為止之整數者。Further, a dimer or the like containing a ruthenium compound may be used as the ruthenium-containing compound, and examples thereof include those in which the nn of the above formula (I) is 2 or 3. In addition, it may be an integer from nn to 20.
矽酸鹽(siliconate)(尤其是烷基矽酸鹽)係例如以下述式所示之化合物：A siliconate (especially an alkyl silicate) is, for example, a compound represented by the following formula:
式：R1aSi(OR2)b(OM)cFormula: R1a Si(OR2 )b (OM)c
[式中，a為0以上之整數(較佳為1)，b為0以上之整數(較佳為2)，c為1以上之整數(較佳為1)，且滿足a＋b＋c=4；R1可為相同或不同，表示碳數1至18之烴基；R2可為相同或不同，表示氫原子或碳數1至18之烴基；M可為相同或不同，表示鹼金屬]。Wherein a is an integer of 0 or more (preferably 1), b is an integer of 0 or more (preferably 2), c is an integer of 1 or more (preferably 1), and satisfies a+b+c=4;1 may be the same or different and represent a hydrocarbon group having 1 to 18 carbon atoms; R2 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms; M may be the same or different and represent an alkali metal].
烴基為例如脂肪族烴基(例如烷基)、脂環式烴基、芳香族烴基或芳香脂肪族烴基。The hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group.
R1可列舉如甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、第三戊基、正己基、正庚基、正辛基、異辛基、2,2,4-三甲基戊基、正壬基、正癸基、正十二烷基、正十八烷基、環戊基、環己基、環庚基、甲基環己基、苯基、萘基、蔥基、菲基、甲苯基、二甲苯基、乙苯基、苯甲基、苯乙基等。其中以甲基、乙基、丙基為佳，尤以甲基為特佳。R1 may, for example, be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, third pentyl or n-hexyl. , n-heptyl, n-octyl, isooctyl, 2,2,4-trimethylpentyl, n-decyl, n-decyl, n-dodecyl, n-octadecyl, cyclopentyl, ring Hexyl, cycloheptyl, methylcyclohexyl, phenyl, naphthyl, onion, phenanthryl, tolyl, xylyl, ethylphenyl, benzyl, phenethyl and the like. Among them, a methyl group, an ethyl group and a propyl group are preferred, and a methyl group is particularly preferred.
就R2而言，除了氫原子以外，可列舉如與R1同樣之基。其中以氫原子、甲基、乙基為佳，尤以氫原子為特佳。R2 is the same as R1 except for a hydrogen atom. Among them, a hydrogen atom, a methyl group, and an ethyl group are preferred, and a hydrogen atom is particularly preferred.
M可列舉如鋰、鈉、鉀等，尤以鈉為特佳。M may, for example, be lithium, sodium, potassium or the like, and particularly sodium is particularly preferred.
烷基矽酸鹽之具體例為甲基矽酸鈉[CH3Si(OH)2(ONa)]、或乙基矽酸鉀[C2H5Si(OH)2(OK)]。Specific examples of the alkyl phthalate are sodium methyl citrate [CH3 Si(OH)2 (ONa)] or potassium ethyl citrate [C2 H5 Si(OH)2 (OK)].
相對於含氟聚合物(1)100重量份，添加劑(3)之量為0至200重量份，例如可為0至50重量份，尤其可為0.1至50重量份。The amount of the additive (3) is from 0 to 200 parts by weight, for example, from 0 to 50 parts by weight, particularly from 0.1 to 50 parts by weight, based on 100 parts by weight of the fluoropolymer (1).
再者，在塗覆劑中，除了上述成分(1)至(3)以外，亦可因應需要而含有其他撥水劑、其他撥油劑、螢光劑、乾燥速度調整劑、交聯劑、製膜助劑、相溶化劑、界面活性劑、凍結防止劑、黏度調整劑、紫外線吸收劑、抗氧化劑、pH調整劑、消泡劑、光滑性調整劑、抗靜電劑、親水化劑、抗菌劑、防腐劑、防蟲劑、芳香劑、阻燃劑、色調調整劑等。Further, in the coating agent, in addition to the above components (1) to (3), other water-repellent agents, other oil-repellent agents, fluorescent agents, drying speed adjusting agents, and crosslinking agents may be contained as needed. Film forming aid, compatibilizing agent, surfactant, freezing inhibitor, viscosity adjusting agent, ultraviolet absorber, antioxidant, pH adjuster, antifoaming agent, smoothness adjusting agent, antistatic agent, hydrophilizing agent, antibacterial Agents, preservatives, insect repellents, fragrances, flame retardants, color tone adjusters, etc.
在本發明中，係將塗覆劑塗佈於基材而對基材賦予防濕性。In the present invention, a coating agent is applied to a substrate to impart moisture resistance to the substrate.
就基材而言，有電子零件及電氣零件等。在本案說明書中，當僅言及「電子零件」時，不僅意指電子零件，亦意指電氣零件。As far as the substrate is concerned, there are electronic parts and electrical parts. In the present specification, when referring only to "electronic parts", it means not only electronic parts but also electrical parts.
不論是在屋外、屋內，基材皆意指在曝露於濕氣之處所配置之電子零件及電氣零件，且該等為裝設有電路及各種元件之電子零件及電氣零件。基材可列舉如電路基板、硬碟之軸承等。電子零件及電氣零件係使用於例如電話、信號機、冷氣機之室外機、配電盤、柱上冷凝器、手機、攜帶式中繼天線、汽車電子機器、船之電子機器、自動販賣機、行動電腦等物品中。Regardless of whether it is outside the house or inside the house, the substrate means electronic parts and electrical parts that are placed in the place where it is exposed to moisture, and these are electronic parts and electrical parts in which circuits and various components are mounted. Examples of the substrate include a circuit board, a bearing of a hard disk, and the like. Electronic parts and electrical parts are used in outdoor units such as telephones, signal machines, air conditioners, switchboards, on-column condensers, mobile phones, portable relay antennas, automotive electronic equipment, marine electronic machines, vending machines, mobile computers. And other items.
電子零件可例示如各種印刷配線基板(電子電路基板)、混合積體電路(hybrid integrated circuit)等，但不限定於此等。The electronic component can be exemplified by various printed wiring boards (electronic circuit boards), hybrid integrated circuits, and the like, but is not limited thereto.
此等電子零件之基板材料係使用環氧樹脂、酚樹脂、BT樹脂、聚醯亞胺、玻璃基布(纖維)、鋁等，並且電路材料係使用銅、銀、金、鉑等金屬，另外，焊料係點狀分布於基板上。本發明之塗覆劑組成物係不會使此等材料變質者。The substrate material of these electronic parts is made of epoxy resin, phenol resin, BT resin, polyimide, glass cloth (fiber), aluminum, etc., and the circuit material is made of metal such as copper, silver, gold or platinum. The solder is dotted on the substrate. The coating composition of the present invention does not degrade such materials.
另外，就電氣零件而言，除了內藏有上述電子零件之各種電氣裝置以外，亦可例示如配電盤等。具體而言，可例示如冷氣機之室外機、手機、汽車導航器、太陽電池面板、照明、信號機、攜帶式中繼天線、汽車電子機器、自動販賣機、行動電腦、無人天線台、無線機、船舶機器、時鐘等。In addition, as for the electrical components, in addition to various electrical devices in which the above-described electronic components are incorporated, for example, a switchboard or the like can be exemplified. Specifically, for example, an outdoor unit such as an air conditioner, a mobile phone, a car navigator, a solar cell panel, an illumination, a signal, a portable relay antenna, a car electronic device, a vending machine, a mobile computer, an unmanned antenna station, and a wireless device can be exemplified. Machines, ship machines, clocks, etc.
將塗覆劑以刷塗法或浸漬法、噴霧法、輥塗法、封膠法(potting method)、澆鑄法等塗佈，將其靜置於周圍環境使水性狀媒質揮發而形成塗覆被膜。The coating agent is applied by a brushing method or a dipping method, a spraying method, a roll coating method, a potting method, a casting method, or the like, and is allowed to stand in the surrounding environment to volatilize the aqueous medium to form a coating film. .
在本發明中，塗覆被膜係由塗覆組成物所製成之薄膜，例如可為澆鑄薄膜。此薄膜係藉由將電子/電氣零件包覆而獲得防濕效果。In the present invention, the coating film is a film made of a coating composition, and may be, for example, a cast film. This film is moisture-proof by coating electronic/electrical parts.
以塗覆劑處理(尤其是塗佈)基材。關於塗覆劑之量，以塗覆劑中之含氟聚合物計，為0.05至50g/m2，例如為0.1至25g/m2，以0.5至5.0g/m2為較佳。塗佈可1次進行，亦可分成複數次進行。The substrate is treated (especially coated) with a coating agent. The amount of coating agent, the coating agent to the fluorine-containing polymer basis, from 0.05 to 50g / m2, for example 0.1 to 25g / m2, 0.5 to 5.0g / m2 is preferred. The coating can be carried out once or in multiples.
「處理」係指將處理劑藉由浸漬、噴霧、塗佈等而使用於基板。藉由處理，即可使處理劑之有效成分之含氟聚合物附著於基材之表面(及/或滲透至基材之內部)。"Processing" means that the treating agent is used for the substrate by dipping, spraying, coating, or the like. By treatment, the fluoropolymer of the active ingredient of the treating agent can be attached to the surface of the substrate (and/or penetrated into the interior of the substrate).
以下，列示實施例及比較例而具體說明本發明，惟此等僅為本發明之具體例，並未因此而限定本發明。以下之「%」若未特別註明，即表示「重量%」。Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but these are only specific examples of the invention, and are not intended to limit the invention. The following "%" means "% by weight" unless otherwise specified.
本發明及以下之實施例中所採用之試驗法及測定法係如下所述。The test methods and assays used in the present invention and the following examples are as follows.
使用接觸角計(協和界面科學股份有限公司製，CONTACT-ANGLE METER CA-DT)評估試驗片之銅箔部之撥水撥油性。The water repellency of the copper foil portion of the test piece was evaluated using a contact angle meter (CONTACT-ANGLE METER CA-DT, manufactured by Kyowa Interface Science Co., Ltd.).
以電阻測定機(Advantest股份有限公司製，ULTRA HIGH RESISTANCE METER R8340A)測定試驗片之表面電阻。The surface resistance of the test piece was measured with a resistance measuring machine (ULTRA HIGH RESISTANCE METER R8340A, manufactured by Advantest Co., Ltd.).
將試驗片浸漬於25℃之脫離子水中24小時。以電阻測定機測定浸漬後之試驗片之表面電阻。The test piece was immersed in deionized water at 25 ° C for 24 hours. The surface resistance of the test piece after the immersion was measured by a resistance measuring machine.
在裝設有梳型電極基板之玻璃纖維補強環氧樹脂板，以刷塗法塗佈塗覆劑後，一邊於室溫乾燥，一邊以電阻測定機測定試驗片之表面電阻。The glass fiber reinforced epoxy resin sheet provided with the comb-shaped electrode substrate was coated with a coating agent by a brush coating method, and then dried at room temperature, and the surface resistance of the test piece was measured by a resistance measuring machine.
將試驗片放入維持於85℃及85%RH之高溫高濕槽中48小時，持續施加16V之恆電壓。測定電阻值時，外加100V之電壓，檢視高溫高濕下之電阻值之經時變化。The test piece was placed in a high-temperature and high-humidity bath maintained at 85 ° C and 85% RH for 48 hours, and a constant voltage of 16 V was continuously applied. When the resistance value is measured, a voltage of 100 V is applied, and the time-dependent change of the resistance value under high temperature and high humidity is examined.
將CF3CF2-(CF2CF2)2-CH2CH2OCOC(CH3)=CH2[Rf(C6)甲基丙烯酸酯]73.30g、甲基丙烯酸二甲基胺基乙酯(DM)26.70g、異丙醇(IPA)150.00g於四口燒瓶中攪拌溶解，一邊進行氮氣取代，一邊保持於60℃中，然後添加過氧化三甲基乙酸第三丁酯2g，於60℃反應6小時而獲得聚合物溶液。以氣相層析法得知單體之轉化率為99%以上，藉此而確認聚合反應之結束。繼而，一邊於60℃攪拌此聚合物溶液，一邊於其中滴入CH3COOH(乙酸)10.20g與離子交換水300g之混合液。然後，減壓去除IPA，將此溶液之固形份於130℃加熱1小時，取得蒸發後之殘餘部分，將其以離子交換水稀釋至固形份成為25質量%，而獲得透明且安定之聚合物水溶液。73.30 g of CF3 CF2 -(CF2 CF2 )2 -CH2 CH2 OCOC(CH3 )=CH2 [Rf(C6) methacrylate], dimethylaminoethyl methacrylate ( DM) 26.70 g and 150.00 g of isopropyl alcohol (IPA) were stirred and dissolved in a four-necked flask, while maintaining nitrogen at 60 ° C, and then adding 2 g of tributyl peroxyacetate to 60 ° C. The reaction was carried out for 6 hours to obtain a polymer solution. The conversion of the monomer was found to be 99% or more by gas chromatography, whereby the end of the polymerization reaction was confirmed. Then, while stirring the polymer solution at 60 ° C, a mixed liquid of 10.20 g of CH3 COOH (acetic acid) and 300 g of ion-exchanged water was added dropwise thereto. Then, the IPA was removed under reduced pressure, and the solid portion of the solution was heated at 130 ° C for 1 hour to obtain a residue after evaporation, which was diluted with ion-exchanged water to a solid content of 25% by mass to obtain a transparent and stable polymer. Aqueous solution.
在製造例1中，除了將Rf(C6)甲基丙烯酸酯及DM分別變更成CF3CF2CF2CF2-CH2CH2OCOC(Cl)=CH2[Rf(C4)氯丙烯酸酯]63.00g及DM37.00g以外，其餘以與製造例1完全相同之方法製造成品，以其作為製造例2。另外，除了變更成CF3CF2-CH2OCOC(CH3)=CH2[Rf(C2)甲基丙烯酸酯]59.62g及DM40.38g以外，其餘以與製造例1完全相同之方法製造成品，以其作為製造例3。In Production Example 1, except that Rf(C6) methacrylate and DM were each changed to CF3 CF2 CF2 CF2 -CH2 CH2 OCOC(Cl)=CH2 [Rf(C4) chloroacrylate] A finished product was produced in the same manner as in Production Example 1 except for 63.00 g and DM 37.00 g, and this was designated as Production Example 2. Further, the finished product was produced in the same manner as in Production Example 1, except that it was changed to CF3 CF2 -CH2 OCOC(CH3 )=CH2 [Rf(C2) methacrylate] 59.62 g and DM 40.38 g. Take it as manufacturing example 3.
在裝設有梳型電極基板之玻璃纖維補強環氧樹脂板(材質：CEM3，板厚：1.6mm，銅箔厚：18μm，圖案寬度：0.75mm或0.3mm)，以刷塗法塗佈塗覆劑(製造例1至3之聚合物水溶液)後，使其乾燥而作成塗覆膜厚為2.7μm之試驗片。對於此試驗片(實施例1之經塗佈聚合物水溶液之試驗片)測定撥水撥油性、電阻值、耐高溫高濕性。結果示於表1至表4。A glass fiber reinforced epoxy resin sheet (material: CEM3, thickness: 1.6 mm, thickness of copper foil: 18 μm, pattern width: 0.75 mm or 0.3 mm) provided with a comb-shaped electrode substrate, coated by brush coating After the coating agent (the aqueous polymer solution of Production Examples 1 to 3), it was dried to prepare a test piece having a coating film thickness of 2.7 μm. The test piece (the test piece of the coated polymer aqueous solution of Example 1) was measured for water repellency, electric resistance, high temperature and high humidity resistance. The results are shown in Tables 1 to 4.
除了將塗覆膜厚變更為0.8μm以外，其餘重複進行與實施例1同樣之步驟。結果示於表1至表4。The same procedure as in Example 1 was repeated except that the coating film thickness was changed to 0.8 μm. The results are shown in Tables 1 to 4.
除了變更塗覆劑之種類及塗覆膜之厚度以外，其餘重複進行與實施例1同樣之步驟。比較例1係使用胺酯系分散液(三井化學聚胺酯股份有限公司製「Takelac W-6020」)與丙烯酸系分散液(日信化學工業股份有限公司製「Vinyblan TO-453N」)。結果示於表1至表4。The same procedure as in Example 1 was repeated except that the type of the coating agent and the thickness of the coating film were changed. In Comparative Example 1, an amine ester-based dispersion ("Takelac W-6020" manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) and an acrylic dispersion ("Vinyblan TO-453N" manufactured by Nissin Chemical Industry Co., Ltd.) were used. The results are shown in Tables 1 to 4.
本發明之塗覆劑係用於電子零件及電氣零件之防濕被覆。電子零件及電氣零件之例為電路基板、硬碟之軸承等。電子零件及電氣零件為例如電話、信號機、冷氣機之室外機、配電盤、柱上冷凝器、手機、攜帶式中繼天線、汽車電子機器、船之電子機器、自動販賣機、行動電腦等。The coating agent of the present invention is used for moisture-proof coating of electronic parts and electrical parts. Examples of the electronic component and the electrical component are a circuit board, a bearing of a hard disk, and the like. Electronic parts and electrical parts are, for example, telephones, signal machines, outdoor units of air conditioners, switchboards, on-column condensers, mobile phones, portable relay antennas, automotive electronic equipment, electronic machines for ships, vending machines, mobile computers, and the like.
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